graphene functionalization thesis

Title: Functionalized graphene for energy storage and conversion

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Organic functionalization of graphene for applications in energy storage devices and optoelectronics Licentiate thesis, 2024

aqueous energy storage

optoelectronics

organic functionalization

2D materials

Chalmers, Chemistry and Chemical Engineering, Chemistry and Biochemistry

A Novel Aqueous Asymmetric Supercapacitor based on Pyrene-4,5,9,10-Tetraone Functionalized Graphene as the Cathode and Annealed Ti3C2Tx MXene as the Anode

Small,; Vol. 19(2023)p. 2301449-

Journal article

Aqueous Asymmetric Supercapacitors with Pyrenetetraone-Derived Pseudocapacitive Polymer-Functionalized Graphene Cathodes Enabling a 1.9 V Operating Window

Advanced Energy and Sustainability Research,; Vol. In Press(2024)

Chemistry of 2D materials

Chalmers, 2018-09-01 -- 2022-12-31.

Chalmers, 2018-09-01 -- .

2D material-based technology for industrial applications (2D-TECH)

VINNOVA (2019-00068), 2020-05-01 -- 2024-12-31.

GKN Aerospace Sweden (2D-tech), 2021-01-01 -- 2024-12-31.

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Opponent: Flavia Ferrara, Department of Chemistry and Chemical Engineering, Chalmers University of Technology

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Synthesis and functionalization of graphene and application in electrochemical biosensing

Deepshikha Saini received her PhD degree (2012) from the Department of Chemistry, Amity University, Noida, India. Then, she joined Peking University, Beijing, China, as a post-doctoral fellow in 2012. At present, she is a Young International Scientist in Institute of Chemistry, Chinese Academy of Sciences, Beijing, China. Her research interests are focused on controlled modification of graphene surfaces for photovoltaic and optoelectronic applications. She has 8 years of research and 7 years of teaching experience. She received the best published paper award by KASCT, Springer (2012), and CAS young international scientist fellowship in 2014.

Graphene is a two-dimensional material with amazing characteristics, which grant it the title “wonder material”. It has grabbed appreciable attention due to its exceptional electrical, optical, thermal, and mechanical properties. Because of these interesting properties, graphene has found its way into a wide variety of biosensing applications. It has been used as a transducer in electrochemical biosensors, bio-field-effect transistors, impedance biosensors, electrochemiluminescence, and fluorescence biosensors. Functionalization of graphene has further opened up novel fundamental and applied frontiers. The present article reviews recent works dealing with synthesis, functionalization of graphene, and its applications related to biosensors. Various synthesis strategies, mechanism and process parameters, and types of functionalization are discussed in view of biosensor development. Some potential areas for biosensor-related applications of functionalized graphene are highlighted, including catalytic biosensors and bio affinity biosensors. Wherever applicable, the limitations of the present knowledgebase and possible research directions have also been discussed.

1 Introduction

Graphene is composed of single-atom thick sheets of sp 2 bonded carbon atoms that are arranged in a perfect two-dimensional (2D) honeycomb lattice. It is often dubbed as “miracle material” for its outstanding characteristics. Graphene is also the fundamental building block of carbon materials such as fullerenes, carbon nanotubes, and graphite [ 1 ], [ 2 ]. Its unique configuration and structure determine a number of fascinating properties such as a high planar surface area (2630 m 2 g -1 ) [ 3 ], superior mechanical strength with a Young’s modulus of 1100 GPa [ 4 ], unparalleled thermal conductivity (5000 W m -1 K -1 ) [ 5 ], remarkable high carrier mobility (10,000 cm 2 V -1 s -1 ) [ 6 ], high opacity (~97.7%), and the ability to quench fluorescence [ 7 ]. Graphene is currently, without any doubt, the most intensively studied material for a wide range of applications that include electronics, energy, and sensing outlets [ 8 ].

However, tuning physicochemical properties becomes necessary [ 9 ] in many graphene applications because of intrinsic graphene properties like zero band gap, high sheet resistance, easy aggregation, and poor solubility, which are the big obstacles to the various applications [ 10 ], [ 11 ]. Functionalization is one of the efficient ways to tailor the electrical properties of graphene. Furthermore, after modification, the as-synthesized hybrid materials could not only overcome the disadvantages of intrinsic graphene but also be inculcated with new desirable properties. Graphene is thought to become especially widespread in biosensors and diagnostics. The large surface area of graphene can enhance the surface loading of desired biomolecules, and excellent conductivity and small band gap can be beneficial for conducting electrons between biomolecules and the electrode surface. Graphene also has significant potential for enabling the development of electrochemical biosensors based on direct electron transfer between the enzyme and the electrode surface. Moreover, other applications including, but not limited to, synthesizing nanoelectronics [ 12 ], high-frequency electronics [ 13 ], energy storage and conversion devices [ 14 ], field-emission displays [ 15 ], and transparent conductors [ 16 ] are also proofs of their versatility.

In this comprehensive review, recent research efforts to the synthesis, functionalization of graphene, and its application in the development of next-generation biosensors are addressed. This covers the latest developments and importantly, offer insights on the underlying detection mechanisms and on the unique advantages of graphene in comparison with other materials. I hope that this article would inspire broader interests across various disciplines and stimulate more exciting developments in this still young, yet very promising, field of research.

2 Synthesis of graphene

Mechanical exfoliation of graphene layers from highly oriented pyrolytic graphite [ 17 ], [ 18 ], [ 19 ]

Chemical vapor deposition with hydrocarbon decomposition on a metal [ 20 ], [ 21 ], [ 22 ], [ 23 ], [ 24 ]

Thermal decomposition of SiC (epitaxial growth) [ 25 ], [ 26 ], [ 27 ], [ 28 ], [ 29 ]

Electrical arc discharge method [ 30 ], [ 31 ], [ 32 ], [ 33 ]

Organic synthesis [ 34 ], [ 35 ], [ 36 ], [ 37 ]

Chemical method using dispersion of graphite. [ 38 ], [ 39 ]

The mainstream methods of graphene synthesis have been summarized in Figure 1 .

Methods for the mass production of graphene. There are several choices depending on the particular application, each with differences in terms of size, quality (e.g. presence of defects and impurities), and price. Reprinted with permission from Ref. [ 8 ] (Copyright 2012 Nature ).

Table 1 summarizes the relative advantages and disadvantages of the above synthesis methods in terms of the feasibility to scale-up the process for mass production, materials and production costs, and the presence of defects.

Comparison of different graphene synthesis methods.

2.1 Significance of graphene for electrochemical biosensing

Capability of automation and miniaturization

High electron transfer rate

Biocompatibility

Easier operation

Extraordinary carrier mobility and capacitance

Excellent transparency

Exceptionally large surface-to-volume ratio

Single atom thickness

Robustness and flexibility

Excellent conductivity

These properties have also led to significant interest in developing graphene-based electrochemical biosensors [ 48 ]. Graphene has been employed as electrode material in various electrochemical biosensors for the detection of a range of analytes like glucose, glutamate, cholesterol, hemoglobin, and more [ 49 ]. Interestingly, the large surface area of and excellent conductivity leads to the superior electrochemical biosensing performance of graphene over carbon nanotubes in terms of sensitivity, signal-to-noise ratio, electron transfer kinetics, and stability [ 50 ], [ 51 ]. Additionally, graphene’s properties can be tuned by amendable synthetic conditions, dimensions, number of layers, and doping components [ 52 ]. Therefore, graphene-based materials are playing, and will continually play, a significant role in sensing applications.

3 Graphene functionalization

The covalent functionalization via the grafting of molecules onto the sp 2 carbon atoms of the π-conjugated skeleton;

The noncovalent functionalization based on the adsorption of polycyclic aromatic compounds or surfactants via π-stacking and hydrophobic interactions on the carbon framework.

Figure 2 summarizes the most important methods for the functionalization of graphene.

Functionalization possibilities for graphene: (A) edge functionalization, (B) basal-plane functionalization, (C) noncovalent adsorption on the basal plane, (D) asymmetric functionalization, and (E) the self-assembly of graphene. Reprinted with permission from Ref. [ 55 ] (Copyright 2014 J. Mater. Chem. A ).

3.1 Covalent functionalization of graphene

By reaction with unsaturated π-bonds of graphene [ 56 ]

Heteroatom doping [ 56 ]

Covalent functionalization is associated with rehybridization of one or more sp 2 carbon atoms of the carbon network into the sp 3 configuration leading to the introduction of a scattering site in graphene. Further, covalent functionalization can play an important role for controlling the carrier density and band gap engineering [ 57 ], [ 58 ]. If graphene is covalently bonded to acceptor functional groups, this may give rise to p-type semiconductor properties. Conversely, if graphene is functionalized by donor functional groups, the formation of n-type semiconductor is possible.

Being highly inert and thermally stable, graphene requires high-energy processes to rehybridize its π-conjugated carbon network. The covalent functionalization of graphene can be achieved in four different ways: nucleophilic substitution, electrophilic addition, condensation, and addition [ 59 ], [ 60 ], [ 61 ], [ 62 ], [ 63 ], [ 64 ], [ 65 ], [ 66 ], [ 67 ], [ 68 ], [ 69 ]. This results in the formation of a large density of sp 3 hybridized carbons in the graphene network [ 70 ], which disrupts the delocalized π cloud, converting graphene into an insulator. Different kinds of functional groups like amino, hydroxyl, sulfonate, or alkyl groups may be introduced onto graphene through covalent bonding [ 71 ], [ 72 ]. These groups can further serve as chemical switches to insert functional molecules (proteins, carbohydrates, polymers) on the graphene surface [ 72 ].

Advantages of covalent functionalization:

Greater stability of the hybrid material,

Controllability over the degree of functionalization,

Reproducibility.

Disadvantages of covalent functionalization:

A loss of the free, sp 2 -associated π electron constituting the π-cloud on graphene.

Causing severe decrease in carrier mobility

Leading to the introduction of a scattering site in graphene

Altering the native electronic structure and physical properties of graphene by converting sp 2 carbons to sp 3 ones.

3.2 Noncovalent functionalization of graphene

Noncovalent functionalization is a simple and economic approach to introduce specific functionalities to the graphene surface. Noncovalent linkages between graphene and other functional groups are mainly achieved through π-π stacking, van der Waals, electrostatic forces, hydrophilic and hydrophobic interactions. Noncovalent functionalization strategies do not affect the transparency or conductivity of the material. This, in turn, introduces scattering sites by creation of high-density electron-hole puddles. Noncovalent strategies also control design-based synthesis of graphene derivatives. For instance, small- molecule aromatics like quinones have been used to functionalize carbonaceous materials and were shown to effectively enhance the performance of energy conversion and storage devices [ 73 ].

Various molecules can physically adsorb onto graphene materials without the need of any coupling reagents. Noncovalent functionalization is primarily achieved by polymer wrapping, adsorption of surfactants such as sodium dodecyl sulfate, and hexadecyltrimethylammonium bromide and interaction with metal nanoparticles (e.g. Au, Ag, Pt), porphyrins, or biomolecules such as deoxyribonucleic acid (DNA) and peptides [ 74 ], [ 75 ], [ 76 ], [ 77 ].

Preserves the intrinsic properties of the graphene

Does not destroy the original sp 2 -conjugated structure of graphene, which further retains the high electroconductivity

Does not create sp 3 -hybridized carbons or defects.

Physical adsorption is nonspecific

There is no control over degree of functionalization

It changes the doping density, increases the density of electron-hole puddles, and creates scattering sites.

Different strategies for covalent and noncovalent functionalization of graphene are categorized in Table 2 .

Different strategies for covalent and noncovalent functionalization of graphene.

4 Current and emerging applications of functionalized graphene in electrochemical biosensors

Biological recognition element: Classified into five different major categories. These categories include antibody/antigen, enzymes, nucleic acids/DNA/RNA, cellular structures/cells, and biomimetic. The enzymes, antibodies, and nucleic acids are the main classes of bioreceptors, which are widely used in biosensor applications.

Transducers: The transducer plays an important role in the detection process of a biosensor. In case of conducting polymer-based polymer biosensor, the conductive polymer acts as a transducer that converts the biological signal to an electrical signal.

Schematic structure and operating principle of a biosensor. Reprinted with permission from Ref. [ 111 ] (Copyright 2011 Nature ).

Graphene, a single layer of sp 2 -bonded carbon atoms packed into a benzene ring structure, has been demonstrated as an ideal electrochemical platform for the construction of biosensors owing to its large specific surface area, high electric conductivity, good biocompatibility, thermal and chemical stability, and low-cost production [ 48 ], [ 112 ]. On the other hand, functionalization of graphene covalently and noncovalently can effectively tune its electrical properties and enhance its electrocatalytic performances [ 113 ], [ 114 ], [ 115 ]. It is inferred that the electrochemically active sites generated by functional groups triggers the adsorption and activation of analytes, anchoring of functional moieties, and accelerating the charge transfer between electrode and analytes/electrolyte. This, in turn, would be advantages to the enhanced electrochemical biosensing performances [ 116 ].

5 Functionalized graphene-based enzyme biosensors

Owing to their unique physical and chemical properties, graphene-based materials have become important candidates for biosensing. The large surface area of graphene can enhance the surface loading of the desired biomolecules and direct electron transfer between enzymes and electrodes. Thus, functionalized graphene could be an excellent electrode material for enzyme biosensors.

5.1 Glucose biosensor

The metabolic disorder of diabetes mellitus results in hyperglycemia. It is reflected by blood glucose concentration higher or lower than the normal range of 80–120 mg dl -1 . Persistent hyperglycemia can lead to stroke, coronary heart disease, and circulation disorders [ 117 ]. One of the main biomedical applications of graphene in biosensors is to develop glucose concentration-measuring devices for patients suffering from diabetes. Electrochemical detections of glucose have been well demonstrated using glucose oxidase (GOx) as the mediator or recognition element [ 118 ], [ 119 ]. The redox reaction mechanism is as follows:

In the absence of oxygen:

In the presence of oxygen:

Functionalized graphene-based glucose biosensors can be divided into the following categories:

5.1.1 Enzymatic functionalized graphene-based glucose biosensors

Glucose oxidase (GOx) has been immobilized on graphene sheets for fabricating glucose biosensors via various methodologies [ 112 ], [ 120 ], [ 121 ]. Shan et al. had designed CS-GR/AuNP nanocomposite films for glucose sensing, which exhibited good amperometric responses to glucose with linear ranges of 2–10 m m at -0.2 V and 2–14 m m at 0.5 V [ 122 ]. This was attributed to the synergy effect of graphene and the AuNP. G. Bharath et al. [ 123 ] have reported the direct electrochemistry of glucose oxidase (GOx) on 1D hydroxyapatite (HAp) on reduced graphene oxide (RGO) nanocomposite-modified glassy carbon electrode (GCE) for glucose sensing ( Figure 4 ). The electrocatalytic and electroanalytical applications of the proposed GOx/HAp/RGO-modified GCE were studied by cyclic voltammetry (CV) and amperometry. The reported biosensor exhibits a superior detection limit (0.03 m m ) and higher sensitivity (16.9 mA m m -1 cm -2 ), respectively, with a wide linear range of 0.1–11.5 m m .

Schematic illustration for the mechanism of glucose sensing based on an RGO/HAp/GOx nanocomposite. Reprinted with permission from Ref. [ 123 ] (Copyright 2015 J. Mater. Chem. B ).

Liu et al. [ 124 ] fabricated a mono- and multilayered biosensor format with controlled biocatalytic activity. GOx was first modified with pyrene functionalities in order to be self-assembled onto a graphene basal plane via noncovalent interactions. Using an alternate layer-upon-layer of self-assembled graphene and pyrene-functionalized GOx, mono- and multilayered enzyme electrodes were readily fabricated ( Figure 5 A). The biocatalytic activity of these enzyme electrodes increased with the number of graphene and GOx layers ( Figure 5B ). Such multilayered enzyme electrodes with controlled nanostructure exhibited reliable application for the analysis of human serum samples with high sensitivity, good stability, and repeatability.

(A) Schematic diagram of the modification of GOD with pyrene and the subsequent fabrication of mono- and multi-layered enzyme electrodes. (B) Cyclic voltammograms of the enzyme electrodes fabricated with mono- and multilayered graphene and pyrene functionalized GOD: (a) one layer, (b) two layers, (c) three layers, and (d) four layers. Data were recorded in 80 m m glucose solution in 0.1 M pH 7.4 phosphate buffer at room temperature and potential scan rate of 10 mV s -1 . Reprinted with permission from Ref. [ 124 ] (Copyright 2013 Analyst ).

The disadvantages of enzymatic electrochemical glucose sensors:

insufficient operational and storage stability

lower reproducibility

influence of oxygen limitation.

5.1.2 Non-enzymatic functionalized graphene-based glucose biosensors

Enzymeless sensing of glucose is feasible using metal nanoparticles and nanowires even under neutral pH. In particular, a remarkable detection limit is obtained for glucose (25 n m ) using a 3D graphene foam modified with Co 3 O 4 nanowires [ 125 ]. Another non-enzymatic glucose biosensor based on nickel-polyaniline-functionalized reduced graphene oxide was fabricated by Bing Zhang et al. [ 126 ]. They had developed a new class of organic-inorganic hybrid nanostructures, which was applied to efficient non-enzymatic sensing of glucose ( Figure 6 ). This biosensor format included a fast response (~2 s), high sensitivity (6050 μA m m -1 cm -2 ), a linear range from 0.1 μ m to 1.0 m m , and a low detection limit (0.08 μ m ).

Schematic illustration for Ni-PANI-rGO-based nonenzymatic glucose sensing. Reprinted with permission from Ref. [ 126 ] (Copyright 2015 Microchim. Acta ).

A novel, stable, and sensitive non-enzymatic glucose sensor was developed by electrodepositing metallic Cu nanoparticles on graphene sheets [ 127 ]. The Cu-graphene electrode sensor presented a wide linear range up to 4.5 m m glucose with a detection limit of 0.5 μ m (signal/noise=3) at a detection potential of 0.5 V in alkaline solution with a very quick (2 s) response. Recently, highly sensitive hybrid structured non-enzymatic glucose sensors were fabricated. Platinum (Pt) nanoparticles were decorated on 3D graphene oxide networks to increase the surface area. Large surface area and high electrocatalytic activity resulted in high glucose sensitivity (137.4 μA m m -1 cm -2 ) and excellent anti-interference characteristics [ 128 ].

5.2 Hydrogen peroxide (H 2 O 2 ) biosensor

H 2 O 2 is also particularly important for the development of biosensing systems. It is a substrate of peroxidases, enzymatic product of oxidases, and an important mediator in clinical as well as pharmaceutical analyses. The detection of H 2 O 2 can be achieved using horseradish peroxidase enzyme (HRP) immobilized onto graphene-based electrodes. The reaction mechanism of the catalytic process can be summarized as follows:

Zonghua Wang et al. [ 129 ] fabricated platinum nanoparticles/graphene nanohybrids (Pt/G) via in situ reduction of PtCl 6 2- in the presence of poly(diallyldimethylammonium chloride)-modified graphene ( Figure 7 ). These nanohybrids were used as a matrix for the immobilization of HRP to construct a HRP/Pt/G/glassy carbon electrode (GC) biosensor for H 2 O 2 . The Pt/G hybrid provides an operative environment for maintaining the bioactivity of HRP. It acts as a bridge for the transfer of electrons between the active center of HRP and the electrode surface ( Figure 8 ). Pt/G effectively reinforced the immobilization of HRP and enhanced the utilization of HRP. The linear range for H 2 O 2 was estimated to be from 3.0×10 -6 mol l -1 to 5.2×10 -3 mol l -1 with a detection limit of 5.0×10 -9 mol l -1 .

Scheme of the fabrication of Pt/G hybrid. Reprinted with permission from Ref. [ 129 ] (Copyright 2013 Anal. Methods ).

Cyclic voltammograms (CVs) of modified electrodes in 0.1 mol l -1 pH ¼ 6.8 PBS, HRP/Pt/G/GC (A), Pt/G/GC (B), HRP/G/GC (C), G/GC (D), HRP/Pt/GC (E), and Pt/GC (F). Reprinted with permission from Ref. [ 129 ] (Copyright 2013 Anal. Methods ).

A sensitive and noble amperometric HRP biosensor is fabricated via the deposition of gold nanoparticles (AuNPs) onto a 3D porous carbonized chicken eggshell membrane (CESM) [ 130 ]. Owing to the synergistic effects of the unique porous carbon architecture and well-distributed AuNPs, the enzyme-modified electrode shows an excellent electrochemical redox behavior ( Figure 9 ). Furthermore, the HRP-AuNPs-CESM/GCE electrode, as a biosensor for H 2 O 2 detection, has a good accuracy and high sensitivity with a linear range of 0.01–2.7 m m H 2 O 2 and a detection limit of 3 μ m H 2 O 2 .

Schematic illustration of the mechanism underlying the detection of H 2 O 2 using HRP-AuNPs- CESM-GCE electrochemical biosensor. Reprinted with permission from Ref. [ 130 ] (Copyright 2015 Plos One ).

A facile one-pot hydrothermal approach was reported for cerium oxide-reduced graphene oxide CeO 2 -RGO nanocomposite formation ( Figure 10 ), which is further assembled with HRP for the detection of hydrogen peroxide (H 2 O 2 ) at trace levels [ 131 ]. This biosensor format exhibited a wide linear range of H 2 O 2 from 0.1 to 500 μM with a detection limit of 0.021 μ m .

H 2 O 2 detection scheme using HRP/CeO 2 -rGO modified glassy carbon electrode. Reprinted with permission from Ref. [ 131 ] (Copyright 2015 RSC Adv. ).

In addition, many novel non-enzyme H 2 O 2 biosensors have been reported [ 132 ], [ 133 ], [ 134 ]. For instance, Dye et al. [ 132 ] developed a highly sensitive amperometric biosensor based on the hybrid material, which is derived from graphene and Pt nanoparticles for the detection of H 2 O 2 and cholesterol. This sensor shows high sensitivity and fast response toward H 2 O 2 up to 12 m m with a detection limit of 0.5 n m (S/N=3) in the absence of any redox mediator or enzyme. The combination of superconductive graphene sheets and catalytically active Pt nanoparticles accelerated electron transfer for the oxidation of H 2 O 2 .

5.3 Cholesterol biosensor

Cholesterol is an organic molecule. It is an essential structural component of all animal cell membranes [ 135 ]. Cholesterol also serves as a precursor for the biosynthesis of steroid hormones, bile acids, and vitamin D. The total blood cholesterol level should be <200 mg/dl in the human body. However, undesired accumulation of cholesterol and its esters causes critical health problems such as hypercholesterolemia, heart diseases, cerebral thrombosis, and atherosclerosis. A smart, quick, accurate determination of cholesterol in blood is an urgent need in clinical diagnosis. The following biochemical reaction occurs as a result of interaction of cholesterol oxidase (ChOx) with cholesterol:

C h o l e s t e r o l + O 2 → C h O x C h o l e s t e r o n e + H 2 O 2

Dey and Raj [ 136 ] developed a highly sensitive amperometric cholesterol biosensor based on a hybrid material derived from PtNP and graphene for the detection of H 2 O 2 ( Figure 11 ). The cholesterol biosensor was developed by immobilizing cholesterol oxidase and cholesterol esterase on the surface of the GR/PtNP hybrid material. The sensitivity and detection limit of the electrode toward cholesterol ester were 2.07±0.1 μA/μ m /cm 2 and 0.2 μ m , respectively.

Scheme illustrating the biosensing of cholesterol ester with the GNS-nPt-based biosensor. Reprinted with permission from Ref. [ 136 ] (Copyright 2010 J. Phys. Chem. C ).

Shiju Abraham et al. [ 137 ] have reported the development of cost-effective bioelectrodes based on a reduced graphene oxide-functionalized gold nanoparticle hybrid system (RGO-Fn Au NPs). The electrodes were fabricated by the electrophoretic deposition technique. A synergistically enhanced electrochemical sensing ability of 193.4 μA m m -1 cm -2 for free cholesterol detection was achieved, which is much higher than that of the traditional RGO system ( Figure 12 ). Moreover, the RGO-Fn Au NP platform promises a wider range of cholesterol detection (0.65–12.93 m m ) with lower detection limit of 0.34 m m for free cholesterol.

Schematic representation of the cholesterol sensing process: (A) EPD set up for the fabrication of RGO and RGO-Fn Au NP thin films; (B) electrophoretically fabricated RGO-Fn Au NP thin film on an ITO substrate; (C) immobilization of ChOx on RGO-Fn Au NPs by EDC-NHS coupling; and (D) the immobilized RGO-Fn Au NP bioelectrode and the electrochemical reaction while adding cholesterol to the electrochemical cell containing the bioelectrode. Reprinted with permission from Ref. [ 137 ] (Copyright 2015 Anal. Methods ).

Deepshikha et al. have fabricated a novel nanobiocomposite bienzymatic amperometric cholesterol biosensor, coupled with cholesterol oxidase (ChOx) and HRP, based on the gold-nanoparticle decorated graphene-nanostructured polyaniline nanocomposite (NSPANI-AuNP-GR) film. The nanocomposite film was electrochemically deposited onto indium-tin-oxide (ITO) electrode from the NSPANI-AuNP-GR nanodispersion [ 138 ]. The overall biochemical reaction for ChOx-HRP/NSPANIAuNP- GR is shown in Figure 13 .

Proposed biochemical reaction on the ChOx-HRP/ NSPANI-AuNP-GR. Reprinted from an Open Access Journal Ref. [ 138 ], 2012.

The gold nanoparticle-decorated graphene-nanostructured polyaniline nanocomposite (NSPANI-AuNP-GR) offers an efficient electron transfer between underlining electrode and enzyme active center. The bienzymatic nanocomposite bioelectrodes ChOx-HRP/NSPANI-AuNPGR/ITO have exhibited wider linearity (35 to 500 mg/dl), higher sensitivity (0.42 μA m m -1 ), low km value of 0.01 m m , and higher accuracy for testing of blood serum samples than monoenzyme system. The novelty of the electrode lies on reusability, extended shelf life, and accuracy of testing blood serum samples.

5.4 NADH biosensor

β-Nicotinamide adenine dinucleotide (NAD + ) and its reduced form (NADH) are a cofactor of many dehydrogenases. NAD + /NADH-dependent dehydrogenases have been attempted in the development of biosensors, biofuel cells, and bioelectronic devices. A large overvoltage is necessary for anodic detection of NADH, and electrode fouling is also encountered due to the formation of reaction products. Apparently, graphene shows promise in addressing these two drawbacks. Graphene functionalization with dyes like methylene green (MG) forms a stable complex via noncovalent bonding [ 139 ]. The oxidation of NADH on MG-graphene electrode takes place at ~0.14 V, which is much lower than that of pristine graphene [ 139 ] and CNTs [ 140 ], [ 141 ].

Shan et al. [ 142 ] showed that graphene electrodes functionalized using ionic liquids could be used for both NADH detection and the biosensing for ethanol. The ionic liquid modified-graphene-based sensor exhibited acceptable analytical outcomes for the determination of NADH. Moreover, process is convenient, and low-cost preparation is involved. Tang et al. adopted chemically reduced GO (CRGO), which showed a remarkable oxidation shift of about 30 mV compared to graphite and bare GC electrodes [ 143 ].

5.5 Dopamine biosensor

Dopamine (DA), an important neurotransmitter, plays an important role in the central nervous, hormonal, renal, and cardiovascular systems. Its deficiency is correlated to Parkinson’s disease, which is a degenerative disorder of the central nervous system. The major symptoms of Parkinson’s disease result from the death of dopamine-generating cells in midbrain. Therefore, a lot of research works aimed at developing sensitive, rapid, and decentralized sensing devices for its detection. With the excellent electroanalytical properties, graphene-based electrodes have demonstrated excellent performances in detecting DA. Gregory Thien Soon How et al. [ 144 ] have reported a reduced graphene oxide/titanium dioxide nanocomposite with highly exposed facets (rGO/TiO 2 {001}) for the detection of DA [ 144 ]. The modified rGO/TiO 2 {001} GCE shows enhanced electrochemical sensing toward DA under the interference effect. This method certainly opens up a new platform of facet manipulation studies for electrochemical applications ( Figure 14 ).

(A) Mechanism for the electrocatalytic oxidation of dopamine at rGO/TiO 2 {001} modified GCE. (B) DPV obtained for rGO/TiO 2 {001} modified GCEs during the addition of 1, 2, 4, 8, 10, 15, 25, 30, 35, 40, 50, 60, 80, and 100 m m DA into the 0.1 M PBS (pH? 6.5). (C) Calibration plot observed for the oxidation peak current vs. concentration of DA. Reprinted with permission from Ref. [ 144 ] (Copyright 2014 Nature ).

DA coexists with endogenous electroactive species such as ascorbic acid (AA) and uric acid (UA). They have an overlapping voltammetric response, resulting in poor selectivity and sensitivity of DA. The presence of sp 2 hybridized planes and various edge defects on the graphene surface might attribute to a better sensing performance toward DA [ 50 ] and can differentiate DA from AA and UA. Liu et al. [ 145 ] have used graphene/ferrocene derivative (graphene/Fc-NH 2 ) nanocomposite to fabricate the Nafion/graphene/Fc-NH 2 -modified GCE for the detection of DA. The Fc-NH 2 embedded on the graphene significantly enhances the electrochemical response toward DA, charge-transport ability, stabilizes the graphene, and prevent the leakage of ferrocene ( Figure 15 ). In the presence of 1 m m AA and 0.1 m m UA, the electrode showed linear response in the range of 0.1 to 4 μ m , and the detection limit was 50 n m (S/N=3).

Schematic illustration of the preparation procedures of the Fc-NH2 modified electrode. Reprinted with permission from Ref. [ 145 ] (Copyright 2012 Analyst ).

5.6 DNA biosensors

Direct absorption via π-π interactions [ 148 ], [ 149 ]

By other binding approaches via functional groups from modified graphene surface [ 150 ], [ 151 ].

Furthermore, the excellent conductivity of graphene makes it possible for fast electron transfer between DNA and electrodes. Recently, the electrochemical detection for target DNA molecules has been reported [ 148 ], [ 149 ], [ 150 ], [ 151 ], [ 152 ]. For example, Huang et al. [ 152 ] synthesized a tungsten sulfide-graphene (WS 2 -Gr) nanocomposite for DNA biosensor application. Graphene served as a 2D conductive support for a highly electrolytic accessible surface. However, the electronic conductivity of WS 2 is much lower compared to graphene materials, thereby, limiting its application for sensitive detection. On the other hand, DNA detections can also be achieved by non-DNA-modified electrodes [ 153 ], [ 154 ], [ 155 ]. For example, Quanbo Wang et al. [ 155 ] have designed a novel peroxidase mimic by loading ferric porphyrin and streptavidin onto graphene, which was used to recognize a biotinylated molecular beacon (MB) for specific electrochemical detection of DNA ( Figure 16 ). The biosensor format had exhibited high specificity and excellent anti-interference ability. The biosensing method could discriminate target DNA from single-base or three-base mismatched oligonucleotides.

Schematic illustration of graphene-supported ferric porphyrin as a HRP mimicking trace label for electrochemical detection of DNA. Reprinted with permission from Ref. [ 155 ] (Copyright 2013 Chem. Commun. ).

A proposed mechanism for an ultrasensitive and highly selective Hg 2+ sensor based on the modified ERGO. Reprinted with permission from Ref. [ 160 ] (Copyright 2013 Chem. Commun. ).

5.7 Heavy metal ions biosensors

Heavy metal ions in potable water and food are major health concerns. Their detection is critical to maintaining a safe food supply [ 156 ], [ 157 ]. Therefore, the highly sensitive, selective, and rapid detection of heavy metal ions has been explored in depth using various analytical methodologies [ 158 ], [ 159 ], [ 160 ], [ 161 ]. Graphene- based sensors have been employed to detect and monitor the presence of heavy metal ions such as Pb 2+ , Cd 2+ , Cu 2+ , and Hg 2+ [ 160 ], [ 162 ], [ 163 ], [ 164 ], [ 165 ], [ 166 ], [ 167 ]. For example, a gold functionalized graphene electrode was produced via noncovalent interaction for the determination of Pb 2+ and Cu 2+ [ 168 ]. Chunmeng Yu et al. [ 160 ] have designed an ultrasensitive and highly selective Hg 2+ sensor through noncovalent modification of an electrochemically reduced GO (ERGO)-based diode with N-[(1-pyrenyl-sulfonamido)-heptyl]-gluconamide (PG) as the modifier. PG is comprised of a glucose residue and a pyrene residue. The glucose residue can work as multiple-receptor sites for Hg 2+ in the medium. The large π system in the pyrene can be stably attached on the ERGO surface ( Figure 17 ). The detection limit of this sensor for Hg 2+ reaches 0.1 n m , which is the best result of electronic sensors and is about 10 times as low as the previously reported results [ 169 ]. Alkanethiol-modified graphene field effect transistors exhibited a sensitivity for Hg 2+ detection at 10 ppm, which provides new opportunities for graphene-based electronics as heavy metal sensors. Sensors based on graphene have also been reported for the detection of Cd 2+ , Cu 2+ , and Ag + [ 170 ], [ 171 ], [ 172 ], [ 173 ].

5.8 Immunosensors

Electrochemical immunosensors are miniaturized analytical devices with higher sensitivity and selectivity. Compared with the other methods like enzyme-linked immunosorbent assay (ELISA), immunosensors are attractive because of their high sensitivity, low cost, short analytical time, simple instrumentation, and high specificity of immunological reactions [ 174 ]. Immunosensors are capable of detecting nucleic acids [ 175 ], viruses [ 176 ], antigens [ 177 ], and hormone [ 178 ] biomarkers. More recently, graphene has been utilized in a number of forms for immunosensor applications [ 179 ], [ 180 ], [ 181 ], [ 182 ], [ 183 ]. Graphene is a material, which has immense potential for the fabrication of immunosensors. A simple electrochemical impedimetric immunosensor for immunoglobulin G (IgG) based on chemically modified graphene (CMG) surfaces was proposed by A.H. Loo et al. [ 184 ]. The group had used graphite oxide, graphene oxide, thermally reduced graphene oxide, and electrochemically reduced graphene oxide for fabrication of immunosensor ( Figure 18 ). It was found that thermally reduced graphene oxide has provided the best performance with the linear detection range from 0.3 mg ml -1 to 7 mg ml -1 .

An illustration of the protocol for IgG immunodetection based on the EIS method. (A) A bare DEP electrode modified with CMG material; (B) a CMG material modified DEP electrode after the immobilization of anti-IgG and blocking with BSA; and (C) an anti-IgG and BSA-modified DEP electrode after the incubation with IgG. Reprinted with permission from Ref. [ 184 ] (Copyright 2012 Nanoscale ).

Simultaneous detection of multiple tumor markers was done by fabricating graphene nanocomposite immunosensor [ 185 ]. In this work, reduced graphene oxide/thionine/gold nanoparticles nanocomposites were synthesized and coated on ITO for the formation of an antibody-antigen immunocomplex. Experimental results revealed that the multiplexed immunoassay enabled the simultaneous determination of tumor markers with linear working ranges of 0.01–300 ng ml -1 .

Characteristic features of various functionalized graphene-based biosensors are summarized in Table 3 .

Characteristic features of functionalized graphene-based biosensors.

6 Conclusion

Graphene, as an amazing and wonderful material among the nanocarbon family, has drawn considerable interest in many fields. Its unique structure contributes to its fascinating chemical and physical properties, which lead to a broad range of applications in sensing. In this review, significant advances in functionalized graphene-based biosensors relative to their bulk counterparts have been reported. The unique electronic structure, biocompatibility, and dimensional compatibility with biomolecules indicate that graphene can provide a new generation of smart transduction matrices for the control of a range of biomolecular interactions, from the molecular to the cellular levels. However, graphene, as a newly discovered material, faces several challenges including improving synthesis methods, extensive understanding of graphene surface, and extending the applications in various practical fields.

Production of large quantities and high-quality uniform graphene

Tailoring and tuning of graphene properties.

The synthesis and cost of making graphene is relatively much cheaper in comparison to other carbon materials such as CNTs. There have also been significant advances in the preparation of graphene, their functionalization with the desired chemical entities, and the immobilization of biomolecules to the functionalized graphene surfaces for biosensor applications. However, most of the bioanalytical applications have been demonstrated using multilayered graphene as the preparation of single-layer graphene is highly expensive. Therefore, there is a need for dedicated research efforts to develop cheaper and highly simplified strategies for the development of single-layer graphene.

It is necessary to better understand the chemistry and physics at the graphene surface and also the interactions of chemicals or biomolecules at the interface of graphene when applied in biosensing. Various functionalization chemistries have already been demonstrated to have high biocompatibility without any apparent cytotoxicity. However, further efforts are desired in order to test the cytotoxicity for a relatively longer period of time. An improved understanding of graphene and its interaction with molecules will lead to advances in graphene science and its application in catalysis and sensor development. Improved methods of functionalization are now emerging. An area poised to produce major benefits is the use of functionalized 2D nanostructures to control biomolecular interactions. This suggests that in the near future, the star of the nanocarbon family, “graphene,” will find fascinating applications in the biomolecular world.

About the author

[1] Sharma PS, Souza FD, Kutner W. Graphene and graphene oxide materials for chemo and biosensing of chemical and bio chemical hazards. Top Curr. Chem. 2014, 348, 237–266. 10.1007/128_2013_448 Search in Google Scholar PubMed

[2] Zhou M, Dong SJ. Electrochemical sensing and biosensing platform based on chemically reduced graphene oxide. Anal. Chem. 2009, 81, 5603–5613. 10.1021/ac900136z Search in Google Scholar PubMed

[3] Stoller MD, Park SJ, Zhu YW, An JH, Ruoff RS. Graphene-based ultracapacitors. Nano Lett. 2008, 8, 3498–3502. 10.1021/nl802558y Search in Google Scholar PubMed

[4] Lee C, Wei XD, Kysar JW, Hone J. Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 2008, 321, 385–388. 10.1126/science.1157996 Search in Google Scholar PubMed

[5] Balandin AA, Ghosh S, Bao W, Calizo I, Teweldebrhan D, Miao F, Lau CN. Superior thermal conductivity of single-layer graphene. Nano Lett. 2008, 8, 902–907. 10.1021/nl0731872 Search in Google Scholar PubMed

[6] Bolotin KI, Sikes KJ, Jiang Z, Klima M, Fudenberg G, Hone J, Kim P, Stormer HL. Ultrahigh electron mobility in suspended graphene. Solid State Commun. 2008, 146, 351–355. 10.1016/j.ssc.2008.02.024 Search in Google Scholar

[7] Bonaccorso F, Sun Z, Hasan T, Ferrari AC. Graphene photonics and optoelectronics. Nat. Photonics 2010, 4, 611–622. 10.1038/nphoton.2010.186 Search in Google Scholar

[8] Novoselov KS, Fal’ko VI, Colombo L, Gellert PR, Schwab MG, Kim K. A roadmap for graphene. Nature 2012, 490, 192–200. 10.1038/nature11458 Search in Google Scholar PubMed

[9] Withers F, Russo S, Dubois M, Craciun MF. Tuning the electronic transport properties of graphene through functionalisation with fluorine. Nanoscale Res. Lett. 2011, 6, 1–11. 10.1186/1556-276X-6-526 Search in Google Scholar PubMed PubMed Central

[10] Li X, Zhu Y, Cai W, Borysiak M, Han B, Chen D, Piner RD, Colombo L, Ruoff RS. Transfer of large-area graphene films for high-performance transparent conductive electrodes. Nano Lett. 2009, 9, 4359–4363. 10.1021/nl902623y Search in Google Scholar PubMed

[11] Krupka J, Strupinski W. Measurements of the sheet resistance and conductivity of thin epitaxial graphene and SiC films. Appl. Phys. Lett. 2010, 96, 082101-1–082101-3. 10.1063/1.3327334 Search in Google Scholar

[12] Du AJ, Zhu ZH, Smith SC. Multifunctional porous graphene for nanoelectronics and hydrogen storage: new properties revealed by first principle calculations. J. Am. Chem. Soc. 2010, 132, 2876–2877. 10.1021/ja100156d Search in Google Scholar

[13] Chen HY, Appenzeller J. Graphene-based frequency tripler. Nano Lett. 2012, 12, 2067–2070. 10.1021/nl300230k Search in Google Scholar

[14] Liu CG, Yu ZL, Neff D, Zhamu A, Jang BJ. Graphene-based supercapacitor with an ultrahigh energy density. Nano Lett. 2010, 10, 4863–4868. 10.1021/nl102661q Search in Google Scholar

[15] Lee SW, Lee SS, Yang EH. A study on field emission characteristics of planar graphene layers obtained from a highly oriented pyrolyzed graphite block. Nanoscale Res. Lett. 2009, 4, 1218–1221. 10.1007/s11671-009-9384-9 Search in Google Scholar

[16] Wassei JK, Kaner RB. Graphene, a promising transparent conductor. Mater. Today 2010, 13, 52–59. 10.1016/S1369-7021(10)70034-1 Search in Google Scholar

[17] Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA. Electric field effect in atomically thin carbon films Science 2004, 306, 666–669. 10.1126/science.1102896 Search in Google Scholar PubMed

[18] Novoselov KS, Jiang D, Schedin F, Booth TJ, Khotkevich VV, Morozov SV, Geim AK. Two-dimensional atomic crystals. Proc. Natl. Acad. Sci. USA 2005, 102, 10451–10453. 10.1073/pnas.0502848102 Search in Google Scholar PubMed PubMed Central

[19] Ritter KA, Lyding JW. Characterization of nanometer-sized, mechanically exfoliated graphene on the H-passivated Si (100) surface using scanning tunneling microscopy. Nanotechnology 2008, 19, 015704–015717. 10.1088/0957-4484/19/01/015704 Search in Google Scholar PubMed

[20] Sutter PW, Flege JI, Sutter EA. Epitaxial graphene on ruthenium. Nat. Mater. 2008, 7, 406–411. 10.1038/nmat2166 Search in Google Scholar PubMed

[21] Dedkov YS, Fonin M, Rüdigger U, Laubschat C. Rashba effect in the graphene/Ni (111) system. Phys. Rev. Lett. 2008, 100, 107602-1–107602-4. 10.1103/PhysRevLett.100.107602 Search in Google Scholar PubMed

[22] Kim KS, Zhao Y, Jang H, Lee SY, Kim JM, Kim KS, Ahn JH, Kim P, Choi JY, Hong BH. Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 2009, 457, 706–710. 10.1038/nature07719 Search in Google Scholar PubMed

[23] Reina A, Jia XT, Ho J, Nezich D, Son HB, Bulovic V, Dresselhaus MS, Kong J. Large area, few-layer graphene films on arbitrary substrates by chemical vapor deposition. Nano Lett. 2009, 9, 30–35. 10.1021/nl801827v Search in Google Scholar PubMed

[24] Coraux J, N’Diaye AT, Busse C, Michely T. Structural coherency of graphene on Ir(111). Nano Lett . 2008, 8, 565–570. 10.1021/nl0728874 Search in Google Scholar PubMed

[25] Berger C, Song ZM, Li XB, Wu XS, Brown N, Naud C, Mayou D, Li TB, Hass J, Marchenkov AN, Conrad EH, First PN, Heer WAD. Electronic confinement and coherence in patterned expitaxial graphene. Science 2006, 312, 1191–1196. 10.1126/science.1125925 Search in Google Scholar PubMed

[26] Ohta T, Bostwick A, Seyller T, Horn K, Rotenberg E. Controlling the electronic structure of bilayer graphene. Science 2006, 313, 951–954. 10.1126/science.1130681 Search in Google Scholar PubMed

[27] Heer WAD, Berger C, Wu X, First PN, Conrad EH, Li X, Li T, Sprinkle M, Hass J, Sadowski ML, Potemski M, Martinez G. Epitaxial graphene. Solid State Commun. 2007, 143, 92–100. 10.1016/j.ssc.2007.04.023 Search in Google Scholar

[28] Hass J, Heer WAD, Conrad EH. The growth and morphology of epitaxial multilayer graphene. J. Phys. Condens. Matter . 2008, 20, 323202–323229. 10.1088/0953-8984/20/32/323202 Search in Google Scholar

[29] Rollings E, Gweon GH, Zhou SY, Mun BS, McChesney JL, Hussain BS, Fedorov AV, First PN, Heer WAD, Lanzara A. Synthesis and characterization of atomically thin graphite films on a silicon carbide substrate. J. Phys. Chem. Solids. 2006, 67, 2172–2177. 10.1016/j.jpcs.2006.05.010 Search in Google Scholar

[30] Duan HG, Xie EQ, Han L, Xu Z. Turning PMMA nanofibers into graphene nanoribbons by in situ electron beam irradiation. Adv. Mater. 2008, 20, 3284–3288. 10.1002/adma.200702149 Search in Google Scholar

[31] Subrahmanyam KS, Panchakarla LS, Govindaraj A, Rao CNR. Simple method of preparing graphene flakes by an arc-discharge method. J. Phys. Chem. C . 2009, 113, 4257–4259. 10.1021/jp900791y Search in Google Scholar

[32] Wu C, Dong G, Guan L. Production of graphene sheets by a simple helium arc-discharge. Phys. E. 2010, 42, 1267–1271. 10.1016/j.physe.2009.10.054 Search in Google Scholar

[33] Wang Z, Li N, Shi Z, Gu Z. Low-cost and large-scale synthesis of graphene nanosheets by arc discharge in air. Nanotechnology 2010, 21, 175602. 10.1088/0957-4484/21/17/175602 Search in Google Scholar PubMed

[34] Wu J, Pisula W, Müllen K. Graphenes as potential material for electronics. Chem. Rev. 2007, 107, 718–747. 10.1021/cr068010r Search in Google Scholar PubMed

[35] Yang X, Dou X, Rouhanipour A, Zhi LJ, Räder HJ, Müllen K. Two-dimensional graphene nanoribbons. J. Am. Chem. Soc . 2008, 130, 4216–4217. 10.1021/ja710234t Search in Google Scholar PubMed

[36] Rouhanipour A, Roy M, Feng X, Räder HJ, Müllen K. Subliming the unsublimable: how to deposite nanographenes. Angew. Chem., Int. Ed. 2009, 48, 4602–4604. 10.1002/anie.200900911 Search in Google Scholar PubMed

[37] Zhi LJ, Müllen K. A bottom-up approach from molecular nanographenes to unconventional carbon materials. J. Mater. Chem. 2008, 18, 1472–1484. 10.1039/b717585j Search in Google Scholar

[38] Eda G, Fanchini G, Chhowalla M. Large-area ultrathin films of reduced graphene oxide as a transparent and flexible electronic material. Nat. Nanotechnol. 2008, 3, 270–274. 10.1038/nnano.2008.83 Search in Google Scholar PubMed

[39] Stankovich S, Dikin DA, Dommett GHB, Kohlhaas KM, Zomney EJ, Stach EA, Piner RD, Nguyen ST, Ruoff RS. Graphene-based composite materials. Nature 2006, 442, 282–286. 10.1038/nature04969 Search in Google Scholar PubMed

[40] Lee V, Whittaker L, Jaye C, Baroudi KM, Fischer DA, Banerjee S. Large-area chemically modified graphene films: electrophoretic deposition and characterization by soft X-ray absorption spectroscopy. Chem. Mater. 2009, 21, 3905–3916. 10.1021/cm901554p Search in Google Scholar

[41] Bon SB, Valentini L, Verdejo R, Fierro JLG, Peponi L, Lopez-Manchado MA, Kenny JM. Plasma fluorination of chemically derived graphene sheets and subsequent modification with butylamine. Chem. Mater. 2009, 21, 3433–3438. 10.1021/cm901039j Search in Google Scholar

[42] Chakraborty S, Guo W, Hauge RH, Billups WE. Reductive alkylation of fluorinated graphite. Chem. Mater. 2008, 20, 3134–3136. 10.1021/cm800060q Search in Google Scholar

[43] Valle CS, Drummond C, Saadaoui RH, Furtado CA, He M, Roubeau O, Ortolani L, Monthioux M, Nicaud AP. Solutions of negatively charged graphene sheets and ribbons. J. Am. Chem. Soc. 2008, 130, 15802–15804. 10.1021/ja808001a Search in Google Scholar

[44] Bourlinos AB, Georgakilas V, Zboril R, Steriotis TA, Stubos AK. Liquid-phase exfoliation of graphite towards solubilized graphenes. Small 2009, 5, 1841–1845. 10.1002/smll.200900242 Search in Google Scholar

[45] Kosynkin DV, Higginbotham AL, Sinitskii A, Lomeda JR, Dimiev A, Price BK, Tour JM. Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons. Nature 2009, 458, 872–876. 10.1038/nature07872 Search in Google Scholar

[46] Jiao LY, Zhang L, Wang XR, Diankov G, Dai HJ. Narrow graphene nanoribbons from carbon nanotubes. Nature 2009, 458, 877–880. 10.1038/nature07919 Search in Google Scholar

[47] Chakrabarti A, Lu J, Jennifer C, Skrabutenas, Xu T, Xiao Z, John AM, Narayan SH. Conversion of carbon dioxide to few-layer graphene. J. Mater. Chem. 2011, 21, 9491–9493. 10.1039/c1jm11227a Search in Google Scholar

[48] Shao YY, Wang J, Wu H, Liu J, Aksay IA, Lin YH. Graphene based electrochemical sensors and biosensors: a review. Electroanalysis 2010, 22, 1027–1036. 10.1002/elan.200900571 Search in Google Scholar

[49] Pumera M. Graphene in biosensing. Mater. Today 2011, 14, 308–315. 10.1016/S1369-7021(11)70160-2 Search in Google Scholar

[50] Alwarappan S, Erdem A, Liu C, Li CZ. Probing the electrochemical properties of graphene nanosheets for biosensing applications. J. Phy. Chem. C 2009, 113, 8853–8857. 10.1021/jp9010313 Search in Google Scholar

[51] Wang Y, Li YM, Tang LH, Lu J, Li JH. Application of graphene-modified electrode for selective detection of dopamine. Electrochem. Comm. 2009, 11, 889–892. 10.1016/j.elecom.2009.02.013 Search in Google Scholar

[52] Zhu Y, Murali S, Cai W, Li X, Suk JW, Potts JR, Ruoff RS. Graphene and graphene oxide: synthesis, properties, and applications. Adv. Mater. 2010, 22, 3906–3924. 10.1002/adma.201001068 Search in Google Scholar PubMed

[53] Bai H, Li C, Shi G. Functional composite materials based on chemically converted graphene. Adv. Mater. 2011, 23, 1089. 10.1002/adma.201003753 Search in Google Scholar PubMed

[54] He Q, Wu S, Yin Z, Zhang H. Graphene-based electronic sensors. Science 2012, 3, 1764–1772. 10.1039/c2sc20205k Search in Google Scholar

[55] Dong WC, Hyun JC, Alan F, Jong BB. Graphene in photovoltaic applications: organic photovoltaic cells (OPVs) and dye-sensitized solar cells (DSSCs). J. Mater. Chem. A 2014, 2, 12136–12149. 10.1039/C4TA01047G Search in Google Scholar

[56] Georgakilas V, Otyepka M, Bourlinos AB, Chandra V, Kim N, Kemp KC, Hobza P, Zboril R, Kim KS. Functionalization of graphene: covalent and non-covalent approaches, derivatives and applications. Chem. Rev. 2012, 112, 6156–6214. 10.1021/cr3000412 Search in Google Scholar PubMed

[57] Loh KP, Bao Q, Ang PK, Yang J. The chemistry of graphene. J. Mater. Chem. 2010, 20, 2277. 10.1039/b920539j Search in Google Scholar

[58] Bekyarova E, Itkis ME, Ramesh P, Berger C, Sprinkle M, Heer WAD, Haddon RC. Chemical modification of epitaxial graphene: spontaneous grafting of aryl groups. J. Am. Chem. Soc. 2009, 131, 1336. 10.1021/ja8057327 Search in Google Scholar PubMed

[59] Matsuo Y, Tabata T, Fukunaga T, Fukutsuka T, Sugie Y. Preparation and characterization of silylated graphite oxide. Carbon 2005, 43, 2875–82. 10.1016/j.carbon.2005.06.006 Search in Google Scholar

[60] Matsuo Y, Sakai Y, Fukutsuka T, Sugie Y. Preparation and characterization of pillared carbons obtained by pyrolysis of silylated graphite oxides. Carbon 2009, 47, 804–11. 10.1016/j.carbon.2008.11.040 Search in Google Scholar

[61] Shen J, Yan B, Shi M, Ma H, Li N, Ye M. Synthesis of graphene oxide-based biocomposites through diimide-activated amidation. J. Colloid Interface Sci. 2011, 356, 543–549. 10.1016/j.jcis.2011.01.052 Search in Google Scholar PubMed

[62] Zhang Y, Ren L, Wang S, Marathe A, Chaudhuri J, Li G. Functionalization of graphene sheets through fullerene attachment. J Mater Chem. 2011, 21, 5386–5391. 10.1039/c1jm10257e Search in Google Scholar

[63] Chen G, Zhai S, Zhai Y, Zhang K, Yue Q, Wang L, Zhao J, Wang H, Liu J, Jia J. Preparation of sulfonic-functionalized graphene oxide as ion exchange material and its application into electrochemiluminescence analysis. Biosens. Bioelectron. 2011, 26, 3136–3141. 10.1016/j.bios.2010.12.015 Search in Google Scholar PubMed

[64] Choi J, Kim KJ, Kim B, Lee H, Kim S. Covalent functionalization of epitaxial graphene by azidotrimethylsilane. J. Phys. Chem. C 2009, 113, 9433–9435. 10.1021/jp9010444 Search in Google Scholar

[65] Georgakilas V, Bourlinos AB, Zboril R, Steriotis TA, Dallas P, Stubos AK, et al. Organic functionalisation of graphenes. Chem. Commun. 2010, 46, 1766–1768. 10.1039/b922081j Search in Google Scholar PubMed

[66] Quintana M, Spyrou K, Grzelczak M, Browne WR, Rudolf P, Prato M. Functionalization of graphene via 1, 3-dipolar cycloaddition. ACS Nano. 2010, 4, 3527–3533. 10.1021/nn100883p Search in Google Scholar PubMed

[67] Vadukumpully S, Gupta J, Zhang Y, Xu GQ, Valiyaveettil S. Functionalization of surfactant wrapped graphene nanosheets with alkylazides for enhanced dispersibility. Nanoscale 2011, 3, 303–308. 10.1039/C0NR00547A Search in Google Scholar

[68] Xu X, Luo Q, Lv W, Dong Y, Lin Y, Yang Q, Shen A, Pang D, Hu J, Qin J, Li Z. Functionalization of graphene sheets by polyacetylene: convenient synthesis and enhanced emission. Macromol. Chem. Phys. 2011, 212, 768–773. 10.1002/macp.201000608 Search in Google Scholar

[69] Zhong X, Jin J, Li S, Niu Z, Hu W, Li R. Aryne cycloaddition: highly efficient chemical modification of graphene. Chem. Commun. 2010, 46, 7340–7342. 10.1039/c0cc02389b Search in Google Scholar PubMed

[70] Dreyer DR, Park S, Bielawski CW, Ruoff RS. The chemistry of graphene oxide. Chem. Soc. Rev. 2010, 39, 228–240. 10.1039/B917103G Search in Google Scholar PubMed

[71] Choi GB, Park H, Yang MH, Jung YM, Lee SY, Hong WH, Park TJ. Microwave-assisted synthesis of highly water-soluble graphene towards electrical DNA sensor. Nanoscale 2010, 2, 2692–2697. 10.1039/c0nr00562b Search in Google Scholar PubMed

[72] Mohanty N, Berry V. Graphene-based single-bacterium resolution biodevice and DNA transistor: interfacing graphene derivatives with nanoscale and microscale biocomponents. Nano Lett. 2008, 8, 4469–4476. 10.1021/nl802412n Search in Google Scholar PubMed

[73] Wang X, Gaoquan S. Flexible graphene devices related to energy conversion and storage. Energy Environ. Sci. 2015, 8, 790–823. 10.1039/C4EE03685A Search in Google Scholar

[74] Huang Y, Dong X, Liu Y, Li LJ, Chen P. Graphene-based biosensors for detection of bacteria and their metabolic activities. J. Mater. Chem. 2011, 21, 12358–12362. 10.1039/c1jm11436k Search in Google Scholar

[75] Huang YX, Dong XC, Shi YM, Li CM, Li LJ, Chen P. Nanoelectronic biosensors based on CVD grown graphene. Nanoscale 2010, 2, 1485–1488. 10.1039/c0nr00142b Search in Google Scholar PubMed

[76] Dong XC, Huang W, Chen P. In situ synthesis of reduced graphene oxide and gold nanocomposites for nanoelectronics and biosensing. Nanoscale Res. Lett. 2011, 6, 60. 10.1007/s11671-010-9806-8 Search in Google Scholar PubMed PubMed Central

[77] Zhou XZ, Huang X, Qi XY, Wu SX, Xue C, Boey FYC, Yan QY, Chen P, Zhang H. In situ synthesis of metal nanoparticles on single-layer graphene oxide and reduced graphene oxide surfaces. J. Phys. Chem. C. 2009, 113, 10842–10846. 10.1021/jp903821n Search in Google Scholar

[78] Sinitskii A, Dimiev A, Corley DA, Fursina AA, Kosynkin DV, Tour JM. Kinetics of diazonium functionalization of chemically converted graphene nanoribbons. ACS Nano. 2010, 4, 1949–1954. 10.1021/nn901899j Search in Google Scholar PubMed

[79] Niyogi S, Bekyarova E, Itkis M E, Zhang H, Shepperd K, Hicks J, Sprinkle M, Berger C, Ning LC, de Heer, WA, Conrad EH, Haddon RC. Spectroscopy of covalently functionalized graphene. Nano Lett. 2010, 10, 4061–4066. 10.1021/nl1021128 Search in Google Scholar PubMed

[80] Jin Z, Lomeda JR, Price BK, Lu W, Zhu Y, Tour JM. Mechanically assisted exfoliation and functionalization of thermally converted graphene sheets. Chem. Mater. 2009, 21, 3045–3047. 10.1021/cm901601g Search in Google Scholar

[81] Zhang X, Hou L, Cnossen A, Coleman AC, Ivashenko O, Rudolf P, van Wees BJ, Browne WR, Feringa BL. One-pot functionalization of graphene with porphyrin through cycloaddition reactions. Chem. Eur. J. 2011, 17, 8957–8964. 10.1002/chem.201100980 Search in Google Scholar PubMed

[82] Liu LH, Lerner MM, Yan M. Derivitization of pristine graphene with well-defined chemical functionalities. Nano Lett. 2010, 10, 3754–3756. 10.1021/nl1024744 Search in Google Scholar PubMed PubMed Central

[83] Yu D, Yang Y, Durstock M, Baek JB, Dai L. Soluble P3HT-grafted graphene for efficient bilayer–heterojunction photovoltaic devices. ACS Nano. 2010, 4, 5633–5640. 10.1021/nn101671t Search in Google Scholar PubMed

[84] Melucci M, Treossi E, Ortolani L, Giambastiani G, Morandi V, Klar P, Casiraghi C, Samor P, Palermo V. Facile covalent functionalization of graphene oxide using microwaves: bottom-up development of functional graphitic materials. J. Mater. Chem. 2010, 20, 9052–9060. 10.1039/c0jm01242d Search in Google Scholar

[85] Xu Y, Liu Z, Zhang X, Wang Y, Tian J, Huang Y, Ma Y, Zhang X, Chen YA. Graphene hybrid material covalently functionalized with porphyrin: synthesis and optical limiting property. Adv. Mater. 2009, 21, 1275–1279. 10.1002/adma.200801617 Search in Google Scholar

[86] Karousis N, Sandanayaka ASD, Hasobe T, Economopoulos SP, Sarantopoulou E, Tagmatarchis N. Graphene oxide with covalently linked porphyrin antennae: synthesis, characterization and photophysical properties. J. Mater. Chem. 2011, 21, 109–117. 10.1039/C0JM00991A Search in Google Scholar

[87] Gonc AG, Marques PAAP, Timmons AB, Bdkin I, Singh MK, Emami N, Grácio J. Graphene oxide modified with PMMA via ATRP as a reinforcement filler. J. Mater. Chem. 2010, 20, 9927–9934. 10.1039/c0jm01674h Search in Google Scholar

[88] Pramoda KP, Hussain H, Koh HM, Tan HR, He CB. Covalent bonded polymer–graphene nanocomposites. J. Polym. Sci., Part A: Polym. Chem. 2010, 48, 4262–4267. 10.1002/pola.24212 Search in Google Scholar

[89] Ramanathan T, Abdala AA, Stankovich S, Dikin DA, Herrera-Alonso M, Piner RD, Adamson DH, Schniepp HC, Chen X, Ruoff RS, Nguyen ST, Aksay IA, Prud’Homme RK, Brinson LC. Functionalized graphene sheets for polymer nanocomposites. Nat. Nanotechnol. 2008, 3, 327–331. 10.1038/nnano.2008.96 Search in Google Scholar PubMed

[90] Chandrachud P, Pujari BS, Haldar S, Sanyal B, Kanhere DG. A systematic study of electronic structure from graphene to graphene. J. Phys. Condens. Matter. 2010, 22, 465502. 10.1088/0953-8984/22/46/465502 Search in Google Scholar PubMed

[91] Savchenko A. Sudden death of entanglement. Science 2009, 323, 598–601. 10.1126/science.1167343 Search in Google Scholar PubMed

[92] Hong X, Cheng SH, Herding C, Zhu J. Colossal negative magnetoresistance in dilute fluorinated graphene. J. Phys. Rev. B 2011, 83, 085410-1–085410-5. 10.1103/PhysRevB.83.085410 Search in Google Scholar

[93] Bourlinos AB, Bakandritsos A, Liaros N, Couris S, Safarova K, Otyepka M, Zboril R. Water dispersible functionalized graphene fluoride with significant nonlinear optical response. Chem. Phys. Lett. 2012, 543, 101–105. 10.1016/j.cplett.2012.06.021 Search in Google Scholar

[94] Grabowski SJ. pi-H···O hydrogen bonds: multicenter covalent pi-H interaction acts as the proton-donating system. J. Phys. Chem. A. 2007, 111, 13537–13543. 10.1021/jp076990t Search in Google Scholar PubMed

[95] Kwon JY, Singh NJ, Kim HA, Kim SK, Kim KS, Yoon J. Fluorescent GTP-sensing in aqueous solution of physiological pH. J. Am. Chem. Soc. 2004, 126, 8892–8893. 10.1021/ja0492440 Search in Google Scholar PubMed

[96] Vaupel S, Brutschy B, Tarakeshwar P, Kim KS. Characterization of weak NH–π intermolecular interactions of ammonia with various substituted π-systems. J. Am. Chem. Soc. 2006, 128, 5416–5426. 10.1021/ja056454j Search in Google Scholar PubMed

[97] Grimme S. On the importance of electron correlation effects for the π-π interactions in cyclophanes. Chem. Eur. J. 2004, 10, 3423–3429. 10.1002/chem.200400091 Search in Google Scholar PubMed

[98] Sinnokrot MO, Sherrill CD. High-accuracy quantum mechanical studies of π–π interactions in benzene dimers. J. Phys. Chem. A. 2006, 110, 10656–10668. 10.1021/jp0610416 Search in Google Scholar PubMed

[99] Lee EC, Kim D, Jurecka P, Tarakeshwar, P, Hobza P, Kim KS. Understanding of assembly phenomena by aromatic–aromatic interactions: benzene dimer and the substituted systems. J. Phys. Chem. A. 2007, 111, 3446–3457. 10.1021/jp068635t Search in Google Scholar PubMed

[100] Oh KS, Lee CW, Choi HS, Lee SJ, Kim KS. Origin of the high affinity and selectivity of novel receptors for NH 4 + over K + : charged hydrogen bonds vs cation–π interaction. Org. Lett. 2000, 2, 2679–2681. 10.1021/ol000159g Search in Google Scholar PubMed

[101] Chellappan K, Singh NJ, Hwang IC, Lee JW, Kim KS. A Calix[4]imidazolium[2]pyridine as an anion receptor. Angew. Chem., Int. Ed. 2005, 44, 2899–2903. 10.1002/anie.200500119 Search in Google Scholar PubMed

[102] Singh NJ, Min SK, Kim DY, Kim KS. Comprehensive energy analysis for various types of π-interaction. J. Chem. Theory Comput. 2009, 5, 515–529. 10.1021/ct800471b Search in Google Scholar PubMed

[103] Xu Z, Singh NJ, Kim SK, Spring DR, Kim KS, Yoon J. Induction-driven stabilization of the anion–π interaction in electron-rich aromatics as the key to fluoride inclusion in imidazolium-cage receptors. Chem. Eur. J. 2011, 17, 1163–1170. 10.1002/chem.201002105 Search in Google Scholar PubMed

[104] Mascal M, Yakovlev I, Nikitin EB, Fettinger JC. Precedent and theory unite in the hypothesis of a highly selective fluoride receptor. Angew. Chem. Int. Ed. 2006, 45, 2890–2893. 10.1002/anie.200504417 Search in Google Scholar PubMed

[105] Kim DY, Singh NJ, Lee JW, Kim KS. Solvent-driven structural changes in anion–π complexes. J. Chem. Theory Comput. 2008, 4, 1162–1169. 10.1021/ct8001283 Search in Google Scholar PubMed

[106] Uchoa B, Lin CY, Castro Neto AH. Tailoring graphene with metals on top. Phys. Rev. B 2008, 77, 035420. 10.1103/PhysRevB.77.035420 Search in Google Scholar

[107] Bertoni G, Calmels L, Altibelli A, Serin V. First-principles calculation of the electronic structure and EELS spectra at the graphene/Ni(111) interface. Phys. Rev. B. 2005, 71, 075402. 10.1103/PhysRevB.71.075402 Search in Google Scholar

[108] Youn IS, Kim DY, Singh NJ, Park SW, Youn J, Kim KS. Intercalation of transition metals into stacked benzene rings: a model study of the intercalation of transition metals into bilayered graphene. J. Chem. Theory Comput. 2012, 8, 99–105. 10.1021/ct200661p Search in Google Scholar PubMed

[109] Thevenot DR, Toth K, Durst RA, Wilson GS. Electrochemical biosensors: recommended definitions and classification. Pure Appl. Chem. 1999, 71, 2333–2348. 10.1351/pac199971122333 Search in Google Scholar

[110] Thevenot DR, Toth K, Durst RA, Wilson GS. Electrochemical biosensors: recommended definitions and classification. Biosens. Bioelectron. 2001, 16, 121–131. Search in Google Scholar

[111] Solanki PR, Kaushik A, Agrawal VV, Malhotra BD. Nanostructured metal oxide-based biosensors. NPG Asia Mater. 2011, 3, 17–24. 10.1038/asiamat.2010.137 Search in Google Scholar

[112] Shan C, Yang H, Song J, Han D, Ivaska A and Niu L. Direct electrochemistry of glucose oxidase and biosensing for glucose based on graphene. Anal. Chem. 2009, 81, 2378–2382. 10.1021/ac802193c Search in Google Scholar

[113] Panchakarla L, Subrahmanyam K, Saha S, Govindaraj A, Krishnamurthy H, Waghmare U, Rao C. Synthesis, structure, and properties of boron- and nitrogen-doped graphene. Adv. Mater. 2009, 21, 4726–4730. 10.1002/adma.200901285 Search in Google Scholar

[114] Wang X, Li X, Zhang L, Yoon Y, Weber PK, Wang H, Guo J, Dai H. N-Doping of Graphene through electrothermal reactions with ammonia. Science 2009, 324, 768–771. 10.1126/science.1170335 Search in Google Scholar

[115] Liu H, Liu Y, Zhu D. Chemical doping of graphene. J. Mater. Chem. 2011, 21, 3335–3345. 10.1039/C0JM02922J Search in Google Scholar

[116] Wang X, Sun G, Routh P, Kim DH, Huang W, Chen P. Heteroatom-doped graphene materials: syntheses, properties and applications. Chem. Soc. 2014, 43, 7067–7098. 10.1039/C4CS00141A Search in Google Scholar

[117] Wang J. Electrochemical glucose biosensors. Chem. Rev. 2008, 108, 814–825. 10.1016/B978-012373738-0.50005-2 Search in Google Scholar

[118] Luo XL, Killard AJ, Smyth MR. Reagentless glucose biosensor based on the direct electrochemistry of glucose oxidase on carbon nanotube-modified electrodes. Electroanal. 2006, 8, 1131–1134. 10.1002/elan.200603513 Search in Google Scholar

[119] Miyawaki O, Wingard Jr. LB. Electrochemical and glucose oxidase coenzyme activity of flavin adenine dinucleotide covalently attached to glassy carbon at the adenine amino group. Biochim. Biophys. Acta. 1985, 838, 60–68. 10.1016/0304-4165(85)90250-8 Search in Google Scholar

[120] Alwarappan S, Liu C, Kumar A, Li CZ. Enzyme-doped graphene nanosheets for enhanced glucose biosensing. J. Phys. Chem. C. 2010, 114, 12920–12924. 10.1021/jp103273z Search in Google Scholar

[121] Chen X, Ye H, Wang W, Qiu B, Lin Z, Chen G. Electrochemiluminescence biosensor for glucose based on graphene/nafion/GOD film modified glassycarbon electrode. Electroanal. 2010, 22, 2347–2352. 10.1002/elan.201000095 Search in Google Scholar

[122] Shan C, Yang H, Han D, Zhang Q, Ivaska A, Niu L. Graphene/AuNPs/chitosan nanocomposites film for glucose biosensing. Biosens. Bioelectron. 2010, 25, 1070–1074. 10.1016/j.bios.2009.09.024 Search in Google Scholar PubMed

[123] Bharath G, Rajesh M, Shen-Ming C, Vediyappan E, Balamurugan A, Mangalaraj D, Viswanathana C, Ponpandian N. Enzymatic electrochemical glucose biosensors by mesoporous 1D hydroxyapatite-on-2D reduced graphene oxide. J. Mater. Chem. B. 2015, 3, 1360–1370. 10.1039/C4TB01651C Search in Google Scholar PubMed

[124] Liu J, Kong N, Li A, Luo X, Cui L, Wang R, Feng S. Graphene bridged enzyme electrodes for glucose biosensing application. Analyst 2013, 138, 2567–2575. 10.1039/c3an36929c Search in Google Scholar PubMed

[125] Dong XC, Xu H, Wang XW, Huang YX, Chan-Park MB, Zhang H, Wang LH, Huang W, Chen P. 3D graphene–cobalt oxide electrode for high performance supercapacitor and enzymeless glucose detection. ACS Nano. 2012, 6, 3206–3213. 10.1021/nn300097q Search in Google Scholar PubMed

[126] Bing Z, Yu H, Bingqian L, Dianping T. Nickel-functionalized reduced graphene oxide with polyanilinefor non-enzymatic glucose sensing. Microchim Acta. 2015, 182, 625–631. 10.1007/s00604-014-1366-7 Search in Google Scholar

[127] Luo J, Jiang SS, Zhang HY, Jiang JQ, Liu XY. A novel non-enzymatic glucose sensor based on Cu nanoparticle modified graphene sheets electrode. Anal. Chim. Acta. 2012, 709, 47–53. 10.1016/j.aca.2011.10.025 Search in Google Scholar PubMed

[128] Le TH, Kang GS, Seung HH. Highly sensitive non-enzymatic glucose sensor based on Ptnanoparticle decorated graphene oxide hydrogel. Sens. Actuat. B. 2015, 210, 618–623. 10.1016/j.snb.2015.01.020 Search in Google Scholar

[129] Zonghua W, Jianfei X, Xinmei G, Yanzhi X, Shuyan Y, Feifei Z, Yanhui L, Linhua X. Platinum/graphene functionalized by PDDA as a novel enzyme carrier for hydrogen peroxide biosensor. Anal. Methods. 2013, 5, 483–488. 10.1039/C2AY25930C Search in Google Scholar

[130] Di Z, He Z, Zhuangjun F, Mingjie L, Penghui D, Chenming L, Yuping L, Haitao L, Hongbin C. A highly sensitive and selective hydrogen peroxide biosensor based on gold nanoparticles and three-dimensional porous carbonized chicken eggshell membrane. Plos One 2015, 1–14. Search in Google Scholar

[131] Sivaprakasam R, Sang JK. An enzymatic biosensor for hydrogen peroxidebased on one-pot preparation of CeO 2 -reducedgraphene oxide nanocomposite. RSC Adv. 2015, 5, 12937–12943. 10.1039/C4RA12841A Search in Google Scholar

[132] Jin G, Lu L, Gao X, Li M-J, Qiu B, Lin Z. Magnetic graphene oxide-based electrochemiluminescent aptasensor for thrombin. Electrochim. Acta. 2013, 89, 13–17. 10.1016/j.electacta.2012.10.155 Search in Google Scholar

[133] Zhang D, Zhang Y, Zheng L, Zhan Y, He L. Graphene oxide/poly-l-lysine assembled layer for adhesion and electrochemical impedance detection of leukemia K562 cancer cells. Biosens. Bioelectron. 2013, 42, 112–118. 10.1016/j.bios.2012.10.057 Search in Google Scholar

[134] Yang G, Cao J, Li L, Rana RK, Zhu J-J. Carboxymethyl chitosan-functionalized graphene for label-free electrochemical cytosensing. Carbon 2013, 51, 124–133. 10.1016/j.carbon.2012.08.020 Search in Google Scholar

[135] Zhang J, Xue RH, Ong WY, Chen P. Roles of cholesterol in vesicle fusion and motion. Biophys. J. 2009, 97, 1371–1380. 10.1016/j.bpj.2009.06.025 Search in Google Scholar

[136] Dey SR, Raj CR. Development of an amperometric cholesterol biosensor based on graphene–Pt nanoparticle hybrid material. J. Phys. Chem. C 2010, 114, 21427–21433. 10.1021/jp105895a Search in Google Scholar

[137] Shiju A, Narsingh R, Nirala, Shobhit P, Monika S, Sunil S, Bernd W, Anchal S. Functional graphene–gold nanoparticle hybrid system for enhanced electrochemical biosensing of free cholesterol. Anal. Methods. 2015, 7, 3993–4002. 10.1039/C5AY00050E Search in Google Scholar

[138] Deepshikha, Ruchika C, Pratima CR, Tinku B. Decorated graphene-nanostructured polyaniline nanocomposite-based bienzymatic platform for cholesterol sensing. ISRN Nanotech. 2012, 2012, 1–12. 10.5402/2012/102543 Search in Google Scholar

[139] Liu H, Gao J, Xue M, Zhu N, Zhang M, Cao T. Processing of graphene for electrochemical application: noncovalently functionalize graphene sheets with water-soluble electroactive methylene green. Langmuir 2009, 25, 12006–12010. 10.1021/la9029613 Search in Google Scholar

[140] Musameh M, Wang J, Merkoci A, Lin Y. Low-potential stable NADH detection at carbon-nanotube-modified glassy carbon electrodes. Electrochem. Commun. 2002, 4, 743–746. 10.1016/S1388-2481(02)00451-4 Search in Google Scholar

[141] Valentini F, Amine A, Orlanducci S, Terranova ML, Palleschi G. Carbon nanotube purification: preparation and characterization of carbon nanotube paste electrodes. Anal. Chem. 2003, 75, 5413–21. 10.1021/ac0300237 Search in Google Scholar PubMed

[142] Shan C, Yang H, Han D, Zhang Q, Ivaska A, Niu L. Electrochemical determination of NADH and ethanol based on ionic liquid-functionalized graphene. Biosens. Bioelectron . 2010, 25, 1504–1508. 10.1016/j.bios.2009.11.009 Search in Google Scholar PubMed

[143] Tang L, Wang Y, Li Y, Feng H, Lu J, Li J. Preparation, structure, and electrochemical properties of reduced graphene sheet films. Adv. Funct. Mater. 2009, 19, 2782–2789. 10.1002/adfm.200900377 Search in Google Scholar

[144] How GTS, Pandikumar A, Huang NM, Lim HN. Highly exposed {001} facets of titanium dioxide modified with reduced graphene oxide for dopamine sensing. Sci. Rep. 2014, 4, 5044. 10.1038/srep05044 Search in Google Scholar PubMed PubMed Central

[145] Liu M, Wang L, Deng J, Chen Q, Li Y, Zhang Y, Li H, Yao S. Highly sensitive and selective dopamine biosensor based on a phenylethynyl ferrocene/graphene nanocomposite modified electrode. Analyst 2012, 137, 4577–4583. 10.1039/c2an35708a Search in Google Scholar PubMed

[146] Sassolas A, Leca-Bouvier BD, Blum LJ. DNA biosensors and microarrays. Chem. Rev. 2008, 108, 109–139. 10.1021/cr0684467 Search in Google Scholar PubMed

[147] Drummond TG, Hill MG, Barton JK. Electrochemical DNA sensors. Nat. Biotechnol . 2003, 21, 1192–1199. 10.1038/nbt873 Search in Google Scholar PubMed

[148] Tian T, Li Z, Lee EC. Sequence-specific detection of DNA using functionalized graphene as an additive. Biosens. Bioelectron. 2014, 53, 336–339. 10.1016/j.bios.2013.09.076 Search in Google Scholar PubMed

[149] Sun W, Lu Y, Wu Y, Zhang Y, Wang P, Chen Y, Li G. Electrochemical sensor for transgenic maize MON810 sequence with electrostatic adsorption DNA on electrochemical reduced graphene modified electrode. Sens. Actuat. B Chem. 2014, 204, 160–166. 10.1016/j.snb.2014.05.072 Search in Google Scholar

[150] Shi A, Wang J, Han X, Fang X, Zhang Y. A sensitive electrochemical DNA biosensor based on gold nanomaterial and graphene amplified signal. Sens. Actuat. B Chem. 2014, 200, 206–212. 10.1016/j.snb.2014.04.024 Search in Google Scholar

[151] Wang J, Shi A, Fang X, Han X, Zhang Y. Ultrasensitive electrochemical supersandwich DNA biosensor using a glassy carbon electrode modified with gold particle-decorated sheets of graphene oxide. Microchim. Acta. 2014, 181, 935–940. 10.1007/s00604-014-1182-0 Search in Google Scholar

[152] Huang KJ, Liu YJ, Wang HB, Gan T, Liu YM, Wang LL. Signal amplification for electrochemical DNA biosensor based on two-dimensional graphene analogue tungsten sulfide–graphene composites and gold nanoparticles. Sens. Actuat. B Chem. 2014, 191, 828–836. 10.1016/j.snb.2013.10.072 Search in Google Scholar

[153] Lu J, Jiang Y, Wang K, Wang J, Huang X, Ma X, Yang X. Electrochemical behavior of human telomere DNA at graphene and hypocrellin a modified glassy carbon electrode and its determination. Sens. J. IEEE 2014, 14, 1904–1913. 10.1109/JSEN.2014.2303114 Search in Google Scholar

[154] He L, Zhang Y, Liu S, Fang S, Zhang Z. A nanocomposite consisting of plasma-polymerized propargylamine and graphene for use in DNA sensing. Microchim. Acta. 2014, 181, 1981–1989. 10.1007/s00604-014-1300-z Search in Google Scholar

[155] Wang Q, Lei J, Deng S, Zhang L, Ju H. Graphene-supported ferric porphyrin as a peroxidase mimic for electrochemical DNA biosensing. Chem. Commun. 2013, 49, 916–918. 10.1039/C2CC37664D Search in Google Scholar

[156] Pumera M, Ambrosi A, Bonanni A, Chng ELK, Poh HL. Graphene for electrochemical sensing and biosensing. Trends Analyt. Chem. 2010, 29, 954–965. 10.1016/j.trac.2010.05.011 Search in Google Scholar

[157] Liu Y, Dong X, Chen P. Biological and chemical sensors based on graphene materials. Chem. Soc. 2012, 41, 2283–2307. 10.1039/C1CS15270J Search in Google Scholar

[158] Liu F, Ha HD, Han DJ, Seo TS. Photoluminescent graphene oxide microarray for multiplex heavy metal ion analysis. Small 2013, 9, 3410–3414. 10.1002/smll.201300499 Search in Google Scholar

[159] Wang B, Chang YH, Zhi LJ. High yield production of graphene and its improved property in detecting heavy metal ions. New Carbon Mater. 2011, 26, 31–35. 10.1016/S1872-5805(11)60064-4 Search in Google Scholar

[160] Yu C, Guo Y, Liu H, Yan N, Xu Z, Yu G, Fang Y, Liu Y. Ultrasensitive and selective sensing of heavy metal ions with modified graphene. Chem. Commun. 2013, 49, 6492–6494. 10.1039/c3cc42377h Search in Google Scholar PubMed

[161] Kuila T, Bose S, Khanra P, Mishra AK, Kim NH, Lee JH. Recent advances in graphene-based biosensors. Biosens. Bioelectron. 2011, 26, 4637–4648. 10.1016/j.bios.2011.05.039 Search in Google Scholar PubMed

[162] Willemse CM, Tlhomelang K, Jahed N, Baker PG, Iwuoha EI. Metallographene nanocomposite electrocatalytic platform for the determination of toxic metal ions. Sensors 2011, 11, 3970–3987. 10.3390/s110403970 Search in Google Scholar PubMed PubMed Central

[163] Lien CH, Chang KH, Hu CC, Wang DSH. Optimizing bismuth-modified graphene–carbon nanotube composite-coated screen printed electrode for lead-ion sensing through the experimental design strategy. J. Electrochem. Soc. 2013, 160, 107–112. 10.1149/2.081308jes Search in Google Scholar

[164] Lien CH, Hu CC, Chang KH, Tsai YD, Wang DSH, A study on the key factors affecting the sensibility of bismuth deposits toward Sn 2+ : effects of bismuth microstructures on the Sn 2+ pre-deposition. Electrochim. Acta. 2013, 105, 665–670. 10.1016/j.electacta.2013.04.121 Search in Google Scholar

[165] Fu X, Lou T, Chen Z, Lin M, Feng W, Chen L. Turn-on fluorescence detection of lead Ions based on accelerated leaching of gold nanoparticles on the surface of graphene. ACS Appl. Mater. Interfaces 2012, 4, 1080–1086. 10.1021/am201711j Search in Google Scholar PubMed

[166] Kong N, Liu J, Kong Q, Wang R, Barrow CJ, Yang W. Graphene modified gold electrode via p–p stacking interaction for analysis of Cu2+ and Pb2+. Sens. Actuat. B Chem. 2013, 178, 426–433. 10.1016/j.snb.2013.01.009 Search in Google Scholar

[167] Zhang JT, Jin ZY, Li WC, Dong W, Lu AH. Graphene modified carbon nanosheets for electrochemical detection of Pb(II) in water. J. Mater. Chem. A. 2013, 1, 13139–13145. 10.1039/c3ta12612a Search in Google Scholar

[168] Zhao XH, Kong RM, Zhang XB, Meng HM, Liu WN, Tan W, Shen GL, Yu RQ. Graphene-DNAzyme based biosensor for amplified fluorescence turn-on detection of Pb 2+ with a high selectivity. Anal. Chem. 2011, 83, 5062–5066. 10.1021/ac200843x Search in Google Scholar PubMed

[169] Zhang T, Cheng Z, Wang Y, Li Z, Wang C, Li Y, Fang Y. Self-assembled 1- octadecanethiol monolayers on graphene for mercury detection. Nano Lett. 2010, 10, 4738–4741. 10.1021/nl1032556 Search in Google Scholar PubMed

[170] Wei Y, Gao C, Meng FL, Li HH, Wang L, Liu JH, Huang XJ. SnO 2 /reduced graphene oxide nanocomposite for the simultaneous electrochemical detection of cadmium(II), lead(II), copper(II), and mercury(II): an interesting favorable mutual interference. J. Phys. Chem. C . 2011, 116, 1034–1041. 10.1021/jp209805c Search in Google Scholar

[171] Gupta VK, Yola ML, Atar N, Ustunda Z. Solak AO. A novel sensitive Cu(II) and Cd(II) nanosensor platform: graphene oxide terminated p-aminophenyl modified glassy carbon surface. Electrochim. Acta . 2013, 112, 541–548. 10.1016/j.electacta.2013.09.011 Search in Google Scholar

[172] Liu M, Zhao H, Chen S, Yu H, Zhang Y, Quan X. A turn-on fluorescent copper biosensor based on DNA cleavage-dependent graphene-quenched DNAzyme. Biosens. Bioelectron. 2011, 26, 4111–4116. 10.1016/j.bios.2011.04.006 Search in Google Scholar PubMed

[173] Wen Y, Xing F, He S, Song S, Wang L, Long Y, Li D, Fan C. A graphene-based fluorescent nanoprobe for silver(I) ions detection by using graphene oxide and a silver-specific oligonucleotide. Chem. Commun . 2010, 46, 2596–2598. 10.1039/b924832c Search in Google Scholar PubMed

[174] Jiang S, Hua E, Liang M, Liu B, Xie G. A novel immunosensor for detecting toxoplasma gondii-specific IgM based on goldmag nanoparticles and graphene sheets. Colloids Surf. B Biointerfaces 2013, 101, 481–486. 10.1016/j.colsurfb.2012.07.021 Search in Google Scholar PubMed

[175] Zhang GJ. Highly sensitive and reversible silicon nanowire biosensor to study nuclear hormone receptor protein and response element DNA interactions. Biosens. Bioelectron . 2010, 26, 365–370. 10.1016/j.bios.2010.07.129 Search in Google Scholar PubMed

[176] Shirale D. Effect of (L:D) aspect ratio on single polypyrrole nanowire FET device. J. Phys. Chem. Part. C Nanomater. Interfaces 2010, 114, 13375–13380. 10.1021/jp104377e Search in Google Scholar PubMed PubMed Central

[177] Tian L, Heyduk T. Antigen peptide-based immunosensors for rapid detection of antibodies and antigens. Anal. Chem . 2009, 8, 5218–5225. 10.1021/ac900845a Search in Google Scholar PubMed PubMed Central

[178] María MG. Ultrasensitive detection of adrenocorticotropin hormone (ACTH) using disposable phenylboronic-modified electrochemical immunosensors. Biosens. Bioelectron . 2012, 35, 82–86. 10.1016/j.bios.2012.02.015 Search in Google Scholar PubMed

[179] Zor E. An electrochemical biosensor based on human serum albumin/graphene oxide/3-aminopropyltriethoxysilane modified ITO electrode for the enantioselective discrimination of d- and l-tryptophan. Biosens. Bioelectron . 2013, 42, 321–325. 10.1016/j.bios.2012.10.068 Search in Google Scholar PubMed

[180] Yu K, Bo Z, Lu G, Mao S, Cui S, Zhu Y, Chen X, Ruoff RS, Chen J. Growth of carbon nanowalls at atmospheric pressure for one-step gas sensor fabrication. Nanoscale Res. Lett . 2011, 6, 1–9. 10.1186/1556-276X-6-202 Search in Google Scholar PubMed PubMed Central

[181] Ohno Y, Maehashi K, Matsumoto K. Label-free biosensors based on aptamer modified graphene field-effect transistors. J. Am. Chem. Soc . 2010, 132, 18012–18013. 10.1021/ja108127r Search in Google Scholar PubMed

[182] Pumera M. Graphene for electrochemical sensing and biosensing. Trends Anal. Chem . 2010, 29, 954–965. 10.1016/j.trac.2010.05.011 Search in Google Scholar

[183] Mao S. Highly sensitive protein sensor based on thermally reduced graphene oxide field-effect transistor. Nano Res. 2011, 4, 921–930. 10.1007/s12274-011-0148-3 Search in Google Scholar

[184] Loo AH, Bonanni A, Ambrosi A, Poh HL, Pumera M. Impedimetric immunoglobulin G immunosensor based on chemically modified graphenes. Nanoscale 2012, 4, 921–925. 10.1039/C2NR11492E Search in Google Scholar

[185] Jia X, Liu Z, Liu N, Ma Z. A label-free immunosensor based on graphene nanocomposites for simultaneous multiplexed electrochemical determination of tumor markers. Biosens. Bioelectron. 2014, 53, 160–166. 10.1016/j.bios.2013.09.050 Search in Google Scholar PubMed

[186] Wang Y, Shao Y, Matson DW, Li J, Lin Y. Nitrogen-doped graphene and its application in electrochemical biosensing. ACS Nano 2010, 4, 1790–1798. 10.1021/nn100315s Search in Google Scholar PubMed

[187] Xu Q, Gu SX, Jin L, Zhou Y, Yang Z, Wang W, Hu X. Graphene/polyaniline/gold nanoparticles nanocomposite for the direct electron transfer of glucose oxidase and glucose biosensing. Sens. Actuat. B Chem. 2014, 190, 562–569. 10.1016/j.snb.2013.09.049 Search in Google Scholar

[188] Jiang D, Liu Q, Wang K, Qian J, Dong X, Yang Z, Du X, Qiu B. Enhanced nonenzymatic glucose sensing based on copper nanoparticles decorated nitrogen-doped graphene. Biosens. Bioelectron. 2014, 54, 273–278. 10.1016/j.bios.2013.11.005 Search in Google Scholar PubMed

[189] Qin X, Asiri AM, Alamry KA, Al-Youbi AO, Sun X. Carbon nitride dots can serve as an effective stabilizing agent for reduced graphene oxide and help in subsequent assembly with glucose oxidase into hybrids for glucose detection application. Electrochim. Acta. 2013, 95, 260–267. 10.1016/j.electacta.2013.02.014 Search in Google Scholar

[190] Singh J, Khanra P, Kuila T, Srivastava M, Das AK, Kim NH. Preparation of sulfonated poly (ether–ether–ketone) functionalized ternary graphene/AuNPs/chitosan nanocomposite for efficient glucose biosensor. Process Biochem. 2013, 48, 1724–1735. 10.1016/j.procbio.2013.07.025 Search in Google Scholar

[191] Zhang Y, Wang L, Lu D, Shi X, Wang C, Duan X. Sensitive determination of bisphenol A base on arginine functionalized nanocomposite graphene film. Electrochim. Acta 2012, 80, 77–83. 10.1016/j.electacta.2012.06.117 Search in Google Scholar

[192] Radhakrishnan S, Kim SJ. An enzymatic biosensor for hydrogen peroxidebased on one-pot preparation of CeO 2 -reducedgraphene oxide nanocomposite. RSC Adv. 2015, 5, 12937–12943. 10.1039/C4RA12841A Search in Google Scholar

[193] Kung CC, Lin PY, Buse FJ, Xue Y, Yu X, Dai L. Preparation and characterization of three dimensional graphene foam supported platinum–ruthenium bimetallic nanocatalysts for hydrogen peroxide based electrochemical biosensors. Biosens. Bioelectron . 2014, 52, 1–7. 10.1016/j.bios.2013.08.025 Search in Google Scholar PubMed

[194] Niu X, Yang W, Wang G, Ren J, Guo H, Gao J. A novel electrochemical sensor of bisphenol A based on stacked graphene nanofibers/gold nanoparticles composite modified glassy carbon electrode. Electrochim Acta . 2013, 98, 167–75. 10.1016/j.electacta.2013.03.064 Search in Google Scholar

[195] Ye D, Li H, Liang G, Luo J, Zhang X, Zhang S. A three dimensional hybrid of MnO2/graphene/carbon nanotubes based sensor for determination of hydrogen-peroxide in milk. Electrochim. Acta . 2013, 109, 195–200. 10.1016/j.electacta.2013.06.119 Search in Google Scholar

[196] Chen XM, Cai ZX, Huang ZY, Oyama M, Jiang YQ, Chen X. Ultrafine palladium nanoparticles grown on graphene nanosheets for enhanced electrochemical sensing of hydrogen peroxide. Electrochim. Acta . 2013, 97, 398–403. 10.1016/j.electacta.2013.02.047 Search in Google Scholar

[197] Cao S, Zhang L, Chai Y, Yuan R. Electrochemistry of cholesterol biosensor based on a novel Pt–Pd bimetallic nanoparticle decorated graphene catalyst. Talanta 2013, 109, 167–72. 10.1016/j.talanta.2013.02.002 Search in Google Scholar PubMed

[198] Nipapan R, Ratthapol R, Nadnudda R, Orawon C. Novel paper-based cholesterol biosensor using graphene/polyvinylpyrrolidone/polyaniline nanocomposite. Biosens. Bioelectron . 2014, 52, 13–19. 10.1016/j.bios.2013.08.018 Search in Google Scholar PubMed

[199] Abraham S, Narsingh R, Nirala, Pandey S, Srivastava M, Srivastava S, Walkenfort B, Srivastava A. Functional graphene–gold nanoparticle hybrid system for enhanced electrochemical biosensing of free cholesterol. Anal. Methods 2015, 7, 3993–4002. 10.1039/C5AY00050E Search in Google Scholar

[200] Wang K, Wu J, Liu Q, Jin Y, Yan J, Cai J. Ultrasensitive photoelectrochemical sensing of nicotinamide adenine dinucleotide based on graphene–TiO 2 nanohybrids under visible irradiation. Anal. Chim. Acta 2012, 745, 131–136. 10.1016/j.aca.2012.07.042 Search in Google Scholar PubMed

[201] Li L, Lu H, Deng L. A sensitive NADH and ethanol biosensor based on graphene–Au nanorods nanocomposites. Talanta 2013, 113, 1–6. 10.1016/j.talanta.2013.03.074 Search in Google Scholar PubMed

[202] Li Z, Huang Y, Chen L, Qin X, Huang Z, Zhou Y. Amperometric biosensor for NADH and ethanol based on electroreduced graphene oxide–polythioninenanocomposite film. Sens. Actuat. B Chem . 2013, 181, 280–287. 10.1016/j.snb.2013.01.072 Search in Google Scholar

[203] Pandikumar A, How GTS, See TP, Omar FS, Jayabal S, Kamali KZ, Yusoff N, Jamil A, Ramaraj R, John SA, Limbe HN, Huang NM. Graphene and its nanocomposite material based electrochemical sensor platform for dopamine. RSC Adv. 2014, 4, 63296–63323. 10.1039/C4RA13777A Search in Google Scholar

[204] Li SM, Yang SY, Wang YS, Lien CH, Tien HW, Hsiao ST, Liao WH, Tsai HP, Chang CL, Ma CCM. Controllable synthesis of nitrogen-doped graphene and its effect on the simultaneous electrochemical determination of ascorbic acid, dopamine, and uric acid. Carbon 2013, 59, 418–429. 10.1016/j.carbon.2013.03.035 Search in Google Scholar

[205] Li SJ, He JZ, Zhang MJ, Zhang RX, Lv XL, Liand SH, Pang H, Electrochemical detection of dopamine using water-soluble sulfonated graphene. Electrochim. Acta 2013, 102, 58–65. 10.1016/j.electacta.2013.03.176 Search in Google Scholar

[206] Li N, Zheng E, Chen X, Sun S, You C, Ruan Y, Weng X. Layer-by-layer assembled multilayer films of nitrogen-doped graphene and polyethylenimine for selective sensing of dopamine. Int. J. Electrochem. Sci. 2013, 8, 6524–6534. Search in Google Scholar

[207] Guo Y, Guo Y, Dong C. Ultrasensitive and label-free electrochemical DNA biosensor based on water-soluble electroactive dye azophloxine-functionalized graphene nanosheets. Electrochim. Acta. 2013, 113, 69–76. 10.1016/j.electacta.2013.09.039 Search in Google Scholar

[208] Wang L, Hua E, Liang M, Ma C, Liu Z, Sheng S. Graphene sheets, polyaniline and AuNPs based DNA sensor for electrochemical determination of BCR/ABL fusion gene with functional hairpin probe. Biosens. Bioelectron. 2014, 51, 201–207. 10.1016/j.bios.2013.07.049 Search in Google Scholar PubMed

[209] Qi X, Gao H, Zhang Y, Wang X, Chen Y, Sun W. Electrochemical DNA biosensor with chitosan–Co 3 O 4 nanorod–graphene composite for the sensitive detection of Staphylococcus aureus nuc gene sequence. Bioelectrochemistry 2012, 88, 42–47. 10.1016/j.bioelechem.2012.05.007 Search in Google Scholar PubMed

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Exploring the effect of the covalent functionalization in graphene-antimonene heterostructures

• Fickert, M.
• Martinez-Haya, R.
• Ruiz, A. M.
• Baldoví, J. J.
• Abellán, G.

van der Waals heterostructure preparation based on hexagonal Sb and graphene, and its subsequent patterning through functionalization with benzyl substituents. The growing field of two-dimensional (2D) materials has recently witnessed the emergence of heterostructures, however those combining monoelemental layered materials remain relatively unexplored. In this study, we present the chemical fabrication and characterization of a heterostructure formed by graphene and hexagonal antimonene. The interaction between these 2D materials is thoroughly examined through Raman spectroscopy and first-principles calculations, revealing that this can be considered as a van der Waals heterostructure. Furthermore, we have explored the influence of the antimonene 2D material on the reactivity of graphene by studying the laser-induced covalent functionalization of the graphene surface. Our findings indicate distinct degrees of functionalization based on the underlying material, SiO2 being more reactive than antimonene, opening the door for the development of controlled patterning in devices based on these heterostructures. This covalent functionalization implies a high control over the chemical information that can be stored but also removed on graphene surfaces, and its use as a patterned heterostructure based on antimonene and graphene. This research provides valuable insights into the antimonene–graphene interactions and their impact on the chemical reactivity during graphene covalent functionalization.

Graphene: Synthesis and Functionalization

• First Online: 19 April 2017

Cite this chapter

• Tomo-o Terasawa 4 &
• Koichiro Saiki 5  

Part of the book series: Nanostructure Science and Technology ((NST))

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2 Citations

Graphene, a two-dimensional honeycomb sheet composed of sp 2 hybridized carbon atoms, is a representative of atomically thin-layered materials and has been extensively studied since its discovery. The peculiar properties of graphene, such as ultra-high carrier mobility, mechanical strength, and so on, have tempted researchers to utilize them in the wide area from fundamental physics to industrial applications. The ways to fabricate graphene and to tune the properties of graphene are established to some extent in this decade. Here, we summarize the recent studies of graphene and its derivatives. As an introduction, the historical background of two-dimensional materials is reviewed briefly. The fascinating properties of graphene are then described, focusing on the mechanical and electronic properties. The fabrication methods on which the quality of graphene strongly depends are described mentioning the merits and flaws of each method. The functionalization of graphene is also explained as the way to tune the properties of graphene directly. Finally, we briefly introduce the graphene-related materials, the studies of which were also initiated by the isolation of graphene.

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Graphene – Properties and Characterization

Graphene Properties, Synthesis and Applications: A Review

Graphene-Based Materials: Synthesis and Applications

Wallace P (1947) The band theory of graphite. Phys Rev 71:622

Google Scholar  

Dresselhaus MS, Dresselhaus G (2002) Intercalation compounds of graphite. Adv Phys 51:1

Nakada K, Fujita M, Dresselhaus G, Dresselhaus MS (1996) Edge state in graphene ribbons: nanometer size effect and edge shape dependence. Phys Rev B 54:17954

Article   CAS   Google Scholar  

Wilson JA, Yoffe AD (1969) The transition metal dichalcogenides discussion and interpretation of the observed optical, electrical and structural properties. Adv Phys 18:193

Wilson JA, Di Salvo FJ, Mahajan S (1974) Charge-density waves in metallic, layered, transition-metal dichalcogenides. Phys Rev Lett 32:882

Saiki K, Yoshimi M, Tanaka S (1978) Modulation spectroscopy on the group IV and VI transition-metal dichalcogenides. Phys Status Solidi 88:607

Koma A, Sunouchi K, Miyajima T (1985) Summary Abstract: fabrication of ultrathin heterostructures with van der Waals epitaxy. J Vac Sci Technol B 3:724

Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y, Dubonos SV, Grigorieva IV, Firsov AA (2004) Electric field effect in atomically Thin Carbon Films. Science 306:666

Blake P, Hill EW, Castro Neto AH, Novoselov KS, Jiang D, Yang R, Booth TJ, Geim AK (2007) Making graphene visible. Appl Phys Lett 91:063124

Novoselov KS, Geim AK, Morozov SV, Jiang D, Katsnelson MI, Grigorieva IV, Dubonos SV, Firsov AA (2005) Two-dimensional gas of massless Dirac fermions in graphene. Nature 438:197

Nair RR, Blake P, Grigorenko AN, Novoselov KS, Booth TJ, Stauber T, Peres NMR, Geim AK (2008) Fine structure constant defines visual transparency of graphene. Science 320:1308

Mermin ND (1968) Crystalline order in two dimensions. Phys Rev 176:250

Stankovich S, Piner RD, Chen X, Wu N, Nguyen ST, Ruoff RS (2006) Stable aqueous dispersions of graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium 4-styrenesulfonate). J Mater Chem 16:155

Berger C, Song Z, Li T, Li X, Ogbazghi AY, Feng R, Dai Z, Marchenkov AN, Conrad EH, First PN, de Heer WA (2004) Ultrathin Epitaxial Graphite: 2D electron gas properties and a route toward graphene-based nanoelectronics. J Phys Chem B 108:19912

Li X, Cai W, An J, Kim S, Nah J, Yang D, Piner R, Velamakanni A, Jung I, Tutuc E, Banerjee SK, Colombo L, Ruoff RS (2009) Large-area synthesis of high-quality and uniform graphene films on copper foils. science 324:1312

Wang X, Li X, Zhang L, Yoon Y, Weber PK, Wang H, Guo J, Dai H (2009) N-Doping of graphene through electrothermal reactions with ammonia. Science 324:768

Cheng H, Shiue R-J, Tsai C-C, Wang W-H, Chen Y-T (2011) High-quality graphene p − n junctions  via  resist-free fabrication and solution-based noncovalent functionalization. ACS Nano 5:2051

Han MY, Özyilmaz B, Zhang Y, Kim P (2007) Energy band-gap engineering of graphene nanoribbons. Phys Rev Lett 98:206805

Bunch JS, Verbridge SS, Alden JS, Van Der Zande AM, Parpia JM, Craighead HG, McEuen PL (2008) Impermeable atomic membranes from graphene sheets. Nano Lett 8:2458

Lee C, Wei X, Kysar JWJJW, Hone J (2008) Measurement of the elastic properties and intrinsic strength of monolayer graphene. Science 321:385

Castro Neto AH, Guinea F, Peres NMR, Novoselov KS, Geim AK (2009) The electronic properties of graphene. Rev Mod Phys 81:109

Geim AK, Novoselov KS (2007) The rise of graphene. Nat Mater 6:183

Boukhvalov DW, Katsnelson MI, Lichtenstein AI (2008) Hydrogen on graphene: electronic structure, total energy, structural distortions and magnetism from first-principles calculations. Phys Rev B 77:035427

Zhang Y, Jiang Z, Small JP, Purewal MS, Tan Y-W, Fazlollahi M, Chudow JD, Jaszczak JA, Stormer HL, Kim P (2006) Landau-level splitting in graphene in high magnetic fields. Phys Rev Lett 96:136806

Zhang Y, Tan Y-W, Stormer HL, Kim P (2005) Experimental observation of the quantum Hall effect and Berry’s phase in graphene. Nature 438:201

Novoselov KS, Jiang Z, Zhang Y, Morozov SV, Stormer HL, Zeitler U, Maan JC, Boebinger GS, Kim P, Geim AK (2007) Room-temperature quantum hall effect in graphene. Science 315:1379

Klitzing KV, Dorda G, Pepper M (1980) New method for high-accuracy determination of the fine-structure constant based on quantized hall resistance. Phys Rev Lett 45:494

Tombros N, Jozsa C, Popinciuc M, Jonkman HT, van Wees BJ (2007) Electronic spin transport and spin precession in single graphene layers at room temperature. Nature 448:571

Xiao D, Yao W, Niu Q (2007) Valley-contrasting physics in graphene: magnetic moment and topological transport. Phys Rev Lett 99:236809

Gorbachev RV, Song JCW, Yu GL, Kretinin AV, Withers F, Cao Y, Mishchenko A, Grigorieva IV, Novoselov KS, Levitov LS, Geim AK (2014) Detecting topological currents in graphene superlattices. Science 346:448

Castro EV, Novoselov KS, Morozov SV, Peres NMR, dos Santos JMBL, Nilsson J, Guinea F, Geim AK, Neto AHC (2007) Biased bilayer graphene: semiconductor with a gap tunable by the electric field effect. Phys Rev Lett 99:216802

Ferrari AC (2007) Raman spectroscopy of graphene and graphite: disorder, electron–phonon coupling, doping and nonadiabatic effects. Solid State Commun 143:47

Malard LM, Pimenta MA, Dresselhaus G, Dresselhaus MS (2009) Raman spectroscopy in graphene. Phys Rep 473:51

Ferrari AC, Basko DM (2013) Raman spectroscopy as a versatile tool for studying the properties of graphene. Nat Nanotechnol 8:235

Hummer WS, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339

Matsumoto M, Saito Y, Park C, Fukushima T, Aida T (2015) Ultrahigh-throughput exfoliation of graphite into pristine ‘single-layer’ graphene using microwaves and molecularly engineered ionic liquids. Nat Chem 7:730

Hernandez Y, Nicolosi V, Lotya M, Blighe FM, Sun Z, De S, McGovern IT, Holland B, Byrne M, Gun’Ko YK, Boland JJ, Niraj P, Duesberg G, Krishnamurthy S, Goodhue R, Hutchison J, Scardaci V, Ferrari AC, Coleman JN (2008) High-yield production of graphene by liquid-phase exfoliation of graphite. Nat Nanotechnol 3:563 (2008)

Paton KR, Varrla E, Backes C, Smith RJ, Khan U, O’Neill A, Boland C, Lotya M, Istrate OM, King P, Higgins T, Barwich S, May P, Puczkarski P, Ahmed I, Moebius M, Pettersson H, Long E, Coelho J, O’Brien SE, McGuire EK, Sanchez BM, Duesberg GS, McEvoy N, Pennycook TJ, Downing C, Crossley A, Nicolosi V, Coleman JN (2014) Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids. Nat Mater 13:624

Kusunoki M, Norimatsu W, Bao J, Morita K, Starke U (2015) Growth and features of epitaxial graphene on SiC. J Phys Soc Jpn 84:121014

Tanabe S, Sekine Y, Kageshima H, Nagase M, Hibino H (2011) Carrier transport mechanism in graphene on SiC(0001). Phys Rev B 84:115458

Hass J, Varchon F, Millán-Otoya JE, Sprinkle M, Sharma N, de Heer WA, Berger C, First PN, Magaud L, Conrad EH (2008) Why multilayer graphene on 4 H −SiC (000¯1) behaves like a single sheet of graphene. Phys Rev Lett 100:125504

Emtsev KV, Bostwick A, Horn K, Jobst J, Kellogg GL, Ley L, McChesney JL, Ohta T, Reshanov SA, Röhrl J, Rotenberg E, Schmid AK, Waldmann D, Weber HB, Seyller T (2009) Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide. Nat Mater 8:203

Wu YQ, Ye PD, Capano MA, Xuan Y, Sui Y, Qi M, Cooper JA, Shen T, Pandey D, Prakash G, Reifenberger R (2008) Top-gated graphene field-effect-transistors formed by decomposition of SiC. Appl Phys Lett 92:092102

Kim KS, Zhao Y, Jang H, Lee SY, Kim JM, Kim KS, Ahn J-H, Kim P, Choi J-Y, Hong BH (2009) Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 457:706

Yu Q, Jauregui LA, Wu W, Colby R, Tian J, Su Z, Cao H, Liu Z, Pandey D, Wei D, Chung TF, Peng P, Guisinger NP, Stach EA, Bao J, Pei SS, Chen YP (2011) Control and characterization of individual grains and grain boundaries in graphene grown by chemical vapour deposition. Nat Mater 10:443

Orofeo CM, Hibino H, Kawahara K, Ogawa Y, Tsuji M, Ikeda K, Mizuno S, Ago H (2012) Influence of Cu metal on the domain structure and carrier mobility in single-layer graphene. Carbon 50:2189

Shelton JC, Patil HR, Blakely JM (1974) Equilibrium segregation of carbon to a nickel (111) surface: a surface phase transition. Surf Sci 43:493

Sutter PW, Flege J-I, Sutter EA (2008) Epitaxial graphene on ruthenium. Nat Mater 7:406

Yu Q, Lian J, Siriponglert S, Li H, Chen YP, Pei S-S (2008) Graphene segregated on Ni surfaces and transferred to insulators. Appl Phys Lett 93:113103

Coraux J, N’Diaye AT, Busse C, Michely T (2008) Structural coherency of graphene on Ir(111). Nano Lett 8:565

Land TA, Michely T, Behm RJ, Hemminger JC, Comsa G (1992) STM investigation of single layer graphite structures produced on Pt(111) by hydrocarbon decomposition. Surf Sci 264:261

Oznuluer T, Pince E, Polat EO, Balci O, Salihoglu O, Kocabas C (2011) Synthesis of graphene on gold. Appl Phys Lett 98:183101

Lee J-H, Lee EK, Joo W-J, Jang Y, Kim B-S, Lim JY, Choi S-H, Ahn SJ, Ahn JR, Park M-H, Yang C-W, Choi BL, Hwang S-W, Whang D (2014) Wafer-scale growth of single-crystal monolayer graphene on reusable hydrogen-terminated germanium. Science 344:286

Li X, Cai W, Colombo L, Ruoff RS (2009) Evolution of graphene growth on Ni and Cu by carbon isotope labeling. Nano Lett 9:4268

Vlassiouk I, Smirnov S, Regmi M, Surwade SP, Srivastava N, Feenstra R, Eres G, Parish C, Lavrik N, Datskos P, Dai S, Fulvio P (2013) Graphene nucleation density on copper: fundamental role of background pressure. J Phys Chem C 117:18919

Vlassiouk I, Regmi M, Fulvio P, Dai S, Datskos P, Eres G, Smirnov S (2011) Role of hydrogen in chemical vapor deposition growth of large single-crystal graphene. ACS Nano 5:6069

Celebi K, Cole MT, Choi JW, Wyczisk F, Legagneux P, Rupesinghe N, Robertson J, Teo KBK, Park HG (2013) Evolutionary kinetics of graphene formation on copper. Nano Lett 13:967

Wang Z-J, Weinberg G, Zhang Q, Lunkenbein T, Klein-Hoffmann A, Kurnatowska M, Plodinec M, Li Q, Chi L, Schloegl R, Willinger M (2015) Direct observation of graphene growth and associated copper substrate dynamics by in Situ scanning electron microscopy. ACS Nano 9:1506

Kidambi PR, Bayer BC, Blume R, Wang Z-J, Baehtz C, Weatherup RS, Willinger M-G, Schloegl R, Hofmann S (2013) Observing graphene grow: catalyst–graphene interactions during scalable graphene growth on polycrystalline copper. Nano Lett 13:4769

Terasawa T, Saiki K (2015) Effect of vapor-phase oxygen on chemical vapor deposition growth of graphene. Appl Phys Express 8:035101

Terasawa T, Saiki K (2015) Radiation-mode optical microscopy on the growth of graphene. Nat Commun 6:6834

Niu T, Zhou M, Zhang J, Feng Y, Chen W (2013) Growth intermediates for CVD graphene on Cu(111): carbon clusters and defective graphene. J Am Chem Soc 135:8409

Puretzky AA, Geohegan DB, Pannala S, Rouleau CM, Regmi M, Thonnard N, Eres G (2013) Real-time optical diagnostics of graphene growth induced by pulsed chemical vapor deposition. Nanoscale 5:6507

Hao Y, Bharathi MS, Wang L, Liu Y, Chen H, Nie S, Wang X, Chou H, Tan C, Fallahazad B, Ramanarayan H, Magnuson CW, Tutuc E, Yakobson BI, McCarty KF, Zhang Y, Kim P, Hone J, Colombo L, Ruoff RS (2013) The role of surface oxygen in the growth of large single-crystal graphene on copper. Science 342:720

Hwang J, Kim M, Campbell D, Alsalman HA, Kwak JY, Shivaraman S, Woll AR, Singh AK, Hennig RG, Gorantla S, Rümmeli MH, Spencer MG (2013) van der Waals epitaxial growth of graphene on sapphire by chemical vapor deposition without a metal catalyst. ACS Nano 7:385

Sun J, Gao T, Song X, Zhao Y, Lin Y, Wang H, Ma D, Chen Y, Xiang W, Wang J, Zhang Y, Liu Z (2014) Direct growth of high-quality graphene on high- κ dielectric SrTiO 3 substrates. J Am Chem Soc 136:6574

Terasawa T, Saiki K (2012) Growth of graphene on Cu by plasma enhanced chemical vapor deposition. Carbon 50:869

Terasawa T, Saiki K (2012) Synthesis of nitrogen-doped graphene by plasma-enhanced chemical vapor deposition. Jpn J Appl Phys 51:055101

Wei D, Lu Y, Han C, Niu T, Chen W, Wee ATS (2013) Critical crystal growth of graphene on dielectric substrates at low temperature for electronic devices. Angew Chem Int Ed Engl 52:14121

Kim J, Ishihara M, Koga Y, Tsugawa K, Hasegawa M, Iijima S (2011) Low-temperature synthesis of large-area graphene-based transparent conductive films using surface wave plasma chemical vapor deposition. Appl Phys Lett 98:091502

Yamada T, Ishihara M, Kim J, Hasegawa M, Iijima S (2012) A roll-to-roll microwave plasma chemical vapor deposition process for the production of 294 mm width graphene films at low temperature. Carbon 50:2615

Weatherup RS, Baehtz C, Dlubak B, Bayer BC, Kidambi PR, Blume R, Schloegl R, Hofmann S (2013) Introducing carbon diffusion barriers for uniform, high-quality graphene growth from solid sources. Nano Lett 13:4624

Tanaka H, Obata S, Saiki K (2013) Reduction of graphene oxide at the interface between a Ni layer and a SiO 2  substrate. Carbon 59:472

Sun Z, Yan Z, Yao J, Beitler E, Zhu Y, Tour JM (2010) Growth of graphene from solid carbon sources. Nature 468:549

Ruan G, Sun Z, Peng Z, Tour JM (2011) Growth of graphene from food, insects, and waste. ACS Nano 5:7601

Obata S, Tanaka H, Saiki K (2011) Reduction of a single layer graphene oxide film on Pt(111). Appl Phys Express 4:025102

Su Q, Pang S, Alijani V, Li C, Feng X, Müllen K (2009) Composites of graphene with large aromatic molecules. Adv Mater 21:3191

Elias DC, Nair RR, Mohiuddin TMG, Morozov SV, Blake P, Halsall MP, Ferrari AC, Boukhvalov DW, Katsnelson MI, Geim AK, Novoselov KS (2009) Control of graphene’s properties by reversible hydrogenation: evidence for graphane. Science 323:610

Sofo JO, Chaudhari AS, Barber GD (2007) Graphane: A two-dimensional hydrocarbon. Phys Rev B 75:153401

Robinson JT, Burgess JS, Junkermeier CE, Badescu SC, Reinecke TL, Perkins FK, Zalalutdniov MK, Baldwin JW, Culbertson JC, Sheehan PE, Snow ES (2010) Properties of fluorinated graphene films. Nano Lett 10:3001

Cheng S-H, Zou K, Okino F, Gutierrez HR, Gupta A, Shen N, Eklund PC, Sofo JO, Zhu J (2010) Reversible fluorination of graphene: evidence of a two-dimensional wide bandgap semiconductor. Phys Rev B 81:205435

Withers F, Dubois M, Savchenko AK (2010) Electron properties of fluorinated single-layer graphene transistors. Phys Rev B 82:073403

Hamwi A (1996) Fluorine reactivity with graphite and fullerenes. fluoride derivatives and some practical electrochemical applications. J Phys Chem Solids 57:677

Sinitskii A, Dimiev A, Corley DA, Fursina AA, Kosynkin DV, Tour JM (2010) Kinetics of diazonium functionalization of chemically converted graphene nanoribbons. ACS Nano 4:1949

Liu H, Ryu S, Chen Z, Steigerwald ML, Nuckolls C, Brus LE (2009) Photochemical reactivity of graphene. J Am Chem Soc 131:17099

Liu L-H, Lerner MM, Yan M (2010) Derivitization of pristine graphene with well-defined chemical functionalities. Nano Lett 10:3754

An X, Simmons T, Shah R, Wolfe C, Lewis KM, Washington M, Nayak SK, Talapatra S, Kar S (2010) Stable aqueous dispersions of noncovalently functionalized graphene from graphite and their multifunctional high-performance applications. Nano Lett 10:4295

Zhang S, Tang S, Lei J, Dong H, Ju H (2011) Functionalization of graphene nanoribbons with porphyrin for electrocatalysis and amperometric biosensing. J Electroanal Chem 656:285

Ghosh A, Rao KV, George SJ, Rao CNR (2010) Noncovalent functionalization, exfoliation, and solubilization of graphene in water by employing a fluorescent coronene carboxylate. Chem. Eur. J. 16:2700

Wang D-W, Li F, Zhao J, Ren W, Chen Z-G, Tan J, Wu Z-S, Gentle I, Lu GQ, Cheng H-M (2009) Fabrication of graphene/polyaniline composite paper  via  in situ anodic electropolymerization for high-performance flexible electrode. ACS Nano 3:1745

Kim T, Lee H, Kim J, Suh KS (2010) Synthesis of phase transferable graphene sheets using ionic liquid polymers. ACS Nano 4:1612

Yoo E, Kim J, Hosono E, Zhou H, Kudo T, Honma I (2008) Large reversible Li storage of graphene nanosheet families for use in rechargeable lithium ion batteries. Nano Lett 8:2277

Sutter P, Sadowski JT, Sutter EA (2010) Chemistry under cover: tuning metal−graphene interaction by reactive intercalation. J Am Chem Soc 132:8175

Schumacher S, Huttmann F, Petrović M, Witt C, Förster DF, Vo-Van C, Coraux J, Martínez-Galera AJ, Sessi V, Vergara I, Rückamp R, Grüninger M, Schleheck N, Meyer zu Heringdorf F, Ohresser P, Kralj M, Wehling TO, Michely T (2014) Europium underneath graphene on Ir(111): intercalation mechanism, magnetism, and band structure. Phys Rev B 90:235437

Masuda Y, Norimatsu W, Kusunoki M (2015) Formation of a nitride interface in epitaxial graphene on SiC (0001). Phys Rev B 91:075421

Riedl C, Coletti C, Iwasaki T, Zakharov AA, Starke U (2009) Quasi-free-standing epitaxial graphene on SiC obtained by hydrogen intercalation. Phys Rev Lett 103:246804

Bult JB, Crisp R, Perkins CL, Blackburn JL (2013) Role of opants in long-range charge carrier transport for p-type and n-type graphene transparent conducting thin films. ACS Nano 7:7251

Panchakarla LS, Subrahmanyam KS, Saha SK, Govindaraj A, Krishnamurthy HR, Waghmare UV, Rao CNR (2009) Synthesis, structure, and properties of boron- and nitrogen-doped graphene. Adv Mater 21:4726

Akada K, Terasawa T, Imamura G, Obata S, Saiki K (2014) Control of work function of graphene by plasma assisted nitrogen doping. Appl Phys Lett 104:131602

Schiros T, Nordlund D, Pálová L, Prezzi D, Zhao L, Kim KS, Wurstbauer U, Gutiérrez C, Delongchamp D, Jaye C, Fischer D, Ogasawara H, Pettersson LGM, Reichman DR, Kim P, Hybertsen MS, Pasupathy AN (2012) Connecting dopant bond type with electronic structure in N-doped graphene. Nano Lett 12:4025

Zhang L, Xia Z (2011) Mechanisms of oxygen reduction reaction on nitrogen-doped graphene for fuel cells. J Phys Chem C 115:11170

Sheng Z-H, Gao H-L, Bao W-J, Wang F-B, Xia X-H (2012) Synthesis of boron doped graphene for oxygen reduction reaction in fuel cells. J Mater Chem 22:390

Wu T, Shen H, Sun L, Cheng B, Liu B, Shen J (2012) Nitrogen and boron doped monolayer graphene by chemical vapor deposition using polystyrene, urea and boric acid. New J Chem 36:1385

Imamura G, Chang CW, Nabae Y, Kakimoto M, Miyata S, Saiki K (2012) Electronic structure and graphenization of hexaphenylborazine. J Phys Chem C 116:16305

Guo B, Liu Q, Chen E, Zhu H, Fang L, Gong JR (2010) Controllable N-doping of graphene. Nano Lett 10:4975

Kim YA, Fujisawa K, Muramatsu H, Hayashi T, Endo M, Fujimori T, Kaneko K, Terrones M, Behrends J, Eckmann A, Casiraghi C, Novoselov KS, Saito R, Dresselhaus MS (2012) Raman spectroscopy of boron-doped single-layer graphene. ACS Nano 6:6293

Pan L, Que Y, Chen H, Wang D, Li J, Shen C, Xiao W, Du S, Gao H, Pantelides ST (2015) Room-temperature, low-barrier boron doping of graphene. Nano Lett 15:6464

Reddy ALM, Srivastava A, Gowda SR, Gullapalli H, Dubey M, Ajayan PM (2010) Synthesis of nitrogen-doped graphene films For lithium battery application. ACS Nano 4:6337

Gebhardt J, Koch RJ, Zhao W, Höfert O, Gotterbarm K, Mammadov S, Papp C, Görling A, Steinrück H-P, Seyller T (2013) Growth and electronic structure of boron-doped graphene. Phys Rev B 87:155437

Cattelan M, Agnoli S, Favaro M, Garoli D, Romanato F, Meneghetti M, Barinov A, Dudin P, Granozzi G (2013) Microscopic view on a chemical vapor deposition route to boron-doped graphene nanostructures. Chem Mater 25:1490

Kawai S, Saito S, Osumi S, Yamaguchi S, Foster AS, Spijker P, Meyer E (2015) Atomically controlled substitutional boron-doping of graphene nanoribbons. Nat Commun 6:8098

Wang X, Dai H (2010) Etching and narrowing of graphene from the edges. Nat Chem 2:661

Jiao L, Zhang L, Wang X, Diankov G, Dai H (2009) Narrow graphene nanoribbons from carbon nanotubes. Nature 458:877

Li X, Wang X, Zhang L, Lee S, Dai H (2008) Chemically derived, Ultrasmooth graphene nanoribbon semiconductors. Science 319:1229

Cai J, Ruffieux P, Jaafar R, Bieri M, Braun T, Blankenburg S, Muoth M, Seitsonen AP, Saleh M, Feng X, Müllen K, Fasel R (2010) Atomically precise bottom-up fabrication of graphene nanoribbons. Nature 466:470

Hayashi K, Sato S, Ikeda M, Kaneta C, Yokoyama N (2012) Selective graphene formation on copper twin crystals. J Am Chem Soc 134:12492

Ago H, Tanaka I, Ogawa Y, Yunus RM, Tsuji M, Hibino H (2013) Lattice-oriented catalytic growth of graphene nanoribbons on heteroepitaxial nickel films. ACS Nano 7:10825

Sprinkle M, Ruan M, Hu Y, Hankinson J, Rubio-Roy M, Zhang B, Wu X, Berger C, de Heer WA (2010) Scalable templated growth of graphene nanoribbons on SiC. Nat Nanotechnol 5:727

Pan D, Zhang J, Li Z, Wu M (2010) Hydrothermal route for cutting graphene sheets into blue-luminescent graphene quantum dots. Adv Mater 22:734

Zhou X, Zhang Y, Wang C, Wu X, Yang Y, Zheng B, Wu H, Guo S, Zhang J (2012) Photo-fenton reaction of graphene oxide: a new strategy to prepare graphene quantum dots for DNA cleavage. ACS Nano 6:6592

Yan X, Cui X, Li L-S (2010) Synthesis of large, stable colloidal graphene quantum dots with tunable size. J Am Chem Soc 132:5944

Güttinger J, Molitor F, Stampfer C, Schnez S, Jacobsen A, Dröscher S, Ihn T, Ensslin K (2012) Transport through graphene quantum dots. Rep Prog Phys 75:126502

Tetsuka H, Asahi R, Nagoya A, Okamoto K, Tajima I, Ohta R, Okamoto A (2012) Optically tunable amino-functionalized graphene quantum dots. Adv Mater 24:5333

Zhu S, Zhang J, Qiao C, Tang S, Li Y, Yuan W, Li B, Tian L, Liu F, Hu R, Gao H, Wei H, Zhang H, Sun H, Yang B (2011) Strongly green-photoluminescent graphenequantum dots for bioimaging applications. Chem Commun 47:6858

Geim AK, Grigorieva IV (2013) Van der Waals heterostructures. Nature 499:419

Novoselov KS, Jiang D, Schedin F, Booth TJ, Khotkevich VV, Morozov SV, Geim AK (2005) Two-dimensional atomic crystals. Proc Natl Acad Sci U S A 102:10451

Kim J, Kwon S, Cho D-H, Kang B, Kwon H, Kim Y, Park SO, Jung GY, Shin E, Kim W-G, Lee H, Ryu GH, Choi M, Kim TH, Oh J, Park S, Kwak SK, Yoon SW, Byun D, Lee Z, Lee C (2015) Direct exfoliation and dispersion of two-dimensional materials in pure water via temperature control. Nat Commun 6:8294

Kim KK, Hsu A, Jia X, Kim SM, Shi Y, Hofmann M, Nezich D, Rodriguez-Nieva JF, Dresselhaus M, Palacios T, Kong J (2012) Synthesis of monolayer hexagonal boron nitride on Cu foil using chemical vapor deposition. Nano Lett 12:161

Vogt P, De Padova P, Quaresima C, Avila J, Frantzeskakis E, Asensio MC, Resta A, Ealet B, Le Lay G (2012) Silicene: compelling experimental evidence for graphene like two-dimensional silicon. Phys Rev Lett 108:155501

De Padova P, Quaresima C, Ottaviani C, Sheverdyaeva PM, Moras P, Carbone C, Topwal D, Olivieri B, Kara A, Oughaddou H, Aufray B, Le Lay G (2010) Evidence of graphene-like electronic signature in silicene nanoribbons. Appl Phys Lett 96:261905

Tao L, Cinquanta E, Chiappe D, Grazianetti C, Fanciulli M, Dubey M, Molle A, Akinwande D (2015) Silicene field-effect transistors operating at room temperature. Nat Nanotechnol 10:227

Fleurence A, Friedlein R, Ozaki T, Kawai H, Wang Y, Yamada-Takamura Y (2012) Experimental evidence for epitaxial silicene on diboride thin films. Phys Rev Lett 108:245501

Koenig SP, Doganov RA, Schmidt H, Castro AH Neto, Özyilmaz B (2014) Electric field effect in ultrathin black phosphorus. Appl Phys Lett 104:103106

Liu H, Neal AT, Zhu Z, Luo Z, Xu X, Tománek D, Ye PD (2014) Phosphorene: an unexplored 2D semiconductor with a high hole mobility. ACS Nano 8:4033

Bianco E, Butler S, Jiang S, Restrepo OD, Windl W, Goldberger JE (2013) Stability and exfoliation of germanane: a germanium graphane analogue. ACS Nano 7:4414

Derivaz M, Dentel D, Stephan R, Hanf M-C, Mehdaoui A, Sonnet P, Pirri C (2015) Continuous germanene layer on Al(111). Nano Lett 15:2510

Dávila ME, Xian L, Cahangirov S, Rubio A, Le Lay G (2014) Germanene: a novel two-dimensional germanium allotrope akin to graphene and silicene. New J Phys 16:095002

Zhu F-F, Chen W-J, Xu Y, Gao C-L, Guan D-D, Liu C-H, Qian D, Zhang S-C, Jia J-F (2015) Epitaxial growth of two-dimensional stanene. Nat Mater 14:1020

Kubota Y, Watanabe K, Tsuda O, Taniguchi T (2007) Deep ultraviolet light-emitting hexagonal boron nitride synthesized at atmospheric pressure. Science 317:932

Lee G-H, Yu Y-J, Lee C, Dean C, Shepard KL, Kim P, Hone J (2011) Electron tunneling through atomically flat and ultrathin hexagonal boron nitride. Appl Phys Lett 99:243114

Zhang Y, Weng X, Li H, Li H, Wei M, Xiao J, Liu Z, Chen M, Fu Q, Bao X (2015) Hexagonal boron nitride cover on Pt(111): a new route to tune molecule–metal interaction and metal-catalyzed reactions. Nano Lett 15:3616

Sutter P, Lahiri J, Zahl P, Wang B, Sutter E (2013) Scalable Synthesis of uniform few-layer hexagonal boron nitride dielectric films. Nano Lett 13:276

Song L, Ci L, Lu H, Sorokin PB, Jin C, Ni J, Kvashnin AG, Kvashnin DG, Lou J, Yakobson BI, Ajayan PM (2010) Large scale growth and characterization of atomic hexagonal boron nitride layers. Nano Lett 10:3209

Xu M, Liang T, Shi M, Chen H (2013) Graphene-like two-dimensional materials. Chem Rev 113:3766

Chhowalla M, Shin HS, Eda G, Li L-J, Loh KP, Zhang H (2013) The chemistry of two-dimensional layered transition metal dichalcogenide nanosheets. Nat Chem 5:263

Mak KF, Lee C, Hone J, Shan J, Heinz TF (2010) Atomically thin MoS 2 : a new direct-gap semiconductor. Phys Rev Lett 105:136805

Zeng H, Dai J, Yao W, Xiao D, Cui X (2012) Valley polarization in MoS 2  monolayers by optical pumping. Nat Nanotechnol 7:490

Yin Z, Li H, Li H, Jiang L, Shi Y, Sun Y, Lu G, Zhang Q, Chen X, Zhang H (2012) Single-layer MoS 2  phototransistors. ACS Nano 6:74

Gong Y, Lin J, Wang X, Shi G, Lei S, Lin Z, Zou X, Ye G, Vajtai R, Yakobson BI, Terrones H, Terrones M, Tay BK, Lou J, Pantelides ST, Liu Z, Zhou W, Ajayan PM (2014) Vertical and in-plane heterostructures from WS 2 /MoS 2 monolayers. Nat Mater 13:1135

Levendorf MP, Kim C-J, Brown L, Huang PY, Havener RW, Muller DA, Park J (2012) Graphene and boron nitride lateral heterostructures for atomically thin circuitry. Nature 488:627

Huang C, Wu S, Sanchez AM, Peters JJP, Beanland R, Ross JS, Rivera P, Yao W, Cobden DH, Xu X (2014) Lateral heterojunctions within monolayer MoSe 2 –WSe 2 semiconductors. Nat Mater 13:1096

Dean CR, Young AF, Meric I, Lee C, Wang L, Sorgenfrei S, Watanabe K, Taniguchi T, Kim P, Shepard KL, Hone J (2010) Boron nitride substrates for high-quality graphene electronics. Nat Nanotechnol 5:722

Wang L, Meric I, Huang P, Gao Q, Gao Y (2013) One-dimensional electrical contact to a two-dimensional material. Science 342:614

Ju L, Shi Z, Nair N, Lv Y, Jin C, Velasco J, Ojeda-Aristizabal C, Bechtel HA, Martin MC, Zettl A, Analytis J, Wang F (2015) Topological valley transport at bilayer graphene domain walls. Nature 520:650

Gao T, Song X, Du H, Nie Y, Chen Y, Ji Q, Sun J, Yang Y, Zhang Y, Liu Z (2015) Temperature-triggered chemical switching growth of in-plane and vertically stacked graphene-boron nitride heterostructures. Nat Commun 6:6835

Koma A (1992) Van der Waals epitaxy—a new epitaxial growth method for a highly lattice-mismatched system. Thin Solid Films 216:72

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Tomo-o Terasawa

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Teruyuki Nakato

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Terasawa, To., Saiki, K. (2017). Graphene: Synthesis and Functionalization. In: Nakato, T., Kawamata, J., Takagi, S. (eds) Inorganic Nanosheets and Nanosheet-Based Materials. Nanostructure Science and Technology. Springer, Tokyo. https://doi.org/10.1007/978-4-431-56496-6_4

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Advances in MXene surface functionalization modification strategies for CO 2 reduction

* Corresponding authors

a College of Sciences/Xinjiang Production & Construction Corps Key Laboratory of Advanced Energy Storage Materials and Technologies, Shihezi University, Shihezi, China E-mail: [email protected] , [email protected]

b Key Laboratory for Green Process of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, China

c Faculty of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, China

MXenes, 2D transition metal carbides and nitrides, show great potential in electrocatalytic CO 2 reduction reaction (ECO 2 RR) applications owing to their tunable structure, abundant surface functional groups, large specific surface area and remarkable conductivity. However, the ECO 2 RR has a complex pathway involving various reaction intermediates. The reaction process yields various products alongside a competitive electrolytic water-splitting reaction. These factors limit the application of MXenes in ECO 2 RRs. Therefore, this review begins by examining the functionalized modification of MXenes to enhance their catalytic activity and stability via the regulation of interactions between carriers and the catalytic centre. The review firstly covers the synthesis methods and characterisation techniques for functionalized MXenes reported in recent years. Secondly, it presents the methods applied for the functionalized modification of carriers through surface loading of single atoms, clusters, and nanoparticles and construction of composites. These methods regulate the stability, active sites, and metal-carrier electronic interactions. Finally, the article discusses the challenges, opportunities, pressing issues, and future prospects related to MXene-based electrocatalysts.

• This article is part of the themed collections: Nanocatalysis and Recent Review Articles

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H. Li, L. Liu, T. Yuan, J. Zhang, T. Wang, J. Hou and J. Chen, Nanoscale , 2024, Advance Article , DOI: 10.1039/D4NR01517G

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