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A Journal of
Accepted Article
Title: Chemistry of graphene derivates: Synthesis, applications and
perceptivity's
Authors: Jiri Sturala, Jan Luxa, Martin Pumera, and Zdenek Sofer
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201704192
Link to VoR: http://dx.doi.org/10.1002/chem.201704192
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10.1002/chem.201704192
Chemistry - A European Journal
REVIEW
Chemistry of graphene derivates: Synthesis, applications
and perceptivity’s
((Insert Picture for Frontispiece here [18.0×18.0 cm]))
[a]
[b]
Title(s), Initial(s), Surname(s) of Author(s) including Corresponding
Author(s)
Department
Institution
Address 1
E-mail:
Title(s), Initial(s), Surname(s) of Author(s)
Department
Institution
Address 2
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
This article is protected by copyright. All rights reserved.
Accepted Manuscript
Jiri Sturala[a], Jan Luxa[a], Martin Pumera[a], [b] and Zdeněk Sofer*[a]
10.1002/chem.201704192
Chemistry - A European Journal
REVIEW
Abstract: The chemistry of graphene and its derivates is one the most actual topic of current material science. The derivatization of
graphene is based on various approaches and up to date was reported functionalization with halogens, hydrogen, various functional
groups containing oxygen, sulfur, nitrogen, phosphorus, boron and several other elements. Most of these functionalizations are based on
sp3 hybridization of carbon atoms in graphene skeleton, which means the formation of out of plane covalent bonds. Several elements were
reported also for substitutional modification of graphene, where the carbon atoms are substituted with atoms like nitrogen, boron and
several others. From tenths of functional groups, only for two of them were reported full functionalization of graphene skeleton and
formation of its stoichiometric counterpart, fluorographene and hydrogenated graphene. The functionalization of graphene is crucial for
most of its applications including energy storage and conversion devices, electronic and optic applications, composites and many others.
Introduction
Dr Jiri Sturala is a postdoctoral researcher at
the University of Chemistry and Technology
Prague since 2017. He received his PhD also
at
the
University
of
Chemistry
and
Technology Prague in 2016, then he spent 15
months
at
Durham
University
(United
Kingdom) as the Experientia Foundation
research fellow. His research interests are
now focused on chemical modifications of
graphene,
other
2D
materials
and
((Author Portrait))
nanomotors. He has published 10 papers (hindex 4) and received several awards (finalist in Merck Displaying Futures
Award 2016, Experientia Fellowship).
[a]
[b]
Dr. Jiri Sturala, Jan Luxa, Prof. Zdeněk Sofer
Department of Inorganic Chemistry
University of Chemistry and Technology Prague
Technická 5, 166 28 Prague 6, Czech Republic
E-mail: zdenek.sofer@vscht.cz
Prof. Martin Pumera
Division of Chemistry & Biological Chemistry
School of Physical and Mathematical Sciences, Nanyang
Technological University
Nanyang Link 21, Singapore 637371, Singapore
This article is protected by copyright. All rights reserved.
Accepted Manuscript
Since its discovery in 2004, graphene has been the most broadly studied 2D material. According to the IUPAC, we can define graphene as
a single layer of carbon atoms derived from graphite structure. This shows its relation to the polyaromatic hydrocarbons, however, its
planar dimension is quasi-infinite.[1]
Similarly to other organic compounds like polyaromatic hydrocarbons, graphene can undergo several reactions which lead to its
modification by the formation of covalent bonds with various functional groups. Principles known from organic synthesis can, in general, be
applied for such type of reaction. However, due to the scale of graphene skeleton and differences in reactivity in comparison with
hydrocarbons, several limitations have to be considered. Many different methods for introduction of functional groups containing halogens
(F, Cl, Br, I), chalcogens (O, S, Se, Te), pnictogens (N, P, As, Sb, Bi) atoms boron, silicon as well as many others more complex functional
groups like alkyl and aryl hydrocarbons have been reported over the last decade. [2] Despite so many reported functionalization methods,
only two covalent functionalizations (with hydrogen and fluorine) result in a stoichiometric graphene counterparts. [3] Fully fluorinated
graphene, named fluorographene was prepared by “top-down” as well as “bottom-up” method based on mechanical exfoliation of
fluorographite and direct fluorination of graphene, respectively. [3a, b]
10.1002/chem.201704192
Chemistry - A European Journal
REVIEW
Jan Luxa has received his M. Sc. title from
inorganic chemistry at the University of
Chemistry and Technology Prague, Czech
Republic in 2014. He is currently a Ph. D.
student under the leadership of Prof. Dr.
Zdeněk Sofer at the University of Chemistry
and Technology Prague. The focus of his
doctoral thesis is on electrochemical and
electrocatalytic properties of transition metal
dichalcogenides and their composites with
graphene. He has published over 50 papers
(h-index 11) which received over 400 citations
Prof. Martin Pumera is a tenured faculty
member
at
University,
Nanyang
Singapore
Technological
since
2010.
He
received his PhD at Charles University,
Czech
Republic,
in
2001.
After
two
postdoctoral stays (in the USA, Spain), he
joined the National Institute for Materials
Science, Japan, in 2006 for a tenure-track
arrangement and stayed there until Spring
2008 when he accepted a tenured position at
NIMS. In 2009, Prof. Pumera received an
ERC-StG award. Prof. Pumera has broad interests in nanomaterials and
microsystems, in the specific areas of electrochemistry
synthetic
((Authorand
Portrait))
chemistry of 2D nanomaterials, nanotoxicity, micro and nanomachines and
3D printing. He is Editor-in-Chief of Appl. Mater. Today, member of Editorial
board
of Chem. Eur. J., Electrochem. Commun., Electrophoresis,
Electroanalysis, The Chemical Records, ChemElectroChem and eight other
journals. He has published over 400 articles, which received over 17000
citations (h-index of 63).
Prof. Zdenek Sofer is an Associate Professor
at
the
University
of
Chemistry
and
Technology Prague since 2013. He received
his PhD also at University of Chemistry and
Technology Prague, Czech Republic, in
2008. During his PhD he spent one year in
Forschungszentrum Julich (Peter Grünberg
Institute, Germany) and also one postdoctoral
stay at University Duisburg-Essen, Germany.
Research interests of prof. Sofer concerning
on nanomaterials graphene based materials
and other 2D materials, its chemical modifications and electrochemistry. He
is a member of Editorial board of Flatchem. He has published over 240
articles, which received over 3500 citations (h-index of 31).
Accepted Manuscript
((Author Portrait))
Methods based on hydrogenation of graphene have been reported for the synthesis of fully hydrogenated graphene (graphane).[3c, d]
Beside these two stoichiometric derivates, there are also huge amount of partially derivatized graphenes with different degree of
functionalization. The most known form of functionalized graphene is graphene oxide. This graphene derivative is a form with not welldefined composition strongly related to the method of synthesis. [4] The graphene oxide synthesis is based on oxidation of graphite (using
permanganate or chlorate methods) and subsequent mechanical exfoliation of graphite oxide. [5] Graphite oxide was historically also named
as graphite acid or graphite hydroxide due to the presence of various oxygen functionalities. [6] The historical name shows the presence of
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10.1002/chem.201704192
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various oxygen functionalities like hydroxyls, carboxylic acid, ketone groups, epoxides and others like lactones and esters. Other methods
of graphene functionalization are based on the introduction of other halogens, amines, hydroxyls, thiols, alkylamines functionalities and
many others. The functionalization is based not only on the sp 3 hybridization of carbon atoms. Some elements can also substitute carbon
atoms within graphene skeletons. Such functionalizations are not typically well defined and reported for elements from 6 th, 5th and 3rd group
like nitrogen, boron, and sulfur.[7]
The main purpose of graphene derivatization is to tailor its physical properties such as resistivity, electronic structure, optical transmittance,
luminescence, surface energy and magnetic properties. Chemical properties which include reactivity, catalytic activity, separation
capabilities are also altered substantially during the derivatization. [8] Band-gap opening, which is crucial for electronic and optoelectronic
applications, is also direct results of graphene derivatization. Importantly, the changes in band-gap structure are also of huge importance in
electrochemical applications like electrocatalysis and sensing. Changes in the surface chemistry are also crucial in biosensi ng and highefficiency separation methods. Apparently, the possibilities of graphene derivatives applications grow as fast as this family of materials.
In this review, we focus on derivates of graphene dominantly formed by covalent attachment of functional groups to the graphene skeleton,
however, substitutional chemical modification and derivatization of graphene will be also discussed.
Accepted Manuscript
1. Carboxylic acid and other oxygen containing functionalization of graphene
The role of graphene oxides is one of the most important in graphene chemistry. Graphene oxide is a typical example of graphene modified
with oxygen functionalities. The major difference here is that various types of functionalities can be bound to the graphene skeleton.
Generally, it is very difficult to introduce only one type of oxygen functionalities onto the graphene in a single step, however, oxidation of
graphite to graphite oxide and subsequent exfoliation to graphene oxide tends to introduce some functionalities more than others
depending on the conditions. Importantly, graphene oxides are widely used as starting materials for the syntheses of other graphene
derivatives and reduced graphene. Chemical, photochemical, thermal, microwave and solvothermal methods are most commonly used for
the reduction of graphene oxide.
There are four basic methods for the oxidation of graphite to graphite oxide. These are usually termed Brodie (BRGO), Staudenmaier
(STGO), Hofmann (HOGO) and Hummers (HUGO) methods. [5a-d] There are also improved versions of these methods such as that
developed by Tour et. al. (TOGO)[9] All these methods use acidic environment in combination with strong oxidation agents such as KClO 3
or KMnO4. The used method strongly influences the amount of specific functional groups (OH, COOH, ketones and epoxides) and the
degree of oxidation (C/O ratio).[10] For example, the C/O ratios are ca. 1.3, 3.1, 2.2, 2.8 and 1.1 for graphene oxides prepared by Brodie’s,
Staudenmeier’s, Hofman’s, Hummers’ and Tour’s methods, respectively. [4b, 11] The concentration of oxygen functionalities can be further
increased by repeating of oxidation procedure. [4b]
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REVIEW
Figure 1. Carboxylic functionality rich graphene can be used as a starting material for further functionalization. Gradual decrease of –
COOH functionality shown here. Reprinted with permission from Elsevier ref. [12]
The chemistry of carboxylic acid derivates is well-established in organic synthesis and therefore it is also one of the starting points of
graphene modification. The COOH groups are mainly present on the edges of graphene sheets, which is the result of higher reactivity of
these sites. Use of carboxyl rich graphene for the synthesis of other derivates is depicted in Figure 1. Nevertheless, their concentration is
not very high due to the limitation by a number of edges and defect site where they can be present. Carboxylic acid rich graphene is
typically obtained by selective reduction of other functional groups present on graphene oxide by e.g. NaBH4,[13] thiourea dioxide or
hydrazine.[14] This selective reduction is highly important because it can be used for precise tuning of graphene properties. The increase of
carboxylic groups content can be also achieved via conversion of hydroxyls with oxalic acids. However, epoxide ring opening by HBr has to
be performed prior to this procedure to ensure that most functional groups in the final product are -COOH.[15] The methods for direct
introduction of the COOH groups were not widely investigated since they require more exotic conditions and are not generally applicable to
graphene. One of few examples of direct introduction of COOH groups to graphene oxide was achieved by Pumera et at. using the KolbeSchmitt reaction (Scheme 1)[16] and more recently by Otyepka by the substitution reaction from fluorographene by cyanide and subsequent
acid hydrolysis of cyanographene.[17] The ball milling of graphite with solid carbon dioxide can be also applied for simultaneous graphite
exfoliation as well as effective functionalization of graphene edges by COOH groups. [18] Repetitive oxidation of graphene oxide by KMnO 4
resulted in graphene acid with a stoichiometry of almost C1(COOH)1.[19]
Scheme 1. Mechanism of Kolbe-Schmitt reaction on graphene-oxide.
Esters of graphene-acids are readily available from any graphene oxide containing sufficient amount of COOH group by simple treatment
with alkaline hydroxide and subsequent reaction with an alkylating agent under phase-transfer conditions.[12] The length of alkyl chain
strongly influences the self-assembly properties and surface area. The alternative way for the conversion of graphene acid into ester is its
reaction with SOCl2, thus making reactive acid chloride and subsequent reaction with an alcohol and a base (e.g., Et 3N) (Scheme 2).
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Accepted Manuscript
Graphene amides are prepared in a similar way as the esters by treatment with SOCl2 and addition of an amine or by coupling reaction
involving EDC[20] and other coupling reagents to yield highly functionalized graphenes.
Scheme 2. a) Activation of graphene-carboxylic acid by its conversion to acyl chloride b) reaction of an acyl chloride with an alcohol or
amine.
On the other hand, Friedel-Crafts reaction has been reported only once to produce substituted graphene using aryl carboxylic acid in the
mixture of P2O5 and polyphosphoric acid.[21] However, an inverse approach using graphene COOH groups to undergo Friedel-Crafts
reaction with ferrocene was reported by Avinash et al. under mild conditions using trifluoroacetic anhydride and acidic alumina to give
Friedel-Crafts reaction product (Scheme 3).[22]
Scheme 3. Friedel-Crafts reaction between graphene carboxylic acid and ferrocene.
There are several reports on attempts to introduce single oxygen functionality in the literature. For example, sonication of graphite in an
aqueous solution of ammonium peroxodisulfate leads to preferential modification with –OH groups.[23] This is allowed by intercalation of
peroxodisulfate ions in between graphite layers and their oxidation. Unlike strong oxidation agents used in methods mentioned previously,
oxidation by ammonium peroxodisulfate is slow and highly chemoselective. Ball milling of graphite with KOH was also used to selectively
introduce –OH functionalities.[24] Shear force milling of graphene-oxide in NaOH solution also resulted in hydroxyl modified graphene with
high hydrophilicity and good biocompatibility.[25] The other approach to control the concentration of hydroxyls functionalities is based on
selective and/or controlled reduction or chemical modification of graphene oxide. Such type of reaction is hydroboration whic h can give a
composition close to the theoretical stoichiometric composition (C 1(OH)1)n.[26] However, the use of graphene oxide instead of graphite or
graphene causes that part of the other functionalities is still present in such material.
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2. Carbon-carbon bond formation on graphene – aryl and alkyl functionalization
Scheme 4. Reaction of graphene with diazonium salts by a) single-electron transfer (radical) mechanism or b) via aromatic carbocation.
Accepted Manuscript
The formation of carbon-carbon bonds on graphene is highly important since it can significantly extend the scale of graphene modification
possibilities. Such structures can be a simple alkyl and aryl functionalities as well as complex supramolecular structures like for example
cyclodextrins, crown-ethers and various dendrimer structures. Up to date, several routes for the formation of such bonds have been
reported and these results are discussed in following paragraphs.
Well established and high yielding method for graphene modification is its functionalization with aryldiazonium salts (Scheme 4), which
offers great variability of aryl substituents to introduce under mild conditions and user-friendly way because diazonium salts tolerate many
functional groups and solvents. The comprehensive study of reactivity of various aryldiazonium salts was made by Sofer et al., [27] although
many other research groups utilized aryldiazonium salts for this purpose on graphene and its derivates prepared by various methods. [28]
Such materials can find the use in microelectronics because their transport properties are easily tuned by the proper choice of aryl
substituent as well as they offer possibilities for further functionalization if arene contains a reactive group, e.g. COOH, NH2, terminal
alkyne, etc.[29]
With the advent of halogenated graphenes, the new avenues of the reactions have been introduced to alkyl graphene chemistry. The
substitution of chlorinated graphene with methylmagnesium bromide was performed by Hossain et al.[30] and for example with
adamantylmagnesium bromide by Sun et al.[31] Better reactivity was achieved by the use of fluorographene (Scheme 5). A comprehensive
study of reactivity towards different Grignard reagents was made by Otyepka et al.[32] Sofer et al. used series of Grignard reagents
including simple alkyl chains, vinyl group, ethynyl, and propargyl group, which contains terminal triple bond, which was used for
subsequent functionalization by the use of “click” chemistry. [33] Other approaches for C-C band formation can be based on alkali metal
interaction with graphene. If the graphene is exfoliated using alkali metals[34] or alkali naphtalenide,[35] reduced graphene is obtained
containing negative charge (counterpart is corresponding alkali cation). Such material can be alkylated/arylated yielding gra phene
monolayers stabilized by the alkyl/aryl substituents.
Scheme 5. Reaction of fluorographene with a Grignard reagent and defluorination.
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Another reactive species, which enable further modification, was successfully used to modify graphene surface. Pumera et al. used
dichlorocarbene generated from CHCl3 under phase-transfer conditions to introduce CCl 2 bridge into the graphene sheet.[36] It was also
found that not only graphene but also fluorographene (C 1F1) is able to react with dichlorocarbene by a two-step process, where
dichlorocarbene eliminates fluorine atoms first and then by cyclic reaction creates the CCl 2 bridge.[37] The addition of other carbenes has
been also investigated, e.g., diaryl carbenes.[38] Bridged structures of graphene were also obtained by the reaction of graphene with highly
reactive arynes - aromates containing triple bond inside the ring, which are generated in situ for example from anthranilic acids or
benzenes containing vicinal Me3Si- and TfO- groups.[39]
Less straightforward introduction of alkyl chains to graphene core was performed by Collins et al., who successfully prepared vinyl ethers
and converted the ethers to directly attached carbon chains by Claissen rearrangement. [40] The main improvement was achieved on
modified substrate (Eschenmoser–Claisen rearrangement), which yielded graphene-acetic acid – derivate with very high solubility in
aqueous media without the need of cosolvent additives. The very popular topic of C-H activations was also introduced to graphene
chemistry. Pumera et al. used copper (II) triflate and DDQ as an oxidant to functionalize graphene in its allylic positions by
tetrahydrothiophen-3-one.[41]
Accepted Manuscript
3. Graphene derivatives based on pnictogen group elements
From the 5th group elements, the functionalization of graphene was dominantly reported for nitrogen containing groups. In contrasts, the
functionalization with other groups containing phosphorus and other pnictogens are extremely limited. Both covalent attachment of groups
(e.g. amines) and substitution of carbon by nitrogen (e.g. pyrrolic, pyridinic and graphitic nitrogen) have been reported for the nitrogen
functionalization. Nitrogen functionalities, mainly amino and azido groups, represent very attractive functionalities because they allow
incorporation of versatile building blocks by amide coupling or so-called “click” reactions. The functionalities are traditionally introduced to
graphene oxide containing epoxy groups (e.g. prepared by Hummer’s method[5c]) by heating together with a nucleophile (e.g., an amine or
sodium azide) to give a product of epoxide opening (Scheme 6). In comparison with other methods of graphene modification, the epoxide
opening reactions proceed very easily even at room temperature and in aqueous media. A variety of aliphatic and aromatic amines and
amino acids were successfully introduced into graphene by this way. Bourlinos et al. introduced series of aliphatic and terminal amino
carboxylic acids.[42] The long alkyl chains make graphene lipophilic, which made it dispersible in organic solvents. On the other hand, the
use of sodium salt of amino acids made graphene hydrophilic. Amino groups were introduced to the graphene also by Bucherer type of
reaction or just by hydrothermal treatment of graphene oxide with aqueous ammonia.[7c, 43] The observation that mainly epoxide groups
lead to the substitution product on graphene oxide was recently confirmed by Ménard-Moyon et al. by 15N solid-state NMR.[44] A different
approach based on substitution reaction on fluorographene was successfully employed for the preparation of alkylamino graphenes by the
reaction of alkylamines,[45] and amino graphene formation by the use of sodium amide. [46] Also, the reaction of fluorographene with urea led
to the partial introduction of amine functionalities and as a consequence to water dispersible fluorographene.[47]
Scheme 6. Epoxide opening on graphene oxide by an amine.
Graphene azide represents very interesting derivate of graphene. The traditional method of preparation is the same as for example amino
substituted analogues, by treatment of graphene oxide with sodium azide. [48] Hirsch et al. also reported that sulfonate groups, which
remained on graphene oxide from its synthesis, can be substituted by sodium azide, which extended the number of connected azido
groups.[49] The azido graphene not only expands the number of graphenes derivatives but also enables an easy functionalization via mild
click-reactions. For example, Salvio et al. used graphene azide as a starting material for the synthesis of amino graphene by its reduction
with LiAlH4. They also demonstrated further derivatization of azides by long terminal alkynes leading to exfoliated graphene and
condensation reaction of the amino group with an isothiocyanate. [50] Graphene oxide modified with 2-chloroethyl isocyanate followed by
reaction with NaN3 was used as a starting precursor for copper-catalysed click reaction with alkynyl-DNA.
Aziridine (nitrogen analogues of carbene) modified graphene can be prepared by nitrene addition to graphene (Scheme 7). This method
was successfully used by Barron et al. to produce azirido-graphene.[51] Pentafluorobenzene[52] and tetraphenylethylene[53] were successfully
introduced by similar reaction.
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Chemistry - A European Journal
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Scheme 7. Generation of nitrene from an azide and its reaction with graphene sheet.
4. Boron functionalities on graphene
Accepted Manuscript
Direct reaction of graphene with ammonia gives an amino group at mild conditions, however, at high temperature the mixture of various
nitrogen functionalities is obtained. [7a, 54] Typically at temperatures exceeding 400 °C, the mixture of functionalities from amino group to
graphitic nitrogen substitution carbon is obtained. [54b]
In contrast to very rich chemistry of nitrogen substituted graphenes, the phosphorus analogues are much less common. The phosphoruscontaining graphenes are used as materials for membranes. However, in this case, phosphorus is not attached to the graphene sheet, but
to the linker (which is usually alkylamino or alkylsiloxide)[55] and the attachment is based on for example graphene oxide-nitrogen or
graphene oxide-silicon chemistry. However, Kim et al. prepared graphene phosphonic acid by ball-milling graphite with red phosphorus.[56]
Similar material with same properties was prepared by Some et al. by treatment of graphene oxide with polyphosphoric acid/phosphoric
acid mixture.[57] The high affinity of phosphorus to oxygen was used to prepare graphene oxide diphenylphosphinite by its reaction with
Ph2PCl.[58] Phosphorus introduction to reduced graphene oxide was also reported by the reaction of graphene oxide with white phosphorus
and phosphine.[59] The reaction of graphene oxide with phosphorus trihalogenide led to concurrent phosphorus and halogen-codoping
together with partial graphene oxide reduction. [60]
The interaction between boronic acids and diols is well-known and leads to the preparation of various graphene boronic acid esters. Buress
et al. linked graphene oxide sheets by benzene-1,4-diboronic acid making a graphene oxide framework.[61] The structure of this material
was later revised by Mercier et al., who proposed that not only crosslinked structures are present but also non-framework structure should
be considered.[62]
High temperature treatment of graphene oxide and other graphene based materials with for example BCl3 led to the introduction of boron,
however, due to the high temperature and high energy reaction, such modifications are chemically not specific. [54a, 63] Such high
temperature reaction led to both carbon substitution with boron as well as ad-atom functionalization.
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5. Sulfur functionalities on graphene
Accepted Manuscript
Sulfur modified derivatives can be most effectively prepared from graphene oxide or halogenated graphenes as a starting material,
however, the chemistry is not broad, because the introduction of sulfur functionalities is much more challenging. Most successful strategies
involve the reaction of oxygen functionalities with a proper reagent which introduces sulfur containing group. An epoxide ring opening
reaction seems to be an efficient strategy for the introduction of sulfur containing functional groups.[64] Importantly, these materials exhibit
improved water dispersibility and can be used for further functionalization. Another possibility is the conversion of epoxy and hydroxyl
groups via the reaction with thiourea and HBr followed by a treatment with NaOH. This led to the formation of thiol groups on the graphene
skeleton.[65] Lastly the halogenated graphene (fluorographene) can serve as an excellent reactant for thiolation of graphene by simple
substitution leading to thiofluorographene (Figure 2d).[66] The catalytic activity of various sulfur functionalities was studied in detail using
theoretical calculations (Figure 2a). [67] The high temperature reaction of graphene oxide led to the non-specific sulfur functionalized
graphene, which contained sulfur atoms in carbon substitution position as well as in the form of ad-atoms (most likely as –SH groups).[68]
Several interesting properties were reported for such type of graphene derivates including room-temperature ferromagnetism and high
electrocatalytic activity.[7b, 68-69] Other more exotic approaches like ball milling of graphite with sulfur can be used for the introduction of
sulfur functionalities to graphene including methods. [70]
Figure 2. a) Several possible sulfur-doped graphene clusters shows from left to right, sulfur atoms adsorbed on the surface, substituting
sulfur atoms at zigzag and armchair edges; SO 2 functional group substituted at zigzag and armchair edges; and sulfur ring cluster
connecting two pieces of graphene (white, grey, yellow and red balls represent hydrogen, carbon, sulfur and oxygen atoms, respectively).
Reprinted from ref.[67] with permission from American Chemical Society, Copyright 2014. b) Scheme of thiofluorographene synthesis by
mechanical exfoliation of fluorographite and its subsequent reaction with sodium hydrogensulfide. Reprinted from ref. [66] with permission
from WILEY-VCH Verlag GmbH, Copyright 2015.
6. Graphane and hydrogenated graphene
Hydrogenated graphenes are materials with features much more interesting than graphene. Structure of graphane is displayed in Figure 3a
and 3b.[71] Probably the most remarkable features of graphane are tuneable band gap (depending on with various degree of
hydrogenation)[72] and ferromagnetism.[73] In general, there are two main approaches for the preparation of hydrogenated graphene.
Currently most broadly studied and effective methods are based on Birch reduction reaction.[74] The other methods use for example
complex hydrides, nascent hydrogen or high energy hydrogen atoms (plasma, combination of high pressure and temperature and many
others such as synthesis from fluorographene (Figure 3c).[71a] Especially plasma methods can be applied more likely to the large surface
area of graphene typically prepared by CVD methods.
Catalytic hydrogenation by hydrogen gas over a metal catalyst (e.g., Pd, Ni or Pt) is one of the most important reactions in the chemical
industry. However, such heterogeneous system can be applied for graphene only with extreme difficulties since substrate and catalyst
must be in contact and it is very difficult to fulfil such condition for reaction containing two heterogeneous systems (graphene and catalyst).
Experimentally were tested the direct hydrogenation procedures using various graphene derivates under high pressure of hydrogen. The
reaction of graphite oxide at high pressure (> 60 bar) and temperature (> 200 °C) yielded hydrogenated graphene, although, not all oxygen
groups were removed by this process and exact composition was based on assumption that all oxygen containing groups were OH groups.
Therefore, the content 3.76 at.% of hydrogen was the worst scenario, but still, the content of hydrogen was pretty low. The advantage is
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Accepted Manuscript
easy scalability of this process.[75] Completely different approach was used by Brazhkin et al., who prepared graphane by high temperature
(700 – 1200 K) and high pressure (<10 GPa) synthesis from benzene. The synthesis also allowed the production of nitrogen doped
graphane by the use of benzene/pyridine mixture.[76]
Figure 3. a) SEM (top) and TEM (middle) images of hydrogenated graphene. Hydrogen elemental map from electron energy loss
spectroscopy (bottom). Reprinted with permission from ref. [71a] with permission from American Chemical Society. b) Chair (top) and boat
(bottom) graphane conformations and their corresponding C-C bond lengths. Reproduced from Ref. [71b] with permission from the Royal
Society of Chemistry. c) Schematic illustration of graphane synthesis from fluorographene. Reprinted with permission from ref. [71a] with
permission from American Chemical Society, copyright 2012.
On the contrary, the wet chemistry processes based on dissolving metals such as alkali metals in liquid ammonia, which serve as a source
of solvated electrons, prove to be very useful in the production of highly hydrogenated graphenes by Birch-type reactions.[77] It has been
demonstrated that single-layer graphene is hydrogenated uniformly but graphene with more layers and sealed edges is not, which supports
the idea that hydrogenation occurs from the edges of graphene by intercalation of alkali metal into the structure, where the defects are
located.[71a] A comprehensive study of alkali metal used for reduction in NH 3 and various proton sources yield graphanes with various
hydrogen content revealed that the best combination, Na in NH3 with water as a proton source, yielded graphane with composition of
C1.4H1O0.3.[78] Besides graphene, carbon nanotubes can be opened by potassium in NH 3 to yield graphane nanostripes with well-defined
structure.[79] Also, various other graphite based nanostructures were used for the synthesis of graphane based sheets with controlled
morphology.[80] Electrochemical exfoliation and in situ hydrogenation led to material with 6.5 wt.%, (C1.2H1), which is comparable to the
reduction by Li in liquid NH3, but the control over the process is easier maintained than in the case of dissolving metal reduction. [81] Birchlike reduction can also be used in the reduction of halogenated graphenes yielding graphane with hydrogen content up to 7.28 wt% (ratio
C1.04H1).[82] The higher content of hydrogen is caused by higher polarization of C-F bonds, which are more susceptible to electron attack.
Hydrogenated graphene is significantly more reactive and can be used for synthesis of mixed hydrogenated / fluorinated graphene
counterparts.[83]
Despite very effective reductions in liquid ammonia, there are other classical organic reactions, which can be used to reduce various
graphene oxides to graphane. Dissolving aluminium in the solution of NaOH or NaOD in H 2O or D2O, respectively, led to reduced graphene
with 6.8 at.% of deuterium in the case of deuterated variant, which can be used as a measure of reduction level.[84] Clemmensen reduction
(Zn in HCl) on graphene has been proved to occur on the contact with the metal surface via carbenoid radical species. The extent of
reduction was also proved by the deuterium experiment (Zn in DCl/D 2O). In the case of graphene oxide prepared by Hofmann method
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(HOGO), the incorporation of deuterium was 10.8 at%.[85] In addition, the other metals were used as reducing agents (Zn, Al, Mg, Mn and
Fe), confirming that Zn is the best metal for the reduction giving graphane with formula C 1.16H1O0.66.[86]
The ability of graphene to interact with alkali metals was used by Hirsh et al., who exfoliated graphite by the action of potassium forming
various graphene-potassium cluster. Negatively charged graphene was exposed to quenching agent to form graphane with formula C1H0.7.
Alcohols were found to be superior quenching agents than water due to their slower reaction with potassium, thus making hydrogenation
more effective. The advantage of this approach is that degree of hydrogenation is easily tuned by potassium stoichiometry, qu enching
agent and graphite used for the reaction[74] The additional value of this approach is also the possibility to introduce other functional group
by this reductive approach, e.g., aryldiazonium or aryliodonium salts, alkyl and aryl iodides, etc..[87]
7. Graphene halogenderivates
Accepted Manuscript
Halogenated graphenes are another huge and growing family of graphene derivatives. Various synthetic routes have been developed for
their synthesis and these include both so-called “bottom-up” and “top-down” approaches.[3a, 88] Although graphenes modified with all
halogen atoms (F, Cl, Br and I) have been reported, the degree of halogenation usually differs significantly. [89] Fluorinated graphene is the
most explored material from this group. This is due to the fact that, unlike the other halogen modified graphenes, fluorographene can be
prepared quite easily by treatment of graphene and its derivates with fluorine at elevated temperature or by simple mechanical exfoliation
of fluorographite.[90] Fluorographite can then be used as a precursor for fluorinated graphene, e.g. by mechanical or chemical exfoliation
(see Figure 4).[88a, 91] In addition, the ease of graphene fluorination (e.g. by XeF2) also highlights this fact.[92] Moreover, fluorinated graphene
is the only halogen derivative of graphene that has been prepared with a stoichiometric composition (C 1F1). According to our best
knowledge, there are reports of only partially chlorinated or brominated graphenes. [89b, 93] This is not very surprising if we consider the
progressively increasing size of halogen atoms which gives rise to sterical issues. The iodination is even more challenging d ue to fact that
iodine is the bulkiest halogen and also the bond is much weaker compared to the other halogens.
Main motivation for modification of graphene with halogens is the possibility to tailor the properties, especially electronic structure and also
to increase the reactivity. Introduction of halogen atoms leads to structural changes, which lead to band gap opening.[92, 94] This is
especially important since pristine graphene is a zero band-gap semiconductor and therefore, its use in electronics is limited. The band-gap
opening can be quite dramatic. For example, fluorographene has a band-gap width of approx. 3.4 eV (Figure 4)..[95] It is evident that
plethora of synthetic routes, some of which are briefly described in the following paragraphs, have been developed for this group of
materials.
Figure 4. a) Band-gap of fluorographene and its chlorinated and hydrogenated counterparts. Reprinted from ref.[95] with permission from
American Chemical Society, copyright 2013 b) Transmission electron microscopy images of graphite fluoride exfoliated with sulfolane. The
inset shows selected area electron diffraction pattern. Reprinted with permission from ref [3a]. Copyright 2010 Wiley. c) Gradual
fluorination of CVD grown graphene in CF4 plasma. Reproduced from ref. [96] with permission from American Chemical Society, copyright
2016.
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High-quality fluorographene sheets can be prepared by mechanical exfoliation of graphite fluoride, however, there are obvious scal ability
issues.[3a, 92, 97] Another “top-down” method of fluorographene synthesis is the chemical exfoliation of graphite fluoride. This usually involves
an appropriate solvent, which can intercalate between the layers, weaken the interlayer interactions and subsequently exfoliate the material
into fluorographene.[91] Some of the typical liquids used for these purposes include dimethylformamide, sulfolane, isopropanol and also
ionic liquids.[3a, 91, 98] It should always be kept in mind that sheets with various thicknesses will be obtained by this method. It is also possible
to utilize methods developed for the synthesis of graphene from graphite oxide. Modified Hummer’s oxidation method yields par tially and
highly fluorinated graphene oxides which substantially differ in their hydrophilicity. [99] Thermal exfoliation of fluorinated HOPG in the
presence of F2 has also been reported for the synthesis of fluorographene. [100]
The second approach is based on direct fluorination of various precursors. Graphene oxide, exfoliated graphite or reduced graphene oxide
are commonly used. The degree of fluorination is highly dependent on the fluorination agent. Fluorination of graphene was reported by
several authors for CVD grown graphene as well as for bulk graphene (prepared from graphite and graphite oxide). For example, XeF2 can
be used for fluorination of graphene due to its in-situ decomposition on fluorine and xenon. For the CVD graphene, the degree of
fluorination depends on the substrate and final products have stoichiometries of C 1F0.25 and C1F1 for one and two side fluorinated graphene,
respectively.[88b] The advantage of XeF2 is the relative ease of manipulation compared to e.g. F2. Other methods include for example
treatment in CF4 plasma at low pressures.[96] Progressive fluorination of graphene in CF4 plasma is shown in Figure 4. Plasma methods
involve the formation of fluorine radicals, which react with graphene. However, these methods usually achieve low degree of fluorine
coverage. Also, the methods are preferentially used for planar graphane structures typically prepared by CVD methods. The bulk synthesis
of fluorographene needs to use more reactive reagents like elemental fluorine. Recently, it has been shown that precise tuning of fluorine
content can be achieved via thermal treatment of graphene in N 2/F2 (20 vol.% F2) mixture.[3b] Prolonged treatment at elevated temperature
resulted in fluorographene with the stoichiometry of C 1F1.05. This work also highlighted the fact that CF 2 and CF3 functional groups are
formed at the edges of fluorographene sheets which explains the stoichiometry. Fluorination of graphene oxide with N2/F2 mixture led to
hydrophilic partially fluorinated graphene. [101] It was also revealed that thermal stability of fluorographenes decreases with increasing
fluorine content, opposite to that observed for brominated or iodinated graphenes. This was attributed to the highly defective structure.
Other approaches usually result in fluorinated graphene with lower fluorine content. Various reagents including hydrofluoric acid, various
organic reagents (e.g. DAST), fluorides of sulfur-based reagents and many others have been used for these purposes. [102] These methods
also allow for graphene selective functionalization, because only some functional groups in the starting graphene oxide are substituted
during the reaction. Thermal decomposition of fluorographite was also reported as an effective method for the synthesis of partially
fluorinated graphene.[103]
Figure 5. Fluorographene can serve as a starting material for the synthesis of graphene modified with various kinds of functional groups.
Reprinted with permission from Wiley-VCH ref. [104]
Reports of the other halogen modified graphenes are much scarcer. The bigger size of heavier halogens and lower reactivity makes the
synthesis of chloro-, bromo- and especially iodo- graphenes much more complicated. With the exception of work by Rao et. al. who have
reported chlorine content as high as 56 wt. %, the most of the works report much lower chlorine content. [89c, 105] Such high level of
chlorination was achieved via the reaction of graphene with liquid chlorine under UV irradiation. Similar results were obtained for bromine.
A very simple halogenation procedure involves thermal treatment of graphene oxide in gaseous halogen atmosphere.[89d] A recent research
has also shown the possibilities of selective and nondestructive graphene chlorination by chlorine plasma reaction. [106] It was also shown
that the chlorination process is likely to follow a two-step pathway, the first one is partially reversible. Reagents known from classical
organic chemistry, which are capable of introducing chlorine onto the graphene backbone can also be used, however, graphene oxide
usually has to be used as a starting material.
As for bromine and iodine modified graphenes, the reports are even rarer. The level of doping is even lower than that observed for chlorine
and does not exceed 10 at. %. Reagents such as hydrobromic or hydroiodic acids are commonly used in these syntheses. In direct
contrast to fluorine and chlorine, these heavier halogens have been shown to improve electrical conductivity of halogen modif ied
graphenes.[89b, d] Also, unlike fluorine, which decreases thermal stability, heavier halogens generally tend to improve this property. [3b, 89b]
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Microwave assisted syntheses have also been reported, but only low halogen concentrations were achieved (around 4 at. %). [93] Recently
was also reported the use of Hunsdiecker reaction for the introduction of bromine on graphene oxide edges.[107]
It has been mentioned previously that band gap opening is one of the main motivations for the synthesis of halogenated graphenes.
Therefore, there are numerous theoretical papers dealing with this phenomenon, especially for the most stable halogenated graphene –
fluorographene. Fluorographene’s band-gap is usually predicted to be quite high – about 3.8 eV, which is in good agreement with
experimental results.[88a, 92, 95, 108] However, different calculation methods may result in various results and give band-gap width as high as
7.5 eV.[108-109] It has also been shown that the band-gap width is strongly dependent on the level of fluorination and presence of adsorbed
molecules on the surface of fluorographene. [110] Both bonding and non-bonding interactions have been predicted for heavier halogens,
which also resulted in a decreasing width of the band gap. [111]
An extensive amount of substitution reactions by Grignard reagents can be used to covalently modify the graphene opening the field of
application of fluorographene even more. [32, 112] Possibilities of fluorine substitution are schematically shown in Figure 5.
Applications of modified graphenes
Accepted Manuscript
One of the most important group of graphenes derivates are graphene oxides. Among them, the carboxylic acids groups on graphene
sheet are of great importance because of their hydrophilicity, thus making the dispersions in aqueous systems more stable. Also, the
COOH groups significantly improve the sorption ability towards heavy metals [113] and for example allows selective detection of the uranyl
ions as well as some other separations.[114] Graphene acid with stoichiometry near C1(COOH)1 exhibited very high affinity towards metal
ions and CO2. The sorption capacity about 2.5 mmol/g for double valent ions like Zn 2+ and Cd2+ shows huge application potential in
environmental remediation issues. The sorption capacity towards CO2 is also increased with increasing content of carboxylic acid group
concentration and reaching over 2 mmol/g of CO 2. Also, such material can be used for assembling of membranes with high transmittance
exceeding 50% for wavelength over 650 nm and further increasing 80% for the NIR region. Graphene oxide materials can also be used for
the fabrication of highly transparent and flexible membranes (Figure 6).
By reduction of graphene oxide, the obtained material is suitable for the synthesis of composites with applications in electrochemistry.
Good conductivity of partially reduced graphene oxide allows it to serve as an efficient highly conductive matrix with high s urface area.
Therefore, numerous reports of modified graphene oxide based composites from the fields of lithium-ion, lithium-sulfur and lithium oxygen
batteries as well as biosensing, catalysis, biocatalysis and supercapacitors can be found in the literature. [11a, 115]
Figure 6. a) Transparent foils from highly carboxylated graphene and their respective b) scanning transmission electron micrographs and c)
Atomic-force microscopy images. Reprinted with permission from Wiley-VCH ref. [19], copyright 2016
The graphene material rich on COOH groups is also used for the preparation of other useful materials. Graphene esters are promising
candidates for application as capacitors and electrode materials. [12] Cyclodextrin moiety connected to graphene COOH groups showed
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biorecognition capability towards haemoglobin.[116] Graphene carboxamides were prepared by Liu et al. by coupling reaction to give
oligothiophene-functionalized graphene with improved solubility, dispersion stability and mainly electronic and photophysical properties. [117]
Ray et al. prepared by amide coupling graphene oxide conjugate with antimicrobial peptide. The conjugate was used to prepare
membrane, which allowed identification, separation and disinfection of water contaminated with Staphylococcus aureus.[118]
Figure 7. Field-effect transistor fabricated from fluorinated graphene and its transfer characteristic showing its high hole mobility. Reprinted
with permission from Nature ref. [125], copyright 2014.
Accepted Manuscript
Another member of graphene family, which has found the application, is fluorographene. Fluorographene has been previously used for
fabrication of transistor structures (Figure 7),[97] because fluorination has been shown to significantly increase resistance in the electroneutrality region of such devices. Excellent dielectric properties and temperature stability up to 400°C in partially fluorinated graphene were
revealed when used as a gate dielectric material.[119] Ultrathin fluorographene has also been reported to exhibit full-colour emission making
it a candidate for light emitting diode fabrication. [120] A very interesting third-order non-linear optical responses were revealed in noncovalently modified exfoliated fluorographenes.[121] Both stoichiometric fluorographene and partially fluorinated graphene exhibit superhydrophobic properties, making them suitable for hydrophobic coatings.[3b, 122] Fluorographene is also interesting due to magnetism.
Although still not fully understood, partially fluorinated graphene exhibits colossal negative magnetoresistance. [123] Furthermore, metal free
magnetic nanoparticles made from fluorinated graphene oxide exhibit the ability to serve as magnetic resonance imaging agent. [124]
Other halogenated graphenes have much lesser applications. Highly chlorinated or brominated graphene can be used to reversibly store
chlorine and bromine, respectively.[105] The chlorination of graphene also significantly influences electrochemical properties and the
iodination enhances its catalytical properties. [89c, 126] DC bias controlled fabrication of field effect transistor from chlorinated graphene
exhibited a threefold increase in hole carrier concentration. [127]
The most important nitrogen containing derivates are prepared by epoxide opening of graphene oxide. Lee et al. prepared alkylamino
substituted graphenes and demonstrated their use as materials for hydrogen gas barrier membranes. [128] The azido group on graphene
was used interconnect alkynyl-DNA with graphene by „click“ reaction. The graphene-DNA adduct was exceptionally stable and might be
used for example as biosensors for DNA detection. [129] Wang et al. used graphene azide to link graphene sheets and used them for the
detection of Cu2+ ions[130] and Namazi et al. connected sugars[131] to graphene making it more hydrophilic. The reaction of graphene with
organic azides is less important, however, it produced few quite interesting materials - azirido-graphene membranes containing
polysulphone groups were recently introduced showing better ion selectivity compared to the commercial Nafion117 membrane.[132]
Boronic acid modified graphenes create frameworks, which seem to be promising for storage of hydrogen and other gases. [61] Haque et al.
used the same type of graphene framework as a material for CO2 capture and storage.[133] The ability of boronic acids to interact with diols
was also used in selective electrode design and glycoproteins recognition. Graphene oxide was deposited onto a gold electrode and
anchored by electrochemical polymerization of 3-aminophenylboronic acid. The electrode exhibited wide response range for xylitol and
fructose[134] and for sialic acid.[135] Luo et al. used similarly modified graphene oxide by 3-aminophenylboronic acid. The obtained material
was then treated with a template glycoprotein (ovalbumin), which is recognized by boronic acid. Organosilanes were used to create a
template matrix by sol-gel process and after washing out the glycoprotein, the graphene oxide -boronic acid matrix showed high recognition
ability towards the same molecule due to synergistic boronic acid recognition and graphene surface. [136] Also, the simple reduction of
graphene oxide by borohydride led to the boron introduction on graphene and its concentration can even exceed hundreds of ppm.[137]
Phosphorus modified graphene applications are quite scarse due to low number of these materials, although these derivates could be very
promising. So far, the material containing phosphonic acids groups on the edges of graphene sheet exhibited flame retardant properties
and was used as materials for the improvement of fire safety in cotton fabrics. [138] The ability of phosphorus to serve as a ligand in lead
authors to prepare phosphinite containing graphene, which showed great effectivity in palladium catalysed reactions. [58]
The same problem as the phosphorus based materials faces sulfur modified graphenes. One of few examples is thiourea functionalized
graphene aerogel resulting in a material with high specific capacitance as high as 1089 F.g -1 at 1 A.g-1.[66, 139] The great importance of sulfur
modified graphene is illustrated in example where it exhibited excellent electrocatalytic activity towards various industrially important
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reactions like oxygen reduction reaction (Figure 8a), e.g. in fuel cells.[68] Graphene containing thiol was also successfully used for
biosensing applications based on immobilized ssDNA (Figure 8b).[66]
Figure 8. b) LSV curves of sulfur doped graphene showing its excellent electrocatalytic activity towards oxygen reduction reaction.
Reprinted from ref. [68] with permission from American Chemical Society, Copyright 2012. c) The use of thiofluorographene for biosensing
applications based on DNA hybridization between immobilized ssDNA and target DNA. Reprinted from ref. [66] with permission from WILEYVCH Verlag GmbH, Copyright 2015.
Conclusion
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Figure 9. The most important graphene derivates and their applications.
Accepted Manuscript
The family of graphene derivates has been rapidly growing especially during the last decade. Despite the large effort on the research in the
field of graphene chemistry, only fully fluorinated and fully hydrogenated graphene termed fluorographene and graphane are well known.
These two materials are wide band-gap semiconductors with application potential in several technological fields including microelectronic
and optoelectronic devices, biosensors, catalysts, composites and many others. These materials also exhibit several outstanding
properties including room temperature ferromagnetism, intensive photoluminescence and fast heterogeneous electron transfer. Their
significantly higher reactivity, in comparison with graphene, makes them suitable precursors for further derivatization. Apart from fully
stoichiometric derivates, there are many other partially functionalized graphene derivates including hydrographene and thiographene
derivates containing hydroxyls and thiol groups. Formation of these and other derivates with high degree of functionalization is significantly
influenced by sterical effects (some functionalities are too bulky to fully cover the graphene surface). Despite the very intensive research on
graphene functionalization over the past decade, the synthesis procedures for high degree functionalization remain unknown for most
functional groups. The effective functionalization of graphene is crucial for most of its applications and will remain an important topic for the
next decades. The intensive work in the chemistry of graphene has led to an interest in general field of 2D materials chemistry. This covers
the elemental analogues of graphene like pnictogens, silicene as well as broad family of compound materials including layered
chalcogenides, nitrides, carbides and many others. The chemical modifications of 2D materials can in general significantly extend the
scope of their applications. [8a-c, 140]
The future perspectives of graphene functionalization are in the field of more complex derivates since in general the reaction well known in
organic chemistry can be broadly applied for graphene. More complex reaction including multistep synthesis will allow future extension of
applications. Methods for the synthesis of stoichiometric graphene derivates are currently known only for fluorine and hydrogen while the
remainder is currently unknown. Correlation with theoretical calculations is essential since probably not all of such derivates can exist or
are sufficiently stable. Much of the recent work was done on the bulk graphene which contains defects and doesn’t possess well defined
population of various functionalities (especially oxygen functionalities). For the future application, the research of graphene chemistry
should also focus on well-defined graphene like CVD grown materials. These results can find very fast broad application use in nano- and
optoelectronic devices.
Acknowledgements
Work was supported by Czech Science Foundation (GACR No. 15-09001S and GACR No. 16-05167S) and by specific university research
(MSMT No. 20-SVV/2017). This work was created with the financial support of the Neuron Foundation for science support. This work was
supported by the project Advanced Functional Nanorobots (reg. No. CZ.02.1.01/0.0/0.0/15_003/0000444 financed by the EFRR).
Keywords: graphene • functionalization • derivates • covalent bond • substitution doping
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