石墨烯（graphene）从实验上发现到现在才五六年光景，而现在全世界关于石墨烯的研究进行得如火如荼，2009年初用web of science检索时才2000多篇论文，现在已经到了5000多。

     近一年以来，各经典权威杂志陆续推出几篇关于graphene的review，如Chem. Rev., Science, Angew. Chem., Int. Ed.,等，然而，这些综述大都还是在侧重讨论石墨烯的物理性质，因此，我们这一篇综述应该是第一篇侧重于石墨烯化学的综述。（Notes：现在看来并不算是第一篇，另一篇名为The Chemistry of graphene oxide的综述几乎同时期在Chem Soc Rev上发表。graphene的review paper竞争也很激烈啊！7 March, 2010补记）

      本工作侧重从以下几个角度来阐述：（1）石墨烯的反应活性；（2）官能化的目的（打开带隙和掺杂）；（3）官能化复合物，包括共价键结合和非共价键作用；（4）石墨烯-聚合物的复合材料；（5）化学途径制备石墨烯。

 

The chemistry of graphene

Kian Ping Loh, Qiaoliang Bao, Priscilla Kailian Ang and Jiaxiang Yang

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A review on the latest developments on graphene, written from the perspective of a chemist, is presented. The role of chemistry in bringing graphene research to the next level is discussed.

 

文章在线发表链接： http://www.rsc.org/publishing/journals/JM/article.asp?doi=B920539J 

部分图形摘录：

Fig. 1 (a) Schematic structure of a double-sided decoration of functional groups (4-(2-(pyridin-4-yl)vinlyl) phenyl) on graphene. (b) Supramolecular by layer-by-layer assembly of functionalized graphene.

Fig. 2 Reactivity of graphene. (a) Pristine graphene flake. (b) Chemisorption of hydrogen on the same sublattice. Strong strain causes obvious deformation after geometry optimization (simulated by DMol3 code). (c) Chemisorption of hydrogen on the different sublattices. Graphane plane maintains flatness by having hydrogen absorbed on both sides of the plane (simulated by DMol3 code). (d) AFM image and cross-section profile of graphene membrane with nearly periodic ripples. Reprinted with permission from Z. H. Ni, Nanyang Technological University. (e) Stoichiometric functionalization of graphene on the ripples which can have enhanced reactivity.

Fig. 5 Schematic showing various covalent functionalization chemistry of graphene or GO. I: Reduction of GO into graphene by various approaches (1, NaBH₄; 2, KOH/H₂O; 3, N₂H₄). II: Covalent surface functionalization of reduced graphene via diazonium reaction (ArN₂X).^88,89 III: Functionalization of GO by the reaction between GO and sodium azide. IV: Reduction of azide functionalized GO (azide–GO) with LiAlH₄ resulting in the amino-functionalized GO. V: Functionalization of azide–GO through click chemistry (R–CCH/CuSO₄).⁹⁰ VI: Modification of GO with long alkyl chains (1, SOCl₂; 2, RNH₂) by the acylation reaction between the carboxyl acid groups of GO and alkylamine (after SOCl₂ activation of the COOH groups).^74,91 VII: Esterification of GO by DCC chemistry or the acylation reaction between the carboxyl acid groups of GO and ROH alkylamine (after SOCl₂ activation of the COOH groups) (1, DCC/DMAP or SOCl₂; 2, ROH).^92,93 VIII: Nucleophilic ring-opening reaction between the epoxy groups of GO and the amine groups of an amine-terminated organic molecular (RNH₂).^94,95 IX: The treatment of GO with organic isocyanates leading to the derivatization of both the edge carboxyl and surface hydroxyl functional groups via formation of amides or carbamate esters (RNCO).⁹⁶

Fig. 6 Noncovalent interactions between (a) small molecules (PBASE), (b) polymer (SPANI) and graphene through PI–PI stacking.

 

Fig. 7 Graphene polymer composites. (a) Graphene–PVAc (poly(vinyl acetate)) membrane on quartz fabricated by electrospinning. (b) Transferring free-standing graphene–polymer membrane onto optical fiber as photonics component. Reprinted with permission from ref. 124, copyright 2010, Wiley-VCH Verlag GmbH & Co. KGaH. (c) Schematic showing pulse shaping mechanism of graphene as saturable absorber. The low intensity wings of the input optical pulse are absorbed by graphene while high intensity components pass through. (d) Schematic of graphene flakes randomly distributed in polymer matrix. (e) Schematic of graphene flakes aligned in polymer matrix. (f) TEM image of graphene–PVDF (poly(vinylidene fluoride)) nanocomposite. Reprinted with permission from ref. 116, copyright 2009, American Institute of Physics. (g) TEM image and small-angle X-ray scattering profile (inset) of the edge plane of GO–Nafion nanocomposite. Reprinted with permission from ref. 117, copyright 2009, Wiley-VCH Verlag GmbH & Co. KGaA.

 

Fig. 8 Schematic shows the various exfoliation routes to graphene. Route 1 shows graphene sheets obtained from graphite intercalation compounds (GIC) in which the graphite interlayer distance is increased by intercalants. A high monolayer yield (90%) of graphene sheets stabilized by surfactants was achieved by Dai and co-workers.¹²⁵ Route 2 illustrates graphene sheets produced via direct sonication of graphite in organic solvents which yield a monolayer yield of 50% by Novoselov and co-workers.¹²⁶ Route 3 displays a recent method which involves ionic-liquid assisted electrochemical exfoliation of graphite anode to obtain graphene sheets with almost complete exfoliation to graphene nanosheets (GNS), demonstrated by Luo and co-workers.¹²⁷

Fig. 9 Chemical approach to immobilize graphene on silicon wafer via the PFPA (perfluorophenylazides)-silane coupling agent.¹⁵⁰ (a) The wafer was soaked in a PFPA-silane toluene solution (12.6 mM) for 4 h, washed with toluene, and cured at room temperature overnight. (b) HOPG (highly ordered pyrolytic graphite) was pressed on PFPA-functionalized wafer at 140 °C for 40 min. (c) One or few layers graphene was obtained after removing HOPG followed with sonicating, washing and drying. (d) Schematic showing the covalent bonding between graphene and PFPA-silane, the latter functions as a coupling agent to immobilize graphene on the silicon substrate.

 

 

PS: 鉴于很多朋友都希望看到PDF版本，现将proof粘贴于此，估计官方版的PDF马上就要出来，到时候再更新。

 几乎同时期，在Chemical Society Reviews上有另外一篇类似的Review发表，是Ruoff他们的工作。

 

 这里是最新更新的官方PDF版本:

JMC-review

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