Selective Functionalization of Graphene at Defect‐Activated Sites by Arylazocarboxylic tert‐Butyl Esters

The development of versatile functionalization concepts for graphene is currently in the focus of research. Upon oxo‐functionalization of graphite, the full surface of graphene becomes accessible for C?C bond formation to introduce out‐of‐plane functionality. Herein, we present the arylation of graphene with arylazocarboxylic tert‐butyl esters, which generates aryl radicals after activation with an acid. Surprisingly, the degree of functionalization is related to the concentration of lattice vacancy defects in the graphene material. Consequently, graphene materials that are free from lattice defects are not reactive. The reaction can be applied to graphene dispersed in solvents and leads to bitopic functionalization as well as monotopic functionalization when the graphene is deposited on surfaces. As the arylazocarboxylic tert‐butyl ester moiety can be attached to various molecules, the presented method paves the way to functional graphene derivatives, with the density of defects determining the degree of functionalization.     

Reversible Hydrogenation of Graphene on Ni(111)—Synthesis of “Graphone”

Understanding the adsorption and reaction between hydrogen and graphene is of fundamental importance for developing graphene‐based concepts for hydrogen storage and for the chemical functionalization of graphene by hydrogenation. Recently, theoretical studies of single‐sided hydrogenated graphene, so called graphone, predicted it to be a promising semiconductor for applications in graphene‐based electronics. Here, we report on the synthesis of graphone bound to a Ni(111) surface. We investigate the formation process by X‐ray photoelectron spectroscopy (XPS), temperature‐programmed desorption (TPD), and density‐functional theory calculations, showing that the hydrogenation of graphene with atomic hydrogen indeed leads to graphone, that is, a hydrogen coverage of 1 ML (4.2 wt %). The dehydrogenation of graphone reveals complex desorption processes that are attributed to coverage‐dependent changes in the activation energies for the associative desorption of hydrogen as molecular H₂.     

Application of Si‐doped graphene as a metal‐free catalyst for decomposition of formic acid: A theoretical study

Using density functional theory calculations, the adsorption and catalytic decomposition of formic acid (HCOOH) over Si‐doped graphene are investigated. For the stable adsorption geometries of HCOOH over Si‐doped graphene, the electronic structure properties are analyzed by adsorption energy, density of states, and charge density difference. A comparison of the reaction pathways reveals that both dehydration and dehydrogenation of HCOOH can occur over Si‐doped graphene. The estimated reaction energies and the activation barriers suggest that for the dehydration of HCOOH on the Si‐doped graphene, the rate‐controlling step is H + OH → H₂O reaction. For the dehydrogenation of HCOOH, the rate‐determining step is the breaking of the C? H bond of the HCOO group to form the CO₂ molecule and the atomic H. Our results reveal that the low cost Si‐doped graphene can be used as an efficient nonmetal catalyst for O? H bond cleavage of HCOOH. © 2015 Wiley Periodicals, Inc.     

Ruthenium‐Catalyzed Cascade CH Functionalization of Phenylacetophenones

Three orthogonal cascade C? H functionalization processes are described, based on ruthenium‐catalyzed C? H alkenylation. 1‐Indanones, indeno indenes, and indeno furanones were accessed through cascade pathways by using arylacetophenones as substrates under conditions of catalytic [{Ru(p‐cymene)Cl₂}₂] and stoichiometric Cu(OAc)₂. Each transformation uses C? H functionalization methods to form C? C bonds sequentially, with the indeno furanone synthesis featuring a C? O bond formation as the terminating step. This work demonstrates the power of ruthenium‐catalyzed alkenylation as a platform reaction to develop more complex transformations, with multiple C? H functionalization steps taking place in a single operation to access novel carbocyclic structures.     

Functionalized graphene/thermoplastic polyester elastomer nanocomposites by reactive extrusion‐based masterbatch: preparation and properties reinforcement

A reactive extrusion process was developed to fabricate polymer/graphene nanocomposites with good dispersion of graphene sheets in the polymer matrix. The functionalized graphene nanosheet (f‐GNS) activated by diphenylmethane diisocyanate was incorporated in thermoplastic polyester elastomer (TPEE) by reactive extrusion process to produce the TPEE/f‐GNS masterbatch. And then, the TPEE/f‐GNS nanocomposites in different ratios were prepared by masterbatch‐based melt blending. The structure and morphology of functionalized graphene were characterized by Fourier transform infrared, X‐ray photoelectron spectroscopy, X‐ray diffraction and transmission electron microscopy (TEM). The incorporation of f‐GNS significantly improved the mechanical, thermal and crystallization properties of TPEE. With the incorporation of only 0.1 wt% f‐GNS, the tensile strength and elongation at break of nanocomposites were increased by 47.6% and 30.8%, respectively, compared with those of pristine TPEE. Moreover, the degradation temperature for 10 wt% mass loss, storage modulus at ?70°C and crystallization peak temperature (T_cp) of TPEE nanocomposites were consistently improved by 17°C, 7.5% and 36°C. The remarkable reinforcements in mechanical and thermal properties were attributed to the homogeneous dispersion and strong interfacial adhesion of f‐GNS in the TPEE matrix. The functionalization of graphene was beneficial to the improvement of mechanical properties because of the relatively well dispersion of graphene sheets in TPEE matrix, as suggested in the TEM images. This simple and effective approach consisting of chemical functionalization of graphene, reactive extrusion and masterbatch‐based melt blending process is believed to offer possibilities for broadening the graphene applications in the field of polymer processing. Copyright © 2014 John Wiley & Sons, Ltd.     

Density functional study of hydrogen adsorption and diffusion on Ni‐loaded graphene and graphene oxide

In this work, we performed density functional calculations to investigate the adsorption and diffusion of hydrogen on Ni‐loaded graphene and single layer graphene oxide (SLGO). We evaluated the feasibility of hydrogen spillover in the presence of Ni₄ cluster and the role of oxygen‐containing groups. Our calculations indicate that the hydrogen diffusion is difficult to take place on the Ni/graphene interface due to the stronger Ni? H bond strength. Further, the chemisorbed H atoms are also hard to diffuse freely on the graphene surface. For the SLGO surface, both hydroxyl and epoxide groups may not facilitate the hydrogen diffusion. Instead, they are readily attracted by the nearby Ni catalyst and hydrogenated to water molecules. © 2014 Wiley Periodicals, Inc.     

Spatially Resolved Bottom‐Side Fluorination of Graphene by Two‐Dimensional Substrate Patterning

Patterned functionalization can, on the one hand, open the band gap of graphene and, on the other hand, program demanding designs on graphene. The functionalization technique is essential for graphene‐based nanoarchitectures. A new and highly efficient method was applied to obtain patterned functionalization on graphene by mild fluorination with spatially arranged AgF arrays on the structured substrate. Scanning Raman spectroscopy (SRS) and scanning electron microscopy coupled with energy‐dispersive X‐ray spectroscopy (SEM‐EDS) were used to characterize the functionalized materials. For the first time, chemical patterning on the bottom side of graphene was realized. The chemical nature of the patterned functionalization was determined to be the ditopic scenario with fluorine atoms occupying the bottom side and moieties, such as oxygen‐containing groups or hydrogen atoms, binding on the top side, which provides information about the mechanism of the fluorination process. Our strategy can be conceptually extended to pattern other functionalities by using other reactants. Bottom‐side patterned functionalization enables utilization of the top side of a material, thereby opening up the possibilities for applications in graphene‐based devices.     

Site‐Selective Remote Radical C−H Functionalization of Unactivated C−H Bonds in Amides Using Sulfone Reagents

A general and practical strategy for remote site‐selective functionalization of unactivated aliphatic C?H bonds in various amides by radical chemistry is introduced. C?H bond functionalization is achieved by using the readily installed N‐allylsulfonyl moiety as an N‐radical precursor. The in situ generated N‐radical engages in intramolecular 1,5‐hydrogen atom transfer to generate a translocated C radical which is subsequently trapped with various sulfone reagents to afford the corresponding C?H functionalized amides. The generality of the approach is documented by the successful remote C?N₃, C?Cl, C?Br, C?SCF₃, C?SPh, and C?C bond formation. Unactivated tertiary and secondary C?H bonds, as well as activated primary C?H bonds, can be readily functionalized by this method.     

Highly Efficient and Reversible Covalent Patterning of Graphene: 2D‐Management of Chemical Information

Patterned graphene‐functionalization with a tunable degree of functionalization can tailor the properties of graphene. Here, we present a new reductive functionalization approach combined with lithography rendering patterned graphene‐functionalization easily accessible. Two types of covalent patterning of graphene were prepared and their structures were unambiguously characterized by statistical Raman spectroscopy together with scanning electron microscopy/energy‐dispersive X‐ray spectroscopy (SEM‐EDS). The reversible defunctionalization processes, as revealed by temperature‐dependent Raman spectroscopy, enable the possibility to accurately modulate the degree of functionalization by annealing. This allows for the management of chemical information through complete write/store/erase cycles. Based on our strategy, controllable and efficient patterning graphene‐functionalization is no longer a challenge and facilitates the development of graphene‐based devices.     

Transition‐Metal‐Catalyzed Redox‐Neutral and Redox‐Green C–H Bond Functionalization

Transition‐metal‐catalyzed C–H bond functionalization has become one of the most promising strategies to prepare complex molecules from simple precursors. However, the utilization of environmentally unfriendly oxidants in the oxidative C–H bond functionalization reactions reduces their potential applications in organic synthesis. This account describes our recent efforts in the development of a redox‐neutral C–H bond functionalization strategy for direct addition of inert C–H bonds to unsaturated double bonds and a redox‐green C–H bond functionalization strategy for realization of oxidative C–H functionalization with O₂ as the sole oxidant, aiming to circumvent the problems posed by utilizing environmentally unfriendly oxidants. In principle, these redox‐neutral and redox‐green strategies pave the way for establishing new environmentally benign transition‐metal‐catalyzed C–H bond functionalization strategies.     

Characteristic Spectral Patterns in the Carbon‐13 Nuclear Magnetic Resonance Spectra of Hexagonal and Crenellated Graphene Fragments

Nuclear magnetic resonance (NMR) spectroscopy is an important molecular characterisation method that may aid the synthesis and production of graphenes, especially the molecular‐scale graphene nanoislands that have gathered significant attention due to their potential electronic and optical applications. Herein, carbon‐13 NMR chemical shifts were calculated using density functional theory methods for finite, increasing‐size fragments of graphene, hydrogenated graphene (graphane) and fluorinated graphene (fluorographene). Both concentric hexagon‐shaped (zigzag boundary) and crenellated (armchair) fragments were investigated to gain information on the effect of different types of flake boundaries. Convergence trends of the ¹³C chemical shift with respect to increasing fragment size and the boundary effects were found and rationalised in terms of low‐lying electronically excited states. The results predict characteristic behaviour in the ¹³C NMR spectra. Particular attention was paid to the features of the signals arising from the central carbon atoms of the fragments, for graphene and crenellated graphene on the one hand and graphane and fluorographene on the other hand, to aid the interpretation of the overall spectral characteristics. In graphene, the central nuclei become more shielded as the system size increases whereas the opposite behaviour is observed for graphane and fluorographene. The ¹³C signals from some of the perimeter nuclei of the crenellated fragments obtain smaller and larger chemical shift values than central nuclei for graphene and graphane/fluorographene, respectively. The diameter of the graphenic quantum dots with zigzag boundary correlates well with the predicted carbon‐13 chemical shift range, thus enabling estimation of the size of the system by NMR spectroscopy. The results provide data of predictive quality for future NMR analysis of the graphene nanoflake materials.     

Tailored Synthesis of Various Nanomaterials by Using a Graphene‐Oxide‐Based Gel as a Nanoreactor and Nanohybrid‐Catalyzed CC Bond Formation

New graphene oxide (GO)‐based hydrogels that contain vitamin B₂/B₁₂ and vitamin C (ascorbic acid) have been synthesized in water (at neutral pH value). These gel‐based soft materials have been used to synthesize various metal nanoparticles, including Au, Ag, and Pd nanoparticles, as well as nanoparticle‐containing reduced graphene oxide (RGO)‐based nanohybrid systems. This result indicates that GO‐based gels can be used as versatile reactors for the synthesis of different nanomaterials and hybrid systems on the nanoscale. Moreover, the RGO‐based nanohybrid hydrogel with Pd nanoparticles was used as an efficient catalyst for C? C bond‐formation reactions with good yields and showed high recyclability in Suzuki–Miyaura coupling reactions.     

Identification of Semiconductive Patches in Thermally Processed Monolayer Oxo‐Functionalized Graphene

The thermal decomposition of graphene oxide (GO) is a complex process at the atomic level and not fully understood. Here, a subclass of GO, oxo‐functionalized graphene (oxo‐G), was used to study its thermal disproportionation. We present the impact of annealing on the electronic properties of a monolayer oxo‐G flake and correlated the chemical composition and topography corrugation by two‐probe transport measurements, XPS, TEM, FTIR and STM. Surprisingly, we found that oxo‐G, processed at 300 °C, displays C?C sp³‐patches and possibly C?O?C bonds, next to graphene domains and holes. It is striking that those C?O?C/C?C sp³‐separated sp²‐patches a few nanometers in diameter possess semiconducting properties with a band gap of about 0.4 eV. We propose that sp³‐patches confine conjugated sp²‐C atoms, which leads to the local semiconductor properties. Accordingly, graphene with sp³‐C in double layer areas is a potential class of semiconductors and a potential target for future chemical modifications.     

Copper‐Catalyzed C(sp3)−H Amidation: Sterically Driven Primary and Secondary C−H Site‐Selectivity

Undirected C(sp³)?H functionalization reactions often follow site‐selectivity patterns that mirror the corresponding C?H bond dissociation energies (BDEs). This often results in the functionalization of weaker tertiary C?H bonds in the presence of stronger secondary and primary bonds. An important, contemporary challenge is the development of catalyst systems capable of selectively functionalizing stronger primary and secondary C?H bonds over tertiary and benzylic C?H sites. Herein, we report a Cu catalyst that exhibits a high degree of primary and secondary over tertiary C?H bond selectivity in the amidation of linear and cyclic hydrocarbons with aroyl azides ArC(O)N₃. Mechanistic and DFT studies indicate that C?H amidation involves H‐atom abstraction from R‐H substrates by nitrene intermediates [Cu](κ²‐N,O‐NC(O)Ar) to provide carbon‐based radicals R^. and copper(II)amide intermediates [Cu^II]‐NHC(O)Ar that subsequently capture radicals R^. to form products R‐NHC(O)Ar. These studies reveal important catalyst features required to achieve primary and secondary C?H amidation selectivity in the absence of directing groups.     

Enhanced Oxygen Reduction Reactions in Fuel Cells on H‐Decorated and B‐Substituted Graphene

In the light of recent experimental research on the oxygen reduction reaction (ORR) with carbon materials doped with foreign atoms, we study the performance of graphene with different defects on this catalytic reaction. In addition to the reported N‐graphene, it is found that H‐decorated and B‐substituted graphene can also spontaneously promote this chemical reaction. The local high spin density plays the key role, facilitating the adsorption of oxygen and OOH, which is the start of ORR. The source of the high spin density for all of the doped graphene is attributed to unpaired single π electrons. Meanwhile, the newly formed C? H covalent bond introduces a higher barrier to the p electron flow, leading to more localized and higher spin density for H‐decorated graphene. At the same time, larger structural distortion should be avoided, which could impair the induced spin density, such as for P‐substituted graphene.     

Degradation of Single‐Layer and Few‐Layer Graphene by Neutrophil Myeloperoxidase

Biodegradability of graphene is one of the fundamental parameters determining the fate of this material in vivo. Two types of aqueous dispersible graphene, corresponding to single‐layer (SLG) and few‐layer graphene (FLG), devoid of either chemical functionalization or stabilizing surfactants, were subjected to biodegradation by human myeloperoxidase (hMPO) mediated catalysis. Graphene biodegradation was also studied in the presence of activated, degranulating human neutrophils. The degradation of both FLG and SLG sheets was confirmed by Raman spectroscopy and electron microscopy analyses, leading to the conclusion that highly dispersed pristine graphene is not biopersistent.     

Rhodium(III)‐Catalyzed [3+2] Annulation of 5‐Aryl‐2,3‐dihydro‐1H‐pyrroles with Internal Alkynes through C(sp2)H/Alkene Functionalization

This study describes a new rhodium(III)‐catalyzed [3+2] annulation of 5‐aryl‐2,3‐dihydro‐1H‐pyrroles with internal alkynes using a Cu(OAc)₂ oxidant for building a spirocyclic ring system, which includes the functionalization of an aryl C(sp²)? H bond and addition/protonolysis of an alkene C?C bond. This method is applicable to a wide range of 5‐aryl‐2,3‐dihydro‐1H‐pyrroles and internal alkynes, and results in the assembly of the spiro[indene‐1,2′‐pyrrolidine] architectures in good yields with excellent regioselectivities.     

Thiol–Yne Click Reactions on Alkynyl–Dopamine‐Modified Reduced Graphene Oxide

The large‐scale preparation of graphene is of great importance due to its potential applications in various fields. We report herein a simple method for the simultaneous exfoliation and reduction of graphene oxide (GO) to reduced GO (rGO) by using alkynyl‐terminated dopamine as the reducing agent. The reaction was performed under mild conditions to yield rGO functionalized with the dopamine derivative. The chemical reactivity of the alkynyl function was demonstrated by post‐functionalization with two thiolated precursors, namely 6‐(ferrocenyl)hexanethiol and 1H,1H,2H,2H‐perfluorodecanethiol. X‐ray photoelectron spectroscopy, UV/Vis spectrophotometry, Raman spectroscopy, conductivity measurements, and cyclic voltammetry were used to characterize the resulting surfaces.     

Copper‐Catalyzed Oxidative C−H Bond Functionalization of N‐Allylbenzamide for Regioselective C−N and C−O Bond Formation

Copper‐catalyzed oxidative couplings of N‐allylbenzamides for C?N and C?O bond formations have been developed through C?H bond functionalization. To demonstrate the utility of this approach, it was applied to the synthesis of β‐aminoimides and imides. To the best of our knowledge, these are the first examples in which different classes of N‐containing compounds have been directly prepared from the readily available N‐allylbenzamides using an inexpensive catalyst/oxidant/base (CuSO₄/TBHP/Cs₂CO₃) system.     

Controlled Chemistry Approach to the Oxo‐Functionalization of Graphene

Graphene is the best‐studied 2D material available. However, its production is still challenging and the quality depends on the preparation procedure. Now, more than a decade after the outstanding experiments conducted on graphene, the most successful wet‐chemical approach to graphene and functionalized graphene is based on the oxidation of graphite. Graphene oxide has been known for more than a century; however, the structure bears variable large amounts of lattice defects that render the development of a controlled chemistry impossible. The controlled oxo‐functionalization of graphene avoids the formation of defects within the σ‐framework of carbon atoms, making the synthesis of specific molecular architectures possible. The scope of this review is to introduce the field of oxo‐functionalizing graphene. In particular, the differences between GO and oxo‐functionalized graphene are described in detail. Moreover analytical methods that allow determining lattice defects and functional groups are introduced followed by summarizing the current state of controlled oxo‐functionalization of graphene.