Hydrogenation of graphene nanoflakes and C-H bond dissociation of hydrogenated graphene nanoflakes： a density functional theory study

The Gibbs free energy change for the hydro- genation of graphene nanoflakes Cn （n = 24, 28, 30 and 32） and the C-H bond dissociation energy of hydrogenated graphene nanoflakes CnHm （n = 24, 28, 30 and 32; and m = 1, 2 and 3） are evaluated using density functional theory calculations. It is concluded that the graphene nanoflakes and hydrogenated graphene nanoflakes accept the orth- aryne structure with peripheral carbon atoms bonded via the most triple bonds and leaving the least unpaired dan- gling electrons. Five-membered rings are formed at the deep bay sites attributing to the stabilization effect from the pairing of dangling electrons. The hydrogenation reactions which eliminate one unpaired dangling electron and thus decrease the overall multiplicity of the graphene nanoflakes or hydrogenated graphene nanoflakes are spontaneous with negative or near zero Gibbs free energy change. And the resulting C-H bonds are stable with bond dissociation energy in the same range as those of aromatic compounds. The other C-H bonds are not as stable attributing to the excessive unpaired dangling electrons being filled into the C-H anti-bond orbital.

Orbital electronic heat capacity of hydrogenated monolayer and bilayer graphene

The tight-binding Harrison model and Green＇s function approach have been utilized in order to investigate the contribution of hybridized orbitals in the electronic density of states（DOS） and electronic heat capacity（EHC） for four hydrogenated structures, including monolayer chair-like, table-like, bilayer AA- and finally AB-stacked graphene. After hydrogenation, monolayer graphene and bilayer graphene are behave as semiconducting systems owning a wide direct band gap and this means that all orbitals have several states around the Fermi level. The energy gap in DOS and Schottky anomaly in EHC curves of these structures are compared together illustrating the maximum and minimum band gaps are appear for monolayer chair-like and bilayer AA-stacked graphane, respectively. In spite of these, our findings show that the maximum and minimum values of Schottky anomaly appear for hydrogenated bilayer AA-stacked and monolayer table-like configurations, respectively.

A nano-engineered graphene/carbon nitride hybrid for photocatalytic hydrogen evolution

A metal-free photocatalytic hydrogen evolution system was successfully fabricated using heteroatom doped graphene materials as electron-transfer co-catalysts and carbon nitride as a semiconductor. The catalytic role of graphene is significantly dependent on the heteroatom dopant of the graphene, such as O, S, B, N doped/undoped graphene co-catalysts, and N-graphene shows the best catalytic hydrogen evolution rate.

Acetic Acid Assistant Hydrogenation of Graphene Sheets with Ferromagnetism

Ferromagnetism of pure carbon-based materials has been widely researched for several years. In therocially and experimentally, semi-hydrogenation graphene sheets exhibit ferromagnitism, which is related to the degree of hydrogenation. Here we reported the controllable hydrogenation of graphene using ball-milling method with acetic acid as hydrogenating agent. The hydrogenation graphene sheets were characterized by means of transmission electron microscopy（TEM）, Raman spectroscopy and X-ray photoelectron spectroscopy, and magnetic measurement. The relusts of Raman spectroscopy demonstrate that the relative intensity of D band increases with the hydrogenation degree. The resluts of magnetic meansurement indicate the maximal magnetic moment of 0.274 A·m^2/kg at 2 K for semi-hydrogenation graphene.

Self-healing Supramolecular Polymer Composites by Hydrogen Bonding Interactions between Hyperbranched Polymer and Graphene Oxide

A self-healing supramolecular polymer composite（HSP-GO） was designed and prepared via incorporation of modified graphene oxide to hyperbranched polymer by hydrogen-bonding interactions. The polymer matrix based on amino-terminated hyperbranched polymer（HSP-NH_2） was synthesized by carboxylation, Curtius rearrangement, and amination of hydroxyl-terminated hyperbranched polyester（HP-OH）, while the modified graphene oxide was prepared by transformation of hydroxyl to isocyanate and further to carbamate ester. Spectroscopic methods were utilized to characterize the obtained polymer composites. Stress-strain test was selected to carefully study the self-healing property of HSP-GO. It is found that a small amount of modified graphene oxide（up to 2 wt%） improves the glass transition temperature（T_g）, tensile strength, Young＇s modulus, and self-healing efficiency of the polymer composites. After healed at room temperature for 10 min, the addition of modified graphene oxide improves the self-healing efficiency to 37% of its original tensile strength. The experiment result shows that the self-healing efficiency is related to the density of hydrogen bonding site and the molecular movement.

Molybdenum sulfide/graphene-carbon nanotube nanocomposite material for electrocatalytic applications in hydrogen evolution reactions

We report a three-dimensional hierarchical ternary hybrid composite of molybdenum disulfide （MoS2）, reduced graphene oxide （GO）, and carbon nano- tubes （CNTs） prepared by a two-step process. Firstly, reduced GO-CNT composites with three-dimensional microstructuresare synthesized by hydrothermal treatment of an aqueous dispersion of GO and CNTs to form a composite structure via π-π interactions. Then, MoS2 nanoparticles are hydrothermally grown on the surfaces of the GO-CNT composite. This ternary composite shows superior electrocatalytic activity and stability in the hydrogen evolution reaction, with a low onset potential of only 35 mV, a Tafel slope of -38 mV.decade-1 and an apparent exchange current density of 74.25 mA.cm-2. The superior hydrogen evolution activity stemmed from the synergistic effect of MoS2 with its electrocatalytically active edge-sites and excellent electrical coupling to the underlying graphene and CNT network.

Au nanoparticles decorated graphene/nickel foam nanocomposite for sensitive detection of hydrogen peroxide

The Au nanoparticles decorated graphene（AuNPs@Gr）/nickel foam（Gr/NiF） nanocomposite（AuNPs@Gr/NiF） was prepared by chemical vapor deposition followed by electrophoretic deposition of AuNPs on Gr/NiF. The morphology, microstructure and sensing performance of the as-prepared AuNPs@Gr/NiF nanocomposite were characterized and measured, respectively by scanning electron microscope, transmission electron microscope, ultraviolet visible spectroscopy and chemical workstation. The asprepared AuNPs@Gr/NiF nanocomposite was used as the electrode to construct a chemical sensor for the detection of hydrogen peroxide（H2O2）. The results showed that the AuNPs distributed homogenously and stably on the surface of Gr/NiF. The chemical sensor exhibits a sensitive and selective performance to the detection of H2O2.

Monodispersed Pt nanoparticles on reduced graphene oxide by a non-noble metal sacrificial approach for hydrolytic dehydrogenation of ammonia borane

Downsizing noble metal nanoparticles,such as Pt,is an essential goal for many catalytic reactions.A non-noble metal sacrificial approach was used to immobilize monodispersed Pt nanoparticles （NPs） with a mean size of 1.2 nm on reduced graphene oxide （RGO）.ZnO co-precipitated with Pt NPs and subsequently sacrificed by acid etching impedes the diffusion of Pt atoms onto the primary Pt particles and also their aggregation during the reduction of precursors.The resulting ultrafine Pt nanoparticles exhibit high activity （a turnover frequency of 284 min-1 at 298 K） in the hydrolytic dehydrogenation of ammonia borane.The non-noble metal sacrificial approach is demonstrated as a general approach to synthesize well-dispersed noble metal NPs for catalysis.

Atomic and electronic structure of Si dangling bonds in quasi-free-standing monolayer graphene

Si dangling bonds at the interface of quasi-free-standing monolayer graphene （QFMLG） are known to act as scattering centers that can severely affect carrier mobility Herein, we investigate the atomic and electronic structure of Si dangling bonds in QFMLG using low-temperature scanning tunneling microscopy/ spectroscopy （STM/STS）, atomic force microscopy （AFM）, and density functional theory （DFT） calculations. Two types of defects with different contrast were observed on a flat graphene terrace by STM and AFM; in particular, their STM contrast varied with the bias voltage. Moreover, these defects showed characteristic STS peaks at different energies, 1.1 and 1.4 eV. The comparison of the experimental data with the DFT calculations indicates that the defects with STS peak energies of 1.1 and 1.4 eV consist of clusters of three and four Si dangling bonds, respectively. The relevance of the present results for the optimization of graphene synthesis is discussed.

Alloying cobalt with ruthenium in nitrogen doped graphene layers for developing highly active hydrogen evolution electrocatalysts in alkaline media

Subject Code:B01With the support by the National Natural Science Foundation of China,a creative study by the research group led by Prof.Chen Qianwang(陈乾旺)from the University of Science and Technology of China and High Magnetic Field Laboratory,Hefei Institutes of Physical Science,Chinese Academy of

CuS/RGO hybrid by one-pot hydrothermal method for efficient electrochemical sensing of hydrogen peroxide

In this study,a non-enzymatic hydrogen peroxide sensor was successfully fabricated on the basis of copper sulfide nanoparticles/reduced graphene oxide（CuS/RGO） electrocatalyst.Using thiourea as reducing agent and sulfur donor,CuS/RGO hybrid was synthesized through a facile one-pot hydrothermal method,where the reduction of GO and deposition of CuS nanoparticles on RGO occur simultaneously.The results confirmed that the CuS/RGO hybrid helps to prevent the aggregation of CuS nanoparticles.Electrochemical investigation showed that the as-prepared hydrogen peroxide sensor exhibited a low detection limit of 0.18μmol/L（S/N = 3）,a good reproducibility（relative standard deviation（RSD） of4.21%）,a wide linear range（from 3 to 1215 μmol/L） with a sensitivity of 216.9 μA L/mmol/cm-2 under the optimal conditions.Moreover,the as-prepared sensor also showed excellent selectivity and stability for hydrogen peroxide detection.The excellent performance of CuS/RGO hybrid,especially the lower detection limit than certain enzymes and noble metal nanomaterials ever reported,makes it a promising candidate for non-enzymatic H2O2 sensors.