Electrochemical codeposition of Pt/graphene catalyst for improved methanol oxidation

Pt/graphene electrocatalyst was uniformly deposited on a glassy carbon substrate using a pulsed galvanostatic electrodeposition method, which facilitated the simultaneous electrochemical reduction of graphene oxide and formation of Pt nanoparticles. Compared to the commercial carbon-supported Pt electrocatalyst, the electrochemically reduced Pt/graphene (Pt/ERG) catalyst exhibited improved electrocatalytic activity for methanol oxidation due to the synergistic effects of an increase in the number of catalytic reaction sites and an enhancement of the charge transfer rate.     

Preparation of highly dispersed Pt-SnOx nanoparticles supported on multi-walled carbon nanotubes for methanol oxidation

To maximize the utilization of catalysts and thereby reduce the high price, a new strategy was developed to prepare highly dispersed Pt-SnO_x nanoparticles supported on 8-Hydroxyquinoline (HQ) functionalized multi-walled carbon nanotubes (MWCNTs). HQ functionalized MWCNTs (HQ-MWCNTs) provide an ideal support for improving the utilization of platinum-based catalysts, and the introduction of SnO_x to the catalyst prevents the CO poisoning effectively. The as-prepared catalysts are characterized by Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. It is found that the HQ functionalization process preserves the integrity and electronic structure of MWCNTs, and the resulting Pt-SnO_x particles are well dispersed on the HQ-MWCNTs with an average diameter of ca. 2.2 nm. Based on the electrochemical properties characterized by cyclic voltammetry and chronoamperometry, the Pt-SnO_x/HQ-MWCNTs catalyst displays better electrocatalytic activity and stability for the methanol oxidation. It is worth mentioning that the forward peak current density of Pt-SnO_x/HQ-MWCNTs catalyst is ca. 1.9 times of that of JM commercial 20% Pt/C catalyst, which makes it the preferable catalyst for direct methanol fuel cells.     

Rare earth cuprates as electrocatalysts for methanol oxidation

A series of rare earth cuprates with overall composition Ln_2−xM_xCu_1−yM_y′O_4−δ (where Ln=La and Nd; M=Sr, Ca and Ba; M′=Ru and Sb: 0.0≤x≤0.4 and y=0.1) have been tested as anode electrocatalysts for methanol oxidation. The evaluation of electrode kinetic parameters was made galvanostatically. The catalyst characterization was carried out by specific conductivity measurements, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and Iodometry. These materials exhibit significant activity for methanol oxidation at higher potentials. The linear correlation between Cu(3+) content and methanol oxidation activity suggests that the active sites for adsorption of methanol is Cu(3+). The methanol oxidation onset potential depends on the ease of Cu(2+)→Cu(3+) oxidation reaction. These materials show better tolerance towards the poisoning by the intermediates of methanol oxidation compared to that of conventional noble metal electrocatalysts (supported and bulk). The lattice oxygen in these oxides could be considered as active oxygen to remove CO intermediates of methanol oxidation reaction.     

Platinum catalyst on ordered mesoporous carbon with controlled morphology for methanol electrochemical oxidation

Ordered mesoporous carbons CMK-3 with various morphologies are synthesized by using various mesoporous silica SBA-15 as template and then support to prepare Pt/CMK-3 catalyst. The obtained catalysts are compared in terms of the electrocatalytic activity for methanol oxidation in sulfuric acidic solutions. The structure characterizations and electrochemical analysis reveal that Pt catalysts with the CMK-3 support of large particle size and long channel lengths possess larger electrochemical active surface area (ECSA) and higher activity toward methanol oxidation than those with the other two supports. The better performance of Pt/CMK-3 catalyst may be due to the larger area of electrode/electrolyte interface and larger ECSA value of Pt catalyst, which will provide better structure in favor of the mass transport and the electron transport.     

Electrocatalytic oxidation of methanol on Pt catalyst supported on nitrogen-doped graphene induced by hydrazine reduction

Hydrazine is often used to reduce graphene oxide (GO) to produce graphene. Recent observations suggested that when hydrazine is used to reduce GO, the resulting reduced graphene actually contains certain amounts of nitrogen dopants, which may influence the properties of the obtained material, and in some cases may be deployed for beneficial advantage. In this work, we prepared graphene oxide by the chemical oxidation method, then used either hydrazine or sodium borohydride (as a control) to reduce the graphene oxide to graphene and to explore the nature of the nitrogen functionalities introduced by hydrazine reduction. Pt nanoparticles were then deposited on the nitrogen doped (hydrazine-reduced) and undoped (control) graphene substrates, and the morphology, structure, and electrocatalytic methanol oxidation activity were characterized and evaluated. The results show that the nitrogen functional groups introduced into the graphene by hydrazine reduction greatly improve the electrocatalytic activity of the underlying Pt nanoparticles towards the methanol oxidation reaction.     

石墨烯基PtCu二元金属催化剂对甲醇吸附性能的理论研究

直接甲醇燃料电池作为最有潜力的能源越来越受到人们的关注。本文主要采用密度泛函理论（DFT),对石墨烯基PtCu催化剂吸附甲醇的结构进行了理论研究。通过分析甲醇吸附前后前线分子轨道、电荷和吸附能的变化,发现PtCu二元金属催化剂与甲醇相互作用中,甲醇容易吸附于Pt位点上。对于PtCu二元金属的Cu位点的吸附能力与纯Cu相比变化不大,但是PtCu二元金属的Pt位点相对于纯Pt催化剂对甲醇的吸附能力却有明显的提高。因此Cu的掺杂对于提高Pt位点的活性起到促进作用     

Structures of Pt clusters on graphene by first-principles calculations

The interactions between Pt_n clusters (n?13) and a graphene sheet have been investigated by first-principles calculations based on density functional theory. For single Pt-atom and Pt₂-dimer adsorptions, the stable adsorption sites are bridge sites between neighboring carbon atoms. When the number of Pt atoms in a cluster increases, the Pt-C interaction energy per contacting Pt atom becomes smaller. For smaller clusters (3?n?7), the adsorption as a vertical planar cluster is more stable than that as parallel planar or three-dimensional (3D) clusters, due to the stability of a planar configuration itself and the stronger planar-edge/graphene interaction, while the adsorption as a parallel planer cluster becomes stable for larger cluster (n?7) via the deformation of the planar configuration so as to attain the planar-edge/graphene contact. For much larger clusters (n?10), the adsorption as a 3D cluster becomes the most stable due to the stability of the 3D configuration itself as well as substantial Pt-C interactions of edge or corner Pt atoms. The interfacial interaction between a Pt cluster and graphene seriously depends on the shape and size of a cluster and the manner of contact on a graphene sheet.     

Two-step method preparation of graphene without hydrogen on methanol pretreatment copper substrate by PECVD at low temperature

Plasma enhanced chemical vapor deposition (PECVD) is one effective method to prepare graphene at low temperature in a short time. However, the low temperature in PECVD could not provide substrate a proper state for large area and few layer graphene preparation. Herein, we propose a two-step method to grow graphene on Cu foils. In the first step, in order to acquire a smooth and oxide-free surface state, methanol was used as a reductant to pretreat Cu. In the second step, graphene films were prepared on Cu foils by PECVD using CH₄ as carbon source with H₂-free. Few-layer graphene sheets with diameter about 1 μm under low temperature (700 °C) and at a short time (10 min) on well pretreated Cu foils were successfully gotten. The effect of methanol pretreatment on graphene synthesis and the graphene growth mechanism on Cu substrate by PECVD are analyzed comprehensively.     

Electrochemical oxidation of methanol on Pt nanoparticles composited MnO2 nanowire arrayed electrode

By use of the membrane-template synthesis route, MnO₂ nanowire arrayed electrodes are successfully synthesized by means of the anodic deposition technique. The Pt nanoparticles composited MnO₂ nanowire arrayed electrodes (PME) are obtained through depositing Pt on MnO₂ nanowire arrayed electrode by cathode deposition technique. For comparison of electrochemical performance, Pt nanowire arrayed electrodes which have the same amount of Pt with PME are also prepared. The electro-oxidation of methanol on PME and Pt nanowire arrayed electrodes is investigated at room temperature by cyclic voltammetry, which show that about 110 mV decreased overpotential and 2.1-fold enhanced votammetric current are achieved on PME. The chronoamperometry result demonstrates that the resistance to carbon monoxide for PME is improved.     

One-step synthesis of a suspended ultrathin graphene oxide film: Application in transmission electron microscopy

Ultrathin graphene films find their use as advantageous support for nano- and biomaterials investigations. Thin film causes a very slight deterioration to measured signals, thus providing more details of the object's structure at nanoscale. The ultimate thinness of graphene works in the best way for this purpose. However, obtaining suspended thin film of a large-area, which is convenient for applications, is often a relatively complicated and time-consuming task. Here we present a one-step 1-min technique for synthesis of an extremely thin (about 1–2 nm) continuous film suspended over cells of a conventional copper grid (50–400 μm mesh). This technique enables us to acquire a large-area film which is water-resistant, stable in organic solvents and can act as a support when studying nanoparticles or biomaterials. Moreover, the very mechanism of the film formation can be interesting from the point of view of other applications of ultrathin graphene oxide papers.     

One-step synthesis of TiC/multilayer graphene composite by thermal plasma

Graphene hybrid materials have been attracting a great deal of attention due to their superior properties. Nevertheless, problems such as expensive and complicated production processes have limited their application to industrial fields. Here, we introduce a one-step synthesis of titanium carbide (TiC) nanoparticles on multilayer graphene nanosheet (TiC/multilayer graphene) composites using thermal plasma. Although there are three types of titanium alkoxides (titanium ethoxide, titanium isopropoxide and titanium n-butoxide), the TiC/multilayer graphene was synthesized from only titanium isopropoxide. The injection temperature of the precursor was varied to investigate the effects of the precursor concentration in the plasma region. A TiC/multilayer graphene hybrid material with crystalline TiC nanoparticles below 50 nm on graphene nanosheets was observed. The number of graphene nanosheet layers varied from one to over 10 according to the injection temperature. When titanium ethoxide and titanium butoxide were injected, TiC with amorphous carbon and graphite were synthesized. The formation of graphene is considered to be affected by the structure of the carbon chain in the precursors and the concentration in the plasma region.     

Platinum particles dispersed poly(diphenylamine) modified electrode for methanol oxidation

A modified potentiostatic method, termed the ‘pulse pontentiostatic method’ (PPSM) was used to get nano fibrillar poly(diphenylamine) (PDPA) film on Indium tin oxide (ITO) coated glass electrode and also for making modified electrode with platinum particles dispersed in PDPA. Platinum clusters were electrodispersed under constant potential on PDPA films to obtain catalytic electrodes for methanol oxidation. Energy dispersive analysis of X-rays (EDAX) results showed that the Pt microparticles are deposited into PDPA film. Scanning electron micrograph, SEM images show that the deposition results spherical catalytic particles. X-ray photoelectron spectroscopy (XPS) results inform that the net electronic charge on carbon atom and also the imine/amine ratio was not affected by Pt loadings. The modification of electrode surface by nano fibular PDPA improves the electrocatalytic activity for methanol oxidation.     

Electrocatalytic activity of ordered intermetallic PtSb for methanol electro-oxidation

Ordered intermetallic PtSb had been synthesized by arc-melted and then sintering treatment. The electro-oxidation of liquid methanol on PtSb was investigated at room temperature by cyclic voltammetry and chronoamperometry. The results are compared to those at a polycrystalline platinum electrode surface. It was found that PtSb intermetallic was catalytically more active than pure platinum according to the onset potential and current density. X-ray diffraction (XRD) and XPS technologies had been used to investigate the crystal structure and electron effect.     

C24N24负载Sc单原子催化剂催化甲烷氧化为甲醇的理论计算

甲醇是一种很有前途的清洁能源,有望替代不可再生的石油能源.因此,将储量巨大,但不易运输的甲烷氧化为甲醇具有十分重要的意义.首先通过密度泛函理论(density functional theory, DFT)计算研究了Sc原子与C₂₄N₂₄之间的稳定性.结果表明,Sc原子与C₂₄N₂₄的结合能(-9.064 eV)小于Sc原子的内聚能(-4.518 eV),即Sc@C₂₄N₂₄具有良好的稳定性.在此基础上,进一步研究了甲烷在Sc@C₂₄N₂₄表面催化氧化制备甲醇的工艺过程,以N₂O为氧化剂在Sc@C₂₄N₂₄单原子上进行甲醇的催化氧化反应.结果表明：N₂O首先吸附在Sc@C₂₄N₂₄上,然后直接分解为N₂和O_ads.N₂...     

Theoretical modeling of experimental HREEL spectra for supported graphene

We present a simple model for the resonant feature designated as the π plasmon in single-layer graphene supported by a metal substrate, which is excited via high-resolution electron energy loss spectroscopy (HREELS) in the off-specular scattering geometry. Using a two-dimensional, two-fluid hydrodynamic model for interband transitions of graphene's π and σ electrons and an empirical Drude–Lorentz model for the metal in the local approximation enables us to reproduce, at the qualitative and semi-quantitative levels, the typical experimental features of the HREEL spectra in the visible to the ultraviolet frequency range.     

Theoretical study on the catalytic properties of single-atom catalyst stabilised on silicon-doped graphene sheets

ABSTRACT

The stable configurations, electronic structures and catalytic activities of single-atom metal catalyst anchored silicon-doped graphene sheets (3Si-graphene-M, M?=?Ni and Pd) are investigated by using density functional theory calculations. Firstly, the adsorption stability and electronic property of different gas reactants (O₂, CO, 2CO, CO/O₂) on 3Si-graphene-M substrates are comparably analysed. It is found that the coadsorption of O₂/CO or 2CO molecules is more stable than that of the isolated O₂ or CO molecule. Meanwhile, the adsorbed species on 3Si-graphene-Ni sheet are more stable than those on the 3Si-graphene-Pd sheet. Secondly, the possible CO oxidation reactions on the 3Si-graphene-M are investigated through Eley–Rideal (ER), Langmuir–Hinshelwood (LH) and new termolecular Eley–Rideal (TER) mechanisms. Compared with the LH and TER mechanisms, the interaction between 2CO and O₂ molecules (O₂?+?CO → CO₃, CO₃?+?CO → 2CO₂) through ER reactions (< 0.2?eV) are an energetically more favourable. These results provide important reference for understanding the catalytic mechanism for CO oxidation on graphene-based catalyst.     

Fabrication of bimetallic Pt/Pd nanoparticles on 2-thiolbenzimidazole functionalized reduced graphene oxide for methanol oxidation

In this study, an electrocatalyst based on 2-thiolbenzimidazole (TBI) functionalized reduced graphene oxide (rGO) with platinum and palladium nanoparticles (Pt-PdNPs) was synthesized. The successful synthesis of nanomaterials and the prepared glassy carbon electrode (GCE) surfaces were confirmed by transmission electron microscope, X-ray photo electron spectroscopy, scanning electron microscope, electrochemical impedance spectroscopy and X-ray diffraction method. The effective surface areas of TBIrGO/GCE, PdNPs/TBIrGO/GCE, PtNPs/TBIrGO/GCE and Pt-PdNPs/TBIrGO/GCE were calculated to be 324, 578, 667 and 1189 cm²/mg, respectively. According to the results, the electrochemical surface area of the Pt-PdNPs/TBIrGO is 3.67, 2.06 and 1.78 times higher than those of TBIrGO, PdNPs/TBIrGO and PtNPs/TBIrGO, respectively. The Pt-PdNPs/TBIrGO/GCE also exhibited higher peak current for methanol oxidation than those of comparable TBIrGO/GCE, PdNPs/TBIrGO/GCE, PtNPs/TBIrGO/GCE modified GCEs, thus providing evidence for its higher electro-catalytic activity.     

Microwave assisted oxidation of some aromatics by hydrogen peroxide at supported tungsten catalyst

Summary The oxidation of some arenes with the alkyl side groups by means of hydrogen peroxide is been presented. As the activator of hydrogen peroxide tungstoboric acid was chosen. The catalyst was examined under both homogeneous and heterogeneous conditions. The reactions under conventional conditions were compared with the microwave assisted reactions.     

Microwave-assisted rapid synthesis of Pt/graphene nanosheet composites and their application for methanol oxidation

Polymer-free Pt/graphene nanosheet (GN) composites have been rapidly prepared by a one-step microwave-assisted reduction method, carried out by ethylene glycol reduction of H₂PtCl₆ in a graphene oxide suspension. Several analytic techniques including UV?Cvis spectroscopy, Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy have been used to characterize the resulting Pt/GN composites. It suggests that such composites exhibit good catalytic activity toward methanol oxidation.