Electrocatalytic Activities of Chemically Reduced Graphene Are Essentially Dominated by the Adhered Carbonaceous Debris

Due to its simple, scalable, and facile qualities, the chemical reduction of graphene oxide seems to be the most popular approach to prepare graphene. We show that such prepared graphene is strongly adhered with carbonaceous debris that has been produced during the synthesis of graphene oxide by the chemical exfoliation of graphite and still remain on graphene sheets through the chemical reduction steps. Interestingly, the presence of the carbonaceous debris causes a significant impact on the electrochemical behavior of the chemical reduced graphene. Herein, we demonstrate that the electrocatalytical activities of the graphene are greatly boosted by the adhered carbonaceous debris. After the removal of the carbonaceous debris, the electrocatalysis of graphene is not superior to conventional graphite.     

Superior Electrochemical Performance of Sulfur/Graphene Nanocomposite Material for High‐Capacity Lithium–Sulfur Batteries

Sulfur/graphene nanocomposite material has been prepared by incorporating sulfur into the graphene frameworks through a melting process. Field‐emission scanning electron microscope analysis shows a homogeneous distribution of sulfur in the graphene nanosheet matrix. The sulfur/graphene nanocomposite exhibits a super‐high lithium‐storage capacity of 1580 mAh g^?1 and a satisfactory cycling performance in lithium–sulfur cells. The enhancement of the reversible capacity and cycle life could be attributed to the flexible graphene nanosheet matrix, which acts as a conducting medium and a physical buffer to cushion the volume change of sulfur during the lithiation and delithiation process. Graphene‐based nanocomposites can significantly improve the electrochemical performance of lithium–sulfur batteries.     

微波合成Pt/WC催化剂及其对甲醇的电催化性能

分别采用微波加热乙二醇还原法(MW)和浸渍还原法(IR)制备以碳化钨(WC)为载体的Pt/WC催化剂, 并分别标记为: MW-Pt/WC及IR-Pt/WC. 用XRD、SEM对两种方法制备的复合材料的结构与形貌进行表征. 循环伏安测试结果表明MW-Pt/WC催化剂在酸性条件下的甲醇氧化性能比IR-Pt/WC催化剂更优, 表现在同一电位下MW-Pt/WC催化剂具有更高的电流且其氧化起始电位负移约30 mV, 还具有更大的电化学比表面积. 此外计时电流法实验结果表明MW-Pt/WC催化剂的稳定性高于IR-Pt/WC催化剂.     

Enhanced Electrocatalytic Performance of a Porous g‐C3N4/Graphene Composite as a Counter Electrode for Dye‐Sensitized Solar Cells

A porous graphitic carbon nitride (g‐C₃N₄)/graphene composite was prepared by a simple hydrothermal method and explored as the counter electrode of dye‐sensitized solar cells (DSCs). The obtained g‐C₃N₄/graphene composite was characterized by XRD, SEM, TEM, FTIR spectroscopy, and X‐ray photoelectron spectroscopy. The results show that incorporating graphene nanosheets into g‐C₃N₄ forms a three‐dimensional architecture with a high surface area, porous structure, efficient electron‐transport network, and fast charge‐transfer kinetics at the g‐C₃N₄/graphene interfaces. These properties result in more electrocatalytic active sites and facilitate electrolyte diffusion and electron transport in the porous framework. As a result, the as‐prepared porous g‐C₃N₄/graphene composite exhibits an excellent electrocatalytic activity. In I^?/I₃^? redox electrolyte, the charge‐transfer resistance of the porous g‐C₃N₄/graphene composite electrode is 1.8 Ω cm², which is much lower than those of individual g‐C₃N₄ (70.1 Ω cm²) and graphene (32.4 Ω cm²) electrodes. This enhanced electrocatalytic performance is beneficial for improving the photovoltaic performance of DSCs. By employing the porous g‐C₃N₄/graphene composite as the counter electrode, the DSC achieves a conversion efficiency of 7.13 %. This efficiency is comparable to 7.37 % for a cell with a platinum counter electrode.     

Mild Synthesis of Pt/SnO2/Graphene Nanocomposites with Remarkably Enhanced Ethanol Electro‐oxidation Activity and Durability

We have designed a new Pt/SnO₂/graphene nanomaterial by using L ‐arginine as a linker; this material shows the unique Pt‐around‐SnO₂ structure. The Sn²⁺ cations reduce graphene oxide (GO), leading to the in situ formation of SnO₂/graphene hybrids. L ‐Arginine is used as a linker and protector to induce the in situ growth of Pt nanoparticles (NPs) connected with SnO₂ NPs and impede the agglomeration of Pt NPs. The obtained Pt/SnO₂/graphene composites exhibit superior electrocatalytic activity and stability for the ethanol oxidation reaction as compared with the commercial Pt/C catalyst owing to the close‐connected structure between the Pt NPs and SnO₂ NPs. This work should have a great impact on the rational design of future metal–metal oxide nanostructures with high catalytic activity and stability for fuel cell systems.     

氮掺杂还原氧化石墨烯负载铂催化剂的制备及甲醇电氧化性能

采用高温热解聚苯胺修饰的氧化石墨烯（PANI-GO）,得到了氮掺杂的还原氧化石墨烯碳材料（N-RGO）,以其负载Pt 制备了Pt/N-RGO纳米结构电催化剂. 采用透射电镜（TEM）、X射线光电子能谱（XPS）、X 射线衍射（XRD）谱及拉曼光谱等技术对N-RGO和Pt/N-RGO的形貌及结构进行了表征,用循环伏安、计时电流等电化学技术研究了Pt/N-RGO电极催化剂对CO溶出反应和甲醇电氧化反应的催化性能. 结果表明：高温热解PANIGO可同时实现GO的还原及其氮掺杂的过程,氮掺杂引起还原氧化石墨烯碳材料表面缺陷结构和导电性的增加;与相应的未掺杂氮样品Pt/RGO相比较,Pt/N-RGO样品上Pt 颗粒的分散更均匀,显示出更强的抗CO毒化能力和更高的甲醇电氧化催化活性及稳定性.     

Unusual Inherent Electrochemistry of Graphene Oxides Prepared Using Permanganate Oxidants

Graphene and graphene oxides are materials of significant interest in electrochemical devices such as supercapacitors, batteries, fuel cells, and sensors. Graphene oxides and reduced graphenes are typically prepared by oxidizing graphite in strong mineral acid mixtures with chlorate (Staudenmaier, Hofmann) or permanganate (Hummers, Tour) oxidants. Herein, we reveal that graphene oxides pose inherent electrochemistry, that is, they can be oxidized or reduced at relatively mild potentials (within the range ±1 V) that are lower than typical battery potentials. This inherent electrochemistry of graphene differs dramatically from that of the used oxidants. Graphene oxides prepared using chlorate exhibit chemically irreversible reductions, whereas graphene oxides prepared through permanganate‐based methods exhibit very unusual inherent chemically reversible electrochemistry of oxygen‐containing groups. Insight into the electrochemical behaviour was obtained through cyclic voltammetry, chronoamperometry, and X‐ray photoelectron spectroscopy experiments. Our findings are of extreme importance for the electrochemistry community as they reveal that electrode materials undergo cyclic changes in charge/discharge cycles, which has strong implications for energy‐storage and sensing devices.     

β‐Cyclodextrin‐Platinum Nanoparticles/Graphene Nanohybrids: Enhanced Sensitivity for Electrochemical Detection of Naphthol Isomers

Naphthol isomers, including α‐naphthol (α‐NAP) and β‐naphthol (β‐NAP), are used widely in various fields and are harmful to the environment and human health. The qualitative and quantitative determination of naphthol isomers is therefore of great significance. Herein, β‐cyclodextrin (β‐CD)‐platinum nanoparticles (Pt NPs)/graphene nanosheets (GNs) nanohybrids (β‐CD‐PtNPs/GNs) were prepared for the first time using a simple wet chemical method and characterized by atomic force microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, and electrochemical methods, and then applied successfully in the ultrasensitive electrochemical detection of naphthol isomers. The results show that the oxidation peak currents of naphthol isomers obtained at the glassy carbon (GC) electrode modified with β‐CD‐PtNPs/GNs are much higher than those at the β‐CD/GNs/GC, PtNPs/GNs/GC, GNs/GC, and bare GC electrodes. Additionally, compared with other electrochemical sensors developed previously, the proposed electrode results in improved detection limits of about one order of magnitude for α‐NAP (0.23 nM ) and three orders of magnitude for β ‐NAP (0.37 nM ).     

氮掺杂还原氧化石墨烯负载铂催化剂的制备及甲醇电氧化性能

采用高温热解聚苯胺修饰的氧化石墨烯(PANI-GO),得到了氮掺杂的还原氧化石墨烯碳材料(N-RGO),以其负载Pt制备了Pt/N-RGO纳米结构电催化剂.采用透射电镜(TEM)、X射线光电子能谱(XPS)、X射线衍射(XRD)谱及拉曼光谱等技术对N-RGO和Pt/N-RGO的形貌及结构进行了表征,用循环伏安、计时电流等电化学技术研究了Pt/N-RGO电极催化剂对CO溶出反应和甲醇电氧化反应的催化性能.结果表明:高温热解PANIGO可同时实现GO的还原及其氮掺杂的过程,氮掺杂引起还原氧化石墨烯碳材料表面缺陷结构和导电性的增加;与相应的未掺杂氮样品Pt/RGO相比较,Pt/N-RGO样品上Pt颗粒的分散更均匀,显示出更强的抗CO毒化能力和更高的甲醇电氧化催化活性及稳定性.     

Pt/CNT纳米催化剂的微波快速合成及其对甲醇电化学氧化的电催化性能

碳纳米管 (CNT)作为制备新型催化剂载体已有广泛的研究 [1～ 8] ,例如 ,在其表面负载 Pt,Ru和Pt Ru后则具有良好的催化性能[1,2 ,6～ 8] .但在 CNT表面负载金属微粒的方法难以获得尺寸和形状均匀的纳米粒子 .因此 ,如何制备超细和均匀的纳米粒子是一项具有重要的学术意义和技术价值的工作 .我们利用微波加热的多元醇工艺合成了 XC-72碳负载铂纳米粒子的催化剂 ,并发现它对甲醇的氧化具有较高的电催化活性 [9] .本文进一步以 CNT作为载体 ,利用微波加热法快速合成了 Pt/ CNT纳米催化剂 ,并对其对甲醇电化学氧化的性能进行了初步研究 …     

Self‐Assembled Platinum Nanoflowers on Polydopamine‐Coated Reduced Graphene Oxide for Methanol Oxidation and Oxygen Reduction Reactions

The morphology‐ and size‐controlled synthesis of branched Pt nanostructures on graphene is highly favorable for enhancing the electrocatalytic activity and stability of Pt. Herein, a facile approach is developed for the efficient synthesis of well‐dispersed Pt nanoflowers (PtNFs) on the surface of polydopamine (PDA)‐modified reduced graphene oxide (PDRGO), denoted as PtNFs/PDRGO, in high yield. The synthesis was performed by a simple heating treatment of an aqueous solution that contained K₂PtCl₄ and PDA‐modified graphene oxide (GO) without the need for any additional reducing agent, seed, surfactant, or organic solvent. The coated PDA serves not only as a reducing agent, but also as cross‐linker to anchor and stabilize PtNFs on the PDRGO support. The as‐prepared PtNFs/PDRGO hybrid, with spatially and locally separated PtNFs on PDRGO, exhibits superior electrocatalytic activity and stability toward both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR) in alkaline solutions.     

Partially Reduced Graphite Oxide as an Electrode Material for Electrochemical Double‐Layer Capacitors

Partially reduced graphite oxide was prepared from graphite oxide by using synthetic graphite as precursor. The reduction of graphite oxide with a layer distance of 0.57 nm resulted in a reduction of the layer distance depending on the degree of reduction. Simultaneously the amount of oxygen functionalities in the graphite oxide was reduced, which was corroborated by elemental analysis and EDX. The electrochemical activation of the partially reduced graphite oxide was investigated for tetraethylammonium tetrafluoroborate in acetonitrile and in propylene carbonate. The activation potential depends significantly on the degree of reduction, that is, on the graphene‐layer distance and on the solvent used. The activation potential decreased with increasing layer distance for both positive and negative activation. The resulting capacitance after activation was found to be affected by the layer distance, the oxygen functionalities and the used electrolyte. For a layer distance of 0.43 nm and with acetonitrile as the solvent, a differential capacitance of 220 Fg^?1 was achieved for the discharge of the positive electrode near the open‐circuit potential and 195 Fg^?1 in a symmetric full‐cell assembly.     

Fabricating Core-Shell WC@C/Pt Structures and its Enhanced Performance for Methanol Electrooxidation

The spray-dried spheres within a W/Pt multi-separation can be used to prepare discrete core-shell WC@C/Pt catalysts through a typical carburization production mechanism at 800℃. In contrast with previous studies of the WC/Pt synthesis, the reaction observed here proceeds through an indirect annealing mechanism at 600℃ wherein species diffuse, thereby resulting in core-shell structure, and Pt nanoparticles were successfully dispersed in size/shape and randomly scattered across the in situ produced C spheres. Through direct carburization or at higher initial hydrochloroplatinic acid concentrations, however, complete reaction with core-shell spheres was not observed. Indirect carburization reduces the strain felt by the bonds featuring the larger WC particles and allows the motion of carbon around WC and Pt nanoparticles to be reserved, influencing the electrocatalytic performance and stability toward methanol oxidation.     

Edge‐Selectively Functionalized Graphene Nanoplatelets

Graphene, as a single layer of graphite, is currently the focal point of research into condensed matter owing to its promising properties, such as exceptional mechanical strength, high thermal conductivity, large specific surface area, and ultrahigh electron‐transport properties. Therefore, various physical and chemical synthetic procedures to prepare graphene and/or graphene nanoplatelets have been rapidly developed. Specifically, the synthesis of edge‐selectively functionalized graphene (EFG) has been recently reported by using simple and scalable approaches, such as “direct” Friedel‐Crafts acylation reactions in a mild acidic medium and a mechanochemical ball‐milling process. In these approaches, chemical functionalization predominantly take place at the edges of the graphitic layers via the covalent attachment of targeted organic “molecular wedges”. In addition, the distortion of the crystalline structures in the basal plane, which is beneficial for preserving the unique properties of the graphitic framework, can be minimized. In addition, the efficient exfoliation of graphene can be achieved, owing to the strong repulsive forces from the covalently linked wedges and strong shear forces during the reaction. Furthermore, EFG shows promising potential in many useful applications, such as highly conductive large‐area films, metal‐free electrocatalysts for the oxygen‐reduction reaction (ORR), and as additives in composite materials with enhanced properties. Herein, we summarize the recent progress and general aspects of EFG, including synthesis, reaction mechanism, properties, and applications.     

Carbon‐Supported Pt Particles as a Catalyst for Electrooxidation of Methanol and Cyclic Voltammetry Studies Under Acidic Conditions

Electrooxidation of methanol on glassy carbon (GC) electrode modified by optimum carbon supported Pt electrocatalyst (Pt‐C/GC) in acid media is investigated. The catalyst is prepared by ultrasonicating Pt/C powders in aqueous media. The activity of prepared Pt‐C/GC electrode is studied in potential range of 0–1000 mV (versus SCE) by cyclic voltammetry. The results showed that the Pt/C dispersed layer at the surface of glassy carbon electrode, behaves as an electrocatalyst for the oxidation of methanol in acid medium by optimum loading of Pt (0.2 mg cm^?2). The electrochemical properties of prepared electrode are studied under various conditions. However the effect of various parameters in the catalytic enhancement of Pt/C, such as platinum loading, sulfuric acid concentration, different scan rates, different final potentials, and medium temperature are considered and examined.