甲醇电化学催化氧化机理研究进展

甲醇催化氧化机理的研究对催化剂的开发具有重要的意义。本文概述了甲醇在铂表面催化氧化的反应机理；催化剂的中毒情况以及抗CO催化剂的研究进展，重点阐述了催化剂的结构和表面组成以及电极电势对催化活性的影响。目前的催化剂是不令人满意的．基础研究将有助于避免用纯经验的方法来寻求更为理想的催化剂。     

甲醇阳极电氧化催化剂的研究

采用化学还原沉积法制备了Ｐｔ－ＷＯ３／Ｃ，Ｐｔ－Ｒｕ／Ｃ和Ｐｔ－ＷＯ３／Ｃ系列催化剂，通过循环伏安与电流－电位极化研究了甲醇在不同催化剂／Ｎａｆｉｏｎ奄极上的电催化氧化。结果表明，三种催化剂的催化活性顺序为：Ｐｔ－Ｒｕ－ＷＯ３／Ｃ〉Ｐｔ－Ｒｕ／Ｃ〉Ｐｔ－ＷＯ３／Ｃ。同时研究了甲醇浓度和催化剂的配比对阳极性能的影响。     

耐甲醇氧还原催化剂四苯基卟啉-铂的研究

用平衡吸附法制备了炭载四苯基铁卟啉—铂（FeTPP-Pt/C)复合催化剂，比较了经不同温度热处理的FeTPP-Pt/C和Pt/C对O2还原的催化活性和耐甲醇能力。结果表明，热处理可改善Pt/C催化剂的耐甲醇能力；热处理的FeTPP-Pt/C复合催化剂具有较高的氧还原催化活性和良好的耐甲醇能力，并且700℃处理的FeTPP-Pt/C对O2还原的催化活性最高。     

高分散度铜基甲醇合成催化剂的研究

高分散度铜基甲醇合成催化剂的研究李基涛高利珍张伟德陈明树（厦门大学化学系物理化学研究所３６１００５）７０年来甲醇合成催化剂被广泛关注，特别是６０年代后期英国ＩＣＩ公司发明低温低压铜基甲醇合成催化剂以来，人们对铜基甲醇合成催化剂的制备与表征进行了深入地...     

甲醇水蒸气重整制氢Pd/ZnO催化剂的研究

采用并流共沉淀法制备Pd／ZnO甲醇水蒸气重整制氢催化剂，考察了Pd的质量分数和还原温度对催化剂性能的影响。结果表明，当Pd质量分数为15．9％，还原温度为573K时，催化剂有较好的甲醇转化率及二氧化碳选择性。TPR结果表明，PdO在室温下被还原为金属Pd，在440K开始有部分ZnO被还原。XRD分析结果表明，PdZn合金是甲醇水蒸气重整反应的活性中心；在21．9％Pd／ZnO催化剂上出现了Pd2Zn合金相，导致催化剂的活性下降；反应过程中还原催化剂形成PdZn合金，其活性不如相同条件下纯氢还原的。15．9％Pd／ZnO催化剂及工业铜基催化剂的初始稳定性结果显示，在8h内，15．9％Pd／ZnO催化剂上甲醇转化率保持在66％以上，而铜基催化剂的活性下降了14．4％。     

ZrO2涂层催化剂用于合成甲醇,异丁醇的初步研究

ＺｒＯ_２涂层催化剂用于合成甲醇、异丁醇的初步研究谭猗生，牛玉琴，钟炳，彭少逸（中国科学院山西煤炭化学研究所，太原０３０００１）关键词ＺｒＯ_２涂层催化剂，甲醇，异丁醇一氧化碳加氢合成低碳醇已研究了多年，所用催化剂为传统的沉淀型催化剂。由于此类催化剂在...     

直接甲醇燃料电池阳极催化剂研究进展

 甲醇氧化电催化剂是决定直接甲醇燃料电池性能、寿命和成本的关键材料之一. 近年来人们从提高阳极催化剂活性和降低催化剂成本两个方面出发进行了大量的研究, 有力推动了直接甲醇燃料电池的发展. 在简要介绍电催化剂上甲醇氧化反应机理的基础上, 综述了近年来直接甲醇燃料电池阳极催化剂的研究进展, 从铂基催化剂、非铂基催化剂和催化剂载体三个方面进行了详细的介绍 (附有 58 篇参考文献), 并展望了甲醇电催化剂的发展趋势     

直接甲醇燃料电池的Ir-Fe/C 阴极催化剂性能

合成了直接甲醇燃料电池的Ir-Fe/C阴极催化剂, 用X射线衍射(XRD)谱和X射线能量色散谱(EDS)等方法对该催化剂进行表征, 研究了碳载Ir-Fe(Ir-Fe/C)催化剂对氧还原的电催化活性和抗甲醇能力. 研究发现, 氧在碳载Ir(Ir/C)和Ir-Fe/C催化剂电极上还原的起始氧还原电位分别为0.57和0.65 V. 在0.2 V下的电流密度分别为4.6和5.8 mA/cm2, 表明Ir-Fe/C催化剂对氧还原的电催化性能要优于Ir/C催化剂, 而且Ir-Fe/C催化剂也有很好的抗甲醇能力.     

甲醇合成Cu—Mu／SiO2催化剂的研究

对浸渍法制备的Ｃｕ－Ｍｎ／ＳｉＯ２催化剂进行了甲醇合成活性评价。同时用ＸＰＳ、Ａｕｇｅｒ、Ｎ２Ｏ分解，ＴＰＲ等技术对催化剂进行了表征。结果表明，在双组份催化剂中、工作态催化剂表面主要存在Ｃｕ（Ｏ）。     

过渡金属助剂对催化甲醇羰基化反应的影响

过渡金属助剂对催化甲醇羰基化反应的影响①彭文庆袁国卿②（中国科学院化学研究所，北京１０００８０）关键词过渡金属助剂铑络合物催化剂羰基化甲醇过渡金属催化剂已广泛地应用于加氢、脱氢、羰基化等反应，并显示了优良的催化活性与选择性，而且过渡金属作为助催化剂在...     

PtRu/C电催化剂上甲醇吸附氧化过程的电化学原位红外光谱

采用调变的多元醇法制备了高分散的Pt/C, PtRu/C和Ru/C电催化剂. XRD计算结果表明, PtRu/C电催化剂的平均粒径和合金度分别为2.2 nm和71%. 采用电化学方法和原位傅里叶变换红外反射光谱方法(in situ FTIRS)研究了甲醇在3种电催化剂上的吸附氧化过程, 发现PtRu/C对甲醇的催化活性明显高于Pt/C, Ru的加入一方面影响了甲醇在Pt上的解离吸附性能, 另一方面提供了Ru-OH物种, 从而抑制了低电位下电催化剂中毒. 红外光谱研究结果表明, 线性吸附态CO(COL)是主要毒化物种, 反应产物主要是CO2, 还有少量的甲酸甲酯. 根据实验结果讨论了甲醇在PtRu/C电催化剂上的氧化机理.     

Effect of wetted graphene on the performance of Pt/PPy-graphene electrocatalyst for methanol electrooxidation in acid medium

Polypyrrole (PPy)-modified graphene can be used as a support of electrocatalyst in methanol oxidation reaction. In this paper, the Pt/PPy-graphene electrocatalyst is prepared through in situ synthetic method. The structure and electrochemical property of the electrocatalyst were investigated. The results show that the ultrathin water film between graphene and PPy was favorable as the PPy was distributed uniformly on the upper surface of graphene. The PPy-modified graphene enables the formation of Pt nanoparticles having a very narrow size profile centered around 8 nm and a very even spatial distribution on the graphene surface. The Pt/PPy-graphene catalyst exhibits a noticeably higher electrochemical activity in methanol oxidation reaction and performance durability than the Pt/graphene catalyst, and thus, PPy-graphene is a promising alternative catalyst support in direct methanol fuel cells.     

Simple synthesis of Pt-Ag/SnO2-C for use as a catalyst of methanol oxidation in alkaline media

Journal of Solid State Electrochemistry - Pt-Ag/SnO2-C is a highly active electrocatalyst for the methanol oxidation reaction (MOR) in alkaline media at different methanol concentrations. Pt-Ag...     

聚合物膜燃料电池用电催化剂研究进展

综述了聚合物膜燃料电池（ＰＥＭＦＣ）用电催化剂最新的研究进展,包括阳极甲醇催化剂有机螯合物催化剂及其它的还原催化剂。     

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.     

Au nanowires with high aspect ratio and atomic shell of Pt-Ru alloy for enhanced methanol oxidation reaction

The methanol oxidation reaction(MOR) is the limiting half-reaction in direct methanol fuel cell(DMFC).Although Pt is the most active single-metal electrocatalyst for MOR,it is hampered by high cost and CO poisoning.Constructing a Pt or Ru monolayer on a second metal substrate by means of galvanic replacement of underpotentially deposited(UPD) Cu monolayer has been shown as an efficient catalyst design strategy for the electrocatalysis of MOR because of the presumed 100% utilization of atoms and resistance to CO poisoning.Herein,we prepared one-dimensional surface-alloyed electrocatalyst from predominantly(111) faceted Au nanowires with high aspect ratio as the substrate of under-potential deposition.The electrocatalyst comprises a core of the Au nanowire and a shell of catalytically active Pt coated by Ru.Coverage-dependent electro-catalytic activity and stability is demonstrated on the Pt/Ru submonolayers on Au wires for MOR.Among all these catalysts,Au@Pt_(ML)@Ru_(ML) exhibits the best electrocatalytic activity and poisoning tolerance to CO.This presents a viable method for the rational catalyst design for achieving high noble-metal utilization efficiency and high catalytic performance.     

固相反应法合成Pt/MoO3及其电催化作用

采用固相合成的方法制得直接甲醇燃料电池催化甲醇氧化的Pt/MoO3. XRD分析、循环伏安测试表明,Pt/MoO3对甲醇的氧化具有较好的催化作用,氧化峰电位出现在0.63V(vs.SCE),峰电流密度可达78.1 mA·cm-2.     

Platinized mesoporous tungsten carbide for electrochemical methanol oxidation

Mesoporous WC with hexagonal crystal structure was synthesized by a surfactant-assisted polymer method. A new electrocatalyst composed of a small amount of Pt supported on the mesoporous WC exhibited higher activity for electrooxidation of methanol than microporous Pt/WC or Pt/W₂C as well as commercial Pt–Ru(1:1)/C catalysts. The mesoporosity and the phase of WC appear important for the high activity. Compared to the commercial Pt–Ru/C catalyst, the Pt/WC (mesoporous) showed the higher activity per mass of Pt by a factor of six even without Ru. Since the catalyst is also stable in electrochemical environment, it could become an alternative electrocatalyst for direct methanol fuel cells.     

直接甲醇燃料电池电催化剂性能衰减研究

通过单电池放电试验, 考察了直接甲醇燃料电池(DMFC)电催化剂的性能衰减情况. 透射电镜(TEM)和X射线衍射分析(XRD)结果表明, 放电试验后阳极电催化剂的粒径变化很小, 而阴极电催化剂的粒径则显著增大. DMFC内部的液相环境是促使Pt粒子聚结的主要原因. 阳极催化剂中Ru的存在抑制了Pt粒子的生长. 阳极和阴极电催化剂的电化学表面积(ECSA)在放电后都有所降低, 且下降幅度均高于比表面积(SSA)的下降幅度. 放电过程中阳极电催化剂发生了Ru的流失.