甲醇在聚苯胺载铂电极上的电催化氧化

用循环伏安法在玻碳电极上电聚合导电高分子聚苯胺用于附载Pt,提高了Pt的分散度。发现甲醇在Pt／PAN／GC电极和Pt／GC电极上均能自发解离出强吸附中间体CO,证实聚苯胺膜的存在有利于提高电极对甲醇的电催化氧化活性,CO在Pt／PAN／GC电极上的氧化峰电流明显高于Pt／GC电极。通过比较甲醇的电催化氧化活性可知,Pt/PAN／GC电极催化氧化甲醇的峰电流为58．68mA/cm^2和50．00mA／cm^2,是Pt／GC电极氧化峰电流的1．6倍和1．7倍。     

Pt基直接乙醇燃料电池阳极催化剂的性能研究

采用水热法制备了高分散碳载Pt/C和Pt-SnOJC电催化剂.采用XRD、SEM、TEM和激光粒度仪等方法对制得的纳米催化剂进行了表面微观结构分析.采用电化学工作站测试循环伏安曲线(CV)等表征Pt/C和Pt-SnO2/C纳米催化剂电催化活性.测试结果表明,Pt-SnO2/C纳米催化剂的峰电流密度(131.05 mA·cm-2)是Pt/C催化剂的峰电流密度(65.48 mA·cm-2)的2倍;Pt-SnO2/C催化的电化学表面积(108.4 m2·g-1)远高于Pt/C催化剂的电化学表面积(99.14 m2· g-1);Pt-SnO2/C纳米粒子比Pt/C纳米粒子具有更强的抗CO中毒能力和更高的电催化活性.     

Pt/PAn/GC电极的制备及对甲酸电催化氧化性能的研究

利用循环伏安法电聚合导电高分子聚苯胺，并制备了Pt／PAn／GC电极和Pt／GC电极，优化了苯胺在玻碳电极上的聚合条件，用在H2SO4中的循环伏安曲线对其进行了表征，Pt／PAn／GC电极的制备提高了Pt的分散度，增加了催化剂Pt的利用率。实验结果表明Pt／PAn／GC电极对甲酸电氧化的催化活性明显高于Pt／GC电极和Pt电极，正向扫描和反向扫描时对应的氧化峰电位分别是0．68V、0．45V。峰电流为54．23mA／cm^2和84．23mA／cm^2，为Pt／GC电极的修饰电极1．7倍和1．9倍，为Pt片电极的3．8倍和4．9倍，有效地提高了铂微粒的催化活性，并得到聚合苯胺的最佳条件为扫描速度50mV／s、扫描上限1．2V。     

碳化钨/碳气凝胶纳米复合材料增强Pt电催化甲醇性能的研究

以间苯二酚和甲醛为原料,采用溶胶-凝胶法原位合成WC纳米颗粒制备了碳化钨/碳气凝胶(WC/CAs);以WC/CAs为载体,利用微波加热乙二醇还原法制备了Pt/WC/CAs催化剂。运用循环伏安法(CV)、线性扫描(LSV)、计时电流法(CA)、能谱(EDS)、透射电子显微镜(TEM)和X射线衍射(XRD)等技术分析Pt/WC/CAs催化剂的组成、结构及其对甲醇的电催化氧化活性的影响。实验结果表明,载体中WC纳米颗粒的加入促进Pt贵金属颗粒对甲醇的电催化氧化活性,正扫电流峰ip与扫描速率的平方根v1/2线性相关,Pt/WC/C催化氧化甲醇的过程受扩散控制;且电催化活性比Pt/C要好。     

乙二醇稳定的Pt/C催化剂的制备与表征

以乙二醇(EG)兼作溶剂和稳定剂,分别通过NaBH4和EG还原法制备了高度细化与分散的Pt/C催化剂,对其形貌、组成、结构和电化学活性比表面等进行了表征比较,并测试了它们对甲醇与乙醇电催化氧化的活性. 结果表明,2种催化剂中,Pt均为面心立方结构,粒径小且分布窄,在炭黑载体上分散均匀,单位质量Pt对甲醇与乙醇电催化氧化的活性相当;NaBH4还原法所制Pt/C催化剂中Pt0和Pt(220)晶面含量更高,Pt对甲醇与乙醇电催化氧化的峰电流密度分别为0.68与0.67 mA/cm2,分别是EG还原法所制Pt/C催化剂的1.2倍;2种催化剂对甲醇与乙醇电催化氧化的活性均与商品E-TEK催化剂相当.     

固相反应制备Pt/C催化剂

利用固相反应法制得具有较高催化活性的Pt/C催化剂,探讨了制备条件对催化剂性能的影响。结果显示:用水作浸渍介质、n(NaOH)/n(H2PtCl6)=6 4、固相还原剂为聚甲醛时,制得的Pt/C催化剂中Pt粒子的平均粒径为3 8nm。线性扫描伏安结果表明:在30℃、扫速为50mV/s时,制得的Pt/C催化剂在c(CH3OH)=0 5mol/L和c(H2SO4)=0 5mol/L混合溶液中,甲醇氧化的峰电流密度为11 3mA/cm2;而同样条件下,E TEK公司商品化的Pt/C催化剂为9 2mA/cm2。     

甲醇在铂微粒修饰碳纳米管/纳米TiO2-聚苯胺膜电极上的电催化氧化

在0.5mol·L-1硫酸介质中,采用循环伏安的电化学聚合方法,以50mv·s-1的扫描速度,在-0.1～0.9V范围内以碳纳米管/纳米TiO2(CNT/nanoTiO2)电极为基体聚合得到了聚苯胺(PAn)复合膜电极,用循环伏安法研究了CNT/nanoTiO2-PAn-Pt电极在0.5mol·L-1H2SO4溶液中的电化学行为以及对甲醇氧化的电催化行为。结果表明,CNT/nanoTiO2-PAn-Pt电极对甲醇的氧化具有很高的电催化活性,并同时存在PAn的协同催化作用。在Pt载量为0.56mg/cm2时,甲醇氧化峰电流达到152mA/cm2,随着Pt载量的增加,甲醇的氧化峰电流最高可达410mA/cm2。     

温度及电解液浓度对电沉积法制备Pt/C电极的影响

用电化学沉积法在活性炭表面沉积Pt来制备Pt/C电极。发现改变电沉积温度和电解液中氯铂酸的浓度制备的Pt/C电极,对甲醇及CO氧化的电催化活性有很大不同。沉积条件为80℃、5 mmol.L-1H2PtC l6 0.5 mol.L-1H2SO4与沉积条件为25℃、15 mmol.L-1H2PtC l6 0.5 mol.L-1H2SO4时沉积出的Pt/C电极对甲醇氧化呈现出较高的电催化活性。     

常温下以甲烷为燃料的质子交换膜燃料电池发电可行性研究

尝试了常温下以甲烷为燃料的质子交换膜燃料电池发电的可能性，研究了温度和阳极催化剂对其燃料电池开路电压和放电性能的影响。结果表明，甲烷在常温下能够进行电化学氧化，随着电池工作温度的升高，燃料电池的开路电压和功率密度逐渐增加。阳极催化剂的铂含量和催化剂的组成对甲烷的电化学氧化具有非常大的影响。90℃下使用Pt（40wt．％）-Ru（20wt．％）／C为阳极催化剂（催化剂担载量：（2mg Pt＋1 mg Ru）·cm^-2），在以甲烷为燃料时，质子交换膜燃料电池功率密度达到了5．4mW·cm^-2。     

Pt-SnO2／C催化剂制备及对乙醇电催化性能测试

使用溶胶凝胶法制备了具有电催化活性的Pt-SnO2／C催化剂,并采用XRD、场透射电子显微镜及电化学测试手段对其进行表征。XRD及场发射透射电子显微镜的结果显示所制得的催化剂平均粒径约为4～20nm。采用循环伏安,交流阻抗的测试手段测试了其在乙醇体系中的电催化活性。该催化剂在乙醇电氧化过程中具有很好的稳定性和较高的电催化活性,其电催化活性高于Pt／C。     

纳米碳化钨的合成及其电催化活性研究

以钨酸和丙烯腈为原料,采用共沉淀法合成碳化钨（WC）前驱体,于H₂和Ar混合气氛中高温还原碳化制备纳米WC。采用傅立叶红外光谱、X射线衍射及扫描电镜等对试样进行表征,在酸性介质中采用循环伏安法测试Pt/WC电化学催化活性。结果表明,实验合成了较纯的纳米碳化钨,其颗粒形貌近似球形,粒径80 nm左右。Pt/WC的电化学表面积（ESA）较传统的Pt/C有较大提高,10%Pt/WC电流密度为51.2 mA·cm^-2。     

Durable Transition‐Metal‐Carbide‐Supported Pt–Ru Anodes for Direct Methanol Fuel Cells

Molybdenum carbide (MoC) and tungsten carbide (WC) are synthesized by direct carbonization method. Pt–Ru catalysts supported on MoC, WC, and Vulcan XC‐72R are prepared, and characterized by X‐ray diffraction, X‐ray photoelectron spectroscopy, and transmission electron microscopy in conjunction with electrochemistry. Electrochemical activities for the catalysts towards methanol electro‐oxidation are studied by cyclic voltammetry. All the electro‐catalysts are subjected to accelerated durability test (ADT). The electrochemical activity of carbide‐supported electro‐catalysts towards methanol electro‐oxidation is found to be higher than carbon‐supported catalysts before and after ADT. The study suggests that Pt–Ru/MoC and Pt–Ru/WC catalysts are more durable than Pt–Ru/C. Direct methanol fuel cells (DMFCs) with Pt–Ru/MoC and Pt–Ru/WC anodes also exhibit higher performance than the DMFC with Pt–Ru/C anode.     

Platinum on nitrogen doped graphene and tungsten carbide supports for ammonia electro-oxidation reaction

Ammonia electrooxidation reaction involving multistep electron-proton transfer is a significant reaction for fuel cells, hydrogen production and understanding nitrogen cycle. Platinum has been established as the best electrocatalyst for ammonia oxidation in aqueous alkaline media. In this study, Pt/nitrogen-doped graphene (NDG) and Pt/tungsten monocarbide (WC)/NDG are synthesized by a wet chemistry method and their ammonia oxidation activities are compared to commercial Pt/C. Pt/NDG exhibits a specific activity of 0.472 mA∙cm^–2, which is 44% higher than commercial Pt/C, thus establishing NDG as a more effective support than carbon black. Moreover, it is demonstrated that WC as a support also impacts the activity with further 30% increase in comparison to NDG. Surface modification with Ir resulted in the best electrocatalytic activity with Pt-Ir/WC/NDG having almost thrice the current density of commercial Pt/C. This work adds insights regarding the role of NDG and WC as efficient supports along with significant impact of Ir surface modification.     

Pt/WC催化剂的制备及其在气体扩散电极上的氧还原性能

以喷雾干燥处理的偏钨酸铵为前驱体,采用CO/CO₂为还原碳化气氛,利用程序升温气固反应法制备了分散性良好的空心球状WC粉体,并分别以WC和Vulcan XC-72R碳粉为载体,采用液相沉积还原法制备了Pt/WC及Pt/C催化剂。XRD和SEM测试结果表明, 所制备催化剂中Pt/WC的Pt粒子粒径要大于Pt/C。酸性条件下氧电极极化曲线测试结果表明, Pt/WC的氧还原催化性能要优于Pt/C,这主要表现在同一电位下较高的电流密度及还原起始电位正移约28 mV。讨论了Pt/WC催化性能提高的可能原因及催化机理,并对控制条件下Pt/WC氧气扩散电极的交流阻抗谱进行了研究。     

碳纳米管载PtPb、PtBi纳米催化剂对甲酸抗CO中毒的研究

混酸法预处理了载体碳纳米管（CNTs）,采用两步法制备PtPb/CNTs和PtB i/CNTs催化剂。以甲酸为研究对象,首次采用循环伏安法长时间连续性扫描的方法研究催化剂的抗CO中毒能力。研究发现,添加了Pb、B i金属后,增强了Pt/CNTs催化剂性能,如甲酸的起始氧化电位明显降低、氧化电流密度增大且抗毒性能增强。PtPb/CNTs、PtB i/CNTs催化甲酸的起始氧化电位都低于Pt/CNTs（0.099V）,依次为-0.108和-0.004V（Vs.Ag/AgC l）;在0.6V处,PtPb/CNTs、PtB i/CNTs催化氧化甲酸产生的电流密度都明显大于Pt/CNTs（0.79 mA/cm2）,依次为3.10和1.77mA/cm2;PtPb/CNTs、PtB i/CNTs催化剂的寿命依次为Pt/CNTs催化剂的4倍和5倍。本文主要进行燃料电池电催化剂材料的研究,对于制造新型电催化剂有一定的探索作用。     

Tungsten Carbide Synthesized by Polystyrene Sphere Template Method Promoting Pd Electrocatalyst for Alcohol Oxidation in Alkaline Media

Tungsten carbide (WC) particles loading on hollow carbon spheres (HCS) have been synthesized by using ammonium metatungstate as W source, glucose as carbon source, P123 as dispersant and polystyrene sphere as template. The typical WC‐HCS composite has the WC particle sizes of 5–20 nm, specific surface area of 445 m² g⁻¹, pore volume of 0.24 cm³ g⁻¹ and hollow spherical structure. The above structures of WC‐HCS favor dispersion of Pd particles and mass transfer. Therefore, the Pd/WC‐HCS electrocatalyst has 4.6 times higher peak current density and 130 mV more negative onset potential than that of Pd/C for ethanol oxidation in alkaline solution. The mass transfer property of WC‐HCS (due to structure effect) and promotion effect of WC on Pd are believed to be the origins of the excellent performances.     

Facile synthesis of tungsten carbide-carbon composites for oxygen reduction reaction

Tungsten carbide-carbon composite (XWC-C, where X=10 or 30 represents the tungsten content) supports were prepared by pyrolyzing tungsten-adsorbed poly(4-vinylpyridine)-functionalized carbon. The supports were used to prepare Pt catalysts (Pt/XWC-C) for oxygen reduction reactions (ORR) in alkaline solution. Prepared XWC-C revealed highly dispersed tungsten carbide species composed of WC and W₂C phases. The tungsten carbide species proved to have a positive effect on the dispersion of Pt particles. Compared to the Pt catalyst supported on carbon (Pt/ C), Pt/XWC-C showed higher ORR performance. In addition, the catalytic performance of Pt/XWC-C was enhanced with increasing tungsten carbide content. The highest ORR activity was achieved for the Pt/30WC-C catalyst, which had a 2.9-fold enhanced performance (at 0.8V vs. RHE) compared to that of Pt/C. It is believed that the unique interaction between Pt and the tungsten carbide species was responsible for the enhanced ORR performance of the Pt/XWC-C catalysts.     

多孔WC-TiC催化剂的戊烷异构化活性

以TiC和MoSi₂为基体,WO₃和仲钨酸铵为WC的前驱体,碳酸氢铵为造孔剂,采用固相合成技术, 1 560 ℃制备碳化钛基复合WC催化材料。分别通过X射线衍射仪、扫描电镜、压汞仪、气相色谱和气质谱表征催化材料的相组成、显微结构、孔径分布和对戊烷的催化性能。结果表明,碳化钛基复合WC材料的相组成为TiC、SiC、MoC、 WC 和 (Ti, Si)C;当WO₃为WC前驱体时,催化材料的孔径呈现单峰分布［（0.3~50 μm）］,350 ℃其对戊烷的转化率为16.21%,异构化选择性为5.68%;当仲钨酸铵为WC前驱体时,催化材料的孔径呈现双峰分布［（100~800） nm和（1 ~5） μm］,WC颗粒在500 nm以下,350 ℃戊烷转化率达到48.44%,异戊烷的选择性为12.91%。