操作条件对DMFC阴极电化学阻抗谱参数的影响

通过降低阴极催化剂载量强化了阴极氧还原反应的电化学极化, 测量了不同操作条件下直接甲醇燃料电池(DMFC)的极化曲线和交流阻抗谱,并提出了改进的等效电路模型LR(CR)(QR(LR))用以分析温度、空气流量和甲醇流量对DMFC阴极电化学反应和传质极化过程的影响. 研究结果表明, 提高工作温度会导致更多的甲醇渗透到阴极, 加大阴极氧气还原反应的电荷转移电阻; 只有采用大的空气流量,才会有效地防止水淹, 加大氧气向催化剂层的传质, 促进阴极反应的进行; 适当提高甲醇的流量可以促进阳极和阴极电化学反应的进行, 但是过高的甲醇流速可能会降低电极表面的温度, 加剧甲醇的渗透.     

CO2原位处理对Sm0.5Sr0.5CoO3-δ电催化剂性能的影响

采用阴极轻度过烧工艺制备了Sm_(0.5)Sr_(0.5)CoO_(3-δ)(SSC)阴极,并在单电池运行条件下利用25%CO2(体积比)对电池阴极进行了原位处理.XRD及TG分析表明,在600℃下,CO2的原位处理导致SSC阴极表面有少量SrCO3和Co3O4生成.空气吹扫下,SrCoO3-δ和Co3O4的存在都有效地改变了阴极材料的表面物理化学性质.阴极电催化剂上氧还原速率的加快显著地降低了阴极的极化电阻,从而导致电池的功率密度提高了约20%.     

Synthesis of an electro-catalyst based on a cobalt(II) complex with dimethylaminoethylamino-N,N-bis(2-methylene-4-tert-butyl-6-methylphenol)

A catalyst based on [LCo(H₂O)] (1) is formed by the reaction of dimethylaminoethylamino-N,N-bis(2-methylene-4-tert-butyl-6-methyl)phenol (H₂L) with CoBr₂ for electrolytic proton or water reduction. 1 catalyzes hydrogen evolution, both from acetic acid with a turnover frequency (TOF) of 17.9 mol of hydrogen per mole of catalyst per hour at an overpotential of 792 mV (in DMF) and from water with a TOF of 260 mol of hydrogen per mole of catalyst per hour at an overpotential of 889 mV (in buffer, pH 7.0).     

Oxygen Evolution and Reduction Reaction Activity Investigations on Fe,Co or Ni embedded Tetragonal Graphene by A Thermodynamical Full-Landscape Searching Scheme

Single transition metal (TM) atoms such as Fe, Co and Ni occupying a carbon divacancy in tetragonal graphene (TG) and bonded with four nitrogen atoms (TM@N₄TG) as electrocatalysts are investigated by means of first-principles calculations. To consider the effect of solvent species on the local configuration of the active single metal, a thermodynamical full-landscape searching (TFLS) scheme is employed. The calculated thermodynamic overpotentials (η_td) from our TFLS indicate that Co@N₄TG displays high catalytic activity toward both oxygen evolution reaction (OER) and reduction reaction (ORR), with η_td^OER and η_td^ORR as 0.397 and 0.357 V, respectively. Its OER potential cannot be captured if only one four electron reaction loop (FERL) is considered. The actual active pathways do not always turn out to be the reactions starting from the bare site. Our findings demonstrate that TG is a promising support and TM confined TD can be used to design effective and cheap multifunctional electrocatalysts.     

PtxCuy/C电催化剂甲醇氧化反应性能及机理研究

直接甲醇燃料电池（DMFC）是一种将甲醇燃料的化学能直接转化为电能的能量转换装置,具有能量转化效率高、环境友好、燃料来源丰富等优势,在移动电源等领域具有广泛应用前景,但阳极铂基电催化剂的性能及成本制约着DMFC的发展。本论文通过简单的液相浸渍还原法,制备了系列PtCu/C纳米电催化剂,电化学性能测试结果表明,电催化剂对甲醇氧化反应（MOR）活性顺序为商品Pt/C < Pt₃Cu/C < PtCu₄/C < PtCu/C < PtCu₃/C,且活性最高的PtCu₃/C电催化剂表现出较为优异的电化学稳定性。结合物相表征、电化学测试及DFT计算,阐释了PtCu₃/C催化剂中存在的少量CuO相能够促进水分子解离产生*OH,通过双功能机制促进类CO反应中间物种氧化为CO₂。因此,相比于商品Pt/C,虽然PtCu₃/C电催化剂的ECSA不足其一半,但质量比活性和面积比活性分别提高1.88倍和3.74倍。     

钯基氧还原和乙醇氧化反应电催化剂:关于结构和机理研究的一些近期见解

质子交换膜燃料电池和直接乙醇燃料电池已成为可持续性清洁能源研究的一个聚焦点。在燃料电池中,氧还原反应和乙醇氧化反应是两个重要的反应,其相关高活性、高稳定性并且廉价的催化剂的研发仍然存在很多问题,极大地制约了燃料电池的大规模商业化应用。其中的挑战主要来自于对纳米催化剂结构和反应机理的有限认识。由于实验表征理论计算的结合,对钯基合金纳米材料电催化剂的研究得到了很大的进展。本文从实验和理论计算两个方面出发,重点讨论了应用于氧还原反应和乙醇氧化反应的钯和钯基电催化剂的结构和反应机理方面的近期研究的一些见解。这些见解对未来催化剂的设计与优化有一定的启发意义。     

负载硫化钴纳米颗粒的N、S共掺杂石墨烯氧还原电催化剂的制备及性能

采用D-氨基葡萄糖作为Co分散剂和碳源,硫脲作为氮源和硫源,以NaCl为模板制备负载硫化钴纳米颗粒的N、S共掺杂三维石墨烯氧还原电催化剂(CoS/N/S/rGO)。CoS/N/S/rGO具有良好的氧还原反应(ORR)活性,起始电位和半波电位分别为960和815 mV,性能与商业Pt/C相当。此外,CoS/N/S/rGO表现出明显的4电子转移特性和超低的过氧化氢产率。与基于Pt/C的锌-空气电池相比,基于CoS/N/S/rGO的锌-空气电池在6 mol·L~(-1) KOH和0.2 mol~(-1) Zn(CH_3COO)_2碱性电解质中显示出更高的恒电流放电性能以及更好的稳定性。     

Pt修饰的Ni/C催化剂电催化氧化乙醇性能

采用两步还原法制备了Pt修饰的Ni/C催化剂(Ni@Pt/C),并应用X射线衍射和透射电子显微镜对催化剂进行了表征.结果表明,载体上催化剂粒子呈两相复合结构,具有较好的分散性,平均粒径为4.4 nm.电化学测试表明,Ni@Pt/C催化氧化乙醇的活性电流高达0.37A/mg,是商业Pt/C催化剂的2.33倍,PtNi/C...     

Energy resolved XPS depth profile of (IrO2, RuO2, Sb2O5, SnO2) electrocatalyst powder to reveal core‐shell nanoparticle structure

Synchrotron‐based energy resolved XPS was used to characterize the structure of IrO₂? RuO₂‐coated Sb₂O₅? SnO₂ nanoparticles. Samples were heat treated at 300, 350, 400, 450 and 500 °C after chloride Ir and Ru precursors were added to Sb₂O₅? SnO₂. Photoelectron kinetic energies of 100, 350 and 1400 eV were employed to obtain an indication of the depth of elemental distributions and chemical shifts. It was shown that the electrocatalyst consists of a core of Sb₂O₅? SnO₂ enriched with Sb₂O₅ towards the surface, with a shell of IrO₂? RuO₂ deposited on this core, and an outer layer of Sb₂O₅? SnO₂ over this shell. No significant chemical interaction occurs between IrO₂? RuO₂ and Sb₂O₅? SnO₂. The energy resolved XPS depth profile technique is effective for studying core‐shell materials. Copyright © 2010 John Wiley & Sons, Ltd.