【作者】 金雅娜；

【导师】 许林；

【作者基本信息】 东北师范大学 ， 无机化学， 2006， 硕士

【摘要】 本文研究了过渡金属取代杂多酸[CoW₁₁O₃₉Cu（H₂O）]^6- (CoW₁₁Cu)在不同pH介质中的电化学及其对NO₂^-的催化情况,研究表明CoW₁₁Cu中W-O中心的峰电位随pH不同而发生位移,Cl-的加入没有使铜从多酸中脱出;同时发现CoW₁₁Cu对NO₂^-的催化主要是CuI与NO₂^-发生了化学反应的结果。近来,自组装超薄膜越来越引起人们的广泛关注,因为它可作为可调控结构的纳米复合膜材料。层接层（LbL）自组装方法,最初产生于一对相反电荷聚电解质的静电吸附,是一种简单而通用的技术。本文利用层接层（LbL）自组装方法,将Dawson型多金属氧酸盐阴离子P₂W₁₈和可溶性阳离子酞菁-阿利新兰（Alcian blue）交替沉积在ITO玻璃和石英表面,制备出（P2W18/AB）多层复合膜,并利用UV-vis;CV等方法对所制成的膜进行了表征。通过在杂多酸阴离子中添加聚电解质阴离子（PSS）,然后与阳离子酞菁共沉积,提高了每层膜中基质的吸附量。循环伏安曲线表明该复合膜具有对NO₂^-催化还原和催化氧化的双重催化功能。本文通过电化学扫描的方法,将不易溶于水的氨基酞菁和Keggin型杂多酸PMo₁₂制成多层膜修饰玻碳电极,并对镀层的电化学性质进行表征,讨论了pH对膜电化学性质的影响,证明了该多层膜中聚氨基酞菁和PMo₁₂基本保持了原来的电化学活性,可以实现对NO₂^-和氧气还原的双催化功能。更多还原

【Abstract】 the electrochemistry properties of copper（II）-substitute Keggin-typepolyoxometalate [CoW₁₁O₃₉Cu（H₂O）]^6- was investigated in different pH and media, theelectrochemistry behavior observed for the reduction of the tungsten oxo centers for theheteropolyanions was found to be pH dependent. Its characterization by cyclicvoltammetry revealed the stepwise reduction of Cu2+ centers within this heteropolyanionsbefore deposition of Cu（0） on the electrode surface. The presence of chloride ions in thesupporting electrolyte does not induce the extraction of the copper centers from theheteropolyanions. the electroreduction for nitrite was studied also. it is proposed that atransient complex between the Cu（I） in HPA and NO2-is formed initially and the catalyedreduction depend upon the ability of the singly or multiply reduced heteropolytungstatesto deliver electrons to the NO group bound to the copper center.The fabrication of self-assembled ultrathin film has recently attracted considerableinterest in view of their importance to nanomaterials with tailored structures andproperties . The layer-by-layer （LbL） self-assembly method, initially developed for pairsof oppositely charged polyelectrolytes , is a facile and versatile technique that has latelyemerged as a viable approach to prepare large area ultrethin films. In this workwater-soluble cationic phthalocyanine — Alcian blue（AB） and 2:18 tungstophosphateanions （P2W18） were alternately deposited on a 3-aminopropyltriethoxysilane（APS）-modified ITO or quartz substrate through a layer-by-layer （LBL） method in thiswork. The resulting organic-inorganic hybrid films were characterized by UV/Visabsorption spectroscopy and cyclic voltammetry（CV）. A stepwise and regular depositionof Alcian Blue and P2W18 in both pure water and 0.01M PSS were investigated.Differences in linear growth were observed between pure water and 0.01M PSS-basedsolutions. The voltemmetric curves show well-defined anodic and cathodic peaks, whichis indicative of both electrocatalytic oxidation and reduction of nitrite.更多还原