二铁六羰基化合物的合成、氧化石墨烯功能化醋酸纤维素制备及催化电极组装-有机化学专业论文.docxVIP

中文摘要 本论文合成了四种全铁氢化酶的模型化合物然后将其与氧化石 墨烯功能化的醋酸纤维素(CA)结合制得催化电极。通过加入 CA 改性 的氧化石墨烯和聚乙烯亚胺(PEI)改善电极的导电性和质子转运性 能。使用红外光谱、核磁共振、热重分析和扫描电镜等手段对制备的 模型化合物和电纺丝纳米纤维膜进行表征。将纺丝膜组装到玻碳电极 表面制成功能化电极，用循环伏安法研究了功能化电极的氧化还原性 能及在 20%醋酸水溶液中电催化还原制氢的响应情况。实验结果表 明：（1）这些功能化的纺丝膜电极都具有电催化制氢响应；（2）催化 剂中含有的羟基基团可以显著增强催化剂的催化性能，并且增强效果 与羟基数目的多少有关；（3）由于催化剂中质子转移增加，PEI 的引 入增强了电催化中的质子还原现象。 本论文中还设计了一种新型电极以用于电化学重复扫描和恒电 压电解实。使用这种电极可以避免在上述实验中出现电纺丝膜掉落的 情况，且其催化效率远远大于玻碳电极的催化效率。 关键词：二铁六羰基化合物; 膜电极; 电催化 ABSTRACT In this dissertation, four diiron hexacarbonyl complexes were synthesized, and combined with cellulose acetate functionalized by graphite oxide (CA-GO) to fabricate catalytic electrode. The conductivity and proton-transfer of the electrodes were improved by adding CA-GO and Polyethyleneimine (PEI). The model complexes and membranes were characterized by technologies such as infrared (IR) spectrum, thermogravimetry (TG) and scanning electron microscope (SEM). Functionalized electrodes were prepared by assembling the membranes to the surface of glass carbon electrodes and their redox property and electrocatalysis of hydrogen evolution in the presence of 20% HAc in 0.1 M KCl electrolyte solution was investigated by cyclic voltammetry. The results show that: (1) all the electrospun membrane electrodes catalyse hydrogen evolution; (2) hydroxyl groups contained in the model complexes could obviously enhance EMFs catalytic efficiency and the enhancement is related to the number of hydroxyl groups; (3) the presence of PEI in the EFMs did improve the electrocatalytic performance of proton reduction, presumably due to the enhancement in proton-transfer in the catalysis. We also designed a novel-type electrode for electrochemical repeatedly scanning and constant pertential electrolysis experiments. Using this electrode could prevent EFM falling from the electrode and its catalytic efficiency was improved. Keyword: diiron hexacarbonyl complex; membrane electrode; electrocatalysis 目 录 HYPERLINK \l _bookmark0 1. 绪论 ................