Development of high-functional electro-oxidation catalyst using a nickel-pincder complex

本文研究了镍钳形配合物的合成及其作为甲醇氧化催化剂的应用。 本文合成了镍钳形配合物，并对其电化学性质进行了研究。钳型配体对中心金属具有较强的供电子能力，因此有望降低配合物的氧化电位。合成了（N，C，N）型和（S，C，N）型镍钳形配合物，用循环伏安法研究了它们的电化学性质。具有较低氧化电位的Ni络合物的生产通过碱处理成在钳形配体的臂中具有两个仲硫代酰胺的Ni络合物而成功。尝试了以该镍钳形配合物为催化剂的甲醇电化学氧化反应。结果，甲醇的氧化在约100 ℃下进行。此外，还研究了将催化剂固定在电极上的方法。

Synthesis of Ni-pincer complexes which are expected to work as an oxidation catalyst of methanol was investigated. In this work, Ni-pincer complexes were synthesized and their electrochemical properties were clarified. Pincer-type ligands show strong electron-donating ability to the centered metal, therefore they are expected to shift the oxidation potential of the complex lower. (N,C,N)- and (S,C,N)-type Ni-pincer complexes were synthesized, and their electrochemical properties were measured by cyclic voltammetry. Production of the Ni complex which has lower oxidation potential was succeeded by treatment of a base to a Ni complex which has two secondary thioamides in the arm of the pincer ligand. Electrochemical oxidation of methanol using this Ni-pincer complex as a catalyst was tried. As a result, oxidation of methanol was progressed at ca. +0.8 V (vs. Ag+/Ag).The method of fixing the catalyst on an electrode was also examined.