Institut Le Bel, Université Louis Pasteur, 4, Rue Blaise Pascal, 67000 Strasbourg, France.
Proc Natl Acad Sci U S A. 1982 Jan;79(2):701-4. doi: 10.1073/pnas.79.2.701.
Visible light irradiation of solutions of Ru(2,2'-bipyridine)(3) (2+), cobalt(II) chloride, and carbon dioxide in acetonitrile/water/triethylamine generates simultaneously carbon monoxide and hydrogen. The reaction involves photoinduced reduction of CO(2) and H(2)O, triethylamine serving as electron donor in the Ru(2,2'-bipyridine)(3) (2+)/Co(2+) system. The amount of gas (CO + H(2)) produced and the selectivity ratio CO/H(2) depend markedly on the composition of the system. Addition of free bipyridine strongly decreases CO generation but increases H(2) production. With different tertiary amines, NR(3), both the quantity (CO + H(2)) and the ratio CO/H(2) increase markedly along the sequence R = methyl, ethyl, propyl. Higher selectivity for CO(2) reduction to CO in preference to water reduction occurs when triethanolamine is used instead of triethylamine. CoCl(2) is the most efficient mediator for both CO and H(2) generation and specifically promotes CO formation, whereas salts of other cations studied only yield H(2). The mechanism of the reaction may involve intermediate formation of Co(I) species. These processes represent an abiotic photosynthetic system allowing simultaneous generation of CO and H(2) and regulation of the CO/H(2) ratio. Mechanistic studies and explorations of other components that may increase efficiency and product selectivity should be carried out. The results obtained are also of significance for solar energy conversion with consumption of a pollutant, CO(2).
可见光照射 Ru(2,2'-联吡啶)(3)(2+)、氯化钴和二氧化碳在乙腈/水/三乙胺中的溶液同时生成一氧化碳和氢气。该反应涉及 CO2 和 H2O 的光诱导还原，三乙胺在 Ru(2,2'-联吡啶)(3)(2+)/Co(2+)体系中作为电子供体。气体（CO+H2）的产生量和 CO/H2 的选择性比值明显取决于体系的组成。添加游离联吡啶强烈降低 CO 的生成，但增加 H2 的生成。对于不同的叔胺 NR3，随着 R 基团从甲基、乙基到丙基的顺序变化，（CO+H2）的量和 CO/H2 的比值都显著增加。与使用三乙胺相比，使用三乙醇胺时更有利于 CO2 还原为 CO 而不是水还原，从而具有更高的 CO 选择性。CoCl2 是 CO 和 H2 生成的最有效介体，特别促进 CO 的形成，而研究的其他阳离子盐仅产生 H2。反应的机制可能涉及 Co(I)物种的中间形成。这些过程代表了一种非生物光合作用系统，允许同时生成 CO 和 H2，并调节 CO/H2 的比值。应该进行机制研究和探索其他可能提高效率和产物选择性的组件。所获得的结果对于利用污染物 CO2 进行太阳能转化也具有重要意义。
