PHOTOCHEMICAL GENERATION OF CARBON-MONOXIDE AND HYDROGEN BY REDUCTION OF CARBON-DIOXIDE AND WATER UNDER VISIBLE-LIGHT IRRADIATION
PHOTOCHEMICAL GENERATION OF CARBON-MONOXIDE AND HYDROGEN BY REDUCTION OF CARBON-DIOXIDE AND WATER UNDER VISIBLE-LIGHT IRRADIATION
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DOI：
10.1073/pnas.79.2.701
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发表时间：
1982-01-01
期刊：
影响因子：
--
通讯作者：
ZIESSEL, R
中科院分区：
文献类型：
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作者：
LEHN, JM;ZIESSEL, R
在乙腈/水/三乙胺中，Ru（2,2′-联吡啶）32+、氯化钴（II）和二氧化碳的溶液在可见光照射下同时产生一氧化碳和氢气。在Ru（2,2′-联吡啶）32+/Co2+体系中，三乙胺作为电子供体，光诱导还原Co2和H2O。气体（CO + H2）的产出量和CO/H2的选择性比明显取决于体系的组成。游离联吡啶的加入大大减少CO的生成，但增加了h2产率。不同叔胺的NR3， CO + H2的数量和CO/H2的比值沿R =甲基、乙基、丙基的顺序显著增加。当使用三乙醇胺代替三乙胺时，二氧化碳还原为CO的选择性高于水还原。cocl2是CO和h2生成的最有效的介质，并特异性地促进CO的形成，而其他阳离子的盐只产生H2。该反应的机理可能涉及Co(I)的中间生成。这些过程代表了一个非生物光合系统，允许同时产生CO和h2和调节CO/H2ratio。应该进行机理研究和探索其他可能提高效率和产品选择性的成分。所得结果对消耗污染物CO2的太阳能转换也具有重要意义。
Visible light irradiation of solutions of Ru(2,2′-bipyridine)32+, cobalt(II) chloride, and carbon dioxide in acetonitrile/water/triethylamine generates simultaneously carbon monoxide and hydrogen. The reaction involves photoinduced reduction of CO2and H2O, triethylamine serving as electron donor in the Ru(2,2′-bipyridine)32+/Co2+system. The amount of gas (CO + H2) produced and the selectivity ratio CO/H2depend markedly on the composition of the system. Addition of free bipyridine strongly decreases CO generation but increases H2production. With different tertiary amines, NR3, both the quantity (CO + H2) and the ratio CO/H2increase markedly along the sequence R = methyl, ethyl, propyl. Higher selectivity for CO2reduction to CO in preference to water reduction occurs when triethanolamine is used instead of triethylamine. CoCl2is the most efficient mediator for both CO and H2generation and specifically promotes CO formation, whereas salts of other cations studied only yield H2. 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 H2and regulation of the CO/H2ratio. 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, CO2.