Heyduk A F, Nocera D G
Department of Chemistry, 6-335, Massachusetts Institute of Technology, Cambridge, MA 02139-4307, USA.
Science. 2001 Aug 31;293(5535):1639-41. doi: 10.1126/science.1062965.
Energy conversion cycles are aimed at driving unfavorable, small-molecule activation reactions with a photon harnessed by a transition metal complex. A challenge that has occupied researchers for several decades is to create molecular photocatalysts to promote the production of hydrogen from homogeneous solution. We now report the use of a two-electron mixed-valence dirhodium compound to photocatalyze the reduction of hydrohalic acid to hydrogen. In this cycle, photons break two RhII-X bonds of a LRh0-RhIIX2 core in the presence of a halogen trap to regenerate the active LRh0-Rh0 catalyst, which reacts with hydrohalic acid to produce hydrogen.
能量转换循环旨在利用过渡金属配合物捕获的光子驱动不利的小分子活化反应。几十年来一直困扰研究人员的一个挑战是制造分子光催化剂以促进从均相溶液中产生氢气。我们现在报告使用一种双电子混合价二铑化合物光催化氢卤酸还原为氢气。在这个循环中，光子在卤素捕获剂存在的情况下打破LRh⁰-RhIIX₂核心的两个RhII-X键，以再生活性LRh⁰-Rh⁰催化剂，该催化剂与氢卤酸反应产生氢气。
