Homogeneous Catalytic System for Photoinduced Hydrogen Production Utilizing Iridium and Rhodium Complexes
作者:Eric D. Cline、Samantha E. Adamson、Stefan Bernhard
DOI:10.1021/ic800988b
日期:2008.11.17
An efficient homogeneous catalytic system for the visible-light-induced production of hydrogen from water utilizing cyclometalatediridium(III) and tris-2,2'-bipyridyl rhodium(III) complexes is described. Synthetic modification of the photosensitizer Ir(C--N) 2(N--N) (+) and water reduction catalyst Rh(N--N) 3 (3+) creates a family of catalysts with diverse photophysical and electrochemical properties
描述了一种有效的均相催化系统,用于利用环金属化的铱(III)和tris-2,2'-联吡啶基铑(III)络合物从水中可见光诱导的氢气生产。光敏剂Ir(C--N)2(N--N)(+)和减水催化剂Rh(N--N)3(3+)的合成改性产生了具有多种光物理和电化学性质的催化剂系列。各种催化剂组合和光反应条件的平行筛选可实现优化光催化系统的快速开发,该系统可实现超过5000次的转换,其量子产率((1)/ 2 H 2吸收的每个光子)大于34%。优化系统的光物理和电化学特性表明,还原淬灭途径为形成[Rh(N--N)2](0)提供了必要的驱动力。汞或CS 2对系统中毒的测试提供了有力的证据,表明该系统是用于光催化制氢的真正均质系统。
Poly(pyridine)ruthenium(II)-photoinduced redox reactions of bipyridinium cations, poly(pyridine)rhodium complexes, and osmium ammines
作者:Carol Creutz、Andrew D. Keller、Norman Sutin、Arden P. Zipp
DOI:10.1021/ja00377a013
日期:1982.6
power of *RuL/sub 3//sup 2 +/ and have been fitted to k/sub 11/ approx. = 2 x 10/sup 9/ M/sup -1/s/sup -1/ and E/sup 0//sub Q,Q/sup -// = -0.97 V for the RhL/sub 3//sup 3 +/-RhL/sub 3//sup 2 +/ couple. This E/sup 0/ value is strikingly similar to that (-0.9 V vs. aqueous SCE) obtained via cyclic voltammetry in acetonitrile. The cyclic voltammetry of the RhL/sub 3//sup 3 +/ complexes in water has been reexamined