Catalytic reduction of proton, oxygen and carbon dioxide with cobalt macrocyclic complexes
Catalytic reduction of proton, oxygen and carbon dioxide with cobalt macrocyclic complexes
复制标题
DOI：
10.1142/s1088424616300111
复制
发表时间：
2016-12
影响因子：
1.5
通讯作者：
Kentaro Mase;Shoko Aoi;K. Ohkubo;S. Fukuzumi
中科院分区：
文献类型：
--
作者：
Kentaro Mase;Shoko Aoi;K. Ohkubo;S. Fukuzumi
通过还原小分子将太阳能转化为化学能为有效的能量储存和运输提供了一个有前途的解决方案。在这篇文章中，我们重点介绍了我们最近的研究钴-大环配合物的催化还原O2，质子和CO2。我们已经成功地澄清了催化O2还原与酞菁钴（CoII（Pc））和钴二氢卟酚（CoII（Ch））的反应机理的基础上详细的动力学研究在均相条件下。这些大环配体上的质子接受部分的存在增强了电子接受能力，导致O2的有效催化双电子还原以产生在酸性溶液中具有高稳定性和较小过电位的过氧化氢（H2 O2）。当CoII（Ch）被吸附在多壁碳纳米管（MWCNTs）上并用作电催化剂时，在水溶液中，在施加的电位为-1.1 V vs. NHE时，CO2被成功地还原为CO，法拉第效率为89%。最后，以CoII（Ch）为催化剂，[Ru（bpy）3]2+（bpy = 2，2 ′-bipyridine）为光催化剂，通过单光子双电子过程实现了抗坏血酸的光催化放氢.
The conversion of solar energy into chemical energy by the reduction of small molecules provides a promising solution for the effective energy storage and transport. In this manuscript, we have highlighted our recent researches on the catalysis of cobalt-macrocycle complexes for the reduction of O2, proton and CO2. We have successfully clarified the reaction mechanisms of catalytic O2 reduction with cobalt phthalocyanine (CoII(Pc)) and cobalt chlorin (CoII(Ch)) based on detailed kinetic study under homogeneous conditions. The presence of proton-accepting moieties on these macrocyclic ligands enhances the electron-accepting ability, leading to the efficient catalytic two-electron reduction of O2 to produce hydrogen peroxide (H2O2) with high stability and less overpotential in acidic solutions. When CoII(Ch) is adsorbed on multi-walled carbon nanotubes (MWCNTs) and employed as an electrocatalyst, CO2 was successfully reduced to form CO with a Faradaic efficiency of 89% at an applied potential of -1.1 V vs. NHE in an aqueous solution. Finally, photocatalytic H2 evolution was attained from ascorbic acid with CoII(Ch) as a catalyst and [Ru(bpy)3]2+ (bpy = 2,2′-bipyridine) as a photocatalyst via a one-photon two-electron process.