Highly Efficient and Robust Photocatalytic Systems for CO2 Reduction Consisting of a Cu(I) Photosensitizer and Mn(I) Catalysts.
Highly Efficient and Robust Photocatalytic Systems for CO2 Reduction Consisting of a Cu(I) Photosensitizer and Mn(I) Catalysts.
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DOI：
10.1021/jacs.8b10619
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发表时间：
2018-11
影响因子：
15
通讯作者：
Hiroyuki Takeda;H. Kamiyama;K. Okamoto;Mina Irimajiri;Toshihide Mizutani;K. Koike;A. Sekine;O. Ish
中科院分区：
文献类型：
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作者：
Hiroyuki Takeda;H. Kamiyama;K. Okamoto;Mina Irimajiri;Toshihide Mizutani;K. Koike;A. Sekine;O. Ish
开发高效、选择性和耐用的、只使用富含地球的元素的光催化二氧化碳减排系统是解决全球变暖和解决能源和碳资源短缺的关键。在这里，我们以[Cu2(P2bph)2]2+(CuPS)(P2bph=4，7-diphenyl-2，9-di(diphenylphosphinotetramethylene)-1，10-phenanthroline))为氧化还原光敏剂，Fac-Mn(X2bpy)(CO)3Br3(Mn(4X))(X2bpy=4，4‘-X2-2，2’-联吡啶(X=-H和-OMe)或Mn(6Mes)(6Mes=6，6‘-(甲苯基)2-2，2’-联吡啶))为催化剂，成功地研制了二氧化碳还原催化剂。以Mn(4OMe)为催化剂的光催化效率最高，CO_2还原产物的总量子产率为57%，基于该催化剂的循环次数超过1300次，CO_2还原选择性为95%。锰络合物中取代基(X)的电子和空间效应对光催化效率和产物选择性都有很大影响。以Mn(4H)为催化剂的光催化体系生成CO的选择性最高(Sco=96.6%)，而以Mn(4H)为催化剂的光催化体系以HCOOH为主(SHCOOH=74.6%)，CO和H2为次要产物(Sco=23.7%，SH2=1.7%)。在这些光催化反应中，CUPS发挥了高效和非常持久的氧化还原光敏剂的作用，即使在转化率达到200之后(所使用的催化剂的转化率超过1000)，它在反应溶液中仍然保持稳定。
The development of highly efficient, selective, and durable photocatalytic CO2 reduction systems that only use earth-abundant elements is key for both solving global warming and tackling the shortage of energy and carbon resources. Here, we successfully developed CO2 reduction photocatalysts using [Cu2(P2bph)2]2+ (CuPS) (P2bph = 4,7-diphenyl-2,9-di(diphenylphosphinotetramethylene)-1,10-phenanthroline) as a redox photosensitizer and fac-Mn(X2bpy)(CO)3Br (Mn(4X)) (X2bpy = 4,4'-X2-2,2'-bipyridine (X = -H and -OMe) or Mn(6mes) (6mes = 6,6'-(mesityl)2-2,2'-bipyridne)) as the catalyst. The most efficient photocatalysis was achieved by Mn(4OMe): The total quantum yield of CO2 reduction products was 57%, the turnover number based on the Mn catalyst was over 1300, and the selectivity of CO2 reduction was 95%. Electronic and steric effects of the substituents (X) in the Mn complexes largely affected both the photocatalytic efficiency and the product selectivity. For example, the highest selectivity of CO formation was achieved by using Mn(6mes) (selectivity SCO = 96.6%), whereas the photocatalytic system using Mn(4H) yielded HCOOH as the main product ( SHCOOH = 74.6%) with CO and H2 as minor products ( SCO = 23.7%, SH2 = 1.7%). In these photocatalytic reactions, CuPS played its role as an efficient and very durable redox photosensitizer, while remaining stable in the reaction solution even after a turnover number of 200 had been reached (the catalyst used had a turnover number of over 1000).