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A photocatalyst for reducing CO2 without precious metals

By Tetsuo Satoh |

The research group of professor Osamu Ishitani at the Tokyo Institute of Technology (Japan; www.titech.ac.jp), in collaboration with the Institute of Advanced Industrial Science and Technology (AIST), has successfully demonstrated highly efficient, selective and durable photocatalytic CO2-reduction systems that only use abundant elements for the first time. The CO2-reduction photocatalysts use [Cu2(P2bph)2]2+ (CuPS) as a redox photosensitizer, where P2bph = 4,7-diphenyl-2,9-di(diphenylphosphinotetramethylene)-1,10-phenanthroline; and fac-Mn(X2bpy)(CO)3B (Mn(4X)) as the catalyst, where X2bpy = 4,4′-X2-2,2′-bipyridine (X = −H and −OMe) or Mn(6mes), where 6mes = 6,6′-(mesityl)2-2,2′-bipyridne). The most efficient photocatalysis was achieved with Mn(4OMe), which had a total quantum yield for CO 2 reduction products of 57%, a turnover number (based on the Mn catalyst) of over 1,300, and a selectivity for CO2 reduction of 95%. Electronic and steric effects of the substituents (X) in the Mn complexes largely affected both the photocatalytic efficiency and the product selectivity, according to the researchers.

For example, the highest selectivity of CO formation was achieved by using Mn(6mes) (selectivity S CO = 96.6%), whereas the photocatalytic system using Mn(4H) yielded HCOOH as the main product (SHCOOH = 74.6%) with CO and H 2 as minor products (SCO = 23.7%, SH2 = 1.7%). In these photocatalytic reactions, CuPS played a 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 1,000).

The researchers are planning to enhance the performance of the newly developed photocatalyst and also to combine their achievement with a semiconductor photocatalyst that uses water as the reducing agent.

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