Photochemical CO2 Reduction Driven by Water-Soluble Copper(I) Photosensitizer with the Catalysis Accelerated by Multi-Electron Chargeable Cobalt Porphyrin

被引：117

作者：

Zhang, Xian ^{[1
,2
]}

Cibian, Mihaela ^{[1
,4
]}

Call, Arnau ^{[2
]}

Yamauchi, Kosei ^{[1
,2
]}

Sakai, Ken ^{[1
,2
,3
]}

机构：

[1] Kyushu Univ, Fac Sci, Dept Chem, Nishi Ku, Motooka 744, Fukuoka, Fukuoka 8190395, Japan

[2] Kyushu Univ, Int Inst Carbon Neutral Energy Res WPI I2CNER, Nishi Ku, Motooka 744, Fukuoka, Fukuoka 8190395, Japan

[3] Kyushu Univ, Ctr Mol Syst CMS, Nishi Ku, Motooka 744, Fukuoka, Fukuoka 8190395, Japan

[4] Univ Quebec Trois Rivieres, Dept Chim Biochim & Phys, Trois Rivieres, PQ, Canada

来源：

ACS CATALYSIS | 2019年 / 9卷 / 12期

关键词：

earth-abundant photosynthesis; CO2; reduction; water-soluble copper photosensitizer; cobalt porphyrin; multielectron chargeable catalysts; PHOTOCATALYTIC HYDROGEN-PRODUCTION; BINUCLEAR RUTHENIUM(II) COMPLEX; VISIBLE-LIGHT; CARBON-DIOXIDE; HIGHLY EFFICIENT; H-2; EVOLUTION; SYSTEM;

D O I：

10.1021/acscatal.9b04023

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Without using precious elements, a highly efficient and selective molecular-based photocatalytic system for CO2-to-CO conversion in fully aqueous media has been developed. Our copper(I)-based water-soluble photosensitizer (CuPS) preserves its highly luminescent and long-lived excited state even in aqueous media. The CuPS-driven CO2 reduction catalyzed by a water-soluble cobalt porphyrin possessing four N-methylpyridinium acceptors at the meso positions (CoTMPyP) achieves the highest catalytic activity among those reported for aqueous systems: TONCO = 2680 and TOFCOmax = 1600-2600 h(-1) with Sel(CO2) = 77-90% (selectivity for CO vs H-2). The observed photocatalytic enhancement is discussed in terms of the 6-electron chargeable character of CoTMPyP, permitting its rapid release of CO via reduction of Co-II to Co-I by intramolecular electron transfer from the reducing equivalent stored at one of the acceptors.

引用

页码：11263 / 11273

页数：21

共 52 条

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