Rapid Exciton Migration and Amplified Funneling Effects of Multi-Porphyrin Arrays in a Re(I)/Porphyrinic MOF Hybrid for Photocatalytic CO2 Reduction

被引：76

作者：

Choi, Sunghan ^{[1
]}

Jung, Won-Jo ^{[1
]}

Park, Kyutai ^{[1
]}

Kim, So-Yeon ^{[1
]}

Baeg, Jin-Ook ^{[2
]}

Kim, Chul Hoon ^{[1
]}

Son, Ho-Jin ^{[1
]}

Pac, Chyongjin ^{[1
]}

Kang, Sang Ook ^{[1
]}

机构：

[1] Korea Univ, Dept Adv Mat Chem, Sejong 30019, South Korea

[2] Korea Res Inst Chem Technol KRICT, Artificial Photosynth Res Grp, Daejeon 34114, South Korea

来源：

ACS APPLIED MATERIALS & INTERFACES | 2021年 / 13卷 / 02期

基金：

新加坡国家研究基金会;

关键词：

metal-organic frameworks (MOFs); energy transfer in porphyrinic array; photocatalytic CO2 reduction; catalyst immobilization; heterogeneous catalysis; METAL-ORGANIC FRAMEWORKS; CARBON-DIOXIDE; ENERGY-TRANSFER; COMPLEXES; CATALYST; INTEGRATION; CHEMISTRY; DYNAMICS; MONOXIDE; HYDROGEN;

D O I：

10.1021/acsami.0c19856

中图分类号：

TB3 [工程材料学];

学科分类号：

0805 ; 080502 ;

摘要：

A porphyrinic metal-organic framework (PMOF) known as PCN-222(Zn) was chemically doped with a molecular Re(I) catalyst-bearing carboxylate anchoring group to form a new type of metal-organic framework (MOF)-Re(I) hybrid photocatalyst. The porphyrinic MOF-sensitized hybrid (PMOF/Re) was prepared with an archetypical CO2 reduction catalyst, (L)-Re-I(CO)(3)Cl (Re(I); L = 4,4'-dicarboxylic-2,2'-bipyridine), in the presence of 3 vol % water produced CO with no leveling-off tendency for 59 h to give a turnover number of >= 1893 [1070 +/- 80 mu mol h(-1) (g MOF)(-1)]. The high catalytic activity arises mainly from efficient exciton migration and funneling from photoexcited porphyrin linkers to the peripheral Re(I) catalytic sites, which is in accordance with the observed fast exciton (energy) migration (approximate to 1 ps) in highly ordered porphyrin photoreceptors and the effective funneling into Re(I) catalytic centers in the Re(I)-doped PMOF sample. Enhanced catalytic performance is convincingly supported by serial photophysical measurements including decisive Stern-Volmer interpretation.

引用

页码：2710 / 2722

页数：13

共 66 条

[41] PHOTOCHEMICAL GENERATION OF CARBON-MONOXIDE AND HYDROGEN BY REDUCTION OF CARBON-DIOXIDE AND WATER UNDER VISIBLE-LIGHT IRRADIATION [J].