H-Bond-Mediated Selectivity Control of Formate versus CO during CO2 Photoreduction with Two Cooperative Cu/X Sites.
J Am Chem Soc
; 143(16): 6114-6122, 2021 Apr 28.
Article
em En
| MEDLINE
| ID: mdl-33871997
ABSTRACT
It is highly desirable to achieve solar-driven conversion of CO2 to valuable fuels with controlled selectivity. The existing catalysts are mainly explored for CO production but rarely for formate generation. Herein, highly selective photoreduction of CO2 to formate (99.7%) was achieved with a high yield of 3040 µmol g-1 in 10 h by hierarchical integration of photosensitizers and monometallic [bpy-Cu/ClX] (X = Cl or adenine) catalysts into a stable Eu-bpy metal-organic framework. However, replacing X with pyridine in [bpy-CuCl/X] significantly reduced formate production while increasing the CO yield to 960 µmol g-1. Systematic investigations revealed that the catalytic process is mediated by the H-bond synergy between Cu-bound X and CO2-derived species, and the selectivity of HCOO- can be controlled by simply replacing the coordination ligands. This work provides a molecularly precise structural model to provide mechanistic insights for selectivity control of CO2 photoreduction.
Texto completo:
1
Base de dados:
MEDLINE
Idioma:
En
Ano de publicação:
2021
Tipo de documento:
Article