Accelerating Charge Kinetics in Photocatalytic CO2 Reduction by Modulating the Cobalt Coordination in Heterostructures of Cadmium Sulfide/Metal–Organic Layer

Artificial photocatalytic CO2 reduction (CO2R) holds great promise to directly store solar energy into chemical bonds. The slow charge and mass transfer kinetics at the triphasic solid–liquid–gas interface calls for the rational design of heterogeneous photocatalysts concertedly boosting interfacial...

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Published in:Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-07, Vol.20 (28), p.e2312020-n/a
Main Authors: Su, Yanhui, Mu, Qiaoqiao, Fan, Ningbo, Wei, Zhihe, Pan, Weiyi, Zheng, Zhangyi, Song, Daqi, Sun, Hao, Lian, Yuebin, Xu, Bin, Yang, Wenjun, Deng, Zhao, Peng, Yang
Format: Article
Language:English
Subjects:
Cadmium sulfide
Carbon dioxide
Carbon dioxide concentration
Catalytic activity
CdS/MOL heterostructures
charge kinetics
Charge transfer
Chemical bonds
Cobalt
Coordination
Energy bands
Heterostructures
Kinetics
Mass transfer
metal–organic layers
Photocatalysis
Photocatalysts
photocatalytic CO2 reduction
Solar energy
Transition metals
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Summary:Artificial photocatalytic CO2 reduction (CO2R) holds great promise to directly store solar energy into chemical bonds. The slow charge and mass transfer kinetics at the triphasic solid–liquid–gas interface calls for the rational design of heterogeneous photocatalysts concertedly boosting interfacial charge transfer, local CO2 concentration, and exposure of active sites. To meet these requirements, in this study heterostructures of CdS/MOL (MOL = metal–organic layer) furnishing different redox Co sites are fabricated for CO2R photocatalysts. It is found that the coordination environment of Co is key to photocatalytic activity. The best catalyst ensemble comprising ligand‐chelated Co2+ with the bipyridine electron mediator demonstrates a high CO yield rate of 1523 µmol h−1 gcat−1, selectivity of 95.8% and TON of 1462.4, which are ranked among the best seen in literature. Comprehensive photochemical and electroanalytical characterizations attribute the high CO2R performance to the improved photocarrier separation and charge kinetics originated from the proper energy band alignment and coordination chemistry. This work highlights the construction of 2D heterostructures and modulation of transition metal coordination to expedite the charge kinetics in photocatalytic CO2 reduction. CdS/MOL (MOL = metal–organic layer) heterostructures with single‐atomic Co2+ selectively anchored on O or N sites are fabricated for photocatalytic CO2 reduction. It is demonstrated that such modulation of cobalt coordination effectively altered the charge kinetics via the perturbation to the electronic band structure.
ISSN:1613-6810
1613-6829
1613-6829
DOI:10.1002/smll.202312020