Do the Hydrogen Evolution Reaction and Oxygen Reduction Reaction Really Need To Be Suppressed in O2-Tolerant CO2 Electroreduction Catalyzed by DAE-BPy-CoPor and Co-TAPP?

Authors:
Publisher website
Google Scholar
Abstract
This letter chooses DAE-BPy-CoPor [DAE, 1,2-bis(5'-formyl-2'-methylthien-3'-yl)cyclopentene; BPy, 2,2'-bipyridine-5,5'-dicarbaldehyde; and CoPor, two-dimensional cobalt porphyrin-based covalent organic framework] and Co-TAPP [10,15,20-tetrakis(4-aminophenyl)porphinatocobalt] as two model catalysts to investigate the effect of the hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) in the O2-tolerant CO2 electroreduction reaction (CO2RR). Both catalysts have been proven to have CO2RR activity at a potential range from -0.60 to -1.10 V when CO2 and O2 are co-feeding (Zhu, H.-J.; Si, D.-H.; Guo, H.; Chen, Z.; Cao, R.; Huang, Y.-B. Oxygen-tolerant CO2 electroreduction over covalent organic frameworks via photoswitching control oxygen passivation strategy. Nat. Commun. 2024, 15, 1479, DOI: 10.1038/s41467-024-45959-9). The calculated results by grand canonical density functional theory (GC-DFT) and microkinetic (MK) simulation show that the effect of HER could be categorized into two groups: (1) Positive *H formation energy: HER would have no effect on the turnover frequency (TOF) of the CO2RR. (2) Negative *H formation energy: HER would also have no effect to the TOF of CO2RR when the calculated limiting potential for HER is larger than that for CO2RR. Otherwise, all active sites would be covered by *H and poisoned before CO2RR can happen. The effect of ORR could be categorized into three types: (1) ORR would have no effect to the TOF of the CO2RR when ORR happened with the CO2RR at the same time. (2) ORR is suppressed; the active site is covered by an intermediate state (such as *OH); and the CO2RR is also suppressed because of the poisoned active site. (3) ORR is suppressed; the active site is not covered; and the TOF of the CO2RR is not affected.
Funding Information
  • National Key Research and Development Program of China (2022YFB3603001)
  • National Natural Science Foundation of China (22120102005)

This publication has 28 references indexed in Scilit: