Mechanistic study of efficient producing CO2 electroreduction via 2D metal-organic frameworks M3(2,3,6,7,10,11-hexaiminotriphenylene)2 surface

• Published in: Electrochimica acta Vol. 378; p. 138028
• Main Authors: Xiao, Yi, Chen, Dazhu, Chen, Rui
• Format: Journal Article
• Language: English
• Published: Oxford Elsevier Ltd 10.05.2021; Elsevier BV
• Subjects: Carbon dioxide; Catalysts; Catalytic activity; Chemical reduction; Co2 electroreduction; Electronic structure; Electrowinning; High throughput calculation; Hydrocarbon fuels; Metal-organic frameworks; Methane; Overpotential; Reaction mechanisms; Selectivity; Thermodynamics; Transition metals; Thermodynamics; Overpotential; High throughput calculation; Co2 electroreduction; Metal-organic frameworks
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2021.138028

M3(HITP)2 prototype 2D MOFs compounds possess a high catalytic activity for CO2 electroreduction to hydrocarbon fuels at low overpotentials. However, the mechanism path selectivity is still a huge challenge during the production of final product species at low potentials. The transition metal coordinated nitrogen active center of M3(HITP)2 catalysts is identified to strong M-C bound coupling, leading to a high selectivity towards CH3OH, Cr3(HITP)2, and Mn3(HITP)2. Further, it also demonstrates a high efficiency catalytic performance for generating CH4. In addition, linear scaling relations and volcano plot of thermodynamic stability are also investigated and compared, suggesting that some M3(HITP)2 compounds have effective selectivity performance to CO2 reduction reaction (CO2RR). Furthermore, linear scaling relationships and volcano plots between different intermediate species are common descriptors used to identity an excellent catalyst for CO2 electroreduction. In order to get a further exploration of the reaction mechanism pathway and final products for the CO2RR, authors considered all the intermediates. It showed that the most favorable reaction pathway and intermediate species can be determined by the metal-carbon (M-C) or metal-oxygen (M-O) bounds. The reduction of CO2 into CH4 with a high overpotential depends on the thermodynamic rate-determining step (RDS) of the largest limiting potential along the minimum energy path, the electronic structure of these catalysts also plays an important role in the selective CO2RR. [Display omitted]