{"title":"Capture-Intensified Electrocatalytic Reduction of Postcombustion CO2 in Transporting and Catalytic Channels of Covalent Organic Frameworks","authors":"Guojuan Liu, Xuewen Li, Minghao Liu, Shuai Yang, Xiubei Yang, Xinqing Chen, Wei Wei*, Qing Xu* and Gaofeng Zeng*, ","doi":"10.1021/acscatal.4c01720","DOIUrl":null,"url":null,"abstract":"<p >Covalent organic frameworks (COFs) have been employed for electrochemical carbon dioxide reduction (CO<sub>2</sub>RR) due to the high degree of molecular controllability. However, catalysis of the CO<sub>2</sub>RR in dilute CO<sub>2</sub> conditions is hardly achieved because of the lacking ability of trapping and then transporting CO<sub>2</sub> to catalytic sites in low-concentration CO<sub>2</sub>. In this work, we have achieved catalysis of the CO<sub>2</sub>RR under simulated flue gas (CO<sub>2</sub>/N<sub>2</sub> = 15/85, at 298 K) by constructing CO<sub>2</sub>-trapping and -transporting channels to the catalytic centers of COFs. With decorating phytic acid (PA) along the pores, the selective capture and transport ability of CO<sub>2</sub> along the pore channels was significantly improved, and the superficial molecular H<sub>2</sub>O close to the catalytic sites was also efficient bound. The optimized catalyst (PA-Co-COF) achieved a Faradaic efficiency for CO of 86.97% at −0.7 V and a maximum turnover frequency of 1208.8 h<sup>–1</sup> at −1.0 V in simulated flue gas, which were 152 and 710% of those from a catalyst with bare channels. The molecular dynamics simulations and theoretical calculation revealed that PA not only promoted CO<sub>2</sub> diffusion across the porous channels but also accelerated the formation of the intermediate COOH* and simulated the suppression of the competing hydrogen evolution reaction in the catalytic process, which contributed to higher activity and selectivity.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":11.3000,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acscatal.4c01720","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Covalent organic frameworks (COFs) have been employed for electrochemical carbon dioxide reduction (CO2RR) due to the high degree of molecular controllability. However, catalysis of the CO2RR in dilute CO2 conditions is hardly achieved because of the lacking ability of trapping and then transporting CO2 to catalytic sites in low-concentration CO2. In this work, we have achieved catalysis of the CO2RR under simulated flue gas (CO2/N2 = 15/85, at 298 K) by constructing CO2-trapping and -transporting channels to the catalytic centers of COFs. With decorating phytic acid (PA) along the pores, the selective capture and transport ability of CO2 along the pore channels was significantly improved, and the superficial molecular H2O close to the catalytic sites was also efficient bound. The optimized catalyst (PA-Co-COF) achieved a Faradaic efficiency for CO of 86.97% at −0.7 V and a maximum turnover frequency of 1208.8 h–1 at −1.0 V in simulated flue gas, which were 152 and 710% of those from a catalyst with bare channels. The molecular dynamics simulations and theoretical calculation revealed that PA not only promoted CO2 diffusion across the porous channels but also accelerated the formation of the intermediate COOH* and simulated the suppression of the competing hydrogen evolution reaction in the catalytic process, which contributed to higher activity and selectivity.
期刊介绍:
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.