TY - JOUR
T1 - Designing N-Confused Metalloporphyrin-Based Covalent Organic Frameworks for Enhanced Electrocatalytic Carbon Dioxide Reduction
AU - Ren, Zhixin
AU - Zhao, Bo
AU - Xie, Jing
N1 - Publisher Copyright:
© 2023 Wiley-VCH GmbH.
PY - 2023/8/16
Y1 - 2023/8/16
N2 - Electrochemical conversion of carbon dioxide (CO2) into value-added products is promising to alleviate greenhouse gas emission and energy demands. Metalloporphyrin-based covalent organic frameworks (MN4-Por-COFs) provide a platform for rational design of electrocatalyst for CO2 reduction reaction (CO2RR). Herein, through systematic quantum-chemical studies, the N-confused metallo-Por-COFs are reported as novel catalysts for CO2RR. For MN4-Por-COFs, among the ten 3d metals, M = Co/Cr stands out in catalyzing CO2RR to CO or HCOOH; hence, N-confused Por-COFs with Co/CrN3C1 and Co/CrN2C2 centers are designed. Calculations indicate CoNxCy-Por-COFs exhibit lower limiting potential (−0.76 and -0.60 V) for CO2-to-CO reduction than its parent CoN4-Por-COFs (−0.89 V) and make it feasible to yield deep-reduction degree C1 products CH3OH and CH4. Electronic structure analysis reveals that substituting CoN4 to CoN3C1/CoN2C2 increases the electron density on Co-atom and raises the d-band center, thus stabilizing the key intermediates of the potential determining step and lowering the limiting potential. For similar reason, changing the core from CrN4 to CrN3C1/CrN2C2 lowers the limiting potential for CO2-to-HCOOH reduction. This work predicts N-confused Co/CrNxCy-Por-COFs to be high-performance CO2RR catalyst candidates. Inspiringly, as a proof-of-concept study, it provides an alternative strategy for coordination regulation and theoretical guidelines for rational design of catalysts.
AB - Electrochemical conversion of carbon dioxide (CO2) into value-added products is promising to alleviate greenhouse gas emission and energy demands. Metalloporphyrin-based covalent organic frameworks (MN4-Por-COFs) provide a platform for rational design of electrocatalyst for CO2 reduction reaction (CO2RR). Herein, through systematic quantum-chemical studies, the N-confused metallo-Por-COFs are reported as novel catalysts for CO2RR. For MN4-Por-COFs, among the ten 3d metals, M = Co/Cr stands out in catalyzing CO2RR to CO or HCOOH; hence, N-confused Por-COFs with Co/CrN3C1 and Co/CrN2C2 centers are designed. Calculations indicate CoNxCy-Por-COFs exhibit lower limiting potential (−0.76 and -0.60 V) for CO2-to-CO reduction than its parent CoN4-Por-COFs (−0.89 V) and make it feasible to yield deep-reduction degree C1 products CH3OH and CH4. Electronic structure analysis reveals that substituting CoN4 to CoN3C1/CoN2C2 increases the electron density on Co-atom and raises the d-band center, thus stabilizing the key intermediates of the potential determining step and lowering the limiting potential. For similar reason, changing the core from CrN4 to CrN3C1/CrN2C2 lowers the limiting potential for CO2-to-HCOOH reduction. This work predicts N-confused Co/CrNxCy-Por-COFs to be high-performance CO2RR catalyst candidates. Inspiringly, as a proof-of-concept study, it provides an alternative strategy for coordination regulation and theoretical guidelines for rational design of catalysts.
KW - N-confused metalloporphyrins
KW - carbon dioxide reduction
KW - covalent organic frameworks
KW - density functional theory calculations
KW - electrocatalytic
UR - http://www.scopus.com/inward/record.url?scp=85151485513&partnerID=8YFLogxK
U2 - 10.1002/smll.202301818
DO - 10.1002/smll.202301818
M3 - Article
AN - SCOPUS:85151485513
SN - 1613-6810
VL - 19
JO - Small
JF - Small
IS - 33
M1 - 2301818
ER -