Understanding the relationship between CO_(2) reduction reaction(CO_(2)RR)performance and surface terminations of MXenes is crucial for designing effective electrocatalysts.This study explores the impact of common ter...Understanding the relationship between CO_(2) reduction reaction(CO_(2)RR)performance and surface terminations of MXenes is crucial for designing effective electrocatalysts.This study explores the impact of common terminations on Mo_(2)CT_(x) using a computational hydrogen electrode(CHE)model integrated with a pseudo-microkinetic model(pseudo-MM).Unlike traditional CHE methods,CHE/pseudo-MM considers the energy differences of all steps,providing a comprehensive view of CO_(2)RR mechanisms while reducing computational cost generated from calculating transitional state.The electrolyte is considered as acetonitrile with 1-ethyl-3-methylimidazolium tetra-fluoroborate(EMIMBF_(4))to inhibit the generation of hydrogen.Theoretical predictions reveal surface terminations dictate the selectivity of C_(1) products,whose proton is provided by EMIMBF_(4).The selectivity for fully-F,-O-and-OH-terminated Mo_(2)CT_(x) surfaces varies with the applied potential,as confirmed by experiments.Electrochemical CO_(2)RR in acetonitrile with EMIMBF_(4) electrolyte confirms these predictions,showing that CH_(4) outperforms CO and gradually becomes the dominant product as the applied potential increases.These findings demonstrate the qualitative accuracy of the proposed CHE/pseudo-MM for predicting CO_(2)RR selectivity,particularly for gaseous products,over Mo_(2)CT_(x) systems.展开更多
基金support from Ministry of Education(MOE),Singapore(MOE2022-T1-RG8/22)support from the Singapore Ministry of Education AcRF Tier 2(MOE-MOET2EP10121-0006)and COE seed grant.
文摘Understanding the relationship between CO_(2) reduction reaction(CO_(2)RR)performance and surface terminations of MXenes is crucial for designing effective electrocatalysts.This study explores the impact of common terminations on Mo_(2)CT_(x) using a computational hydrogen electrode(CHE)model integrated with a pseudo-microkinetic model(pseudo-MM).Unlike traditional CHE methods,CHE/pseudo-MM considers the energy differences of all steps,providing a comprehensive view of CO_(2)RR mechanisms while reducing computational cost generated from calculating transitional state.The electrolyte is considered as acetonitrile with 1-ethyl-3-methylimidazolium tetra-fluoroborate(EMIMBF_(4))to inhibit the generation of hydrogen.Theoretical predictions reveal surface terminations dictate the selectivity of C_(1) products,whose proton is provided by EMIMBF_(4).The selectivity for fully-F,-O-and-OH-terminated Mo_(2)CT_(x) surfaces varies with the applied potential,as confirmed by experiments.Electrochemical CO_(2)RR in acetonitrile with EMIMBF_(4) electrolyte confirms these predictions,showing that CH_(4) outperforms CO and gradually becomes the dominant product as the applied potential increases.These findings demonstrate the qualitative accuracy of the proposed CHE/pseudo-MM for predicting CO_(2)RR selectivity,particularly for gaseous products,over Mo_(2)CT_(x) systems.
