Potential-Dependent Free Energy Relationship in Interpreting theElectrochemical Performance of CO(2)Reduction on Single AtomCatalysts br

Cao, Hao1,2,3; Zhang, Zisheng4; Chen, Jie-Wei1,2,3; Wang, Yang-Gang1,2,3

2022-06-03

10.1021/acscatal.2c01470

ACS Catalysis   Impact Factor & Quartile

2155-5435

Acquiring the fundamental understanding ofelectrochemical processes occurring at the complex electrode-liquid interface is a grand challenge in catalysis. Herein, to gaintheoretical insights into the experimentally observed potential-dependent activity and selectivity for the CO2reduction reaction(CO2RR) on the popular single-iron-atom catalyst, we performedab initio molecular dynamics (AIMD) simulation, constrained MDsampling, and thermodynamic integration to acquire the freeenergy profiles for the proton and electron transfer processes ofCO2at different potentials. We have demonstrated that theadsorption of CO2is significantly coupled with the electrontransfer from the substrate while the further protonation does notshow distinct charge variation. This strongly suggests that CO2adsorption is potential-dependent and optimizing the electrodepotential is vital to achieve the efficient activated adsorption of CO2. We further identified a linear scaling relationship between thereaction free energy (Delta G) and the potential for key elementary steps of CO2RR and HER, of which the slope is adsorbate-specificand not as simple as 1 eV per volt as suggested by the traditional computational hydrogen electrode (CHE) model. The derivedscaling relationship can reproduce the experimental onset potential (Uonset)ofCO2RR, potential of the maximal CO2-to-CO Faradayefficiency (FECO), and potential where FECO=FEH2. This suggests that our state-of-the-art model could precisely interpret theactivity and selectivity of CO2RR/HER on the Fe-N4-C catalyst under different electrode potentials. In general, our study not onlyprovides an innovative insight into the theoretical explanation of the origin of the solvation effect from the perspective of chargetransfer but also emphasizes the critical role of electrode potential in the theoretical consideration of catalytic activity, which offers aprofound understanding of the electrochemical environment and bridges the gap between theoretical predictions and experimentalresults

ab initio molecular dynamics thermodynamic integration single-atom catalysis CO(2)electroreduction hydrogen evolution reaction potential-dependent reaction free energy

SCI ; EI

English

First ; Corresponding

NSFC of China[22022504] ; Guangdong "Pearl River" Talent Plan[2019QN01L353] ; Higher Education Innovation Strong School Project of Guangdong Province of China[2020KTSCX122] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002] ; Shenzhen Science and Technology Innovation Committee[ZDSYS20200421111001787]

Chemistry

Chemistry, Physical

WOS:000810516000031

AMER CHEMICAL SOC

20222712307369

Atoms ; Binary alloys ; Carbon dioxide ; Catalyst activity ; Catalyst selectivity ; Charge transfer ; Electrochemical electrodes ; Electron transitions ; Iron compounds ; Molecular dynamics ; Reaction kinetics

Thermodynamics:641.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Atomic and Molecular Physics:931.3

Web of Science

1.Southern Univ Sci & Technol, Shenzhen Key Lab Energy Chem, Shenzhen 518055, Peoples R China
2.Southern Univ Sci & Technol, Dept Chem, Shenzhen 518055, Guangdong, Peoples R China
3.Southern Univ Sci & Technol, Guangdong Prov Key Lab Catalysis, Shenzhen 518055, Guangdong, Peoples R China
4.Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

Cao, Hao,Zhang, Zisheng,Chen, Jie-Wei,et al. Potential-Dependent Free Energy Relationship in Interpreting theElectrochemical Performance of CO(2)Reduction on Single AtomCatalysts br[J]. ACS Catalysis,2022,12(11):6606-6617.

Cao, Hao,Zhang, Zisheng,Chen, Jie-Wei,&Wang, Yang-Gang.(2022).Potential-Dependent Free Energy Relationship in Interpreting theElectrochemical Performance of CO(2)Reduction on Single AtomCatalysts br.ACS Catalysis,12(11),6606-6617.

Cao, Hao,et al."Potential-Dependent Free Energy Relationship in Interpreting theElectrochemical Performance of CO(2)Reduction on Single AtomCatalysts br".ACS Catalysis 12.11(2022):6606-6617.