Critical Role of Explicit Inclusion of Solvent and Electrode Potential in the Electrochemical Description of Nitrogen Reduction

Qian，Sheng Jie1; Cao，Hao1; Chen，Jie Wei1; Chen，Jun Chi1; Wang，Yang Gang1; Li，Jun1,2

2022

10.1021/acscatal.2c03186

ACS Catalysis   Impact Factor & Quartile

2155-5435

2155-5435

The electrocatalytic nitrogen reduction reaction (NRR) is one of the most promising ways to achieve NH3 production at room temperature and pressure. However, there exists significant disagreement between the theoretically predicted potentials required for the NRR by the conventional quantum-theoretical calculations and those observed experimentally. Here, an explicit computational model incorporating the solvation effect and electrode potential has been proposed for NRR on single iron atoms supported on nitrogen-doped graphene. We find that the aqueous environment plays an essential role in NRR by promoting N2 adsorption, whereas the electrode potential impacts considerably on the electrode-electrolyte interface where NRR occurs. The constrained molecular dynamics (cMD) simulations and a thermodynamic integration method are used to explore the free energy profiles of N2 adsorption and the proton transfer process. The results are consistent with experimental observations, i.e., the NRR can take place at a relatively low electrode potential, thus revealing the critical role of the explicit inclusion of the solvation effect and electrode potential in computationally studying electrochemical reactions. With this approach, we have provided atomic-level mechanistic insights into the electrode-electrolyte interface for NRR through electrochemical catalysis.

ab initio molecular dynamics electrode potential N2electroreduction single-atom catalysis solvation effect

SCI

English

First ; Corresponding

National Natural Science Foundation of China (NSFC)["22022504","22033005"] ; 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]

Chemistry

Chemistry, Physical

WOS:000862265800001

AMER CHEMICAL SOC

2-s2.0-85138106003

Scopus

1.Department of Chemistry,Guangdong Provincial Key Laboratory of Catalytic Chemistry,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China
2.Department of Chemistry,Tsinghua University,Key Laboratory of Organic Optoelectronics and Molecular Engineering of Ministry of Education,Beijing,100084,China

Qian，Sheng Jie,Cao，Hao,Chen，Jie Wei,et al. Critical Role of Explicit Inclusion of Solvent and Electrode Potential in the Electrochemical Description of Nitrogen Reduction[J]. ACS Catalysis,2022,12(18):11530-11540.

Qian，Sheng Jie,Cao，Hao,Chen，Jie Wei,Chen，Jun Chi,Wang，Yang Gang,&Li，Jun.(2022).Critical Role of Explicit Inclusion of Solvent and Electrode Potential in the Electrochemical Description of Nitrogen Reduction.ACS Catalysis,12(18),11530-11540.

Qian，Sheng Jie,et al."Critical Role of Explicit Inclusion of Solvent and Electrode Potential in the Electrochemical Description of Nitrogen Reduction".ACS Catalysis 12.18(2022):11530-11540.