Engineering Single-Atom Electrocatalysts for Enhancing Kinetics of Acidic Volmer Reaction

Cao，Hao1,2; Wang，Qilun3; Zhang，Zisheng4; Yan，Hui Min1,2; Zhao，Hongyan1,2; Yang，Hong Bin3; Liu，Bin3,5; Li，Jun6; Wang，Yang Gang1,2

2023-06-21

10.1021/jacs.2c13418

Journal of the American Chemical Society   Impact Factor & Quartile

0002-7863

1520-5126

The design of active and low-cost electrocatalyst for hydrogen evolution reaction (HER) is the key to achieving a clean hydrogen energy infrastructure. The most successful design principle of hydrogen electrocatalyst is the activity volcano plot, which is based on Sabatier principle and has been used to understand the exceptional activity of noble metal and design of metal alloy catalysts. However, this application of volcano plot in designing single-atom electrocatalysts (SAEs) on nitrogen doped graphene (TM/N4C catalysts) for HER has been less successful due to the nonmetallic nature of the single metal atom site. Herein, by performing ab initio molecular dynamics simulations and free energy calculations on a series of SAEs systems (TM/N4C with TM = 3d, 4d, or 5d metals), we find that the strong charge-dipole interaction between the negatively charged *H intermediate and the interfacial H2O molecules could alter the transition path of the acidic Volmer reaction and dramatically raise its kinetic barrier, despite its favorable adsorption free energy. Such kinetic hindrance is also experimentally confirmed by electrochemical measurements. By combining the hydrogen adsorption free energy and the physics of competing interfacial interactions, we propose a unifying design principle for engineering the SAEs used for hydrogen energy conversion, which incorporates both thermodynamic and kinetic considerations and allows going beyond the activity volcano model.

SCI

English

NI Journal Papers ; NI论文

First

NSFC of China["22102207","22022504"] ; Guangdong "Pearl River" Talent Plan[2019QN01L353] ; Shenzhen Science and Technology Program[JCYJ2021-03241036-08023] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry

Chemistry, Multidisciplinary

WOS:001008499500001

AMER CHEMICAL SOC

2-s2.0-85163919932

Scopus

1.Department of Chemistry,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China
2.Guangdong Provincial Key Laboratory of Catalysis,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China
3.School of Chemistry,Chemical Engineering and Biotechnology,Nanyang Technological University,Singapore,637459,Singapore
4.Department of Chemistry and Biochemistry,University of California,Los Angeles,90095,United States
5.Department of Materials Science and Engineering,City University of Hong Kong,999077,Hong Kong
6.Department of Chemistry,Tsinghua University,Beijing,100084,China

Cao，Hao,Wang，Qilun,Zhang，Zisheng,et al. Engineering Single-Atom Electrocatalysts for Enhancing Kinetics of Acidic Volmer Reaction[J]. Journal of the American Chemical Society,2023,145(24):13038-13047.

Cao，Hao.,Wang，Qilun.,Zhang，Zisheng.,Yan，Hui Min.,Zhao，Hongyan.,...&Wang，Yang Gang.(2023).Engineering Single-Atom Electrocatalysts for Enhancing Kinetics of Acidic Volmer Reaction.Journal of the American Chemical Society,145(24),13038-13047.

Cao，Hao,et al."Engineering Single-Atom Electrocatalysts for Enhancing Kinetics of Acidic Volmer Reaction".Journal of the American Chemical Society 145.24(2023):13038-13047.