Prognostication of two-dimensional transition-metal atoms embedded rectangular tetrafluorotetracyanoquinodimethane single-atom catalysts for high-efficiency electrochemical nitrogen reduction

Sheng-Yao Lv; Guoliang Li; Li-Ming Yang

doi:10.1016/j.jcis.2022.04.005

Prognostication of two-dimensional transition-metal atoms embedded rectangular tetrafluorotetracyanoquinodimethane single-atom catalysts for high-efficiency electrochemical nitrogen reduction

J Colloid Interface Sci. 2022 Sep:621:24-32. doi: 10.1016/j.jcis.2022.04.005. Epub 2022 Apr 8.

Authors

Sheng-Yao Lv¹, Guoliang Li², Li-Ming Yang³

Affiliations

¹ MOE Key Laboratory of Theoretical Chemistry of Environment, School of Chemistry, South China Normal University, Guangzhou 510006, China; Center for Computational Quantum Chemistry, School of Chemistry, South China Normal University, Guangzhou 510006, China; Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica, Wuhan 430074, China; Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Wuhan 430074, China; Hubei Key Laboratory of Materials Chemistry and Service Failure, Wuhan 430074, China; Hubei Engineering Research Center for Biomaterials and Medical Protective Materials, Wuhan 430074, China; School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
² MOE Key Laboratory of Theoretical Chemistry of Environment, School of Chemistry, South China Normal University, Guangzhou 510006, China; Center for Computational Quantum Chemistry, School of Chemistry, South China Normal University, Guangzhou 510006, China. Electronic address: glli@scnu.edu.cn.
³ Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica, Wuhan 430074, China; Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Wuhan 430074, China; Hubei Key Laboratory of Materials Chemistry and Service Failure, Wuhan 430074, China; Hubei Engineering Research Center for Biomaterials and Medical Protective Materials, Wuhan 430074, China; School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China. Electronic address: Lmyang@hust.edu.cn.

PMID: 35447519
DOI: 10.1016/j.jcis.2022.04.005

Abstract

Extensive investigations on the electrocatalytic nitrogen reduction reactions (eNRR) and the high-efficiency single-atom catalysts (SACs) have increasingly given us confidence in intensive arrival of nitrogen (N₂) fixation into ammonia (NH₃) under ambient conditions in the future, which prompts us to speed up the exploration for highly active SACs for eNRR. Excellent SACs in eNRR should have three advantages: high selectivity, low overpotential, and high stability. Based on these aspects, we employed high-throughput screening method and first-principles calculations to study the catalytic performance of 30 transition-metal atoms (TMs) embedded rectangular tetrafluorotetracyanoquinodimethane (denoted as TM-rF₄TCNQ) monolayers (TM = 3d, 4d, and 5d series transition metal atoms) for the eNRR process, and four potential catalysts, i.e., Ti-, Mo-, Nb-, and Tc-rF₄TCNQ, were obtained. Among them, Ti-rF₄TCNQ catalyzing the N₂ reduction to NH₃ through an enzymatic mechanism needs a theoretical onset potential of only -0.41 V. When Mo-rF₄TCNQ catalyzes eNRR through a distal mechanism, the theoretical onset potential is as low as -0.43 V. The band structures show that these materials are all metallic, ensuring good charge transport during the eNRR process. Analyzing the projected density of states (PDOSs) before and after N₂ adsorption, the differential charge density, and the spin density reveals that the Ti-, Mo-, Nb-, and Tc-rF₄TCNQ monolayers all can effectively adsorb and activate inert N₂, which may be mainly attributed to the "acceptance-donation" interaction between TM and N₂.

Keywords: 2D TM-rF(4)TCNQ monolayers; Electrocatalytic nitrogen reduction reaction; First-principles calculations; High-throughput screening; Single-atom catalysts.

MeSH terms

Adsorption
Ammonia*
Catalysis
Nitrogen* / chemistry

Substances

Ammonia
Nitrogen