首页|p-d Orbital Hybridization Engineered Single-Atom Catalyst for Electrocatalytic Ammonia Synthesis

p-d Orbital Hybridization Engineered Single-Atom Catalyst for Electrocatalytic Ammonia Synthesis

扫码查看
原文链接
  • NETL
  • NSTL
  • 万方数据
The rational design of metal single-atom catalysts(SACs)for electrochemical nitrogen reduction reaction(NRR)is challenging.Two-dimensional metal-organic frameworks(2DMOFs)is a unique class of promising SACs.Up to now,the roles of individual metals,coordination atoms,and their synergy effect on the electroanalytic performance remain unclear.Therefore,in this work,a series of 2DMOFs with different metals and coordinating atoms are systematically investigated as electrocatalysts for ammonia synthesis using density functional theory calculations.For a specific metal,a proper metal-intermediate atoms p-d orbital hybridization interaction strength is found to be a key indicator for their NRR catalytic activities.The hybridization interaction strength can be quantitatively described with the p-/d-band center energy difference(Δd-p),which is found to be a sufficient descriptor for both the p-d hybridization strength and the NRR performance.The maximum free energy change(ΔGmax)and Δd-p have a volcanic relationship with OsC4(Se)4 located at the apex of the volcanic curve,showing the best NRR performance.The asymmetrical coordination environment could regulate the band structure subtly in terms of band overlap and positions.This work may shed new light on the application of orbital engineering in electrocatalytic NRR activity and especially promotes the rational design for SACs.

first-principle calculationsNitrogen reductionp-d orbital hybridizationsingle-atom catalysts

Jingkun Yu、Xue Yong、Siyu Lu

展开 >

Green Catalysis Center,and College of Chemistry,Zhengzhou University,Zhengzhou 450001,China

Department of Chemistry,University of Sheffield,SheffieldS37HF,UK

National Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNational Natural Science Foundation of ChinaNatural Science Foundation of HenanNational Supercomputing Center in Zhengzhou

219052535197320052122308202300410372

2024

10.1002/eem2.12587

能源与环境材料(英文)

能源与环境材料(英文)

ISSN：
年,卷(期)：2024.7(2)