巨正则密度泛函理论研究新型多孔BC4N纳米结构上光电催化氮气还原反应
Novel metal-free holey BC4N nanostructure for enhanced photoelectrocatalytic nitrogen reduction:insight from grand-canonical density functional theory
李允译 1安炜 1王艺博 1刘明明 1郭瑞娴 1史绪根 1代恩铎 1门勇1
作者信息
- 1. College of Chemistry and Chemical Engineering,Shanghai University of Engineering Science,Shanghai 201620,China
- 折叠
摘要
无金属类石墨烯结构碳基催化剂已被证明在促进光和电催化反应方面非常有效.在此,在恒电势模型(CPM)框架下,我们计算探索了所提出的新型二维BC4N结构的材料和催化性能,以促进光电催化(PEC)N2还原(NRR).结果表明,BC4N作为光电阴极能够高效地捕获可见光和紫外光,光生电子可以提供Ue=-1.07 V的电势,这足以克服在电解质水溶液中发生的PEC NRR的电势限制步骤.此外,还发现共吸附反应中间体在介导/促进NRR生成NH3方面起着重要作用.从头算分子动力学模拟表明,质子耦合电子转移可以与分子间氢转移发生相互作用,使NRR机制在原子尺度上更加复杂.我们还讨论了CPM和领域内广泛使用的恒电荷模型之间的潜在差异.本研究为无金属半导体材料近真实条件下驱动光辅助PEC NRR的工作机制提供了基本见解.
Abstract
The carbon-based metal-free catalysts with graphene-like structures have been demonstrated to be highly efficient in promoting both photocatalytic and electrocatalytic reactions.Here,in the framework of constant potential model(CPM),we computationally explore material and catalytic properties of the proposed novel two-dimensional BC4N structure for promoting the photoelectrocatalytic(PEC)N2 reduction reaction(NRR).The results reveal that BC4N as a photocathode exhibits high efficiency of harvesting visible light and ultraviolet light.The photogenerated electrons can deliver a potential of Ue=-1.07 V,sufficient to overcome the potential-limiting step in PEC NRR in continuum aqueous electrolyte solution.Moreover,it is found that the co-adsorbed reaction intermediates play an important role in mediating/facilitating the NRR towards NH3 formation.Ab-initio mole-cular dynamics simulations indicate that the proton-coupled electron transfer can interplay with the intermolecular hy-drogen transfer,leaving NRR mechanism even complicated at the atomic scale.The underlying disparity in CPM and the popular constant charge model was also discussed.This study provides fundamental insight into working mechanism of metal-free semiconducting materials driving photo-assisted PEC NRR under quasi-realistic conditions.
关键词
photoelectrocatalysis/N2 reduction/metal-free cata-lyst/grand-canonical density functional theory/constant poten-tial modelKey words
photoelectrocatalysis/N2 reduction/metal-free cata-lyst/grand-canonical density functional theory/constant poten-tial model引用本文复制引用
基金项目
国家自然科学基金(21673137)
国家自然科学基金(22179081)
Class ⅢPeak Discipline of Shanghai-Materials Science and Engineering(High-Energy Beam Intelligent Processing and Green Manuf()
DFT calculations were performed using resources of the Center for Functional Nanomaterials,which is a U.S.DOE Office of Scie()
Scientific Data and Computing Center()
Computational Science Initiative,at Brookhaven National Laboratory(DE-SC0012704)
出版年
2024
NETL
NSTL
万方数据