物理化学学报2024，Vol.40Issue(11)：45-46,2.DOI:10.3866/PKU.WHXB202407013
d带中心调控过渡金属单原子负载COF吸附O2的理论计算研究
d-Band Center Regulated O2 Adsorption on Transition Metal Single Atoms Loaded COF:A DFT Study
摘要
Abstract
Covalent organic framework(COF)materials are promising photocatalysts because of their fantastic structural and physicochemical features.To enhance photocatalytic performance,numerous metal single atoms(MSA)are loaded on COF to improve molecule adsorption.However,the inherent mechanisms and dominant factors of the heightened adsorption property are not deeply unveiled.Herein,four MSA-COF systems were constructed by severally introducing Fe,Co,Ni,and Cu single atoms in monolayer TpBpy-COF.The effect of various metal atoms modification on the electronic property and O2 adsorption of COF was investigated using density functional theory calculations.The results show that the metal atoms are bonded to the pyridinic N atoms,forming stable MSA-COF configurations.The anchoring of metal atoms reduces the band gap and raises the Fermi level of COF.Moreover,as the atomic number of the metals increases,the d orbitals of the metal atoms gradually move to lower energy levels,manifesting a negative shift of the d-band centers.After metal atoms loading,the weak physical adsorption of O2 on pristine COF is converted to robust chemisorption with the formation of M―Oads bonds and intense electron transfer.Intriguingly,the adsorption energy presents a strong correlation with the d-band centers of the metal atoms.This finding is comprehended from the perspective of electron occupancy in antibonding orbitals in the adsorption systems.This work provides a feasible approach for modifying molecule adsorption on MSA-COF by regulating the d-band centers of metal atoms.关键词
共价有机框架/金属单原子/O2吸附/d带中心/光催化Key words
Covalent organic framework/Metal single atom/O2 adsorption/d-band center/Photocatalysis分类
化学化工引用本文复制引用
谢斐,袁成成,谭海燕,Alireza Z.Moshfegh,朱必成,余家国..d带中心调控过渡金属单原子负载COF吸附O2的理论计算研究[J].物理化学学报,2024,40(11):45-46,2.基金项目
This work was supported by the National Key Research and Development Program of China(2022YFE0115900),the National Natural Science Foundation of China(52372294,22262012,22238009,52173065,and 22361142704),and the Natural Science Foundation of Hubei Province of China(2022CFA001).The project was also supported by the Fundamental Research Funds for the Central Universities,China University of Geosciences(Wuhan)(CUG22061). 国家重点研发计划(2022YFE0115900),国家自然科学基金(52372294,51932007,22238009,52173065,22361142704),湖北省自然科学基金(2022CFA001)和中央高校基本科研业务费专项资金,中国地质大学(武汉)(CUG22061)资助 （2022YFE0115900）
