{"title":"A-Site Doping Promotes CO2 Activation and Prolongs Charge Carrier Lifetimes in SrTiO3: Insight from Quantum Dynamics.","authors":"Xiaodan Yan,Jinlu He","doi":"10.1021/acs.jpclett.4c02649","DOIUrl":null,"url":null,"abstract":"Using time-dependent density functional theory and nonadiabatic molecular dynamics, we systematically investigated the effect of A-site doping on the CO2 activation and charge carrier lifetimes in SrTiO3(STO). Our simulations revealed that A-site doping significantly enhances the chemical adsorption of CO2 on SrTiO3 surfaces, which is beneficial for promoting CO2 activation. Moreover, we found that A-site doping can efficiently stabilize the lowest unoccupied molecular orbital (LUMO) of CO2 near the conduction band minimum of STO, promoting the photogenerated electron transfer from the conduction band of STO to the CO2 LUMO. Importantly, A-site doping causes a significant nonadiabatic coupling reduction and prolongs the charge recombination time by a factor of 1.86 compared to the pristine STO. Our study clarifies the influencing mechanism of A-site doping on CO2 activation and charge carrier lifetimes and suggests important principles for the design of high-performance photocatalytic semiconductors.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":null,"pages":null},"PeriodicalIF":4.8000,"publicationDate":"2024-10-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry Letters","FirstCategoryId":"1","ListUrlMain":"https://doi.org/10.1021/acs.jpclett.4c02649","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Using time-dependent density functional theory and nonadiabatic molecular dynamics, we systematically investigated the effect of A-site doping on the CO2 activation and charge carrier lifetimes in SrTiO3(STO). Our simulations revealed that A-site doping significantly enhances the chemical adsorption of CO2 on SrTiO3 surfaces, which is beneficial for promoting CO2 activation. Moreover, we found that A-site doping can efficiently stabilize the lowest unoccupied molecular orbital (LUMO) of CO2 near the conduction band minimum of STO, promoting the photogenerated electron transfer from the conduction band of STO to the CO2 LUMO. Importantly, A-site doping causes a significant nonadiabatic coupling reduction and prolongs the charge recombination time by a factor of 1.86 compared to the pristine STO. Our study clarifies the influencing mechanism of A-site doping on CO2 activation and charge carrier lifetimes and suggests important principles for the design of high-performance photocatalytic semiconductors.
利用时变密度泛函理论和非绝热分子动力学,我们系统地研究了 A 位掺杂对 SrTiO3(STO)中二氧化碳活化和电荷载流子寿命的影响。模拟结果表明,A 位掺杂能显著增强 SrTiO3 表面对 CO2 的化学吸附,有利于促进 CO2 的活化。此外,我们还发现 A 位掺杂能有效地稳定 CO2 的最低未占分子轨道(LUMO),使其靠近 STO 的导带最小值,从而促进光生电子从 STO 的导带转移到 CO2 的 LUMO。重要的是,与原始 STO 相比,A 位掺杂导致非绝热耦合显著降低,电荷重组时间延长了 1.86 倍。我们的研究阐明了 A 位掺杂对二氧化碳活化和电荷载流子寿命的影响机制,并为设计高性能光催化半导体提出了重要原则。
期刊介绍:
The Journal of Physical Chemistry (JPC) Letters is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, chemical physicists, physicists, material scientists, and engineers. An important criterion for acceptance is that the paper reports a significant scientific advance and/or physical insight such that rapid publication is essential. Two issues of JPC Letters are published each month.