Density functional theory(DFT)calculations were employed to investigate the adsorption behavior of NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)molecules on both pristine and mono-vacancy phosphorene sheets.The pristine pho...Density functional theory(DFT)calculations were employed to investigate the adsorption behavior of NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)molecules on both pristine and mono-vacancy phosphorene sheets.The pristine phosphorene surface showsweak physisorption with all the gasmolecules,inducing onlyminor changes in its structural and electronic properties.However,the introduction ofmono-vacancies significantly enhances the interaction strength with NH_(3),PH_(3),CO_(2),and CH_(4).These variations are attributed to substantial charge redistribution and orbital hybridization in the presence of defects.The defective phosphorene sheet also exhibits enhanced adsorption energies,along with favorable sensitivity and recovery characteristics,highlighting its potential as a promising gas sensor for NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)at ambient conditions.展开更多
Exploring high-performance electrocatalysts for the nitrate reduction reaction(NO_(3)RR)is crucial for environmental nitrate removal and ammonia synthesis.Single-atom collaboration with cluster can provide sufficient ...Exploring high-performance electrocatalysts for the nitrate reduction reaction(NO_(3)RR)is crucial for environmental nitrate removal and ammonia synthesis.Single-atom collaboration with cluster can provide sufficient active sites for catalysts to promote NO_(3)RR,yet the unclear synergistic effect between the two hinders their rational design.Herein,a series of Ir_(3)clusters and metal single atoms co-embedded in graphitic carbon nitride(g-CN)catalysts(Ir_(3)M1)were constructed,and the synergistic effects of Ir_(3)clusters and M1 single atoms on the NO_(3)RR catalytic mechanism and activity were systematically explored using density functional theory(DFT)calculations combined with machine learning.Comprehensive evaluations of structural stability and catalytic activity demonstrate that the synergy between single atoms and clusters effectively balances the adsorption energies of key intermediates,yielding exceptional catalytic performance(the limiting potential of Ir_(3)Ti_(1)can reach−0.22 V).Machine learning models further clarify the synergistic mechanism,where the geometric configurations of clusters serve as critical features for modulating the catalytic activity of single-atom sites,whereas the electronic structures of single atoms directly govern the reactivity of cluster sites.This DFT-machine learning approach provides theoretical guidelines for catalyst design and a predictive framework for efficient NO_(3)RR electrocatalysts.展开更多
Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-inv...Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-invasive dual external field(DEF) approach combining solvent effects and an oriented external electric field(OEEF) to construct hyperhalogens,as demonstrated by density functional theory(DFT) calculations.Our DEF strategy proves versatile,successfully designing hyperhalogens not only in simplified Ag_n^(-) model systems but also in the experimentally synthesized Ag_(25) nanocluster.Using the 3D Ag_(19)^(-) structure as a model,we further reveal the DEF's pivotal role in O_(2) activation,where solvent-OEEF synergy induces tunable O-O bond elongation and charge transfer,proportional to field strength.Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition,providing a theoretical foundation for tailoring high-performance catalysts through precise activesite modulation.展开更多
A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescenc...A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.展开更多
采用密度泛函理论的M06-2X和MN15方法,研究了生理环境(水液相、1.013×10^(5)Pa、310.15 K)下双丙氨酸螯合二价钙[α-Ala_(2)→Ca^(2+),缩写:α-A_(2)→Ca^(2+)]消除羟基自由基(OH)的反应机理.研究发现,α-A_(2)→Ca^(2+)与OH的反...采用密度泛函理论的M06-2X和MN15方法,研究了生理环境(水液相、1.013×10^(5)Pa、310.15 K)下双丙氨酸螯合二价钙[α-Ala_(2)→Ca^(2+),缩写:α-A_(2)→Ca^(2+)]消除羟基自由基(OH)的反应机理.研究发现,α-A_(2)→Ca^(2+)与OH的反应有抽氢、加成和电子转移3个通道.势能面研究表明:OH与α-A2→Ca^(2+)的抽H反应自由能垒在13.2至56.8 k J/mol之间;OH与α-A_(2)→Ca^(2+)的加成反应自由能垒在61.0至66.2 kJ/mol之间;电子从α-A_(2)→Ca^(2+)向OH转移反应的自由能垒是179.0 k J/mol.结果表明,在生命体内α-A_(2)→Ca^(2+)可通过向OH提供H原子以及OH与C的加成过程消除OH,双丙氨酸螯合钙具有较好的清除羟自由基能力.展开更多
基金financial support to conduct this research from the Science and Engineering Research Board(SERB)through a state university research excellence(SURE)grant(SUR/2022/004935).
文摘Density functional theory(DFT)calculations were employed to investigate the adsorption behavior of NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)molecules on both pristine and mono-vacancy phosphorene sheets.The pristine phosphorene surface showsweak physisorption with all the gasmolecules,inducing onlyminor changes in its structural and electronic properties.However,the introduction ofmono-vacancies significantly enhances the interaction strength with NH_(3),PH_(3),CO_(2),and CH_(4).These variations are attributed to substantial charge redistribution and orbital hybridization in the presence of defects.The defective phosphorene sheet also exhibits enhanced adsorption energies,along with favorable sensitivity and recovery characteristics,highlighting its potential as a promising gas sensor for NH_(3),AsH_(3),PH_(3),CO_(2),and CH_(4)at ambient conditions.
基金the financial support from the Shandong Province colleges and universities youth innovation technology plan innovation team project(2022KJ285)the Natural Science Foundation of Shandong Province(ZR2022QE076)+1 种基金the National Natural Science Foundation of China(52202092)the Science and Technology Support Plan for Youth Innovation of Colleges and Universities of Shandong Province of China(2023KJ104).
文摘Exploring high-performance electrocatalysts for the nitrate reduction reaction(NO_(3)RR)is crucial for environmental nitrate removal and ammonia synthesis.Single-atom collaboration with cluster can provide sufficient active sites for catalysts to promote NO_(3)RR,yet the unclear synergistic effect between the two hinders their rational design.Herein,a series of Ir_(3)clusters and metal single atoms co-embedded in graphitic carbon nitride(g-CN)catalysts(Ir_(3)M1)were constructed,and the synergistic effects of Ir_(3)clusters and M1 single atoms on the NO_(3)RR catalytic mechanism and activity were systematically explored using density functional theory(DFT)calculations combined with machine learning.Comprehensive evaluations of structural stability and catalytic activity demonstrate that the synergy between single atoms and clusters effectively balances the adsorption energies of key intermediates,yielding exceptional catalytic performance(the limiting potential of Ir_(3)Ti_(1)can reach−0.22 V).Machine learning models further clarify the synergistic mechanism,where the geometric configurations of clusters serve as critical features for modulating the catalytic activity of single-atom sites,whereas the electronic structures of single atoms directly govern the reactivity of cluster sites.This DFT-machine learning approach provides theoretical guidelines for catalyst design and a predictive framework for efficient NO_(3)RR electrocatalysts.
基金supported by the National Natural Science Foundation of China (NSFC,Nos.12474274,92161101)the Innovation Project of Jinan Science and Technology Bureau(No.2021GXRC032)the Natural Science Foundation of Shandong Province (No.ZR2024MA091)。
文摘Traditional strategies for designing hyperhalogens,superatoms with exceptional electron-withdrawing capacity,rely on complex superhalogen assembly,posing significant experimental challenges.Here,we introduce a non-invasive dual external field(DEF) approach combining solvent effects and an oriented external electric field(OEEF) to construct hyperhalogens,as demonstrated by density functional theory(DFT) calculations.Our DEF strategy proves versatile,successfully designing hyperhalogens not only in simplified Ag_n^(-) model systems but also in the experimentally synthesized Ag_(25) nanocluster.Using the 3D Ag_(19)^(-) structure as a model,we further reveal the DEF's pivotal role in O_(2) activation,where solvent-OEEF synergy induces tunable O-O bond elongation and charge transfer,proportional to field strength.Our findings establish a field-driven paradigm for hyperhalogen design that preserves native cluster composition,providing a theoretical foundation for tailoring high-performance catalysts through precise activesite modulation.
文摘A series of blue and blue‑green Ir(Ⅲ)complexes has been investigated theoretically to explore their electronic structures,photophysical properties,efficiency roll‑off effect,and thermal activation delayed fluorescence(TADF)properties.All calculations were performed using density functional theory(DFT)and time‑dependent density functional theory(TDDFT).Calculations for electronic structures,frontier molecular orbital characteristics(which determine the efficiency roll‑off effect of the complexes),and photophysical properties were conducted using the Gaussian 09 software package.The calculation of spin‑orbit coupling matrix elements<T|HSOC|S>,which determine the TADF properties of the complexes,was performed using the ORCA software package.The calculation results show that the auxiliary ligand tetraphenylimidodiphosphinate(tpip),a strong electron‑withdrawing group,can mitigate the efficiency roll‑off effect of the complex.Furthermore,TADF is observed in one of the designed complexes,(F_(3)Phppy)_(2)Ir(tpip),where F_(3)Phppy=2‑[4‑(2,4,6‑trifluorophenyl)phenyl]pyridine.
文摘采用密度泛函理论的M06-2X和MN15方法,研究了生理环境(水液相、1.013×10^(5)Pa、310.15 K)下双丙氨酸螯合二价钙[α-Ala_(2)→Ca^(2+),缩写:α-A_(2)→Ca^(2+)]消除羟基自由基(OH)的反应机理.研究发现,α-A_(2)→Ca^(2+)与OH的反应有抽氢、加成和电子转移3个通道.势能面研究表明:OH与α-A2→Ca^(2+)的抽H反应自由能垒在13.2至56.8 k J/mol之间;OH与α-A_(2)→Ca^(2+)的加成反应自由能垒在61.0至66.2 kJ/mol之间;电子从α-A_(2)→Ca^(2+)向OH转移反应的自由能垒是179.0 k J/mol.结果表明,在生命体内α-A_(2)→Ca^(2+)可通过向OH提供H原子以及OH与C的加成过程消除OH,双丙氨酸螯合钙具有较好的清除羟自由基能力.
