In molybdenum chemistry,the oxidative addition of o-quinone or 1,2-dicarbonyl compounds to molybdenum has been widely used in Mo-catalyzed C—C bond construction.The carbonyl oxidative addition to Mo(0)or Mo(Ⅱ)is the...In molybdenum chemistry,the oxidative addition of o-quinone or 1,2-dicarbonyl compounds to molybdenum has been widely used in Mo-catalyzed C—C bond construction.The carbonyl oxidative addition to Mo(0)or Mo(Ⅱ)is the critical elementary reaction of molybdenum catalysis.However,the relevant density functional theory(DFT)studies are relatively scarce,especially regarding the rational selection of functionals.In this work,14 functionals were employed to investigate the Mo-catalyzed carbonyl oxidative addition step.A benchmark study was carried out to evaluate their performance in structure optimization and energy calculation.Analyses of mean absolute error(MAE)and mean squared error(MSE)indicated that the B3LYP-D3(BJ),TPSSh,and ωB97X-D functionals exhibited superior performance in structure optimization.Using the DLPNO-CCSD(T)functional as the reference,the M06,M06-L,and MN15-L functionals exhibited good performance for energy calculation based on the structures optimized using the B3LYP-D3(BJ)functional.In particular,MN15-L provided the best performance with the smallest MAE and MSE.展开更多
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
N,N,N',N'-tetraoctyl diglycolamide(TODGA)is a potential extractant for the co-extraction of lanthanides and actinides in high-level liquid waste.In this study,the radiolysis and extraction properties of TODGA ...N,N,N',N'-tetraoctyl diglycolamide(TODGA)is a potential extractant for the co-extraction of lanthanides and actinides in high-level liquid waste.In this study,the radiolysis and extraction properties of TODGA in kerosene solvents contacted with the aqueous phase of varying HNO_(3) concentrations were systematically investigated,and the complexation mechanism was analyzed in conjunction with density functional theory(DFT)calculations.After γ-irradiation,the variation of TODGA concentration was detected,and the variation trends in the relative content of radiolysis products(RPs)with sample type and absorbed dose were demonstrated.Results indicated that the breaking of the amide bond,ether bond,and C_(amide)-C_(ether)bond was the primary radiolysis routes.The aqueous-phase precipitate was studied as a potential new mode of TODGA radiolysis in ultrapure water aqueous phase.Moreover,TODGA/kerosene exhibited excellent extraction capabilities for lanthanides even after absorbing 100 kGy,and HNO_(3) can maintain a portion of TODGA's extraction capacity.The DFT method was applied to calculate and evaluate the complexing ability of TODGA and some of its RPs toward lanthanides.The results revealed that the complexing ability of TODGA for Ce(Ⅲ),Eu(Ⅲ),and Dy(Ⅲ)was enhanced successively,and the complexing ability of the RPs with intact oxygen-containing structures could not be neglected.展开更多
Machine learning(ML)is recognized as a potent tool for the inverse design of environmental functional material,particularly for complex entities like biochar-based catalysts(BCs).Thus,the tailored BCs can have a disti...Machine learning(ML)is recognized as a potent tool for the inverse design of environmental functional material,particularly for complex entities like biochar-based catalysts(BCs).Thus,the tailored BCs can have a distinct ability to trigger the nonradical pathway in advance oxidation processes(AOPs),promising a stable,rapid and selective degradation of persistent contaminants.However,due to the inherent“black box”nature and limitations of input features,results and conclusions derived from ML may not always be intuitively understood or comprehensively validated.To tackle this challenge,we linked the front-point interpretable analysis approaches with back-point density functional theory(DFT)calculations to form a chained learning strategy for deeper sight into the intrinsic activation mechanism of BCs in AOPs.At the front point,we conducted an easy-to-interpret meta-analysis to validate two strategies for enhancing nonradical pathways by increasing oxygen content and specific surface area(SSA),and prepared oxidized biochar(OBC500)and SSA-increased biochar(SBC900)by controlling pyrolysis conditions and modification methods.Subsequently,experimental results showed that OBC500 and SBC900 had distinct dominant degradation pathways for 1O2 generation and electron transfer,respectively.Finally,at the end point,DFT calculations revealed their active sites and degradation mechanisms.This chained learning strategy elucidates fundamental principles for BC inverse design and showcases the exceptional capacity to integrate computational techniques to accelerate catalyst inverse design.展开更多
Excessive phosphorus and arsenic in water bodies not only destroy ecosystems but also pose a serious threat to human health.In this study,a series of Al-doped modified metal-organic frameworks(Zr-Al-MOF)were prepared ...Excessive phosphorus and arsenic in water bodies not only destroy ecosystems but also pose a serious threat to human health.In this study,a series of Al-doped modified metal-organic frameworks(Zr-Al-MOF)were prepared by solvothermal method,which achieved efficient removal of phosphate and arsenate in water.Due to the use of inexpensive Al salts,the material has a lower cost and is more economical.The molar ratio of metal salts,adsorption time,solution pH,initial concentration,temperature and coexisting anions were studied,and it was found that when the molar ratio of Zr:Al was 2,Zr-Al-MOF had the best adsorption performance for phosphate and arsenate,and the maximum adsorption capacity was 93.04 mg P/g and 173.83 mg As/g,respectively.It traps phosphate and arsenate at a fast reaction rate and can be recycled repeatedly.In addition,0.15 g/L of 2Zr-Al-MOF can effectively reduce the phosphate and arsenate content in the contaminated spring water samples of Yangzonghai Lake to the standard range of drinking water,which further confirms the application potential of 2Zr-Al-MOF.By FT-IR and XPS analysis,it was found that the adsorption mechanism was ligand exchange,electrostatic attraction and hydrogen bond formation.The theoretical calculation shows that the adsorption energy is negative,which indicates that 2Zr-Al-MOF is attractive to phosphate and arsenate,and the adsorption state is stable.The results show that 2Zr-Al-MOF is an effective phosphate and arsenate adsorbent and has broad application prospects in eutrophication water treatment.展开更多
Efficient surface passivation is critical for achieving high-performance perovskite solar cells(PSCs),yet the discovery of optimal passivators remains a time-consuming,trial-and-error process.Here,we report a synergis...Efficient surface passivation is critical for achieving high-performance perovskite solar cells(PSCs),yet the discovery of optimal passivators remains a time-consuming,trial-and-error process.Here,we report a synergistic machine learning(ML)and density functional theory(DFT)approach that enables predictive and rapid identification of effective passivation materials.By training an XGBoost model(91.3%accuracy)with DFT-derived molecular descriptors and activity calculations,we identify 2-(4-aminophenyl)-3H-benzimidazol-5-amine(APBIA)as a promising passivator.Experimental validation demonstrates that APBIA effectively removes surface impurities and passivates defects within perovskite films,leading to a significant increase in power conversion efficiency(PCE)from 22.48%to 25.55%(certified as 25.02%).This ML-DFT framework provides a generalizable pathway for accelerating the development of advanced functional materials for photovoltaic applications.展开更多
为了提升DFT-S-OFDM系统在瑞利信道下的传输性能,采用位交织编码调制迭代译码方案(BICM-ID)、旋转映射(R-QAM)和Turbo码等技术,设计了基于Turbo-BICM-ID的DFT-S-OFDM系统。给出了系统原理框图,对编码调制系统的解调译码迭代算法进行了推...为了提升DFT-S-OFDM系统在瑞利信道下的传输性能,采用位交织编码调制迭代译码方案(BICM-ID)、旋转映射(R-QAM)和Turbo码等技术,设计了基于Turbo-BICM-ID的DFT-S-OFDM系统。给出了系统原理框图,对编码调制系统的解调译码迭代算法进行了推导,对系统进行了Matlab仿真验证。仿真结果表明,与传统的卷积码设计方案相比,该设计方案在误码率为10-5时,可以获得5.7 d B的增益改善,同时可以获得更低的错误平层,有效地改善了DFT-S-OFDM系统在瑞利信道下的性能。展开更多
基金Project supported by the Fundamental Research Funds for the Central Universities(No.2042025kf0052)。
文摘In molybdenum chemistry,the oxidative addition of o-quinone or 1,2-dicarbonyl compounds to molybdenum has been widely used in Mo-catalyzed C—C bond construction.The carbonyl oxidative addition to Mo(0)or Mo(Ⅱ)is the critical elementary reaction of molybdenum catalysis.However,the relevant density functional theory(DFT)studies are relatively scarce,especially regarding the rational selection of functionals.In this work,14 functionals were employed to investigate the Mo-catalyzed carbonyl oxidative addition step.A benchmark study was carried out to evaluate their performance in structure optimization and energy calculation.Analyses of mean absolute error(MAE)and mean squared error(MSE)indicated that the B3LYP-D3(BJ),TPSSh,and ωB97X-D functionals exhibited superior performance in structure optimization.Using the DLPNO-CCSD(T)functional as the reference,the M06,M06-L,and MN15-L functionals exhibited good performance for energy calculation based on the structures optimized using the B3LYP-D3(BJ)functional.In particular,MN15-L provided the best performance with the smallest MAE and MSE.
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.
文摘N,N,N',N'-tetraoctyl diglycolamide(TODGA)is a potential extractant for the co-extraction of lanthanides and actinides in high-level liquid waste.In this study,the radiolysis and extraction properties of TODGA in kerosene solvents contacted with the aqueous phase of varying HNO_(3) concentrations were systematically investigated,and the complexation mechanism was analyzed in conjunction with density functional theory(DFT)calculations.After γ-irradiation,the variation of TODGA concentration was detected,and the variation trends in the relative content of radiolysis products(RPs)with sample type and absorbed dose were demonstrated.Results indicated that the breaking of the amide bond,ether bond,and C_(amide)-C_(ether)bond was the primary radiolysis routes.The aqueous-phase precipitate was studied as a potential new mode of TODGA radiolysis in ultrapure water aqueous phase.Moreover,TODGA/kerosene exhibited excellent extraction capabilities for lanthanides even after absorbing 100 kGy,and HNO_(3) can maintain a portion of TODGA's extraction capacity.The DFT method was applied to calculate and evaluate the complexing ability of TODGA and some of its RPs toward lanthanides.The results revealed that the complexing ability of TODGA for Ce(Ⅲ),Eu(Ⅲ),and Dy(Ⅲ)was enhanced successively,and the complexing ability of the RPs with intact oxygen-containing structures could not be neglected.
基金supported by Project of National and Local Joint Engineering Research Center for Biomass Energy Development and Utilization(Harbin Institute of Technology,No.2021A004).
文摘Machine learning(ML)is recognized as a potent tool for the inverse design of environmental functional material,particularly for complex entities like biochar-based catalysts(BCs).Thus,the tailored BCs can have a distinct ability to trigger the nonradical pathway in advance oxidation processes(AOPs),promising a stable,rapid and selective degradation of persistent contaminants.However,due to the inherent“black box”nature and limitations of input features,results and conclusions derived from ML may not always be intuitively understood or comprehensively validated.To tackle this challenge,we linked the front-point interpretable analysis approaches with back-point density functional theory(DFT)calculations to form a chained learning strategy for deeper sight into the intrinsic activation mechanism of BCs in AOPs.At the front point,we conducted an easy-to-interpret meta-analysis to validate two strategies for enhancing nonradical pathways by increasing oxygen content and specific surface area(SSA),and prepared oxidized biochar(OBC500)and SSA-increased biochar(SBC900)by controlling pyrolysis conditions and modification methods.Subsequently,experimental results showed that OBC500 and SBC900 had distinct dominant degradation pathways for 1O2 generation and electron transfer,respectively.Finally,at the end point,DFT calculations revealed their active sites and degradation mechanisms.This chained learning strategy elucidates fundamental principles for BC inverse design and showcases the exceptional capacity to integrate computational techniques to accelerate catalyst inverse design.
基金supported by the NSFC-Yunnan Joint Fund(No.U2102210)the National Natural Science Foundation of China(No.22168044)+1 种基金Yunnan Provincial Department of Science and Technology(No.202201BF070001-013)the Research Innovation Fund for Graduate Students of Yunnan University(No.KC-23234004).
文摘Excessive phosphorus and arsenic in water bodies not only destroy ecosystems but also pose a serious threat to human health.In this study,a series of Al-doped modified metal-organic frameworks(Zr-Al-MOF)were prepared by solvothermal method,which achieved efficient removal of phosphate and arsenate in water.Due to the use of inexpensive Al salts,the material has a lower cost and is more economical.The molar ratio of metal salts,adsorption time,solution pH,initial concentration,temperature and coexisting anions were studied,and it was found that when the molar ratio of Zr:Al was 2,Zr-Al-MOF had the best adsorption performance for phosphate and arsenate,and the maximum adsorption capacity was 93.04 mg P/g and 173.83 mg As/g,respectively.It traps phosphate and arsenate at a fast reaction rate and can be recycled repeatedly.In addition,0.15 g/L of 2Zr-Al-MOF can effectively reduce the phosphate and arsenate content in the contaminated spring water samples of Yangzonghai Lake to the standard range of drinking water,which further confirms the application potential of 2Zr-Al-MOF.By FT-IR and XPS analysis,it was found that the adsorption mechanism was ligand exchange,electrostatic attraction and hydrogen bond formation.The theoretical calculation shows that the adsorption energy is negative,which indicates that 2Zr-Al-MOF is attractive to phosphate and arsenate,and the adsorption state is stable.The results show that 2Zr-Al-MOF is an effective phosphate and arsenate adsorbent and has broad application prospects in eutrophication water treatment.
基金supported by the National Key Research and Development Program of China (Grant No. 2024YFB4205101)the National Natural Science Foundation of China (No. 62274098 and No. 62074084)+2 种基金the Natural Science Foundation of Tianjin (No.22JCYBJC01300, No. 23JCYBJC01620 and No. 21JCYBJC00270)the Overseas Expertise Introduction Project for Discipline Innovation of Higher Edu cation of China (Grant No. B16027)the Fundamental Research Funds for the Central Universities,Nankai University (No. 63241568)
文摘Efficient surface passivation is critical for achieving high-performance perovskite solar cells(PSCs),yet the discovery of optimal passivators remains a time-consuming,trial-and-error process.Here,we report a synergistic machine learning(ML)and density functional theory(DFT)approach that enables predictive and rapid identification of effective passivation materials.By training an XGBoost model(91.3%accuracy)with DFT-derived molecular descriptors and activity calculations,we identify 2-(4-aminophenyl)-3H-benzimidazol-5-amine(APBIA)as a promising passivator.Experimental validation demonstrates that APBIA effectively removes surface impurities and passivates defects within perovskite films,leading to a significant increase in power conversion efficiency(PCE)from 22.48%to 25.55%(certified as 25.02%).This ML-DFT framework provides a generalizable pathway for accelerating the development of advanced functional materials for photovoltaic applications.
文摘为了提升DFT-S-OFDM系统在瑞利信道下的传输性能,采用位交织编码调制迭代译码方案(BICM-ID)、旋转映射(R-QAM)和Turbo码等技术,设计了基于Turbo-BICM-ID的DFT-S-OFDM系统。给出了系统原理框图,对编码调制系统的解调译码迭代算法进行了推导,对系统进行了Matlab仿真验证。仿真结果表明,与传统的卷积码设计方案相比,该设计方案在误码率为10-5时,可以获得5.7 d B的增益改善,同时可以获得更低的错误平层,有效地改善了DFT-S-OFDM系统在瑞利信道下的性能。
