Ethylene(C2H4)in vehicle exhaust is a highly reactive volatile organic compound(VOC).Its photooxidative reaction with NOx contributes to the formation of O3 and secondary organic aerosols(SOA),the latter being a...Ethylene(C2H4)in vehicle exhaust is a highly reactive volatile organic compound(VOC).Its photooxidative reaction with NOx contributes to the formation of O3 and secondary organic aerosols(SOA),the latter being a key precursor of PM2.5.In this study,a novel MgO-supported Ag-Cu bimetallic catalyst was designed and investigated using density functional theory(DFT).The effects of Ag and Cu loading on the geometric structure,stability,and reactant adsorption characteristics of the catalyst were analyzed,and the catalytic oxidation pathways of C2H4over AgCu-MgO was elucidated.The results indicate that loading Ag significantly enhances the adsorption of C2H4.The incorporation of Cu into Ag-MgO to form a AgCu-MgO bimetallic catalyst(dual atom catalyst,DACS)further improves the oxidative activity toward C2H4.Based on the binding energies of the Ag and Cu bimetallic sites and the adsorption energies of C2H4and O2,three representative configurations were selected for detailed reaction pathway analysis.Among them,Configuration 6 of AgCu-MgO exhibited the highest catalytic oxidation performance.This study provides new atomic-scale insights for the rational design of efficient catalysts targeting olefinic pollutants in automotive emissions and offers valuable guidance for advancing exhaust after-treatment technologies.展开更多
In order to improve the through-thickness homogeneity and properties of aviation aluminum alloy thick plate.The effect of heating-cooling retrogression and re-ageing on the performance of Al-8Zn-2Mg-2Cu alloy thick pl...In order to improve the through-thickness homogeneity and properties of aviation aluminum alloy thick plate.The effect of heating-cooling retrogression and re-ageing on the performance of Al-8Zn-2Mg-2Cu alloy thick plate was investigated by hardness tests, electrical conductivity tests and transmission electron microscopy(TEM) observation.Results revealed that, during retrogression heating, the fine pre-precipitates in surface layer dissolve more and the undissolved η′ or η phases are more coarsened than that of center layer. During slow cooling after retrogression,precipitates continue coarsening but with a lower rate and the secondary precipitation occurs in both layers. Finer precipitates resulting from the secondary precipitation are more in surface. However, the coarsening and secondary precipitation behaviors are restrained in both layers under quick cooling condition. The electrical conductivity and through-thickness homogeneity of precipitates increases while the hardness decreases with cooling rate decreasing. After the optimized non-isothermal retrogression and re-ageing(NRRA) including air-cooling retrogression, the throughthickness homogeneity which is evaluated by integrated retrogression effects has been improved to 94%. The tensile strength, fracture toughness and exfoliation corrosion grade of Al-8Zn-2Mg-2Cu alloy plate is 619 MPa, 24.7 MPa·m1/2and EB, respectively, which indicates that the non-isothermal retrogression and re-aging(NRRA) could improve the mechanical properties and corrosion resistance with higher through-thickness homogeneity.展开更多
Cu/SiO2 catalysts prepared by a convenient and efficient method using the urea hydrolysis deposition-precipitation (UHDP) technique have been proposed focusing on the effect of copper loading.The texture,structure a...Cu/SiO2 catalysts prepared by a convenient and efficient method using the urea hydrolysis deposition-precipitation (UHDP) technique have been proposed focusing on the effect of copper loading.The texture,structure and composition are systematically characterized by ICP,FTIR,N 2-physisorption,N2O chemisorption,TPR,XRD and XPS.The formation of copper phyllosilicate is observed in Cu/SiO2 catalyst by adopting UHDP method,and the amount of copper phyllosilicate is related to copper loading.It is found the structure properties and catalytic performance is profoundly affected by the amount of copper phyllosilicate.The excellent catalytic activity is attributed to the synergetic effect between Cu0 and Cu +.DMO conversion and EG selectivity are determined by the amount of Cu0 and Cu+,respectively.The proper copper loading (30 wt%) provides with the highest ratio of Cu + /Cu0,giving rise to the highest EG yield of 95% under the reaction conditions of p=2.0 MPa,T=473 K,H2/DMO=80 and LHSV=1.0h-1.展开更多
The Cu/SiO2catalysts were in situ synthesized by the hydrolysis of tetraethyl orthosilicate(TEOS)in one phase solution using ethanol as co-solvent or TEOS/H_2O two phases solution,followed by the precipitation of c...The Cu/SiO2catalysts were in situ synthesized by the hydrolysis of tetraethyl orthosilicate(TEOS)in one phase solution using ethanol as co-solvent or TEOS/H_2O two phases solution,followed by the precipitation of copper on SiO2by ammonia evaporation.In the hydrogenation of dimethyl oxalate,the catalyst prepared by one phase hydrolysis exhibited higher activity and ethylene glycol(EG)selectivity at lower temperature than that of two phases due to its larger BET surface area and multimodal pore distribution.At 488-503 K,the catalyst prepared in one phase solution with water/ethanol(W/E)volume ratio of 3:1 exhibited 90-95%EG selectivity,while catalyst prepared by two phase hydrolysis reached 90%EG selectivity only at 498-503 K.展开更多
The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. I...The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_(cat)^(–1) h^(–1) with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~+/(Cu^0+Cu~+). Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~+ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.展开更多
基金Supported by the National Natural Science Foundation of China Project(22362018)the Yunnan Fundamental Research Projects(202401AS070102)。
摘要Ethylene(C2H4)in vehicle exhaust is a highly reactive volatile organic compound(VOC).Its photooxidative reaction with NOx contributes to the formation of O3 and secondary organic aerosols(SOA),the latter being a key precursor of PM2.5.In this study,a novel MgO-supported Ag-Cu bimetallic catalyst was designed and investigated using density functional theory(DFT).The effects of Ag and Cu loading on the geometric structure,stability,and reactant adsorption characteristics of the catalyst were analyzed,and the catalytic oxidation pathways of C2H4over AgCu-MgO was elucidated.The results indicate that loading Ag significantly enhances the adsorption of C2H4.The incorporation of Cu into Ag-MgO to form a AgCu-MgO bimetallic catalyst(dual atom catalyst,DACS)further improves the oxidative activity toward C2H4.Based on the binding energies of the Ag and Cu bimetallic sites and the adsorption energies of C2H4and O2,three representative configurations were selected for detailed reaction pathway analysis.Among them,Configuration 6 of AgCu-MgO exhibited the highest catalytic oxidation performance.This study provides new atomic-scale insights for the rational design of efficient catalysts targeting olefinic pollutants in automotive emissions and offers valuable guidance for advancing exhaust after-treatment technologies.
基金Project(51801082) supported by National Natural Science Foundation of ChinaProjects(GY2021003, GY2021020)supported by the Key Research and Development Program of Zhenjiang City,China+1 种基金Project(KYCX21_3453) supported by Graduate Research and Innovation Projects in Jiangsu Province,ChinaProject(202110289002Z) supported by Undergraduate Innovation and Entrepreneurship Training Program of Jiangsu Province,China。
摘要In order to improve the through-thickness homogeneity and properties of aviation aluminum alloy thick plate.The effect of heating-cooling retrogression and re-ageing on the performance of Al-8Zn-2Mg-2Cu alloy thick plate was investigated by hardness tests, electrical conductivity tests and transmission electron microscopy(TEM) observation.Results revealed that, during retrogression heating, the fine pre-precipitates in surface layer dissolve more and the undissolved η′ or η phases are more coarsened than that of center layer. During slow cooling after retrogression,precipitates continue coarsening but with a lower rate and the secondary precipitation occurs in both layers. Finer precipitates resulting from the secondary precipitation are more in surface. However, the coarsening and secondary precipitation behaviors are restrained in both layers under quick cooling condition. The electrical conductivity and through-thickness homogeneity of precipitates increases while the hardness decreases with cooling rate decreasing. After the optimized non-isothermal retrogression and re-ageing(NRRA) including air-cooling retrogression, the throughthickness homogeneity which is evaluated by integrated retrogression effects has been improved to 94%. The tensile strength, fracture toughness and exfoliation corrosion grade of Al-8Zn-2Mg-2Cu alloy plate is 619 MPa, 24.7 MPa·m1/2and EB, respectively, which indicates that the non-isothermal retrogression and re-aging(NRRA) could improve the mechanical properties and corrosion resistance with higher through-thickness homogeneity.
摘要Cu/SiO2 catalysts prepared by a convenient and efficient method using the urea hydrolysis deposition-precipitation (UHDP) technique have been proposed focusing on the effect of copper loading.The texture,structure and composition are systematically characterized by ICP,FTIR,N 2-physisorption,N2O chemisorption,TPR,XRD and XPS.The formation of copper phyllosilicate is observed in Cu/SiO2 catalyst by adopting UHDP method,and the amount of copper phyllosilicate is related to copper loading.It is found the structure properties and catalytic performance is profoundly affected by the amount of copper phyllosilicate.The excellent catalytic activity is attributed to the synergetic effect between Cu0 and Cu +.DMO conversion and EG selectivity are determined by the amount of Cu0 and Cu+,respectively.The proper copper loading (30 wt%) provides with the highest ratio of Cu + /Cu0,giving rise to the highest EG yield of 95% under the reaction conditions of p=2.0 MPa,T=473 K,H2/DMO=80 and LHSV=1.0h-1.
基金supported by the International Science and Technology Cooperation Program(No 2009DFA61050)National High Technology Research and Development Program of China(863 program)(Nos 2007AA05Z334&2009AA05Z407)National Basic Research Program of China(No2007CB210200)
摘要The Cu/SiO2catalysts were in situ synthesized by the hydrolysis of tetraethyl orthosilicate(TEOS)in one phase solution using ethanol as co-solvent or TEOS/H_2O two phases solution,followed by the precipitation of copper on SiO2by ammonia evaporation.In the hydrogenation of dimethyl oxalate,the catalyst prepared by one phase hydrolysis exhibited higher activity and ethylene glycol(EG)selectivity at lower temperature than that of two phases due to its larger BET surface area and multimodal pore distribution.At 488-503 K,the catalyst prepared in one phase solution with water/ethanol(W/E)volume ratio of 3:1 exhibited 90-95%EG selectivity,while catalyst prepared by two phase hydrolysis reached 90%EG selectivity only at 498-503 K.
摘要The efficient synthesis of methanol and ethylene glycol via the chemoselective hydrogenation of ethylene carbonate(EC) is important for the sustainable utilization of CO_2 to produce commodity chemicals and fuels. In this work, a series of β-cyclodextrin-modified Cu/SiO_2 catalysts were prepared by ammonia evaporation method for the selective hydrogenation of EC to co-produce methanol and ethylene glycol. The structure and physicochemical properties of the catalysts were characterized in detail by N_2 physisorption, XRD, N_2O titration, H_2-TPR, TEM, and XPS/XAES. Compared with the unmodified 25 Cu/SiO_2 catalyst, the involvement of β-cyclodextrin in 5β-25 Cu/SiO_2 could remarkably increase the catalytic activity—excellent activity of 1178 mgEC g_(cat)^(–1) h^(–1) with 98.8%ethylene glycol selectivity, and 71.6% methanol selectivity could be achieved at 453 K. The remarkably improved recyclability was primarily attributed to the remaining proportion of Cu~+/(Cu^0+Cu~+). Furthermore, the DFT calculation results demonstrated that metallic Cu^0 dissociated adsorbed H_2, while Cu~+ activated the carbonyl group of EC and stabilized the intermediates. This study is a facile and efficient method to prepare highly dispersed Cu catalysts—this is also an effective and stable heterogeneous catalyst system for the sustainable synthesis of ethylene glycol and methanol via indirect chemical utilization of CO_2.