In this paper,the research progress of Cu-based catalyst and the activity enhancement strategies in the hydrogenation of dimethyl oxalate(DMO)to ethylene glycol(EG)was reviewed.As a green and economical ethylene glyco...In this paper,the research progress of Cu-based catalyst and the activity enhancement strategies in the hydrogenation of dimethyl oxalate(DMO)to ethylene glycol(EG)was reviewed.As a green and economical ethylene glycol production path,the core of DMO hydrogenation of EG lies in the rational design and optimization of catalysts.This paper first introduces the background of the DMO hydrogenation system EG significance and the important effect of Cu-based catalyst in the reaction,particularly emphasizing the coordination with the Cu^(+)-Cu^(0) species catalytic effect.Then,many factors affecting the activity of Cu-based catalysts were analyzed in detail,including the equilibrium effect between Cu^(0) and Cu+species,the surface dispersion of Cu species,the interaction between metal and support,and the morphology effect of the catalyst.Regarding strategies for improving catalyst performance,this paper summarized effective measures such as optimizing support structure,adding promoters and optimizing preparation methods,and demonstrated the practical application effects of these strategies through representative catalyst examples.In addition,this paper also discusses the complex relationship between the influencing factors and catalyst performance.It points out the key directions for future research,with in-depth exploration of the correlation between catalyst structure and performance,the development of new catalysts,and the application of machine learning and big data technology in the catalyst research and development.In summary,this paper provides comprehensive theoretical guidance and practical reference for the performance optimization of Cu-based catalysts for DMO hydrogenation to EG.展开更多
The next-generation lithium(Li)metal batteries suffer severe low-temperature capacity degradation,appealing for expeditions on solutions.Herein,the feasibility of copper-based skeletons(i.e.,2D Cu foil,3D Cu mesh,and ...The next-generation lithium(Li)metal batteries suffer severe low-temperature capacity degradation,appealing for expeditions on solutions.Herein,the feasibility of copper-based skeletons(i.e.,2D Cu foil,3D Cu mesh,and CuZn mesh)frequently adopted in the stabilization of Li are evaluated at low temperatures.Li growth patterns and stripping behaviors on different skeletons and at different temperatures uncover the dendrite-free and dead-Li-less Li deposition/dissolution on CuZn mesh.Three-electrode impedance indicates the dynamic advantages of CuZn mesh,driving fast Li^(+)crossing through solidelectrolyte-interphase and charge transfer process.Notably,CuZn mesh enables the stable operation and fast charging(1.8 mA cm^(-2))of Li||LiFePO_(4)cells for over 120 cycles at-10℃ with a superior capacity retention of 88%.The success of CuZn mesh can be translated into lower temperature(-20℃)and 1.0-Ah-level pouch cells.This work provides fundamentals on improving low-temperature battery performances by skeletons with regulated spatial structure and lithiophilicity.展开更多
The contamination of water resources by phenolic compounds(PCs)presents a significant environmental hazard,necessitating the development of novel materials and methodologies for effective mitigation.In this study,a me...The contamination of water resources by phenolic compounds(PCs)presents a significant environmental hazard,necessitating the development of novel materials and methodologies for effective mitigation.In this study,a metallic copper-doped zeolitic imidazolate framework was pyrolyzed and designated as CuNC-20 for the activation of peroxymonosulfate(PMS)to degrade phenol(PE).Cu-NC-20 could effectively address the issue of metal agglomeration while simultaneously diminishing copper dissolution during the activation of PMS reactions.The Cu-NC-20 catalyst exhibited a rapid degradation rate for PE across a broad pH range(3-9)and demonstrated high tolerance towards coexisting ions.According to scavenger experiments and electron paramagnetic resonance analysis,singlet oxygen(^(1)O_(2))and high-valent copperoxo(Cu(Ⅲ))were the predominant reactive oxygen species,indicating that the system was nonradicaldominated during the degradation process.The quantitative structure-activity relationship(QSAR)between the oxidation rate constants of various substituted phenols and Hammett constants was established.It indicated that the Cu-NC-20/PMS system had the optimal oxidation rate constant withσ^(-)correlation and exhibited a typical electrophilic reaction pattern.This study provides a comprehensive understanding of the heterogeneous activation process for the selective removal of phenolic compounds.展开更多
本文以辽河油田沈阳采油厂某采油作业区石油污染土壤为研究对象,探究H2O2浓度、FeSO4浓度、反应体系pH、水土比、反应时间等因素对石油污染土壤中石油烃降解效果的影响。研究结果表明,H2O2投加浓度对石油烃的降解效果影响显著,氧化剂和...本文以辽河油田沈阳采油厂某采油作业区石油污染土壤为研究对象,探究H2O2浓度、FeSO4浓度、反应体系pH、水土比、反应时间等因素对石油污染土壤中石油烃降解效果的影响。研究结果表明,H2O2投加浓度对石油烃的降解效果影响显著,氧化剂和催化剂浓度对Fenton反应过程中石油烃的氧化效果有较大影响,反应体系pH值为6.0时石油烃的去除效果最佳,合理的水土比能够提高氧化效率。不同程度污染土壤的修复效果表明,反应24 h后,Fenton反应基本完成,石油烃去除率分别为49.22%,55.31%和61.98%,该研究结果可为污染土壤环境修复提供科学依据。In this paper, the effects of H2O2 concentration, FeSO4 concentration, reaction system pH, water and soil ratio, and reaction time on the degradation of petroleum hydrocarbons in oil-polluted soil were studied in an oil production area of Shenyang oil production plant of Liaohe Oilfield. The research results show that the concentration of H2O2 has a significant impact on the degradation effect of petroleum hydrocarbons, and the concentration of oxidant and catalyst has a great impact on the oxidation effect of petroleum hydrocarbons in the Fenton reaction process. When the pH value of the reaction system is 6.0, the removal effect of petroleum hydrocarbons is the best, and reasonable water and soil ratio can improve the oxidation efficiency. The remediation effects of contaminated soil of different degrees show that after 24 h of reaction, Fenton reaction is basically completed, and the removal rates of petroleum hydrocarbons are 49.22%, 55.31% and 61.98%, respectively. The research results can provide scientific basis for the remediation of contaminated soil environment.展开更多
The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support,...The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support, one （ZrO2-1） was obtained from the commercial ZrO2 and the other （ZrO2-2） was issued from the thermal decomposition of zirconium nitrate. It was found that the CuO/ZrO2-2 catalyst was more active than CuO/ZrO2-1. N2 adsorption, H2-TPR and XRD measurements showed that larger surface area, better reduction property, presence of tetragonal ZrO2 and higher dispersion of active component for CuO/ZrO2-2 than that of CuO/ZrO2-1. These factors could be the dominating reasons for its higher activity for methane combustion.展开更多
Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescen...Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescence field,due to their lead-free,cost-effective,earth-abundant and low electronic dimensionality.Ascribed to flexible valence charge of Cu(Cu1+and Cu2+)and complex competing phases,the crystal structures and phase stabilities of CHPs are complicated and ambiguous,which limits their experimental applications.Via comprehensive first-principles calculations,we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database(ICSD).Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs,i.e.Rb3 Cu2 Br5,Rb3 Cu2 I5,Rb Cu2 Cl3,Rb2 Cu I3,Rb2 Cu Br4,Rb Cu Br3,Rb3 Cu2 Br7,Cs3 Cu2 Br7,Cs3 Cu2 Cl7 and Cs4 Cu5 Cl9,which have not yet been reported in experiments.This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.展开更多
Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation ...Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation methods of aluminum emulsions on physicochemical and catalytic properties of catalysts were studied by XRD, SEM, XPS,N2 adsorption-desorption techniques and methanol synthesis from syngas. The preparation methods of aluminum emulsions were found to influence the catalytic activity, CuO crystallite size, surface area and Cu0 surface area and reduction process. The results show that the catalyst CN using the aluminum source prepared by addition the ammonia into the aluminum nitrate （NP） exhibited the best catalytic performance for methanol synthesis from syngas.展开更多
Catalytic wet air oxidation(CWAO) can degrade some refractory pollutants at a low cost to improve the biodegradability of wastewater. However, in the presence of high temperature and high pressure and strong oxidizing...Catalytic wet air oxidation(CWAO) can degrade some refractory pollutants at a low cost to improve the biodegradability of wastewater. However, in the presence of high temperature and high pressure and strong oxidizing free radicals, the stability of catalysts is often insufficient, which has become a bottleneck in the application of CWAO. In this paper, a copper-based catalyst with excellent hydrothermal stability was designed and prepared. TiO_(2) with excellent stability was used as the carrier to ensure the longterm anchoring of copper and reduce the leaching of the catalyst. The one pot sol–gel method was used to ensure the super dispersion and uniform distribution of copper nanoparticles on the carrier, so as to ensure that more active centers could be retained in a longer period. Experiments show that the catalyst prepared by this method has good stability and catalytic activity, and the catalytic effect is not significantly reduced after 10 cycles of use. The oxidation degradation experiment of m-cresol with the strongest biological toxicity and the most difficult to degrade in coal chemical wastewater was carried out with this catalyst. The results showed that under the conditions of 140℃, 2 MPa and 2 h, m-cresol with a concentration of up to 1000 mg·L^(-1) could be completely degraded, and the COD removal rate could reach 79.15%. The biological toxicity of wastewater was significantly reduced. The development of the catalyst system has greatly improved the feasibility of CWAO in the treatment of refractory wastewater such as coal chemical wastewater.展开更多
Chemical looping combustion(CLC)is an energy conversion technology with high efficiency and inherent separation of CO_(2).The existence of sulfur in coal may affect the CO_(2) purity and the performance of oxygen carr...Chemical looping combustion(CLC)is an energy conversion technology with high efficiency and inherent separation of CO_(2).The existence of sulfur in coal may affect the CO_(2) purity and the performance of oxygen carrier due to the interactions between sulfur contaminants and oxygen carrier.The migration of sulfur in Beisu coal during the in-situ gasification chemical looping combustion(i G-CLC)process using two oxygen carriers(iron ore and Cu O/Si O_(2))was investigated respectively.The thermodynamic analysis results showed the formation of metal sulfides was thermodynamically favored at low temperatures and low oxygen excess coefficients,while they were obviously inhibited and the production of SO_(2) was significantly promoted with an increase in temperature and oxygen excess coefficient.Moreover,part of sulfur was captured and fixed in the forms of alkali/alkaline earth metal sulfate due to the high amount of alkali/alkaline earth metal oxides in the coal ash or/and oxygen carrier.The experimental results showed that the sulfur in coal mainly released in the form of SO_(2),and the sulfur conversion efficiency(XS)in the reduction stage were 51.04%and 48.24%when using iron ore and Cu O/Si O_(2) respectively.The existence of metal sulfides was observed in the reduced oxygen carriers.The values of XSin the reoxidation process reached 3.80%and 7.64%when using iron ore and Cu O/Si O_(2) respectively.The residue and accumulation of sulfur were also found on the surfaces of two oxygen carriers.展开更多
基金supported by Guangxi Science and Technology Major Program(GuikeAA23062018)the Academic Newcomer Award Project of Guangxi University(2025GXUXSXR07)。
文摘In this paper,the research progress of Cu-based catalyst and the activity enhancement strategies in the hydrogenation of dimethyl oxalate(DMO)to ethylene glycol(EG)was reviewed.As a green and economical ethylene glycol production path,the core of DMO hydrogenation of EG lies in the rational design and optimization of catalysts.This paper first introduces the background of the DMO hydrogenation system EG significance and the important effect of Cu-based catalyst in the reaction,particularly emphasizing the coordination with the Cu^(+)-Cu^(0) species catalytic effect.Then,many factors affecting the activity of Cu-based catalysts were analyzed in detail,including the equilibrium effect between Cu^(0) and Cu+species,the surface dispersion of Cu species,the interaction between metal and support,and the morphology effect of the catalyst.Regarding strategies for improving catalyst performance,this paper summarized effective measures such as optimizing support structure,adding promoters and optimizing preparation methods,and demonstrated the practical application effects of these strategies through representative catalyst examples.In addition,this paper also discusses the complex relationship between the influencing factors and catalyst performance.It points out the key directions for future research,with in-depth exploration of the correlation between catalyst structure and performance,the development of new catalysts,and the application of machine learning and big data technology in the catalyst research and development.In summary,this paper provides comprehensive theoretical guidance and practical reference for the performance optimization of Cu-based catalysts for DMO hydrogenation to EG.
基金the funding support of the National Natural Science Foundation of China(52103342,22209032 and 22479134)Natural Science Foundation of Zhejiang Province(LY24B030008)+1 种基金China Jiliang University Research Fund Program for Young Scholars(221040)the funding support of the Zhejiang Provincial College Students’Scientific Research and Innovation Activity(Xinmiao Talent)Program(2023R409A045)。
文摘The next-generation lithium(Li)metal batteries suffer severe low-temperature capacity degradation,appealing for expeditions on solutions.Herein,the feasibility of copper-based skeletons(i.e.,2D Cu foil,3D Cu mesh,and CuZn mesh)frequently adopted in the stabilization of Li are evaluated at low temperatures.Li growth patterns and stripping behaviors on different skeletons and at different temperatures uncover the dendrite-free and dead-Li-less Li deposition/dissolution on CuZn mesh.Three-electrode impedance indicates the dynamic advantages of CuZn mesh,driving fast Li^(+)crossing through solidelectrolyte-interphase and charge transfer process.Notably,CuZn mesh enables the stable operation and fast charging(1.8 mA cm^(-2))of Li||LiFePO_(4)cells for over 120 cycles at-10℃ with a superior capacity retention of 88%.The success of CuZn mesh can be translated into lower temperature(-20℃)and 1.0-Ah-level pouch cells.This work provides fundamentals on improving low-temperature battery performances by skeletons with regulated spatial structure and lithiophilicity.
基金the financial support from Sichuan Program of Science and Technology(No.2021ZDZX0012)the National Natural Science Foundation of China(No.52200105)。
文摘The contamination of water resources by phenolic compounds(PCs)presents a significant environmental hazard,necessitating the development of novel materials and methodologies for effective mitigation.In this study,a metallic copper-doped zeolitic imidazolate framework was pyrolyzed and designated as CuNC-20 for the activation of peroxymonosulfate(PMS)to degrade phenol(PE).Cu-NC-20 could effectively address the issue of metal agglomeration while simultaneously diminishing copper dissolution during the activation of PMS reactions.The Cu-NC-20 catalyst exhibited a rapid degradation rate for PE across a broad pH range(3-9)and demonstrated high tolerance towards coexisting ions.According to scavenger experiments and electron paramagnetic resonance analysis,singlet oxygen(^(1)O_(2))and high-valent copperoxo(Cu(Ⅲ))were the predominant reactive oxygen species,indicating that the system was nonradicaldominated during the degradation process.The quantitative structure-activity relationship(QSAR)between the oxidation rate constants of various substituted phenols and Hammett constants was established.It indicated that the Cu-NC-20/PMS system had the optimal oxidation rate constant withσ^(-)correlation and exhibited a typical electrophilic reaction pattern.This study provides a comprehensive understanding of the heterogeneous activation process for the selective removal of phenolic compounds.
文摘本文以辽河油田沈阳采油厂某采油作业区石油污染土壤为研究对象,探究H2O2浓度、FeSO4浓度、反应体系pH、水土比、反应时间等因素对石油污染土壤中石油烃降解效果的影响。研究结果表明,H2O2投加浓度对石油烃的降解效果影响显著,氧化剂和催化剂浓度对Fenton反应过程中石油烃的氧化效果有较大影响,反应体系pH值为6.0时石油烃的去除效果最佳,合理的水土比能够提高氧化效率。不同程度污染土壤的修复效果表明,反应24 h后,Fenton反应基本完成,石油烃去除率分别为49.22%,55.31%和61.98%,该研究结果可为污染土壤环境修复提供科学依据。In this paper, the effects of H2O2 concentration, FeSO4 concentration, reaction system pH, water and soil ratio, and reaction time on the degradation of petroleum hydrocarbons in oil-polluted soil were studied in an oil production area of Shenyang oil production plant of Liaohe Oilfield. The research results show that the concentration of H2O2 has a significant impact on the degradation effect of petroleum hydrocarbons, and the concentration of oxidant and catalyst has a great impact on the oxidation effect of petroleum hydrocarbons in the Fenton reaction process. When the pH value of the reaction system is 6.0, the removal effect of petroleum hydrocarbons is the best, and reasonable water and soil ratio can improve the oxidation efficiency. The remediation effects of contaminated soil of different degrees show that after 24 h of reaction, Fenton reaction is basically completed, and the removal rates of petroleum hydrocarbons are 49.22%, 55.31% and 61.98%, respectively. The research results can provide scientific basis for the remediation of contaminated soil environment.
文摘The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support, one （ZrO2-1） was obtained from the commercial ZrO2 and the other （ZrO2-2） was issued from the thermal decomposition of zirconium nitrate. It was found that the CuO/ZrO2-2 catalyst was more active than CuO/ZrO2-1. N2 adsorption, H2-TPR and XRD measurements showed that larger surface area, better reduction property, presence of tetragonal ZrO2 and higher dispersion of active component for CuO/ZrO2-2 than that of CuO/ZrO2-1. These factors could be the dominating reasons for its higher activity for methane combustion.
基金funding support from National Natural Science Foundation of China(grant No.11674237 and 51602211)National Key Research and Development Program of China(grant No.2016YFB0700700)+2 种基金Natural Science Foundation of Jiangsu Province of China(grant No.BK20160299)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)China Post-doctoral Foundation(grant No.7131705619).
文摘Recently,inorganic copper-based halide perovskites and their derivatives(CHPs)with chemical formulas AlCumXn(A=Rb and Cs;X=Cl,Br and I;l,m,and n are integers.),have received increasing attention in the photoluminescence field,due to their lead-free,cost-effective,earth-abundant and low electronic dimensionality.Ascribed to flexible valence charge of Cu(Cu1+and Cu2+)and complex competing phases,the crystal structures and phase stabilities of CHPs are complicated and ambiguous,which limits their experimental applications.Via comprehensive first-principles calculations,we have investigated thermodynamic stabilities of possible crystal phases for AlCumXn by considering all the possible secondary phases existing in inorganic crystal structure database(ICSD).Our results are in agreement with existing experiments and further predicted the existence of 10 stable CHPs,i.e.Rb3 Cu2 Br5,Rb3 Cu2 I5,Rb Cu2 Cl3,Rb2 Cu I3,Rb2 Cu Br4,Rb Cu Br3,Rb3 Cu2 Br7,Cs3 Cu2 Br7,Cs3 Cu2 Cl7 and Cs4 Cu5 Cl9,which have not yet been reported in experiments.This work provides a phase and compositional map that may guide experiments to synthesize more novel inorganic CHPs with diverse properties for potential functional applications.
文摘Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation methods of aluminum emulsions on physicochemical and catalytic properties of catalysts were studied by XRD, SEM, XPS,N2 adsorption-desorption techniques and methanol synthesis from syngas. The preparation methods of aluminum emulsions were found to influence the catalytic activity, CuO crystallite size, surface area and Cu0 surface area and reduction process. The results show that the catalyst CN using the aluminum source prepared by addition the ammonia into the aluminum nitrate （NP） exhibited the best catalytic performance for methanol synthesis from syngas.
基金support provided by the National Natural Science Foundation of China (21978143 and 21878164)。
文摘Catalytic wet air oxidation(CWAO) can degrade some refractory pollutants at a low cost to improve the biodegradability of wastewater. However, in the presence of high temperature and high pressure and strong oxidizing free radicals, the stability of catalysts is often insufficient, which has become a bottleneck in the application of CWAO. In this paper, a copper-based catalyst with excellent hydrothermal stability was designed and prepared. TiO_(2) with excellent stability was used as the carrier to ensure the longterm anchoring of copper and reduce the leaching of the catalyst. The one pot sol–gel method was used to ensure the super dispersion and uniform distribution of copper nanoparticles on the carrier, so as to ensure that more active centers could be retained in a longer period. Experiments show that the catalyst prepared by this method has good stability and catalytic activity, and the catalytic effect is not significantly reduced after 10 cycles of use. The oxidation degradation experiment of m-cresol with the strongest biological toxicity and the most difficult to degrade in coal chemical wastewater was carried out with this catalyst. The results showed that under the conditions of 140℃, 2 MPa and 2 h, m-cresol with a concentration of up to 1000 mg·L^(-1) could be completely degraded, and the COD removal rate could reach 79.15%. The biological toxicity of wastewater was significantly reduced. The development of the catalyst system has greatly improved the feasibility of CWAO in the treatment of refractory wastewater such as coal chemical wastewater.
基金supported by the National Natural Science Foundation of China(51606087)Start-Up Foundation of Jiangsu University(15JDG157)Foundation of State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering(2020-KF-07)。
文摘Chemical looping combustion(CLC)is an energy conversion technology with high efficiency and inherent separation of CO_(2).The existence of sulfur in coal may affect the CO_(2) purity and the performance of oxygen carrier due to the interactions between sulfur contaminants and oxygen carrier.The migration of sulfur in Beisu coal during the in-situ gasification chemical looping combustion(i G-CLC)process using two oxygen carriers(iron ore and Cu O/Si O_(2))was investigated respectively.The thermodynamic analysis results showed the formation of metal sulfides was thermodynamically favored at low temperatures and low oxygen excess coefficients,while they were obviously inhibited and the production of SO_(2) was significantly promoted with an increase in temperature and oxygen excess coefficient.Moreover,part of sulfur was captured and fixed in the forms of alkali/alkaline earth metal sulfate due to the high amount of alkali/alkaline earth metal oxides in the coal ash or/and oxygen carrier.The experimental results showed that the sulfur in coal mainly released in the form of SO_(2),and the sulfur conversion efficiency(XS)in the reduction stage were 51.04%and 48.24%when using iron ore and Cu O/Si O_(2) respectively.The existence of metal sulfides was observed in the reduced oxygen carriers.The values of XSin the reoxidation process reached 3.80%and 7.64%when using iron ore and Cu O/Si O_(2) respectively.The residue and accumulation of sulfur were also found on the surfaces of two oxygen carriers.
