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
Lithium-sulfur(Li-S) batteries are considered one of the most promising next-generation secondary batteries owing to their ultrahigh theoretical energy density.However,practical applications are hindered by the shuttl...Lithium-sulfur(Li-S) batteries are considered one of the most promising next-generation secondary batteries owing to their ultrahigh theoretical energy density.However,practical applications are hindered by the shuttle effect of soluble lithium polysulfides(Li PSs) and sluggish redox kinetics,which result in low active material utilization and poor cycling stability.Various copper-based materials have been used to inhibit the shuttle effect of Li PSs,owing to the strong anchoring effect caused by the lithiophilic/sulphilic sites and the accelerated conversion kinetics caused by excellent catalytic activity.This study briefly introduces the working principles of Li-S batteries,followed by a summary of the synthetic methods for copper-based materials.Moreover,the recent research progress in the utilization of various copper-based materials in cathodes and separators of Li-S batteries,including copper oxides,copper sulfides,copper phosphides,copper selenides,copper-based metal-organic frameworks(MOFs),and copper single-atom,are systematically summarized.Subsequently,three strategies to improve the electrochemical performance of copper-based materials through defect engineering,morphology regulation,and synergistic effect of different components are presented.Finally,our perspectives on the future development of copper-based materials are presented,highlighting the major challenges in the rational design and synthesis of high-performance Li-S batteries.展开更多
Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability o...Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.展开更多
Copper-based azide(Cu(N_(3))2 or CuN_(3),CA)chips synthesized by in-situ azide reaction and utilized in miniaturized explosive systems has become a hot research topic in recent years.However,the advantages of in-situ ...Copper-based azide(Cu(N_(3))2 or CuN_(3),CA)chips synthesized by in-situ azide reaction and utilized in miniaturized explosive systems has become a hot research topic in recent years.However,the advantages of in-situ synthesis method,including small size and low dosage,bring about difficulties in quantitative analysis and differences in ignition capabilities of CA chips.The aim of present work is to develop a simplified quantitative analysis method for accurate and safe analysis of components in CA chips to evaluate and investigate the corresponding ignition ability.In this work,Cu(N_(3))2 and CuN_(3)components in CA chips were separated through dissolution and distillation by utilizing the difference in solubility and corresponding content was obtained by measuring N_(3)-concentration through spectrophotometry.The spectrophotometry method was optimized by studying influencing factors and the recovery rate of different separation methods was studied,ensuring the accuracy and reproducibility of test results.The optimized method is linear in range from 1.0-25.0 mg/L,with a correlation coefficient R^(2)=0.9998,which meets the requirements of CA chips with a milligram-level content test.Compared with the existing ICP method,component analysis results of CA chips obtained by spectrophotometry are closer to real component content in samples and have satisfactory accuracy.Moreover,as its application in miniaturized explosive systems,the ignition ability of CA chips with different component contents for direct ink writing CL-20 and the corresponding mechanism was studied.This study provided a basis and idea for the design and performance evaluation of CA chips in miniaturized explosive systems.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
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
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
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
[Objectives] The effects of copper-based nutrient foliar fertilizer on photosynthetic characteristics,yield,accumulation and distribution of trace elements in various organs,disease prevention effect and soil enzyme a...[Objectives] The effects of copper-based nutrient foliar fertilizer on photosynthetic characteristics,yield,accumulation and distribution of trace elements in various organs,disease prevention effect and soil enzyme activity were studied,so as to provide a theoretical basis for the application of foliar fertilizers in cotton production. [Methods]Through two years of field experiments,six treatments were set in total,namely spraying water( CK),traditional Bordeaux mixture( BDM),Kocide 2000( KCD),copper-based nutrient foliar fertilizer( CF),iron-copper-based nutrient foliar fertilizer( CFFe),and zinc-boron-copper-based nutrient foliar fertilizer( CFZnB). Randomized block arrangement was adopted. Chlorophyll content in leaves was measured at each growth stage of the cotton. Photosynthetic characteristics of leaves were measured at the peak bolling stage. Plants were sampled at initial boll opening stage. The whole plant was divided into root,stem,leaf and cotton boll parts,in which the total copper,total zinc,total iron contents and accumulations were determined. Soil samples were collected from each plot,followed by the determination of soil enzyme activity. Disease index was investigated at bud,flowering and boll-forming and boll opening stage. [Results]( 1) Spraying CFFe,CFZnB,CF and KCD could significantly improve chlorophyll content of cotton leaves,and the CFFe treatment had the highest increase up to13. 30%,followed by the CFZnB treatment,which was 11. 40% higher than the CK; and photosynthetic rate,stomata conductance and transpiration rate could be improved significantly,and the CFFe treatment showed the highest photosynthetic rate,which increased by 26. 35% compared with the CK,followed by the CFZnB treatment,which increased by 17. 96% compared with CK; and intercellular CO2 concentration was significantly reduced.( 2) Spraying BDM,KCD,CF,CFFe and CFZnB can significantly increase total copper content and accumulation in various cotton organs( except the total copper content in the stem part of the CFZnB treatment; the CFZnB and CFFe treatments can significantly increase total zinc content and accumulation in various cotton organs; and spraying CFFe,CFZnB and CF can significantly increase total iron content and accumulation in various cotton organs( except the total iron content in the stem part of the CF treatment).( 3)Spraying CFFe,CFZnB,CF,KCD and BDM greatly reduced the disease index at flowering and boll-forming and boll opening stages.( 4) The CFZnB and CFFe treatments had the highest soil urease activity,which was 7. 14% higher than that of the CK,but the difference from the CK was not significant; the catalase activity of each treatment was significantly higher than that of the BDM treatment; and the sucrase activity of each treatment was significantly higher than that of the CK.( 5) Spraying CFFe,CFZnB,CF and KCD significantly improved lint yield of cotton,and the CFZnB treatment showed the highest yield increase up to 12. 34%,followed by the CFFe treatment,with an increase in the range of 8. 77%-10. 20%. [Conclusions]Copper-based nutrient foliar fertilizers have dual functions of disease control and prevention and plant nutrition and health care,and not only can significantly increase cotton yield,but also has certain disease prevention effect.It is recommended to use copper-based nutrient foliar fertilizers.展开更多
The microstructure and properties of boron-modified copper-base alloys were investigated by tension,corrosion,corrosive wear and erosion tests.The results show that by adding boron in copper-base alloys,the strength a...The microstructure and properties of boron-modified copper-base alloys were investigated by tension,corrosion,corrosive wear and erosion tests.The results show that by adding boron in copper-base alloys,the strength and hardness of alloys increase,the plasticity decreases somewhat;the corrosion,corrosive wear and erosion resistance of boron-modified copper-base alloys improve obviously.The microalloying mechanism of boron in copper-base alloys was found.展开更多
The effect of Al, Zn, Sn, Mn, Si and Ni on the color characteristics of binary copper-base alloys has been researched systematically and quantitatively. The results show that all alloying elements decrease the red con...The effect of Al, Zn, Sn, Mn, Si and Ni on the color characteristics of binary copper-base alloys has been researched systematically and quantitatively. The results show that all alloying elements decrease the red content of an alloy at different levels but have different effects on the yellow color. Al and Zn enhance the yellow content of an alloy, whereas Sn, Mn, Si and Ni decrease the yellow content. When the alloys with different karat gold colors are imitated, Al and Zn are the most important color mixing elements and Sn, Mn, Si and Ni can be used as auxiliary.展开更多
The tarnishing test in the presence of hydrogen sulfide（H2S） vapors has been used to investigate the tarnish resistance capability of copper-based alloys coated with Si02-like films by means of plasma-enhanced chemi...The tarnishing test in the presence of hydrogen sulfide（H2S） vapors has been used to investigate the tarnish resistance capability of copper-based alloys coated with Si02-like films by means of plasma-enhanced chemical vapor deposition（PECVD） fed with a tetraethoxysilane/oxygen mixture.The chemical and morphological properties of the films have been characterized by using infrared absorption spectroscopy（IR） and scanning electron microscopy（SEM）with energy disperse spectroscopy（EDS）.The corrosion products of the samples after the tarnishing test have been identified by X-ray diffraction analysis（XRD）.It has been found that SiO2-like films formed via PECVD with a high O2 flow rate could protect copper-based alloys from H2S vapor tarnishing.The alloys coated at the O2 flow rate of 20 sccm remain uncorroded after 54days of H2S vapor tarnish testing.The corrosion products for the alloys deposited at a low O2flow rate after 54 days of tarnish testing are mainly composed of brochantite.展开更多
Adsorption, surface reaction and process dynamics on the surface of a commercial copper-based catalyst for methanol synthesis from CO/CO2/H2 were systematically studied by means of temperature programmed desorption (T...Adsorption, surface reaction and process dynamics on the surface of a commercial copper-based catalyst for methanol synthesis from CO/CO2/H2 were systematically studied by means of temperature programmed desorption (TPD), temperature programmed surface reaction (TPSR), in-situ Fourier transform-inferred spec-troscopy(FTIR) and stimulus-response techniques. As a part of results, an elementary step sequence was suggested and a group of ordinary differential equations (ODEs) for describing transient conversations relevant to all species on the catalyst surface and in the gas phase in a micro-fixed-bed reactor was derived. The values of the parameters referred to dynamic kinetics were estimated by fitting the solution of the ODEs with the transient response data obtained by the stimulus-response technique with a FTIR analyzer as an on-line detector.展开更多
A calculation formula of ln γ i 0 for solute element i in liquid alloys was derived by use of free volume theory and Miedema formation enthalpy model. The values of ln γ i 0 of solute elements in liqui...A calculation formula of ln γ i 0 for solute element i in liquid alloys was derived by use of free volume theory and Miedema formation enthalpy model. The values of ln γ i 0 of solute elements in liquid copper at 1273 K were obtained. The results obtained show that the coincidence rate of sign (positive or negative) was 90% for the calculated and experimental values, which were basically in the same magnitude.展开更多
Copper plays a crucial role in the civilization of our lives.This review examines the flow of copper from the mining of ores to the end-of-life product,with particular emphasis on the recovery and re-functionalization...Copper plays a crucial role in the civilization of our lives.This review examines the flow of copper from the mining of ores to the end-of-life product,with particular emphasis on the recovery and re-functionalization of copper and copper-containing wastes.Beginning with the analysis of the global copper market,reserves,supply,and demand,a comprehensive account of the general copper recycling processes is presented,followed by the recycling of copper from traditional application fields such as power transmission,construction,and printed circuit boards,which contribute 10%-20%of the raw materials for annual refined copper products.Considering that copper is increasingly utilized in emerging fields such as batteries,catalysts,and biomedicine,the challenge of dealing with waste products from these sectors will become increasingly acute.This review not only explores and analyses the current state of copper recycling as a metal but also comprehensively investigates the areas of repair,reuse,and re-functionalization of waste products,providing a theoretical basis and technical directions for the future development and transformation of the copper market.展开更多
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 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
Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals.Electrocatalytic CO_(2) reduction toward carbon-containing ...Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals.Electrocatalytic CO_(2) reduction toward carbon-containing products,including C1 products(carbon monoxide,formic acid,etc),C2 products(ethylene,ethanol,etc.)and multi-carbon products(e.g.,n-propanol),provides beneficial fuel and chemicals for industrial production.The complexity of the multi-proton transfer processes and difficulties of C-C coupling in electrochemical CO_(2) reduction toward multi-carbon(C2+)products have attracted increasing concerns on the design of catalysts in comparison with those of C1 products.In this paper,we review the main advances in the syntheses of multi-carbon products through electrocatalytic carbon dioxide reduction in recent years,introduce the basic principles of electrocatalytic CO_(2)RR,and detailly elucidate two widely accepted mechanisms of C-C coupling reactions.Among abundant nanomaterials,copper-based catalysts are outstanding catalysts for the preparation of multi-carbon chemicals in electrochemical CO_(2)RR attributing to effective C-C coupling reactions.Regarding the different selectivity of multi-carbon chemicals but extensively applied copper-based catalysts,we classify and summarize various Cu-based catalysts through separating diverse multi-carbon products,where the modification of spatial and electronic structures is beneficial to increase the coverage of CO or lower the activation energy barrier for forming C-C bond to form the key intermediates and increase the production of multi-carbon products.Challenges and prospects involving the fundamental and development of copper-based catalysts in electrochemical CO_(2) reduction reaction are also proposed.展开更多
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supported by the National Natural Science Foundation of China (No.51962002)Natural Science Foundation of Guangxi (No.2022GXNSFAA035463)。
文摘Lithium-sulfur(Li-S) batteries are considered one of the most promising next-generation secondary batteries owing to their ultrahigh theoretical energy density.However,practical applications are hindered by the shuttle effect of soluble lithium polysulfides(Li PSs) and sluggish redox kinetics,which result in low active material utilization and poor cycling stability.Various copper-based materials have been used to inhibit the shuttle effect of Li PSs,owing to the strong anchoring effect caused by the lithiophilic/sulphilic sites and the accelerated conversion kinetics caused by excellent catalytic activity.This study briefly introduces the working principles of Li-S batteries,followed by a summary of the synthetic methods for copper-based materials.Moreover,the recent research progress in the utilization of various copper-based materials in cathodes and separators of Li-S batteries,including copper oxides,copper sulfides,copper phosphides,copper selenides,copper-based metal-organic frameworks(MOFs),and copper single-atom,are systematically summarized.Subsequently,three strategies to improve the electrochemical performance of copper-based materials through defect engineering,morphology regulation,and synergistic effect of different components are presented.Finally,our perspectives on the future development of copper-based materials are presented,highlighting the major challenges in the rational design and synthesis of high-performance Li-S batteries.
基金support from the National Natural Science Foundation of China(22078130)the Fundamental Research Funds for the Central Universities(1042050205225990/010)Starting Research Fund of Qingyuan Innovation Laboratory(00523001).
文摘Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.
基金the financial support provided by the National Natural Science Foundation of China(Grant No.11872013).
文摘Copper-based azide(Cu(N_(3))2 or CuN_(3),CA)chips synthesized by in-situ azide reaction and utilized in miniaturized explosive systems has become a hot research topic in recent years.However,the advantages of in-situ synthesis method,including small size and low dosage,bring about difficulties in quantitative analysis and differences in ignition capabilities of CA chips.The aim of present work is to develop a simplified quantitative analysis method for accurate and safe analysis of components in CA chips to evaluate and investigate the corresponding ignition ability.In this work,Cu(N_(3))2 and CuN_(3)components in CA chips were separated through dissolution and distillation by utilizing the difference in solubility and corresponding content was obtained by measuring N_(3)-concentration through spectrophotometry.The spectrophotometry method was optimized by studying influencing factors and the recovery rate of different separation methods was studied,ensuring the accuracy and reproducibility of test results.The optimized method is linear in range from 1.0-25.0 mg/L,with a correlation coefficient R^(2)=0.9998,which meets the requirements of CA chips with a milligram-level content test.Compared with the existing ICP method,component analysis results of CA chips obtained by spectrophotometry are closer to real component content in samples and have satisfactory accuracy.Moreover,as its application in miniaturized explosive systems,the ignition ability of CA chips with different component contents for direct ink writing CL-20 and the corresponding mechanism was studied.This study provided a basis and idea for the design and performance evaluation of CA chips in miniaturized explosive systems.
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.
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.
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.
文摘[Objectives] The effects of copper-based nutrient foliar fertilizer on photosynthetic characteristics,yield,accumulation and distribution of trace elements in various organs,disease prevention effect and soil enzyme activity were studied,so as to provide a theoretical basis for the application of foliar fertilizers in cotton production. [Methods]Through two years of field experiments,six treatments were set in total,namely spraying water( CK),traditional Bordeaux mixture( BDM),Kocide 2000( KCD),copper-based nutrient foliar fertilizer( CF),iron-copper-based nutrient foliar fertilizer( CFFe),and zinc-boron-copper-based nutrient foliar fertilizer( CFZnB). Randomized block arrangement was adopted. Chlorophyll content in leaves was measured at each growth stage of the cotton. Photosynthetic characteristics of leaves were measured at the peak bolling stage. Plants were sampled at initial boll opening stage. The whole plant was divided into root,stem,leaf and cotton boll parts,in which the total copper,total zinc,total iron contents and accumulations were determined. Soil samples were collected from each plot,followed by the determination of soil enzyme activity. Disease index was investigated at bud,flowering and boll-forming and boll opening stage. [Results]( 1) Spraying CFFe,CFZnB,CF and KCD could significantly improve chlorophyll content of cotton leaves,and the CFFe treatment had the highest increase up to13. 30%,followed by the CFZnB treatment,which was 11. 40% higher than the CK; and photosynthetic rate,stomata conductance and transpiration rate could be improved significantly,and the CFFe treatment showed the highest photosynthetic rate,which increased by 26. 35% compared with the CK,followed by the CFZnB treatment,which increased by 17. 96% compared with CK; and intercellular CO2 concentration was significantly reduced.( 2) Spraying BDM,KCD,CF,CFFe and CFZnB can significantly increase total copper content and accumulation in various cotton organs( except the total copper content in the stem part of the CFZnB treatment; the CFZnB and CFFe treatments can significantly increase total zinc content and accumulation in various cotton organs; and spraying CFFe,CFZnB and CF can significantly increase total iron content and accumulation in various cotton organs( except the total iron content in the stem part of the CF treatment).( 3)Spraying CFFe,CFZnB,CF,KCD and BDM greatly reduced the disease index at flowering and boll-forming and boll opening stages.( 4) The CFZnB and CFFe treatments had the highest soil urease activity,which was 7. 14% higher than that of the CK,but the difference from the CK was not significant; the catalase activity of each treatment was significantly higher than that of the BDM treatment; and the sucrase activity of each treatment was significantly higher than that of the CK.( 5) Spraying CFFe,CFZnB,CF and KCD significantly improved lint yield of cotton,and the CFZnB treatment showed the highest yield increase up to 12. 34%,followed by the CFFe treatment,with an increase in the range of 8. 77%-10. 20%. [Conclusions]Copper-based nutrient foliar fertilizers have dual functions of disease control and prevention and plant nutrition and health care,and not only can significantly increase cotton yield,but also has certain disease prevention effect.It is recommended to use copper-based nutrient foliar fertilizers.
基金Supported by the National Natural Science Foundation of China。
文摘The microstructure and properties of boron-modified copper-base alloys were investigated by tension,corrosion,corrosive wear and erosion tests.The results show that by adding boron in copper-base alloys,the strength and hardness of alloys increase,the plasticity decreases somewhat;the corrosion,corrosive wear and erosion resistance of boron-modified copper-base alloys improve obviously.The microalloying mechanism of boron in copper-base alloys was found.
基金Financially supported by China National Gold Management Bureau for basic theory research
文摘The effect of Al, Zn, Sn, Mn, Si and Ni on the color characteristics of binary copper-base alloys has been researched systematically and quantitatively. The results show that all alloying elements decrease the red content of an alloy at different levels but have different effects on the yellow color. Al and Zn enhance the yellow content of an alloy, whereas Sn, Mn, Si and Ni decrease the yellow content. When the alloys with different karat gold colors are imitated, Al and Zn are the most important color mixing elements and Sn, Mn, Si and Ni can be used as auxiliary.
基金supported by the Special Fund for Talent of Wuhan Institute of Technology,China(No.237127)the"Fellowship for Junior Researchers"from Politecnico di Torino and Regione Piemonte,Italy
文摘The tarnishing test in the presence of hydrogen sulfide（H2S） vapors has been used to investigate the tarnish resistance capability of copper-based alloys coated with Si02-like films by means of plasma-enhanced chemical vapor deposition（PECVD） fed with a tetraethoxysilane/oxygen mixture.The chemical and morphological properties of the films have been characterized by using infrared absorption spectroscopy（IR） and scanning electron microscopy（SEM）with energy disperse spectroscopy（EDS）.The corrosion products of the samples after the tarnishing test have been identified by X-ray diffraction analysis（XRD）.It has been found that SiO2-like films formed via PECVD with a high O2 flow rate could protect copper-based alloys from H2S vapor tarnishing.The alloys coated at the O2 flow rate of 20 sccm remain uncorroded after 54days of H2S vapor tarnish testing.The corrosion products for the alloys deposited at a low O2flow rate after 54 days of tarnish testing are mainly composed of brochantite.
基金Supported by the National Natural Science Foundation of China(N.29476223) and Ministry of Chemical Industry of China under a contract(No.95-23-01).
文摘Adsorption, surface reaction and process dynamics on the surface of a commercial copper-based catalyst for methanol synthesis from CO/CO2/H2 were systematically studied by means of temperature programmed desorption (TPD), temperature programmed surface reaction (TPSR), in-situ Fourier transform-inferred spec-troscopy(FTIR) and stimulus-response techniques. As a part of results, an elementary step sequence was suggested and a group of ordinary differential equations (ODEs) for describing transient conversations relevant to all species on the catalyst surface and in the gas phase in a micro-fixed-bed reactor was derived. The values of the parameters referred to dynamic kinetics were estimated by fitting the solution of the ODEs with the transient response data obtained by the stimulus-response technique with a FTIR analyzer as an on-line detector.
文摘A calculation formula of ln γ i 0 for solute element i in liquid alloys was derived by use of free volume theory and Miedema formation enthalpy model. The values of ln γ i 0 of solute elements in liquid copper at 1273 K were obtained. The results obtained show that the coincidence rate of sign (positive or negative) was 90% for the calculated and experimental values, which were basically in the same magnitude.
基金supported by the National Natural Science Foundation of China(Nos.52350710207,21938003 and 51974162)Shenzhen Key Laboratory of Interfacial Science and Engineering of Materials(No.ZDSYS20200421111401738)Leading Talents of Guangdong Province Program(No.2016LJ06C536).
文摘Copper plays a crucial role in the civilization of our lives.This review examines the flow of copper from the mining of ores to the end-of-life product,with particular emphasis on the recovery and re-functionalization of copper and copper-containing wastes.Beginning with the analysis of the global copper market,reserves,supply,and demand,a comprehensive account of the general copper recycling processes is presented,followed by the recycling of copper from traditional application fields such as power transmission,construction,and printed circuit boards,which contribute 10%-20%of the raw materials for annual refined copper products.Considering that copper is increasingly utilized in emerging fields such as batteries,catalysts,and biomedicine,the challenge of dealing with waste products from these sectors will become increasingly acute.This review not only explores and analyses the current state of copper recycling as a metal but also comprehensively investigates the areas of repair,reuse,and re-functionalization of waste products,providing a theoretical basis and technical directions for the future development and transformation of the copper market.
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 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.
基金supported by the National Key R&D Program of China(2021YFA1500700)the National Nature Science Foundation of China(22102057)Shanghai Sailing Program(21YF1409400).
文摘Electrocatalytic carbon dioxide reduction reaction(CO_(2)RR)holds the promise of both overcoming the greenhouse effect and synthesizing a wealth of chemicals.Electrocatalytic CO_(2) reduction toward carbon-containing products,including C1 products(carbon monoxide,formic acid,etc),C2 products(ethylene,ethanol,etc.)and multi-carbon products(e.g.,n-propanol),provides beneficial fuel and chemicals for industrial production.The complexity of the multi-proton transfer processes and difficulties of C-C coupling in electrochemical CO_(2) reduction toward multi-carbon(C2+)products have attracted increasing concerns on the design of catalysts in comparison with those of C1 products.In this paper,we review the main advances in the syntheses of multi-carbon products through electrocatalytic carbon dioxide reduction in recent years,introduce the basic principles of electrocatalytic CO_(2)RR,and detailly elucidate two widely accepted mechanisms of C-C coupling reactions.Among abundant nanomaterials,copper-based catalysts are outstanding catalysts for the preparation of multi-carbon chemicals in electrochemical CO_(2)RR attributing to effective C-C coupling reactions.Regarding the different selectivity of multi-carbon chemicals but extensively applied copper-based catalysts,we classify and summarize various Cu-based catalysts through separating diverse multi-carbon products,where the modification of spatial and electronic structures is beneficial to increase the coverage of CO or lower the activation energy barrier for forming C-C bond to form the key intermediates and increase the production of multi-carbon products.Challenges and prospects involving the fundamental and development of copper-based catalysts in electrochemical CO_(2) reduction reaction are also proposed.
