Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), sc...Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.展开更多
The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are stri...The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.展开更多
The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the...The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the pyrite surface to render the mineral surface hydrophilic and hinder the adsorption of the collector.This review summarizes the advances in depressants for the flotation separation of Cu–Fe sulfide minerals at low alkalinity.These advances include use of inorganic depressants (oxidants and sulfur–oxygen compounds),natural polysaccharides (starch,dextrin,konjac glucomannan,and galactomannan),modified polymers (carboxymethyl cellulose,polyacrylamide,lignosulfonate,and tricarboxylate sodium starch),organic acids (polyglutamic acid,sodium humate,tannic acid,pyrogallic acid,salicylic acid,and lactic acid),sodium dimethyl dithiocarbamate,and diethylenetriamine.The potential application of specific inorganic and organic depressants in the flotation separation of Cu–Fe sulfide minerals at low alkalinity is reviewed.The advances in the use of organic depressants with respect to the flotation separation of Cu–Fe sulfide minerals are comprehensively detailed.Additionally,the depression performances and mechanisms of different types of organic depressants on mineral surfaces are summarized.Finally,several perspectives on depressants vis-à-vis flotation separation of Cu–Fe sulfide minerals at low alkalinity are proposed.展开更多
In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited...In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.展开更多
Nafion as a universal polymer ionomer was widely applied for nanocatalysts electrode preparation.However,the effect of Nafion on electrocatalytic performance was often overlooked,especially for CO_(2)electrolysis.Here...Nafion as a universal polymer ionomer was widely applied for nanocatalysts electrode preparation.However,the effect of Nafion on electrocatalytic performance was often overlooked,especially for CO_(2)electrolysis.Herein,the key roles of Nafion for CO_(2)RR were systematically studied on Cu nanoparticles(NPs)electrocatalyst.We found that Nafion modifier not only inhibit hydrogen evolution reaction(HER)by decreasing the accessibility of H_(2)O from electrolyte to Cu NPs,and increase the CO_(2)concentration at electrocatalyst interface for enhancing the CO_(2)mass transfer process,but also activate CO_(2)molecule by Lewis acid-base interaction between Nafion and CO_(2)to accelerate the formation of^(*)CO,which favor of C–C coupling for boosting C_(2)product generation.Owing to these features,the HER selectivity was suppressed from 40.6%to 16.8%on optimal Cu@Nafion electrode at-1.2 V versus reversible hydrogen electrode(RHE),and as high as 73.5%faradaic efficiencies(FEs)of C_(2)products were achieved at the same applied potential,which was 2.6 times higher than that on bare Cu electrode(~28.3%).In addition,Nafion also contributed to the long-term stability by hinder Cu NPs morphology reconstruction.Thus,this work provides insights into the impact of Nafion on electrocatalytic CO_(2)RR performance.展开更多
Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a ch...Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a challenge.Herein,cuprous sulfide nanosheets with different Cu vacancy concentration were employed to study IEF modulation and corresponding direct charge transfer.Among the samples,Cu_(1.8)S nanosheets possessed intensified IEF intensity compared with those of Cu_(2)S and Cu_(1.95)S nanosheets,suggesting that an enhanced IEF intensity could be achieved by introducing more Cu vacancies.This intensified IEF of Cu_(1.8)S nanosheets induced numerous photogenerated electrons to migrate to its surface,and the dissociative electrons were then captured by Cu vacancies,resulting in efficient charge separation spatially.In addition,the Cu vacancies on Cu_(1.8)S nanosheets accumulated electrons as active sites to lower the energy barrier of rate-determining step of CO_(2)photoreduction,leading to the selective conversion of CO_(2)to CO.Herein,the manipulation of IEF intensity through Cu vacancy concentration regulation of cuprous sulfide photocatalysts for efficient charge separation has been discussed,providing a scientific strategy to rationally improve photocata lytic performances for solar energy conversion.展开更多
Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedra...Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedral local structures.To determine the microstructures of Zr–Cu clusters, the stable and metastable geometry of Zr_(n)Cu(n=2–12) clusters are screened out via the CALYPSO method using machine-learning potentials, and then the electronic structures are investigated using density functional theory. The results show that the Zr_(n)Cu(n ≥ 3) clusters possess three-dimensional geometries, Zr_(n)Cu(n≥9) possess cage-like geometries, and the Zr_(12)Cu cluster has icosahedral geometry. The binding energy per atom gradually gets enlarged with the increase in the size of the clusters, and Zr_(n)Cu(n=5,7,9,12) have relatively better stability than their neighbors. The magnetic moment of most Zr_(n)Cu clusters is just 1μB, and the main components of the highest occupied molecular orbitals(HOMOs) in the Zr_(12)Cu cluster come from the Zr-d state. There are hardly any localized two-center bonds, and there are about 20 σ-type delocalized three-center bonds.展开更多
基金Funded by Shenzhen-Hong Kong Innovative Collaborative Research and Development Program (Nos.SGLH20181109 110802117, CityU 9240014)Innovation Project of Southwestern Institute of Physics (Nos.202001XWCXYD002, 202301XWCX003)CNNC Young Talent Program (No.2023JZYF-01)。
文摘Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.
基金This research was funded by the National Natural Science Foundation of China(No.41862007)the Key Disciplines Construction of Kunming University of Science and Technology(No.14078384)the Yunnan Ten Thousand Talents Plan Young&Elite Talents Project(YNWR-QNBJ-2018-093)。
文摘The Yangla Cu skarn deposit is located in the central part of the Jinshajiang Suture Zone,southwest China,with a total reserve of 150 Mt Cu@1.03%.The newly discovered antimony orebodies at the depth of Yangla are strictly controlled by the stratum,structure,and lithology,which are lenticular and vein-like within the marble fracture zone,which can provide a window into multistage miner-alization and ore genesis at Yangla.Mineralization can be divided into three types,Cu–Pb–Zn(skarn)pyrite,galena,and sphalerite,Cu(porphyry)chalcopyrite and pyrite,and Sb(hydrothermal)stibnite and pyrite.The mineral assem-blages were stibnite+pyrite+calcite+quartz±minor scheelite in antimony ores.This study presents quantitative measurements of the trace element compositions of pyrite and stibnite from the Yangla antimony ores.Analysis of pyrite with electron probe microanalysis(EPMA)showed enrichment in Co,Ni,Sb,As,and Mo,and deficit in its S and Fe contents when compared to the stoichiometric con-centrations of S and Fe in pyrite.The Sb-related pyrite may belong to sedimentary-reworked genesis and may be modi-fied by hydrothermalfluids,thereby presenting a certain dif-ference(i.e.,crystal morphology,texture,and chemical com-position)compared to the skarn and porphyry Cu-related pyrite in the Yangla Cu skarn deposit.Analysis of stibnite with EPMA and inductively coupled plasma-mass spectrom-etry showed enrichment in As,Pb,Sn,Pb,Cu,and Zn,and presented much higher Sb contents and slightly lower S con-tents when compared to the stoichiometric concentrations of Sb and S in stibnite.Statistical analysis of the stibnite trace elements showed correlations for the elemental pairs Cu–Pb,As–Sb,and Sn–Pb,and the coupled substitution equations Sb^(3+)↔Cu^(+)+Pb^(2+),Sb^(3+)↔As^(3+),and Sn^(2+)↔Pb^(2+)may be the major factors governed the incorporating Cu,Pb,As and Sn within the stibnite.Moreover,this study preliminary shows that the antimony mineralization may belong to a car-bonate replacement hydrothermal genesis at Yangla.
基金financially supported by the Yunnan Major Scientific and Technological Projects,China (No.202202AG050015)the National Natural Science Foundation of China (No.51464029)。
文摘The flotation separation of Cu–Fe sulfide minerals at low alkalinity can be achieved using selective depressants.In the flotation system of Cu–Fe sulfide minerals,depressants usually preferentially interact with the pyrite surface to render the mineral surface hydrophilic and hinder the adsorption of the collector.This review summarizes the advances in depressants for the flotation separation of Cu–Fe sulfide minerals at low alkalinity.These advances include use of inorganic depressants (oxidants and sulfur–oxygen compounds),natural polysaccharides (starch,dextrin,konjac glucomannan,and galactomannan),modified polymers (carboxymethyl cellulose,polyacrylamide,lignosulfonate,and tricarboxylate sodium starch),organic acids (polyglutamic acid,sodium humate,tannic acid,pyrogallic acid,salicylic acid,and lactic acid),sodium dimethyl dithiocarbamate,and diethylenetriamine.The potential application of specific inorganic and organic depressants in the flotation separation of Cu–Fe sulfide minerals at low alkalinity is reviewed.The advances in the use of organic depressants with respect to the flotation separation of Cu–Fe sulfide minerals are comprehensively detailed.Additionally,the depression performances and mechanisms of different types of organic depressants on mineral surfaces are summarized.Finally,several perspectives on depressants vis-à-vis flotation separation of Cu–Fe sulfide minerals at low alkalinity are proposed.
基金supported by the National Natural Science Foundation of China(32371407,82160421)the Natural Science Foundation of Jiangsu Province(BK20211322)。
文摘In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.
基金financially supported by the Natural Science Foundation of Guangdong Province (2022A1515012359)the National Natural Science Foundation of China (21902121)+1 种基金the STU Scientific Research Foundation for Talents (NTF21020)the 2020 Li Ka Shing Foundation Cross-Disciplinary Research Grant (2020LKSFG09A)。
文摘Nafion as a universal polymer ionomer was widely applied for nanocatalysts electrode preparation.However,the effect of Nafion on electrocatalytic performance was often overlooked,especially for CO_(2)electrolysis.Herein,the key roles of Nafion for CO_(2)RR were systematically studied on Cu nanoparticles(NPs)electrocatalyst.We found that Nafion modifier not only inhibit hydrogen evolution reaction(HER)by decreasing the accessibility of H_(2)O from electrolyte to Cu NPs,and increase the CO_(2)concentration at electrocatalyst interface for enhancing the CO_(2)mass transfer process,but also activate CO_(2)molecule by Lewis acid-base interaction between Nafion and CO_(2)to accelerate the formation of^(*)CO,which favor of C–C coupling for boosting C_(2)product generation.Owing to these features,the HER selectivity was suppressed from 40.6%to 16.8%on optimal Cu@Nafion electrode at-1.2 V versus reversible hydrogen electrode(RHE),and as high as 73.5%faradaic efficiencies(FEs)of C_(2)products were achieved at the same applied potential,which was 2.6 times higher than that on bare Cu electrode(~28.3%).In addition,Nafion also contributed to the long-term stability by hinder Cu NPs morphology reconstruction.Thus,this work provides insights into the impact of Nafion on electrocatalytic CO_(2)RR performance.
基金supported by the National Natural Science Foundation of China(52200123)the Open Project of Key Laboratory of Green Chemical Engineering Process of Ministry of Education(GCP2022007)the Scientific Research and Innovation Team Program of Sichuan University of Science and Engineering(SUSE652A014)。
文摘Although the internal electric field(IEF)of photocatalysts is acknowledged as a potent driving force for photocharge separation,modulating the IEF intensity to achieve enhanced photocatalytic performances remains a challenge.Herein,cuprous sulfide nanosheets with different Cu vacancy concentration were employed to study IEF modulation and corresponding direct charge transfer.Among the samples,Cu_(1.8)S nanosheets possessed intensified IEF intensity compared with those of Cu_(2)S and Cu_(1.95)S nanosheets,suggesting that an enhanced IEF intensity could be achieved by introducing more Cu vacancies.This intensified IEF of Cu_(1.8)S nanosheets induced numerous photogenerated electrons to migrate to its surface,and the dissociative electrons were then captured by Cu vacancies,resulting in efficient charge separation spatially.In addition,the Cu vacancies on Cu_(1.8)S nanosheets accumulated electrons as active sites to lower the energy barrier of rate-determining step of CO_(2)photoreduction,leading to the selective conversion of CO_(2)to CO.Herein,the manipulation of IEF intensity through Cu vacancy concentration regulation of cuprous sulfide photocatalysts for efficient charge separation has been discussed,providing a scientific strategy to rationally improve photocata lytic performances for solar energy conversion.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.11864040,11964037,and 11664038)。
文摘Zr-based amorphous alloys have attracted extensive attention because of their large glassy formation ability, wide supercooled liquid region, high elasticity, and unique mechanical strength induced by their icosahedral local structures.To determine the microstructures of Zr–Cu clusters, the stable and metastable geometry of Zr_(n)Cu(n=2–12) clusters are screened out via the CALYPSO method using machine-learning potentials, and then the electronic structures are investigated using density functional theory. The results show that the Zr_(n)Cu(n ≥ 3) clusters possess three-dimensional geometries, Zr_(n)Cu(n≥9) possess cage-like geometries, and the Zr_(12)Cu cluster has icosahedral geometry. The binding energy per atom gradually gets enlarged with the increase in the size of the clusters, and Zr_(n)Cu(n=5,7,9,12) have relatively better stability than their neighbors. The magnetic moment of most Zr_(n)Cu clusters is just 1μB, and the main components of the highest occupied molecular orbitals(HOMOs) in the Zr_(12)Cu cluster come from the Zr-d state. There are hardly any localized two-center bonds, and there are about 20 σ-type delocalized three-center bonds.
基金supports from the National Natural Science Foundation of China(No.52075495)the Natural Science Foundation of Zhejiang Province,China(No.LY22E050017)the Fundamental Research Funds for the Provincial Universities of Zhejiang,China(No.RF-A2020009).
