采用沉淀法-水热法合成了电催化Bi_(2)O_(3)-CuO复合材料.利用X-射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X-射线光电子能谱(XPS)等方法对样品的结构和形貌进行了研究.用电化学测试方法对材料电催化性能进行研究,用...采用沉淀法-水热法合成了电催化Bi_(2)O_(3)-CuO复合材料.利用X-射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X-射线光电子能谱(XPS)等方法对样品的结构和形貌进行了研究.用电化学测试方法对材料电催化性能进行研究,用气相色谱和核磁共振氢谱对产物进行分析.电催化实验结果表明,Bi_(2)O_(3)-CuO复合材料的电催化性能及对甲酸盐的选择性远高于Bi_(2)O_(3)和CuO.其中比例为1∶1的Bi_(2)O_(3)-CuO复合材料性能最好,在-1.2 V vs.RHE的电位下,甲酸盐的法拉第效率为90.3%,电流密度为20 mA/cm^(2),测试10 h保持稳定.展开更多
The metal promoted In_(2)O_(3) catalysts for CO_(2) hydrogenation to methanol have attracted wide attention because of their high activity with high methanol selectivity.However,there was still no experimental confirm...The metal promoted In_(2)O_(3) catalysts for CO_(2) hydrogenation to methanol have attracted wide attention because of their high activity with high methanol selectivity.However,there was still no experimental confirmation if copper could be a good promoter for In_(2)O_(3).Herein,the Cu promoted In_(2)O_(3) catalyst was prepared using a deposition-precipitation method.Such prepared Cu/In_(2)O_(3) catalyst shows significantly higher CO_(2) conversion and space time yield(STY)of methanol,compared to the un-promoted In_(2)O_(3) catalyst.The loading of Cu facilitates the activation of both H_(2) and CO_(2) with the interface between the Cu cluster and defective In_(2)O_(3) as the active site.The Cu/In_(2)O_(3) catalyst takes the CO hydrogenation pathway for methanol synthesis from CO_(2) hydrogenation.It exhibits a unique size effect on the CO adsorption.At temperatures below 250℃,CO adsorption on Cu/In_(2)O_(3) is stronger than that on In_(2)O_(3),causing higher methanol selectivity.With increasing temperatu res,the Cu catalyst aggregates,which leads to the formation of weak CO adsorption site and causes a decrease in the methanol selectivity.Compared with other metal promoted In_(2)O_(3) catalysts,it can be concluded that the catalyst with stronger CO adsorption possesses higher methanol selectivity.展开更多
利用可再生的电能将CO_(2)还原为高附加值的化学品和燃料,对于缓解温室效应并实现碳中和具有重要的意义。开发了一种简单有效的方法制备非金属P元素掺杂的In_(2)O_(3)纳米颗粒,并将其用于电催化CO_(2)还原制甲酸盐。在H型电解池中,在-1....利用可再生的电能将CO_(2)还原为高附加值的化学品和燃料,对于缓解温室效应并实现碳中和具有重要的意义。开发了一种简单有效的方法制备非金属P元素掺杂的In_(2)O_(3)纳米颗粒,并将其用于电催化CO_(2)还原制甲酸盐。在H型电解池中,在-1.45 V vs.RHE电位下,P掺杂的In_(2)O_(3)纳米催化剂的产甲酸法拉第效率达到88.2%,同时具有优异的稳定性。进一步的实验分析和理论研究表明,掺杂在In_(2)O_(3)晶格中的P元素显著促进了CO_(2)分子的吸附和活化,降低了形成*HCOO中间体的吉布斯自由能,同时加强了对*HCOO的吸附作用,最终促进了甲酸盐的合成。阐明了非金属元素P掺杂对提升CO_(2)还原反应性能的分子机制,同时也为其他金属氧化物基的高性能电催化剂的设计提供了一种可行的策略。展开更多
TiO_(2) nanobelts and Co_(3)O_(4)/TiO_(2) catalytic materials were prepared using the hydrothermal method.The cat-alyst was characterized by X-ray diffraction,scanning electron microscopy,transmission electron microsc...TiO_(2) nanobelts and Co_(3)O_(4)/TiO_(2) catalytic materials were prepared using the hydrothermal method.The cat-alyst was characterized by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,X-ray electron spectroscopy,and fluorescence spectroscopy.At room temperature,with a relative humidity of 50.0%,the total gas flow rate of 1.0 L·min-1,the space velocity of 1.05×10^(4) h^(-1),and toluene volume concentration of 25.0µL·L^(-1),two 6 W vacuum ultraviolet lamps were used as light sources to catalyze,degrade,and mineralize toluene.The results show that the prepared catalyst is in the shape of nano-ribbons.The loading of Co_(3)O_(4) inhibits the recombina-tion of photogenerated electrons and holes and can effectively improve the catalytic performance.The Co_(3)O_(4)/TiO_(2) with a load of 6.0%Co_(3)O_(4) has the best catalytic effect.When N2 was used as a carrier gas,the degradation rate of tol-uene was only 34.7%.The toluene degradation is mainly due to the photolysis of vacuum ultraviolet light.When air was used as a carrier gas,O_(3) was produced.The Co_(3)O_(4)/TiO_(2) with a load of 6.0%and vacuum ultraviolet synergistical-ly promote toluene degradation.The highest degradation rate of toluene was 91.7%and the mineralization rate was 74.6%.The degradation rate of toluene was 2.6 times that of nitrogen as a carrier gas.展开更多
Since the catalytic activity of most nanozymes is still far lower than the corresponding natural enzymes,there is urgent need to discover novel highly efficient enzyme-like materials.In this work,Co_(3)V_(2)O_(8)with ...Since the catalytic activity of most nanozymes is still far lower than the corresponding natural enzymes,there is urgent need to discover novel highly efficient enzyme-like materials.In this work,Co_(3)V_(2)O_(8)with hollow hexagonal prismatic pencil structures were prepared as novel artificial enzyme mimics.They were then decorated by photo-depositing Ag nanoparticles(Ag NPs)on the surface to further improve its catalytic activities.The Ag NPs decorated Co_(3)V_(2)O_(8)(ACVPs)showed both excellent oxidase-and peroxidase-like catalytic activities.They can oxidize the colorless 3,3’,5,5’-tetramethylbenzidine rapidly to induce a blue change.The enhanced enzyme mimetic activities can be attributed to the surface plasma resonance(SPR)effect of Ag NPs as well as the synergistic catalytic effect between Ag NPs and Co_(3)V_(2)O_(8),accelerating electron transfer and promoting the catalytic process.ACVPs were applied in constructing a colorimetric sensor,validating the occurrence of the Fenton reaction,and disinfection,presenting favorable catalytic performance.The enzyme-like catalytic mechanism was studied,indicating the chief role of⋅O_(2)-radicals in the catalytic process.This work not only discovers a novel functional material with double enzyme mimetic activity but also provides a new insight into exploiting artificial enzyme mimics with highly efficient catalytic ability.展开更多
Indium oxide(In_(2)O_(3)),as a promising candidate for CO_(2)hydrogenation to C_(1) products,often suffers from sintering and activity decline,closely related to the undesirable structural evolution under reaction con...Indium oxide(In_(2)O_(3)),as a promising candidate for CO_(2)hydrogenation to C_(1) products,often suffers from sintering and activity decline,closely related to the undesirable structural evolution under reaction conditions.Based on the comprehension of the dynamic evolution,this study presents an efficient strategy to alleviate the agglomeration of In_(2)O_(3)nanoparticles by the surface decoration with highly dispersed silica species(SiO_(x)).Various structural characterizations combined with density functional theory calculations demonstrated that the sintering resulted from the over-reduction,while the enhanced stability originated from the anchoring effect of highly stable In-OSi bonds,which hinders the substantial formation of metallic In(In^(0))and the subsequent agglomeration.0.6Si/In_(2)O_(3)exhibited CO_(2)conversion rate of10.0 mmol g^(-1)h^(-1)at steady state vs.3.5 mmol g^(-1)h^(-1)on In_(2)O_(3)in CO_(2)hydrogenation.Enhanced steady-state activity was also achieved on Pd-modified catalysts.Compared to the traditional Pd/In_(2)O_(3)catalyst,the methanol production rate of Pd catalyst supported on 0.6Si/In_(2)O_(3)was enhanced by 23%,showing the potential of In_(2)O_(3)modified by SiO_(x)in serving as a platform material.This work provides a promising method to design new In_(2)O_(3)-based catalysts with improved activity and stability in CO_(2)hydrogenation.展开更多
High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface...High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.展开更多
文摘采用沉淀法-水热法合成了电催化Bi_(2)O_(3)-CuO复合材料.利用X-射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X-射线光电子能谱(XPS)等方法对样品的结构和形貌进行了研究.用电化学测试方法对材料电催化性能进行研究,用气相色谱和核磁共振氢谱对产物进行分析.电催化实验结果表明,Bi_(2)O_(3)-CuO复合材料的电催化性能及对甲酸盐的选择性远高于Bi_(2)O_(3)和CuO.其中比例为1∶1的Bi_(2)O_(3)-CuO复合材料性能最好,在-1.2 V vs.RHE的电位下,甲酸盐的法拉第效率为90.3%,电流密度为20 mA/cm^(2),测试10 h保持稳定.
基金supported by the National Natural Science Foundation of China(22138009)the Fundamental Research Funds for the Central Universities of China。
文摘The metal promoted In_(2)O_(3) catalysts for CO_(2) hydrogenation to methanol have attracted wide attention because of their high activity with high methanol selectivity.However,there was still no experimental confirmation if copper could be a good promoter for In_(2)O_(3).Herein,the Cu promoted In_(2)O_(3) catalyst was prepared using a deposition-precipitation method.Such prepared Cu/In_(2)O_(3) catalyst shows significantly higher CO_(2) conversion and space time yield(STY)of methanol,compared to the un-promoted In_(2)O_(3) catalyst.The loading of Cu facilitates the activation of both H_(2) and CO_(2) with the interface between the Cu cluster and defective In_(2)O_(3) as the active site.The Cu/In_(2)O_(3) catalyst takes the CO hydrogenation pathway for methanol synthesis from CO_(2) hydrogenation.It exhibits a unique size effect on the CO adsorption.At temperatures below 250℃,CO adsorption on Cu/In_(2)O_(3) is stronger than that on In_(2)O_(3),causing higher methanol selectivity.With increasing temperatu res,the Cu catalyst aggregates,which leads to the formation of weak CO adsorption site and causes a decrease in the methanol selectivity.Compared with other metal promoted In_(2)O_(3) catalysts,it can be concluded that the catalyst with stronger CO adsorption possesses higher methanol selectivity.
文摘利用可再生的电能将CO_(2)还原为高附加值的化学品和燃料,对于缓解温室效应并实现碳中和具有重要的意义。开发了一种简单有效的方法制备非金属P元素掺杂的In_(2)O_(3)纳米颗粒,并将其用于电催化CO_(2)还原制甲酸盐。在H型电解池中,在-1.45 V vs.RHE电位下,P掺杂的In_(2)O_(3)纳米催化剂的产甲酸法拉第效率达到88.2%,同时具有优异的稳定性。进一步的实验分析和理论研究表明,掺杂在In_(2)O_(3)晶格中的P元素显著促进了CO_(2)分子的吸附和活化,降低了形成*HCOO中间体的吉布斯自由能,同时加强了对*HCOO的吸附作用,最终促进了甲酸盐的合成。阐明了非金属元素P掺杂对提升CO_(2)还原反应性能的分子机制,同时也为其他金属氧化物基的高性能电催化剂的设计提供了一种可行的策略。
文摘TiO_(2) nanobelts and Co_(3)O_(4)/TiO_(2) catalytic materials were prepared using the hydrothermal method.The cat-alyst was characterized by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,X-ray electron spectroscopy,and fluorescence spectroscopy.At room temperature,with a relative humidity of 50.0%,the total gas flow rate of 1.0 L·min-1,the space velocity of 1.05×10^(4) h^(-1),and toluene volume concentration of 25.0µL·L^(-1),two 6 W vacuum ultraviolet lamps were used as light sources to catalyze,degrade,and mineralize toluene.The results show that the prepared catalyst is in the shape of nano-ribbons.The loading of Co_(3)O_(4) inhibits the recombina-tion of photogenerated electrons and holes and can effectively improve the catalytic performance.The Co_(3)O_(4)/TiO_(2) with a load of 6.0%Co_(3)O_(4) has the best catalytic effect.When N2 was used as a carrier gas,the degradation rate of tol-uene was only 34.7%.The toluene degradation is mainly due to the photolysis of vacuum ultraviolet light.When air was used as a carrier gas,O_(3) was produced.The Co_(3)O_(4)/TiO_(2) with a load of 6.0%and vacuum ultraviolet synergistical-ly promote toluene degradation.The highest degradation rate of toluene was 91.7%and the mineralization rate was 74.6%.The degradation rate of toluene was 2.6 times that of nitrogen as a carrier gas.
基金supported by National Natural Science Foundation of China(52208272,41706080 and 51702328)the Basic Scientific Fund for National Public Research Institutes of China(2020S02 and 2019Y03)+3 种基金the Basic Frontier Science Research Program of Chinese Academy of Sciences(ZDBS-LY-DQC025)the Young Elite Scientists Sponsorship Program by CAST(No.YESS20210201)the Strategic Leading Science&Technology Program of the Chinese Academy of Sciences(XDA13040403)the Key Research and Development Program of Shandong Province(Major Scientific and Technological Innovation Project)(2019JZZY020711).
文摘Since the catalytic activity of most nanozymes is still far lower than the corresponding natural enzymes,there is urgent need to discover novel highly efficient enzyme-like materials.In this work,Co_(3)V_(2)O_(8)with hollow hexagonal prismatic pencil structures were prepared as novel artificial enzyme mimics.They were then decorated by photo-depositing Ag nanoparticles(Ag NPs)on the surface to further improve its catalytic activities.The Ag NPs decorated Co_(3)V_(2)O_(8)(ACVPs)showed both excellent oxidase-and peroxidase-like catalytic activities.They can oxidize the colorless 3,3’,5,5’-tetramethylbenzidine rapidly to induce a blue change.The enhanced enzyme mimetic activities can be attributed to the surface plasma resonance(SPR)effect of Ag NPs as well as the synergistic catalytic effect between Ag NPs and Co_(3)V_(2)O_(8),accelerating electron transfer and promoting the catalytic process.ACVPs were applied in constructing a colorimetric sensor,validating the occurrence of the Fenton reaction,and disinfection,presenting favorable catalytic performance.The enzyme-like catalytic mechanism was studied,indicating the chief role of⋅O_(2)-radicals in the catalytic process.This work not only discovers a novel functional material with double enzyme mimetic activity but also provides a new insight into exploiting artificial enzyme mimics with highly efficient catalytic ability.
基金financially supported by the National Natural Science Foundation of China(22172013)the Special Project for Key Research and Development Program of Xinjiang Autonomous Region(2022B01033-3)+3 种基金the Liaoning Revitalization Talent Program(XLYC2008032 and XLYC2203126)the Fundamental Research Funds for the Central Universities(DUT22LK24,DUT22QN207 and DUT22LAB602)the CUHK Research Startup Fund(No.#4930981)financial support from Catalyst:Seeding funding(CSG-VUW2201)provided by the New Zealand Ministry of Business,Innovation and Employment and administered by the Royal Society Aparangi。
文摘Indium oxide(In_(2)O_(3)),as a promising candidate for CO_(2)hydrogenation to C_(1) products,often suffers from sintering and activity decline,closely related to the undesirable structural evolution under reaction conditions.Based on the comprehension of the dynamic evolution,this study presents an efficient strategy to alleviate the agglomeration of In_(2)O_(3)nanoparticles by the surface decoration with highly dispersed silica species(SiO_(x)).Various structural characterizations combined with density functional theory calculations demonstrated that the sintering resulted from the over-reduction,while the enhanced stability originated from the anchoring effect of highly stable In-OSi bonds,which hinders the substantial formation of metallic In(In^(0))and the subsequent agglomeration.0.6Si/In_(2)O_(3)exhibited CO_(2)conversion rate of10.0 mmol g^(-1)h^(-1)at steady state vs.3.5 mmol g^(-1)h^(-1)on In_(2)O_(3)in CO_(2)hydrogenation.Enhanced steady-state activity was also achieved on Pd-modified catalysts.Compared to the traditional Pd/In_(2)O_(3)catalyst,the methanol production rate of Pd catalyst supported on 0.6Si/In_(2)O_(3)was enhanced by 23%,showing the potential of In_(2)O_(3)modified by SiO_(x)in serving as a platform material.This work provides a promising method to design new In_(2)O_(3)-based catalysts with improved activity and stability in CO_(2)hydrogenation.
基金supported by the National Key R&D Program of China(Grant No.2023YFB2503900)the National Natural Science Foundation of China(Grant No.52372203)+1 种基金the National Natural Science Foundation of China(Grant No.52202259)the Shandong Province Natural Science Foundation(ZR2022QE093).
文摘High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.
