Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for d...Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for degradation of antibiotics still faces some challenges.In this study,a CoFe_(2)O_(4)/MgAl-LDH composite catalyst was synthesized using a hydrothermal coprecipitation method.Comprehensive characterization reveals that the surface of MgAl-LDH is covered with nanometer CoFe_(2)O_(4) particles.The specific surface area of CoFe_(2)O_(4)/MgAl-LDH is 82.84 m^(2)·g^(-)1,which is 2.34 times that of CoFe_(2)O_(4).CoFe_(2)O_(4)/MgAl-LDH has a saturation magnetic strength of 22.24 A·m^(2)·kg^(-1) facilitating efficient solid-liquid separation.The composite catalyst was employed to activate peroxymonosulfate(PMS)for the efficient degradation of tetracycline hydrochloride(TCH).It is found that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH significantly exceeds that of CoFe_(2)O_(4).The maximum TCH removal reaches 98.2%under the optimal conditions([TCH]=25 mg/L,[PMS]=1.5 mmol/L,CoFe_(2)O_(4)/MgAl-LDH=0.20 g/L,pH 7,and T=25℃).Coexisting ions in the solution,such as SO_(4)^(2-),Cl-,H_(2)PO_(4)^(-),and CO_(3)^(2-),have a negligible effect on catalytic performance.Cyclic tests demonstrate that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH remains 67.2%after five cycles.Mechanism investigations suggest that O_(2)^(•-)and ^(1)O_(2) produced by CoFe_(2)O_(4)/MgAl-LDH play a critical role in the catalytic degradation.展开更多
A SiC/ZrSiO4？SiO2 （SZS） coating was successfully fabricated on the carbon/carbon （C/C） composites by pack cementation, slurry painting and sintering to improve the anti-oxidation property and thermal shock r...A SiC/ZrSiO4？SiO2 （SZS） coating was successfully fabricated on the carbon/carbon （C/C） composites by pack cementation, slurry painting and sintering to improve the anti-oxidation property and thermal shock resistance. The anti-oxidation properties under different oxygen partial pressures （OPP） and thermal shock resistance of the SZS coating were investigated. The results show that the SZS coated sample under low OPP, corresponding to the ambient air, during isothermal oxidation was 0.54% in mass gain after 111 h oxidation at 1500 ° C and less than 0.03% in mass loss after 50 h oxidation in high OPP, corresponding to the air flow rate of 36 L/h. Additionally, the residual compressive strengths （RCS） of the SZS coated samples after oxidation for 50 h in high OPP and 80 h in low OPP remain about 70% and 72.5% of those of original C/C samples, respectively. Moreover, the mass loss of SZS coated samples subjected to the thermal cycle from 1500 ° C in high OPP to boiling water for 30 times was merely 1.61%.展开更多
Transition metal Ni anchored in carbon material represents outstanding 2e^(-) oxygen reduction reaction(ORR)catalytic selectivity,but enhancing the adsorption strength of intermediate*OOH to promote its selectivity re...Transition metal Ni anchored in carbon material represents outstanding 2e^(-) oxygen reduction reaction(ORR)catalytic selectivity,but enhancing the adsorption strength of intermediate*OOH to promote its selectivity remains a major challenge.Herein,the NiX/Ni@NCHS composite catalyst with heteroatom doping(O,S)is modulated by controlling partial pyrolysis strategies on honeycomb-like porous carbon to manipulate the electronic structure of the metal Ni.With the synergistic effect of honeycomb structure and O atom,NiO/Ni@NCHS-700 exhibits an exceptional H_(2)O_(2)selectivity of above 89.1%across a wide potential range from 0.1 to 0.6 V in an alkaline electrolyte,and an unexpected H_(2)O_(2)production rate up to 1.47 mol gcat^(-1) h^(-1)@0.2 V,which outperforms most of the state-of-the-art catalyst.Meanwhile,NiS/Ni@NCHS exhibits excellent electrocatalytic performance,with 2e^(-) ORR selectivity of 91.3%,H_(2)O_(2)yield of 1.85@0.3 V.Density functional theory simulations and experiments results reveal that the heteroatom doping(O,S)method has been employed to regulate the adsorption strength of Ni atoms with*OOH,and combined with the self-sacrificing template-assisted pyrolysis approach to improve the microstructure of catalysts and optimize the active site.The heteroatom doping method in this work provides significant guidance for promoting 2e^(-) ORR electrocatalysis to produce H_(2)O_(2).展开更多
BNp/Al2O3-SiO2 system ceramic matrix composites with different volume fractions （10%-60%） of hexagonal BN particulates （BNp） were prepared by hot-press sintering technique. Phase components, microstructure, mechan...BNp/Al2O3-SiO2 system ceramic matrix composites with different volume fractions （10%-60%） of hexagonal BN particulates （BNp） were prepared by hot-press sintering technique. Phase components, microstructure, mechanical properties and plasma erosion resistance were also investigated. With the increase of h-BNp content, relative density and Vickers＇ hardness of the composite ceramics decrease, while the flexural strength, elastic modulus and fracture toughness increase and then decrease. The plasma erosion resistance linearly deteriorated with the increase of BNp content which is mainly determined by the density, crystal structure and atomic number of the elements.展开更多
The utilization of metal oxide‐zeolite catalysts in the syngas‐to‐olefin reaction is a promising strategy for producing C_(2)–C_(4) olefins from non‐petroleum resources.However,the effect of the crystal phase of ...The utilization of metal oxide‐zeolite catalysts in the syngas‐to‐olefin reaction is a promising strategy for producing C_(2)–C_(4) olefins from non‐petroleum resources.However,the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous.Herein,typical metal oxides(ZnO/ZrO_(2))with different crystal phases(monoclinic(m‐ZrO_(2))and tetragonal(t‐ZrO_(2)))were employed for syngas conversion.The(ZnO/m‐ZrO_(2)+SAPO‐34)composite catalyst exhibited 80.5%selectivity for C_(2)–C_(4) olefins at a CO conversion of 27.9%,where the results are superior to those(CO conversion of 16.4%and C_(2)–C_(4) olefin selectivity of 76.1%)obtained over(ZnO/t‐ZrO_(2)+SAPO‐34).The distinct differences are ascribed to the larger number of hydroxyl groups,Lewis acid sites,and oxygen defects in ZnO/m‐ZrO_(2) compared to ZnO/t‐ZrO_(2).These features result in the formation of more formate and methoxy intermediate species on the ZnO/m‐ZrO_(2) oxides during syngas conversion,followed by the formation of more light olefins over SAPO‐34.The present findings provide useful information for the design of highly efficient ZrO_(2)‐based catalysts for syngas conversion.展开更多
This article reports the production of COx free hydrogen and carbon nanofibers by the catalytic decomposition of methane over Ni-Al2O3-SiO2 catalysts. The influence of reaction temperature, pretreatment temperature, a...This article reports the production of COx free hydrogen and carbon nanofibers by the catalytic decomposition of methane over Ni-Al2O3-SiO2 catalysts. The influence of reaction temperature, pretreatment temperature, and effect of reductive pretreatment on the decomposition of methane activity is investigated. The physico-chemical characteristics of fresh and deactivated samples were characterized using BET-SA, XRD, TPR, SEM/TEM, CHNS analyses and correlated with the methane decomposition results obtained. The Ni-Al-Si （4 ： 0.5 ： 1.5） catalyst reduced with hydrazine hydrate produced better H2 yields of ca. 1815 mol H2/mol Ni than the catalyst reduced with 5% H2/N2.展开更多
Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO...Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO 2(a natase), Al 2SiO 5, and ZrO 2 in these membranes. Changing the molar ratio of Al∶Si∶Ti∶Zr,the kinds and content of crystal phases of composite membranes could be different, which may lead to a variety of microstructure of membranes. The surface nanoscale topography and microstructure of membranes were investiga ted by XRD,SEM,AFM,EPMA. The effects of additives and heat treatments on the sur face nanoscale topography and microstructure of composite ceramic membranes were also analyzed.展开更多
TiO2-coated activated carbon surface （TAs） composites were prepared by a sol-gel method with supercritical pretreatment. The photocatalytic degradation of acid yellow （AY） was investigated under UV radiation to es...TiO2-coated activated carbon surface （TAs） composites were prepared by a sol-gel method with supercritical pretreatment. The photocatalytic degradation of acid yellow （AY） was investigated under UV radiation to estimate activity of catalysts and determine the kinetics. And the effects of parameters including the initial concentration of AY, light intensity and TiO2 content in catalysts were examined. The results indicate that TAs has a higher efficiency in decomposition of AY than P25, pure TiO2 particles as well as the mixture of TiO2 powder and active carbon. The photocatalytic degradation rate is found to follow the pseudo-first order kinetics with respect to the AY concentration. The new kinetic model fairly resembles the classic Langmuir-Hinshelwood equation, and the rate constant is proportional to the square root of the light intensity in a wide range. However, its absorption performance depends on the surface areas of catalysts. The model fits quite well with the experimental data and elucidates phenomena about the effects of the TiO2 content in TAs on the degradation rate.展开更多
A series of polymer- supported Pd -Fe2O3 composite catalysts were prepared and their hydrogenation property mas investigated. It was found that the above catalysts have good catalytic hydrogenation activity for carbon...A series of polymer- supported Pd -Fe2O3 composite catalysts were prepared and their hydrogenation property mas investigated. It was found that the above catalysts have good catalytic hydrogenation activity for carbon - carbon double bonds systems and reusability. Furthermore, XPS and IR spectra shouted that active component in the composite catalysts is atomic Pd(0). An addition of a small amount of Fe2O3 has a promotive action upon hydrogenation activity of the catalysts, which indicated that there are some strong interactions (electron transfer) between Pd(0) and Fe(Ⅲ) species. Based on these results, a possible catalytic hydrogenation mechanism was also suggested.展开更多
Over the past decade,electrocatalytic reduction of CO_(2)has gained substantial attention.However,hardly any of the previous reviews have focused on the systematic discussion of polymer-molecular catalyst composites a...Over the past decade,electrocatalytic reduction of CO_(2)has gained substantial attention.However,hardly any of the previous reviews have focused on the systematic discussion of polymer-molecular catalyst composites as an emerging system for the electrochemical transformation of CO_(2)to value-added products.In this review,we first give a brief overview of the general features of solid-state and molecular catalysts,and then advance the discussion to polymer-catalyst composite systems,with particular emphasis on polymer-encapsulated molecular catalysts,where the coordination environment surrounding molecular catalysts can be modified via polymer encapsulation to promote the overall performance of CO_(2)electrocatalysis.The elucidation of the possible reaction mechanisms of this emerging electrocat-alytic system along with proposed optimization strategies is also summarized and discussed based on recently published reports,followed by the challenges and prospects of their industrial applications at the end of this review.From this review,we hope the audience can gain a comprehensive understanding of the electrocatalytic mechanism of the coordinating polymers and valuable insights into engineering the microenvironment surrounding the metal complexes for potential future research directions.展开更多
基金University Synergy Innovation Program of Anhui Province(GXXT-2022-083)Science and Technology Plan Project of Wuhu City,China(2023kx12)Anhui Provincial Department of Education New Era Education Project(2023xscx070)。
文摘Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for degradation of antibiotics still faces some challenges.In this study,a CoFe_(2)O_(4)/MgAl-LDH composite catalyst was synthesized using a hydrothermal coprecipitation method.Comprehensive characterization reveals that the surface of MgAl-LDH is covered with nanometer CoFe_(2)O_(4) particles.The specific surface area of CoFe_(2)O_(4)/MgAl-LDH is 82.84 m^(2)·g^(-)1,which is 2.34 times that of CoFe_(2)O_(4).CoFe_(2)O_(4)/MgAl-LDH has a saturation magnetic strength of 22.24 A·m^(2)·kg^(-1) facilitating efficient solid-liquid separation.The composite catalyst was employed to activate peroxymonosulfate(PMS)for the efficient degradation of tetracycline hydrochloride(TCH).It is found that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH significantly exceeds that of CoFe_(2)O_(4).The maximum TCH removal reaches 98.2%under the optimal conditions([TCH]=25 mg/L,[PMS]=1.5 mmol/L,CoFe_(2)O_(4)/MgAl-LDH=0.20 g/L,pH 7,and T=25℃).Coexisting ions in the solution,such as SO_(4)^(2-),Cl-,H_(2)PO_(4)^(-),and CO_(3)^(2-),have a negligible effect on catalytic performance.Cyclic tests demonstrate that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH remains 67.2%after five cycles.Mechanism investigations suggest that O_(2)^(•-)and ^(1)O_(2) produced by CoFe_(2)O_(4)/MgAl-LDH play a critical role in the catalytic degradation.
基金Project supported by the Nonferrous Metal Oriented Advanced Structural Materials and Manufacturing Cooperative Innovation Center,ChinaProject(51205417)supported by the National Natural Science Foundation of China
文摘A SiC/ZrSiO4？SiO2 （SZS） coating was successfully fabricated on the carbon/carbon （C/C） composites by pack cementation, slurry painting and sintering to improve the anti-oxidation property and thermal shock resistance. The anti-oxidation properties under different oxygen partial pressures （OPP） and thermal shock resistance of the SZS coating were investigated. The results show that the SZS coated sample under low OPP, corresponding to the ambient air, during isothermal oxidation was 0.54% in mass gain after 111 h oxidation at 1500 ° C and less than 0.03% in mass loss after 50 h oxidation in high OPP, corresponding to the air flow rate of 36 L/h. Additionally, the residual compressive strengths （RCS） of the SZS coated samples after oxidation for 50 h in high OPP and 80 h in low OPP remain about 70% and 72.5% of those of original C/C samples, respectively. Moreover, the mass loss of SZS coated samples subjected to the thermal cycle from 1500 ° C in high OPP to boiling water for 30 times was merely 1.61%.
文摘Transition metal Ni anchored in carbon material represents outstanding 2e^(-) oxygen reduction reaction(ORR)catalytic selectivity,but enhancing the adsorption strength of intermediate*OOH to promote its selectivity remains a major challenge.Herein,the NiX/Ni@NCHS composite catalyst with heteroatom doping(O,S)is modulated by controlling partial pyrolysis strategies on honeycomb-like porous carbon to manipulate the electronic structure of the metal Ni.With the synergistic effect of honeycomb structure and O atom,NiO/Ni@NCHS-700 exhibits an exceptional H_(2)O_(2)selectivity of above 89.1%across a wide potential range from 0.1 to 0.6 V in an alkaline electrolyte,and an unexpected H_(2)O_(2)production rate up to 1.47 mol gcat^(-1) h^(-1)@0.2 V,which outperforms most of the state-of-the-art catalyst.Meanwhile,NiS/Ni@NCHS exhibits excellent electrocatalytic performance,with 2e^(-) ORR selectivity of 91.3%,H_(2)O_(2)yield of 1.85@0.3 V.Density functional theory simulations and experiments results reveal that the heteroatom doping(O,S)method has been employed to regulate the adsorption strength of Ni atoms with*OOH,and combined with the self-sacrificing template-assisted pyrolysis approach to improve the microstructure of catalysts and optimize the active site.The heteroatom doping method in this work provides significant guidance for promoting 2e^(-) ORR electrocatalysis to produce H_(2)O_(2).
基金Project(HIT.NSRIF.2010112)supported by the Fundamental Research Fund for the Central Universities,ChinaProjects(50902030,51021002)supported by the National Natural Science Foundation of China
文摘BNp/Al2O3-SiO2 system ceramic matrix composites with different volume fractions （10%-60%） of hexagonal BN particulates （BNp） were prepared by hot-press sintering technique. Phase components, microstructure, mechanical properties and plasma erosion resistance were also investigated. With the increase of h-BNp content, relative density and Vickers＇ hardness of the composite ceramics decrease, while the flexural strength, elastic modulus and fracture toughness increase and then decrease. The plasma erosion resistance linearly deteriorated with the increase of BNp content which is mainly determined by the density, crystal structure and atomic number of the elements.
文摘The utilization of metal oxide‐zeolite catalysts in the syngas‐to‐olefin reaction is a promising strategy for producing C_(2)–C_(4) olefins from non‐petroleum resources.However,the effect of the crystal phase of metal oxides on the catalytic activity of these oxides is still ambiguous.Herein,typical metal oxides(ZnO/ZrO_(2))with different crystal phases(monoclinic(m‐ZrO_(2))and tetragonal(t‐ZrO_(2)))were employed for syngas conversion.The(ZnO/m‐ZrO_(2)+SAPO‐34)composite catalyst exhibited 80.5%selectivity for C_(2)–C_(4) olefins at a CO conversion of 27.9%,where the results are superior to those(CO conversion of 16.4%and C_(2)–C_(4) olefin selectivity of 76.1%)obtained over(ZnO/t‐ZrO_(2)+SAPO‐34).The distinct differences are ascribed to the larger number of hydroxyl groups,Lewis acid sites,and oxygen defects in ZnO/m‐ZrO_(2) compared to ZnO/t‐ZrO_(2).These features result in the formation of more formate and methoxy intermediate species on the ZnO/m‐ZrO_(2) oxides during syngas conversion,followed by the formation of more light olefins over SAPO‐34.The present findings provide useful information for the design of highly efficient ZrO_(2)‐based catalysts for syngas conversion.
文摘This article reports the production of COx free hydrogen and carbon nanofibers by the catalytic decomposition of methane over Ni-Al2O3-SiO2 catalysts. The influence of reaction temperature, pretreatment temperature, and effect of reductive pretreatment on the decomposition of methane activity is investigated. The physico-chemical characteristics of fresh and deactivated samples were characterized using BET-SA, XRD, TPR, SEM/TEM, CHNS analyses and correlated with the methane decomposition results obtained. The Ni-Al-Si （4 ： 0.5 ： 1.5） catalyst reduced with hydrazine hydrate produced better H2 yields of ca. 1815 mol H2/mol Ni than the catalyst reduced with 5% H2/N2.
文摘Al 2O 3-SiO 2-TiO 2-ZrO 2 supported membranes were prepar ed by Sol-Gel method. These composite ceramic membranes are level, even and no macro crack. There exist several crystalline phases such as Al 2O 3, TiO 2(a natase), Al 2SiO 5, and ZrO 2 in these membranes. Changing the molar ratio of Al∶Si∶Ti∶Zr,the kinds and content of crystal phases of composite membranes could be different, which may lead to a variety of microstructure of membranes. The surface nanoscale topography and microstructure of membranes were investiga ted by XRD,SEM,AFM,EPMA. The effects of additives and heat treatments on the sur face nanoscale topography and microstructure of composite ceramic membranes were also analyzed.
基金Project(50802034) supported by the National Natural Science Foundation of ChinaProject(11A093) supported by the Key Project Foundation by the Education Department of Hunan Province,China
文摘TiO2-coated activated carbon surface （TAs） composites were prepared by a sol-gel method with supercritical pretreatment. The photocatalytic degradation of acid yellow （AY） was investigated under UV radiation to estimate activity of catalysts and determine the kinetics. And the effects of parameters including the initial concentration of AY, light intensity and TiO2 content in catalysts were examined. The results indicate that TAs has a higher efficiency in decomposition of AY than P25, pure TiO2 particles as well as the mixture of TiO2 powder and active carbon. The photocatalytic degradation rate is found to follow the pseudo-first order kinetics with respect to the AY concentration. The new kinetic model fairly resembles the classic Langmuir-Hinshelwood equation, and the rate constant is proportional to the square root of the light intensity in a wide range. However, its absorption performance depends on the surface areas of catalysts. The model fits quite well with the experimental data and elucidates phenomena about the effects of the TiO2 content in TAs on the degradation rate.
文摘A series of polymer- supported Pd -Fe2O3 composite catalysts were prepared and their hydrogenation property mas investigated. It was found that the above catalysts have good catalytic hydrogenation activity for carbon - carbon double bonds systems and reusability. Furthermore, XPS and IR spectra shouted that active component in the composite catalysts is atomic Pd(0). An addition of a small amount of Fe2O3 has a promotive action upon hydrogenation activity of the catalysts, which indicated that there are some strong interactions (electron transfer) between Pd(0) and Fe(Ⅲ) species. Based on these results, a possible catalytic hydrogenation mechanism was also suggested.
基金supported by the National Energy R&D Center of Petroleum Refining Technology(RIPP,SINOPEC)the National Key R&D Program of China(Nos.2021YFE0191200 and 2022YFA1504200).
文摘Over the past decade,electrocatalytic reduction of CO_(2)has gained substantial attention.However,hardly any of the previous reviews have focused on the systematic discussion of polymer-molecular catalyst composites as an emerging system for the electrochemical transformation of CO_(2)to value-added products.In this review,we first give a brief overview of the general features of solid-state and molecular catalysts,and then advance the discussion to polymer-catalyst composite systems,with particular emphasis on polymer-encapsulated molecular catalysts,where the coordination environment surrounding molecular catalysts can be modified via polymer encapsulation to promote the overall performance of CO_(2)electrocatalysis.The elucidation of the possible reaction mechanisms of this emerging electrocat-alytic system along with proposed optimization strategies is also summarized and discussed based on recently published reports,followed by the challenges and prospects of their industrial applications at the end of this review.From this review,we hope the audience can gain a comprehensive understanding of the electrocatalytic mechanism of the coordinating polymers and valuable insights into engineering the microenvironment surrounding the metal complexes for potential future research directions.
