The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO2 from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonizatio...The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO2 from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H2S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al2O3(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO2 hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H2S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO2 hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO2 Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnOx in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO2 hydrogenation to methanol,promoting the carbon emission reduction in steel industry.展开更多
The introduction of mesoporous nanosize zirconia to the catalyst for methanol synthesis dedicates the nanosized catalyst and mesoporous duplicated properties. The catalyst bears the larger surface area, larger mesopor...The introduction of mesoporous nanosize zirconia to the catalyst for methanol synthesis dedicates the nanosized catalyst and mesoporous duplicated properties. The catalyst bears the larger surface area, larger mesoporous volume and more uniform diameter, more surface metal atoms and oxygen vacancies than the catalyst prepared with the conventional coprecipitation method. The modification of microstructure and electronic effect could result in the change of the reduced chemical state and decrease of reducuction temperature of copper, donating the higher activity and methanol selectivity to the catalyst. The results of methanol synthesis demonstrate that the Cu^+ is the optimum active site. Also, the interaction between the copper and zirconia shows the synergistic effect to fulfil the methanol synthesis.展开更多
Pairing in the cuprate high-temperature superconductors and its origin remain among the most enduring mysteries in condensed matter physics. With cross-sectional scanning tunneling microscopy/spectroscopy, we clearly ...Pairing in the cuprate high-temperature superconductors and its origin remain among the most enduring mysteries in condensed matter physics. With cross-sectional scanning tunneling microscopy/spectroscopy, we clearly reveal the spatial-dependence or inhomogeneity of the superconducting gap structure of Bi2Sr2CaCu2O8+δ (Bi2212) and YBa2Cu3O7-x (YBCO) along their c-axes on a scale shorter than the interlayer spacing. By tunneling into the (100) plane of a Bi2212 single crystal and a YBCO film, we observe both U-shaped tunneling spectra with extended fiat zero-conductance bottoms, and V-shaped gap structures, in different regions of each sample. On the YBCO film, tunneling into a (110) surface only reveals a U-shaped gap without any zero-bias peak. Our analysis suggests that the U-shaped gap is likely a nodeless superconducting gap. The V-shaped gap has a very small amplitude, and is likely proximity-induced by regions having the larger U-shaped gap.展开更多
A modified co-precipitation method for the production of Cu/ZnO/Al2O3 complex was studied. The modification was that part of Al was introduced by adding Al^(3+) into Cu^(2+)/Zn^(2+) solution, and the rest of ...A modified co-precipitation method for the production of Cu/ZnO/Al2O3 complex was studied. The modification was that part of Al was introduced by adding Al^(3+) into Cu^(2+)/Zn^(2+) solution, and the rest of Al was added after co-precipitation step in the form of pseudo-boehmite. The prepared samples were characterized by different techniques such as X-ray diffraction, N2 adsorption, H2-N2O titration, temperature programmed reduction and scanning electron microscopy. X-ray diffraction characterizations revealed that Al^(3+) can be doped in aurichalcite lattice, and the maximum doping amount of Al^(3+) was 5.0% of total Cu and Zn atoms. The Cu/ZnO/Al2O3 sample produced by the modified method, in which co-precipitated Al^(3+) was 2.5% of total Cu and Zn atoms showed much better activity and stability in water-gas shift reaction than commercial sample. The high Cu surface area(26.1 m^2/g) obtained by decompositon of doped aurichalcite is believed to be responsible for the activity enhancement. The stability was enhanced mainly because of the support effect of γ-Al2O3, which was decomposed from pseudo-boehmite in the calcination step.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22276060 and 21976059)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515012636)China Scholarship Council Scholarship(No.201906155006)。
摘要The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO2 from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H2S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al2O3(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO2 hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H2S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO2 hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO2 Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnOx in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO2 hydrogenation to methanol,promoting the carbon emission reduction in steel industry.
摘要The introduction of mesoporous nanosize zirconia to the catalyst for methanol synthesis dedicates the nanosized catalyst and mesoporous duplicated properties. The catalyst bears the larger surface area, larger mesoporous volume and more uniform diameter, more surface metal atoms and oxygen vacancies than the catalyst prepared with the conventional coprecipitation method. The modification of microstructure and electronic effect could result in the change of the reduced chemical state and decrease of reducuction temperature of copper, donating the higher activity and methanol selectivity to the catalyst. The results of methanol synthesis demonstrate that the Cu^+ is the optimum active site. Also, the interaction between the copper and zirconia shows the synergistic effect to fulfil the methanol synthesis.
基金Supported by the National Natural Science Foundation of Chinathe National Key Research and Development Program of China under Grant No 2016YFA0300203
摘要Pairing in the cuprate high-temperature superconductors and its origin remain among the most enduring mysteries in condensed matter physics. With cross-sectional scanning tunneling microscopy/spectroscopy, we clearly reveal the spatial-dependence or inhomogeneity of the superconducting gap structure of Bi2Sr2CaCu2O8+δ (Bi2212) and YBa2Cu3O7-x (YBCO) along their c-axes on a scale shorter than the interlayer spacing. By tunneling into the (100) plane of a Bi2212 single crystal and a YBCO film, we observe both U-shaped tunneling spectra with extended fiat zero-conductance bottoms, and V-shaped gap structures, in different regions of each sample. On the YBCO film, tunneling into a (110) surface only reveals a U-shaped gap without any zero-bias peak. Our analysis suggests that the U-shaped gap is likely a nodeless superconducting gap. The V-shaped gap has a very small amplitude, and is likely proximity-induced by regions having the larger U-shaped gap.
基金the National Natural Science Foundation of China(51572201)
摘要A modified co-precipitation method for the production of Cu/ZnO/Al2O3 complex was studied. The modification was that part of Al was introduced by adding Al^(3+) into Cu^(2+)/Zn^(2+) solution, and the rest of Al was added after co-precipitation step in the form of pseudo-boehmite. The prepared samples were characterized by different techniques such as X-ray diffraction, N2 adsorption, H2-N2O titration, temperature programmed reduction and scanning electron microscopy. X-ray diffraction characterizations revealed that Al^(3+) can be doped in aurichalcite lattice, and the maximum doping amount of Al^(3+) was 5.0% of total Cu and Zn atoms. The Cu/ZnO/Al2O3 sample produced by the modified method, in which co-precipitated Al^(3+) was 2.5% of total Cu and Zn atoms showed much better activity and stability in water-gas shift reaction than commercial sample. The high Cu surface area(26.1 m^2/g) obtained by decompositon of doped aurichalcite is believed to be responsible for the activity enhancement. The stability was enhanced mainly because of the support effect of γ-Al2O3, which was decomposed from pseudo-boehmite in the calcination step.