CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were ...CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were examined by means of a microreactor-GC system, HRTEM, XRD, TPR and XPS techniques. The results show that CuO has not catalytic activity and the activity of CeO2 is quite low for CO oxidation. However, the catalytic activity of CuO/CeO2 and Cu/ CeO2 catalysts increases significantly. Furthermore, the activity of CuO/CeO2 is higher than that of Cu/CeO2 catalysts.展开更多
Cu-based catalysts have been extensively used in methanol steam reforming(MSR)reactions because of their low cost and high effi ciency.ZnO is often used in commercial Cu-based catalysts as both a structural and an ele...Cu-based catalysts have been extensively used in methanol steam reforming(MSR)reactions because of their low cost and high effi ciency.ZnO is often used in commercial Cu-based catalysts as both a structural and an electronic promoter to stabilize metal Cu nanoparticles and modify metal–support interfaces.Still,the further addition of chemical promoters is essential to further enhance the MSR reaction performance of the Cu/ZnO catalyst.In this work,CeO_(2)-doped Cu/ZnO catalysts were prepared using the coprecipitation method,and the eff ects of CeO_(2)on Cu-based catalysts were systematically investigated.Doping with appropriate CeO_(2)amounts could stabilize small Cu nanoparticles through a strong interaction between CeO_(2)and Cu,leading to the formation of more Cu+–ZnO x interfacial sites.However,higher CeO_(2)contents resulted in the formation of larger Cu nanoparticles and an excess of Cu+–CeO x interfacial sites.Consequently,the Cu/5CeO_(2)/ZnO catalyst with maximal Cu–ZnO interfaces exhibited the highest H 2 production rate of 94.6 mmolH2/(gcat·h),which was 1.5 and 10.2 times higher than those of Cu/ZnO and Cu/CeO_(2),respectively.展开更多
Cu/CeO2-ZrO2 catalysts for water-gas shift （WGS） reaction were prepared with co-precipitation method, and the influence of ZrO2 content on the catalytic structure and properties was investigated by the techniques of...Cu/CeO2-ZrO2 catalysts for water-gas shift （WGS） reaction were prepared with co-precipitation method, and the influence of ZrO2 content on the catalytic structure and properties was investigated by the techniques of N2 physical adsorption analysis, XRD and H2-TPR. The results indicate that the BET surface areas of the catalysts are increased in varying degrees due to the presence of ZrO2. With increasing ZrO2 content, the pore size distribution is centered on 1.9 nm. ZrO2 can efficiently restrain the growth of Cu crystal particles. The appropriate amount of ZrO2 in the Cu/CeO2 catalysts can help the catalyst keep better copper dispersion in the WGS reaction, which can lead to both higher catalytic activity and better thermal stability. When ZrO2 content is 10% （atom fraction）, Cu/CeO2-Zr02 catalyst reaches a CO conversion rate of 73.7% at the reaction temperature of 200℃.展开更多
The size of the nanoparticles and the number of oxygen vacancies have a significant effect on the catalytic activity of copper-based catalysts used for the synthesis of methanol from syngas.In this study,the authors p...The size of the nanoparticles and the number of oxygen vacancies have a significant effect on the catalytic activity of copper-based catalysts used for the synthesis of methanol from syngas.In this study,the authors prepared a series of catalysts CuO/ZnO/Al_(2)O_(3)/CeO_(2)(CZAC)with CuO particles of different sizes and varying number of oxygen vacancies on the surface by changing the added volume of CeO2 by using the co-precipitation method.The properties of the catalysts were characterized and their activity was evaluated by using high-pressure fixed-bed reaction equipment.The results showed that the addition of CeO_(2)to CuO/ZnO/Al_(2)O_(3)not only influenced the size of the CuO particles and metal-metal interactions,but also had an effect on the concentrations of oxygen vacancies and strongly basic sites.The presence of CuO particles of small sizes and a large numbers of oxygen vacancies on the surface of the catalyst were beneficial to its activity for the synthesis of methanol.The catalyst CZAC,when modified by 5%of CeO_(2),recorded CuO particles of the smallest size(8.9 nm),strong intermetallic interactions,and the highest concentrations of oxygen vacancies and strongly basic sites.It also exhibited the highest catalytic activity,with a space-time yield of methanol of 0.315 g/(h·g)that was higher than that of the enterprise RK-5 catalyst[0.215 g/(h·g)].展开更多
Developing an efficiently supported Cu-based catalyst with promoters to substitute the existing non-supported Cu-based catalysts is highly desirable to the Rochow-Müller reaction. Using a simple ball-milling meth...Developing an efficiently supported Cu-based catalyst with promoters to substitute the existing non-supported Cu-based catalysts is highly desirable to the Rochow-Müller reaction. Using a simple ball-milling method and CeO_(2) support, we prepared a high-performance CuO-ZnO-P-Sn/CeO_(2) catalyst by integrating highly dispersed multicomponent promoters of ZnO, Sn, and P with the active component CuO. This catalyst shows a significantly enhanced dimethyldichlorosilane selectivity because these promoters can substantially increase the Cu+ content and the formation of an active CuxSi phase. This work provides a new approach to efficiently designing Cu-based catalysts for the Rochow-Müller reaction.展开更多
气氛环境下原位研究催化剂的烧结行为,能够为理解催化剂在预处理以及反应条件下的烧结机理和高稳定催化剂的设计提供重要的实验依据。本文以Au/CeO_(2)模型纳米催化剂为研究对象,利用环境透射电子显微镜原位观察其在O_(2)与CO气氛下的...气氛环境下原位研究催化剂的烧结行为,能够为理解催化剂在预处理以及反应条件下的烧结机理和高稳定催化剂的设计提供重要的实验依据。本文以Au/CeO_(2)模型纳米催化剂为研究对象,利用环境透射电子显微镜原位观察其在O_(2)与CO气氛下的高温动态烧结过程。实验发现,负载在CeO_(2)上的Au纳米颗粒在O_(2)与CO气氛环境中表现出不同的烧结行为,其在O_(2)气氛下具有较高的烧结速度,同时存在颗粒迁移与聚集长大(particle migration and coalescence,PMC)和奥斯特瓦尔德熟化(Ostwald ripening,OR)两种烧结过程;在CO气氛下烧结速度较慢,烧结过程以OR为主。对比不同气氛环境下烧结后催化剂的表面结构可知,CO增加了CeO_(2)表面台阶的数量以及表面氧空位浓度,增强了载体对Au颗粒的锚定作用,从而提升Au/CeO_(2)催化剂的稳定性。展开更多
基金Projected supported by the National Natural Science Foundation of China (20271028) and Tianjin Natural Science Foundation(033602511)
文摘CeO2 was synthesized via sol-gel process and used as supporter to prepare CuO/CeO2, Cu/CeO2 catalysts by impregnation method. The catalytic properties and characterization of CeO2, CuO/CeO2 and Cu/CeO2 catalysts were examined by means of a microreactor-GC system, HRTEM, XRD, TPR and XPS techniques. The results show that CuO has not catalytic activity and the activity of CeO2 is quite low for CO oxidation. However, the catalytic activity of CuO/CeO2 and Cu/ CeO2 catalysts increases significantly. Furthermore, the activity of CuO/CeO2 is higher than that of Cu/CeO2 catalysts.
基金This work was supported by the National Key R&D Program of China(2022YFB3805504),National Natural Science Foundation of China(22078089)China Postdoctoral Science Foundation(2023M731081)+3 种基金Shanghai Pilot Program for Basic Research(22TQ1400100-7)the Basic Research Program of Science and Technology Commission of Shanghai Municipality(22JC1400600)Open Foundation of Shanghai Jiao Tong University Shaoxing Research Institute of Renewable Energy and Molecular Engineering(Grant No.JDSX2022046)Shanghai Super Postdoctoral Fellow.
文摘Cu-based catalysts have been extensively used in methanol steam reforming(MSR)reactions because of their low cost and high effi ciency.ZnO is often used in commercial Cu-based catalysts as both a structural and an electronic promoter to stabilize metal Cu nanoparticles and modify metal–support interfaces.Still,the further addition of chemical promoters is essential to further enhance the MSR reaction performance of the Cu/ZnO catalyst.In this work,CeO_(2)-doped Cu/ZnO catalysts were prepared using the coprecipitation method,and the eff ects of CeO_(2)on Cu-based catalysts were systematically investigated.Doping with appropriate CeO_(2)amounts could stabilize small Cu nanoparticles through a strong interaction between CeO_(2)and Cu,leading to the formation of more Cu+–ZnO x interfacial sites.However,higher CeO_(2)contents resulted in the formation of larger Cu nanoparticles and an excess of Cu+–CeO x interfacial sites.Consequently,the Cu/5CeO_(2)/ZnO catalyst with maximal Cu–ZnO interfaces exhibited the highest H 2 production rate of 94.6 mmolH2/(gcat·h),which was 1.5 and 10.2 times higher than those of Cu/ZnO and Cu/CeO_(2),respectively.
文摘Cu/CeO2-ZrO2 catalysts for water-gas shift （WGS） reaction were prepared with co-precipitation method, and the influence of ZrO2 content on the catalytic structure and properties was investigated by the techniques of N2 physical adsorption analysis, XRD and H2-TPR. The results indicate that the BET surface areas of the catalysts are increased in varying degrees due to the presence of ZrO2. With increasing ZrO2 content, the pore size distribution is centered on 1.9 nm. ZrO2 can efficiently restrain the growth of Cu crystal particles. The appropriate amount of ZrO2 in the Cu/CeO2 catalysts can help the catalyst keep better copper dispersion in the WGS reaction, which can lead to both higher catalytic activity and better thermal stability. When ZrO2 content is 10% （atom fraction）, Cu/CeO2-Zr02 catalyst reaches a CO conversion rate of 73.7% at the reaction temperature of 200℃.
基金supported by the Nature Science Foundation of China(Grant 22262006,22068009)the Supported by Guizhou Provincial Science and Technology Projects(ZK[2023]ordinary 050,[2023]General 403)+4 种基金the Science and Technology Support Plan Projects of Guizhou Province(Grant(2018)2192)the Scientific and Technological Innovation Talents Team of Guizhou(2018-5607)the Science and Technology Foundation of Guizhou Province(20177254)the One hundred Person Project of Guizhou Province(No.20165655)the Innovation Group Project of Education Department in Guizhou Province(No.2021010)。
文摘The size of the nanoparticles and the number of oxygen vacancies have a significant effect on the catalytic activity of copper-based catalysts used for the synthesis of methanol from syngas.In this study,the authors prepared a series of catalysts CuO/ZnO/Al_(2)O_(3)/CeO_(2)(CZAC)with CuO particles of different sizes and varying number of oxygen vacancies on the surface by changing the added volume of CeO2 by using the co-precipitation method.The properties of the catalysts were characterized and their activity was evaluated by using high-pressure fixed-bed reaction equipment.The results showed that the addition of CeO_(2)to CuO/ZnO/Al_(2)O_(3)not only influenced the size of the CuO particles and metal-metal interactions,but also had an effect on the concentrations of oxygen vacancies and strongly basic sites.The presence of CuO particles of small sizes and a large numbers of oxygen vacancies on the surface of the catalyst were beneficial to its activity for the synthesis of methanol.The catalyst CZAC,when modified by 5%of CeO_(2),recorded CuO particles of the smallest size(8.9 nm),strong intermetallic interactions,and the highest concentrations of oxygen vacancies and strongly basic sites.It also exhibited the highest catalytic activity,with a space-time yield of methanol of 0.315 g/(h·g)that was higher than that of the enterprise RK-5 catalyst[0.215 g/(h·g)].
基金support from the National Natural Science Foundation of China(Nos.21978299 and 21878301)supported by the Open Research Fund of State Key Laboratory of Multiphase Complex Systems(MPCS-2021-D-08)+2 种基金GRINM Group(G12620213102035)Y.J.thanks the financial support from the Outstanding Youth Cultivation Program of Beijing Technology and Business University(No.19008021144)the Research Foundation for Advanced Talents of Beijing Technology and Business University(No.19008020159).
文摘Developing an efficiently supported Cu-based catalyst with promoters to substitute the existing non-supported Cu-based catalysts is highly desirable to the Rochow-Müller reaction. Using a simple ball-milling method and CeO_(2) support, we prepared a high-performance CuO-ZnO-P-Sn/CeO_(2) catalyst by integrating highly dispersed multicomponent promoters of ZnO, Sn, and P with the active component CuO. This catalyst shows a significantly enhanced dimethyldichlorosilane selectivity because these promoters can substantially increase the Cu+ content and the formation of an active CuxSi phase. This work provides a new approach to efficiently designing Cu-based catalysts for the Rochow-Müller reaction.
文摘气氛环境下原位研究催化剂的烧结行为,能够为理解催化剂在预处理以及反应条件下的烧结机理和高稳定催化剂的设计提供重要的实验依据。本文以Au/CeO_(2)模型纳米催化剂为研究对象,利用环境透射电子显微镜原位观察其在O_(2)与CO气氛下的高温动态烧结过程。实验发现,负载在CeO_(2)上的Au纳米颗粒在O_(2)与CO气氛环境中表现出不同的烧结行为,其在O_(2)气氛下具有较高的烧结速度,同时存在颗粒迁移与聚集长大(particle migration and coalescence,PMC)和奥斯特瓦尔德熟化(Ostwald ripening,OR)两种烧结过程;在CO气氛下烧结速度较慢,烧结过程以OR为主。对比不同气氛环境下烧结后催化剂的表面结构可知,CO增加了CeO_(2)表面台阶的数量以及表面氧空位浓度,增强了载体对Au颗粒的锚定作用,从而提升Au/CeO_(2)催化剂的稳定性。
