Three series of CeO2/CuO samples were prepared by impregnation method and characterized by XRD, N2 adsorption-desorption, temperatureprogrammed reduction （TPR）, XPS and TEM techniques. In comparison with the samples...Three series of CeO2/CuO samples were prepared by impregnation method and characterized by XRD, N2 adsorption-desorption, temperatureprogrammed reduction （TPR）, XPS and TEM techniques. In comparison with the samples prepared with CuO as initial support, the samples with Cu（OH）2 as initial support have higher reducibilities and smaller relative TPR peak areas, and also larger specific surface areas at calcina- tion temperatures of 400 ℃--600 ℃. As a result, Cu（OH）2 is better than CuO as initial support for preferential oxidation of CO in excess H2 （CO-PROX）. The best catalytic performance was achieved on the sample calcined at 600 ℃ and with an atomic ratio of Ce/Cu at 40%. XPS analyses indicate that more interface linkages Ce-O-Cu could be formed when it was calcined at 600 ℃. And the atomic ratio of Ce/Cu at 40% led to a proper reducibility for the sample as illustrated by the TPR measurements.展开更多
The hollow inverse CeO2/CuO@SiO2 catalysts with different Ce/Cu mass ratios were synthesized by the two-step hydrothermal and incipient wetness impregnation methods,and characterized by multitechnique characterization...The hollow inverse CeO2/CuO@SiO2 catalysts with different Ce/Cu mass ratios were synthesized by the two-step hydrothermal and incipient wetness impregnation methods,and characterized by multitechnique characterizations,such as SEM,TEM,XRD,H2-TPR,XPS and N2 adsorption-desorption techniques.It is found that the hollow shell is composed of CuO and SiO2,and CeO2 nanoparticles are coated on the surface of CuO@SiO2 support.And the CeO2/CuO@SiO2 catalyst with the Ce/Cu mass ratios of 1:1 denoted as 1 CeO2/CuO@SiO2,which possesses a maximum amount of highly dispersed copper species and medium-sized CuO as well as the highest concentration of oxygen vacancies,exhibits the highest catalytic activity and widest full CO conversion window.The barrier effect of the SiO2 shell effectively prevents the reduction of CuO species,which broadens temperature window of CO total conversion and enhances CO2 selectivity above 155℃over the 1 CeO2/CuO@SiO2 catalyst in comparison with the CuO-CeO2 and CeO2-CuO catalysts.展开更多
采用柠檬酸为络合剂,溶胶-凝胶法制备系列CeO_2-CuO/ZnO/Al_2O_3,在3.0 MPa压力和220~230℃反应条件下,甲苯二胺(TDA)和乙烯催化合成二乙基甲苯二胺(DETDA)为探针反应,考察其催化性能,其中CeO_2掺杂量为3%,催化活性最高。通过X射线衍射(...采用柠檬酸为络合剂,溶胶-凝胶法制备系列CeO_2-CuO/ZnO/Al_2O_3,在3.0 MPa压力和220~230℃反应条件下,甲苯二胺(TDA)和乙烯催化合成二乙基甲苯二胺(DETDA)为探针反应,考察其催化性能,其中CeO_2掺杂量为3%,催化活性最高。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、差热重量分析法(DTG-DTA)、核磁氢谱1 H NMR对CeO_2-CuO/ZnO/Al_2O_3、DETDA、TDA进行检测和表征,揭示了它们的微观结构和内在规律性。XRD检测发现CeO_2掺杂量增多,CeO_2-CuO/ZnO/Al_2O_3衍射峰强度增强,提高了晶化程度,金属原子存在协同效应,增多了活性中心。FT-IR揭示了DETDA内部化学键键型,拥有甲基、亚甲基的多取代芳胺。DTG-DTA检测出的质量变化与热效应两种信息,DETDA的DTG-DTA曲线在66.0、271.0℃存在二个吸热峰,分别为氨基脱离苯环、DETDA的分解产生。通过1 H NMR对DETDA、TDA检测,得到DETDA、TDA的氢原子的数目分别为18和10,分子中各个氢核对应所归属的吸收峰,分别和它们分子式中的氢原子数目吻合。CeO_2-CuO/ZnO/Al_2O_3催化合成DETDA,反应条件温和,工艺流程简单,容易实现高效率和连续化工业生产,因此具有广阔的发展前景。展开更多
本文采用铈掺杂的CuO-SiO_2复合氧化物作为催化剂,双氧水为氧化剂,以氧化脱除模拟油中苯并噻吩反应为探针,通过单因素实验考察氧化剂用量、溶剂用量、催化剂用量、氧化温度和氧化时间等因素对脱硫效果的影响。研究结果表明,铈掺杂的0.02...本文采用铈掺杂的CuO-SiO_2复合氧化物作为催化剂,双氧水为氧化剂,以氧化脱除模拟油中苯并噻吩反应为探针,通过单因素实验考察氧化剂用量、溶剂用量、催化剂用量、氧化温度和氧化时间等因素对脱硫效果的影响。研究结果表明,铈掺杂的0.02CeO_2-0.1CuO-SiO_2复合氧化物比表面积比未掺杂的比表面积略高,在模拟油用量10 m L、复合氧化物催化剂用量0.10 g、溶剂乙腈用量2.0 m L,氧化剂30%H_2O_20.2 m L、氧化反应温度65℃的条件下反应60 min,脱硫率为88.23%。展开更多
文摘Three series of CeO2/CuO samples were prepared by impregnation method and characterized by XRD, N2 adsorption-desorption, temperatureprogrammed reduction （TPR）, XPS and TEM techniques. In comparison with the samples prepared with CuO as initial support, the samples with Cu（OH）2 as initial support have higher reducibilities and smaller relative TPR peak areas, and also larger specific surface areas at calcina- tion temperatures of 400 ℃--600 ℃. As a result, Cu（OH）2 is better than CuO as initial support for preferential oxidation of CO in excess H2 （CO-PROX）. The best catalytic performance was achieved on the sample calcined at 600 ℃ and with an atomic ratio of Ce/Cu at 40%. XPS analyses indicate that more interface linkages Ce-O-Cu could be formed when it was calcined at 600 ℃. And the atomic ratio of Ce/Cu at 40% led to a proper reducibility for the sample as illustrated by the TPR measurements.
基金Project supported by the National Natural Science Foundation of China(21466024)the Natural Science Foundation of Inner Mongolia(2018MS02020,2018BS02008)
文摘The hollow inverse CeO2/CuO@SiO2 catalysts with different Ce/Cu mass ratios were synthesized by the two-step hydrothermal and incipient wetness impregnation methods,and characterized by multitechnique characterizations,such as SEM,TEM,XRD,H2-TPR,XPS and N2 adsorption-desorption techniques.It is found that the hollow shell is composed of CuO and SiO2,and CeO2 nanoparticles are coated on the surface of CuO@SiO2 support.And the CeO2/CuO@SiO2 catalyst with the Ce/Cu mass ratios of 1:1 denoted as 1 CeO2/CuO@SiO2,which possesses a maximum amount of highly dispersed copper species and medium-sized CuO as well as the highest concentration of oxygen vacancies,exhibits the highest catalytic activity and widest full CO conversion window.The barrier effect of the SiO2 shell effectively prevents the reduction of CuO species,which broadens temperature window of CO total conversion and enhances CO2 selectivity above 155℃over the 1 CeO2/CuO@SiO2 catalyst in comparison with the CuO-CeO2 and CeO2-CuO catalysts.
文摘采用柠檬酸为络合剂,溶胶-凝胶法制备系列CeO_2-CuO/ZnO/Al_2O_3,在3.0 MPa压力和220~230℃反应条件下,甲苯二胺(TDA)和乙烯催化合成二乙基甲苯二胺(DETDA)为探针反应,考察其催化性能,其中CeO_2掺杂量为3%,催化活性最高。通过X射线衍射(XRD)、傅里叶红外光谱(FT-IR)、差热重量分析法(DTG-DTA)、核磁氢谱1 H NMR对CeO_2-CuO/ZnO/Al_2O_3、DETDA、TDA进行检测和表征,揭示了它们的微观结构和内在规律性。XRD检测发现CeO_2掺杂量增多,CeO_2-CuO/ZnO/Al_2O_3衍射峰强度增强,提高了晶化程度,金属原子存在协同效应,增多了活性中心。FT-IR揭示了DETDA内部化学键键型,拥有甲基、亚甲基的多取代芳胺。DTG-DTA检测出的质量变化与热效应两种信息,DETDA的DTG-DTA曲线在66.0、271.0℃存在二个吸热峰,分别为氨基脱离苯环、DETDA的分解产生。通过1 H NMR对DETDA、TDA检测,得到DETDA、TDA的氢原子的数目分别为18和10,分子中各个氢核对应所归属的吸收峰,分别和它们分子式中的氢原子数目吻合。CeO_2-CuO/ZnO/Al_2O_3催化合成DETDA,反应条件温和,工艺流程简单,容易实现高效率和连续化工业生产,因此具有广阔的发展前景。
文摘本文采用铈掺杂的CuO-SiO_2复合氧化物作为催化剂,双氧水为氧化剂,以氧化脱除模拟油中苯并噻吩反应为探针,通过单因素实验考察氧化剂用量、溶剂用量、催化剂用量、氧化温度和氧化时间等因素对脱硫效果的影响。研究结果表明,铈掺杂的0.02CeO_2-0.1CuO-SiO_2复合氧化物比表面积比未掺杂的比表面积略高,在模拟油用量10 m L、复合氧化物催化剂用量0.10 g、溶剂乙腈用量2.0 m L,氧化剂30%H_2O_20.2 m L、氧化反应温度65℃的条件下反应60 min,脱硫率为88.23%。
