A series of copper manganese oxides were prepared using a selective etching technique with various amounts of ammonia added during the co-precipitation process. The effect of the ammonia etching on the structure and c...A series of copper manganese oxides were prepared using a selective etching technique with various amounts of ammonia added during the co-precipitation process. The effect of the ammonia etching on the structure and catalytic properties of the copper manganese oxides was investigated using elemental analysis, nitrogen physisorption, X-ray powder diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, H2 temperature-programmed reduc- tion, and Oz temperature-programmed desorption combined with catalytic oxidation of CO. It was found that ammonia can selectively remove copper species from the copper manganese oxides, which correspondingly generates more defects in these oxides. An oxygen spillover from the man- ganese to the copper species was observed by H2 temperature-programmed desorption, indicating that ammonia etching enhanced the mobility of lattice oxygen species in these oxides. The Oz tem- perature-programmed desorption measurements further revealed that ammonia etching improved the ability of these oxides to release lattice oxygen. The improvement in redox properties of the copper manganese oxides following ammonia etching was associated with enhanced catalytic performance for CO oxidation.展开更多
A series of mesoporous Cu-Mn-Al2O3（CMA） materials was synthesized at moderate temperature and their structures were characterized by XRD, N2 physical adsorption and TPR techniques. It was found that using metal comp...A series of mesoporous Cu-Mn-Al2O3（CMA） materials was synthesized at moderate temperature and their structures were characterized by XRD, N2 physical adsorption and TPR techniques. It was found that using metal complex ion[Cu（NH3） 4^2＋-Mn（NH3）6^2＋] as raw materials is easier to form good-structure mesoporous Cu-Mn-Al2O3 materials than using its nitrate salt [Cu（NO3）2-Mn（NO3）2]. The TPR tests results indicate that CuO and MnOx were homogeneously dispersed in the mesoporous materials. Their catalytic application to preferential catalytic oxidation of CO in a hydrogen-rich stream was studied. The activity varies in the order of CMA（1：1, molar ratio）〉 CMA（1：2）〉CMA（2：1）〉CMA（CP）〉CMA（1：0）≈CMA（0：1）. The CMA（1：0） and CMA（0：1） have lower activity compared to other samples, implying that there existed coordination effect between Cu-Mn in the samples. The selectivity varied in the order of CMA（0：1）≥CMA（1：2）〉CMA（1：1）〉CMA（2：1）〉CMA（1：0） at higher temperature （≥ 120 ℃）, indicating that increasing the Cu content enhanced the conversion of H2. The sample CMA（CP） made by coprecipitation method has a lower CO oxidation activity and selectivity than its counter-parts of mesoporous Cu-Mn-Al2O3 materials[CMA（1：2）], this attributed to the lower surface area of the former and poor interaction of CuO with MnOx.展开更多
基金supported by the National Basic Research Program of China (973 Program,2013CB934104)the China Postdoctoral Science Foundation(2014M560202)~~
文摘A series of copper manganese oxides were prepared using a selective etching technique with various amounts of ammonia added during the co-precipitation process. The effect of the ammonia etching on the structure and catalytic properties of the copper manganese oxides was investigated using elemental analysis, nitrogen physisorption, X-ray powder diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy, H2 temperature-programmed reduc- tion, and Oz temperature-programmed desorption combined with catalytic oxidation of CO. It was found that ammonia can selectively remove copper species from the copper manganese oxides, which correspondingly generates more defects in these oxides. An oxygen spillover from the man- ganese to the copper species was observed by H2 temperature-programmed desorption, indicating that ammonia etching enhanced the mobility of lattice oxygen species in these oxides. The Oz tem- perature-programmed desorption measurements further revealed that ammonia etching improved the ability of these oxides to release lattice oxygen. The improvement in redox properties of the copper manganese oxides following ammonia etching was associated with enhanced catalytic performance for CO oxidation.
基金Supported by the Science and Technology Development Project of Shandong Province,China(No.2007GG3WZ03018)
文摘A series of mesoporous Cu-Mn-Al2O3（CMA） materials was synthesized at moderate temperature and their structures were characterized by XRD, N2 physical adsorption and TPR techniques. It was found that using metal complex ion[Cu（NH3） 4^2＋-Mn（NH3）6^2＋] as raw materials is easier to form good-structure mesoporous Cu-Mn-Al2O3 materials than using its nitrate salt [Cu（NO3）2-Mn（NO3）2]. The TPR tests results indicate that CuO and MnOx were homogeneously dispersed in the mesoporous materials. Their catalytic application to preferential catalytic oxidation of CO in a hydrogen-rich stream was studied. The activity varies in the order of CMA（1：1, molar ratio）〉 CMA（1：2）〉CMA（2：1）〉CMA（CP）〉CMA（1：0）≈CMA（0：1）. The CMA（1：0） and CMA（0：1） have lower activity compared to other samples, implying that there existed coordination effect between Cu-Mn in the samples. The selectivity varied in the order of CMA（0：1）≥CMA（1：2）〉CMA（1：1）〉CMA（2：1）〉CMA（1：0） at higher temperature （≥ 120 ℃）, indicating that increasing the Cu content enhanced the conversion of H2. The sample CMA（CP） made by coprecipitation method has a lower CO oxidation activity and selectivity than its counter-parts of mesoporous Cu-Mn-Al2O3 materials[CMA（1：2）], this attributed to the lower surface area of the former and poor interaction of CuO with MnOx.
