Xing Yue, Wu Jiaxin, Liu Daosheng, Zhang Caishun, Han Jiao, Wang Honghao, Li Yinfu, Hou Xiaoning, Zhang Lei, Gao Zhixian
School of Petrochemical Engineering, Liaoning Petrochemical University, Fushun, Liaoning 113001, China.
Graduate School, Liaoning Petrochemical University, Fushun, Liaoning 113001, China.
Phys Chem Chem Phys. 2024 Apr 17;26(15):11618-11630. doi: 10.1039/d3cp06125f.
In this work, CuM/CeO (M = Mn, Fe, Co, Ni, and Zr) catalysts with a low Cu content of 1 wt% were purposely designed and prepared using the co-impregnation method. The samples were characterized using various techniques (TG-DTA, XRD, N-adsorption/desorption measurements, H-TPR, XPS and Raman spectroscopy) and CO preferential oxidation (CO-Prox) under H/CO-rich conditions was performed. The results have shown that enhanced catalytic performance was achieved upon the introduction of Mn, Co and Ni, and little impact was observed with Zr doping, but Fe showed a negative effect, as compared with the Cu/CeO catalyst. Characterization data revealed that the M doping strongly changed the surface composition, revealing the decreased Cu/Ce ratios on the surface, which could be accounted for by the formation of more M/Cu-O-Ce solid solution, or strong Cu-M interactions. When Mn was used, the obtained CuMn/CeO catalyst revealed the highest concentration of the oxygen vacancies and Ce ions, which could be correlated well with its superior catalytic performance. Compared with the Cu/CeO catalyst, the CO conversion rate increased by 24.7% at a low temperature of 90 °C over the CuMn/CeO catalyst. At 130 °C, the maximum CO conversion was 94.7% and the CO selectivity was 78.9%. Conversely, the Fe doped Cu/CeO catalyst demonstrated the poorest catalytic activity, which was due to the blockage effect of Fe species on Cu showing a high Fe/Cu ratio of 1.9 on the surface.
在本工作中,采用共浸渍法特意设计并制备了Cu含量低至1 wt%的CuM/CeO(M = Mn、Fe、Co、Ni和Zr)催化剂。使用多种技术(TG-DTA、XRD、N吸附/脱附测量、H-TPR、XPS和拉曼光谱)对样品进行了表征,并在富H/CO条件下进行了CO优先氧化(CO-Prox)。结果表明,引入Mn、Co和Ni后催化性能得到增强,Zr掺杂影响不大,但与Cu/CeO催化剂相比,Fe表现出负面影响。表征数据显示,M掺杂强烈改变了表面组成,表面Cu/Ce比降低,这可能是由于形成了更多的M/Cu-O-Ce固溶体或强烈的Cu-M相互作用。使用Mn时,所得的CuMn/CeO催化剂显示出最高浓度的氧空位和Ce离子,这与其优异的催化性能密切相关。与Cu/CeO催化剂相比,在90℃的低温下,CuMn/CeO催化剂上的CO转化率提高了24.7%。在130℃时,最大CO转化率为94.7%,CO选择性为78.9%。相反,Fe掺杂的Cu/CeO催化剂表现出最差的催化活性,这是由于Fe物种对Cu的堵塞效应,表面Fe/Cu比高达1.9。