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碱金属和碱土金属氧化物掺杂的CuO-CeO2催化剂的原位漫反射红外傅里叶变换光谱研究

[Study on CuO-CeO2 catalysts doped with alkali and alkaline earth metal oxides by in-situ DRIFTS].

作者信息

Zou Han-Bo, Chen Sheng-Zhou, Wang Qi-Ying, Liu Zi-Li, Lin Wei-Ming

机构信息

School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, China.

出版信息

Guang Pu Xue Yu Guang Pu Fen Xi. 2010 Mar;30(3):672-6.

Abstract

CuO-CeO2 series catalysts are the effective catalysts for the selective CO oxidation in hydrogen-rich gas. The adsorption species on the CuO-CeO2 catalysts doped with alkali and alkaline earth metal oxides were investigated with in situ diffuse reflectance FTIR spectroscopy (in-situ DRIFTS) technique. The results showed that a bane at 2 106 cm(-1), due to the carbonyl species, appeared on the CuO-CeO2 catalysts. In the reaction atmosphere, the intensity of this band increased first and then decreased with increasing the temperatures. It was noted that the main active adsorption sites of the CuO-CeO2 catalysts were Cu+ species. At lower temperatures, the carbonyl species were desorbed from the surface of CuO-CeO2 catalysts in the reversible form, while they were desorbed mainly in the irreversible form at the higher temperatures. A sharp peak at 3 660 cm(-1), attributed to the geminal Ce(OH)2 group, was also apparent on the surface of reduced CuO-CeO2 catalyst. The peaks at 1 568, 2 838 and 2 948 cm(-1) were attributed to formate species and the peaks centered at 1 257 and 1 633 cm(-1) were assigned to carbonate species. CO could react with the active hydroxyl species and generate formate species. At higher temperatures, the C-H bond of formate species could break and form carbonate species. These two species would decrease the performance of CuO-CeO2 catalysts at higher temperatures. The stronger IR peaks attributed to CO2 and formate species were observed, moreover there was still a weak IR peak assigned to carbonyl species for Cu1 Li1 Ce9Odelta catalyst when the temperature was above 180 degrees C. It was shown that as the electron donor, the doping of Li2 O on CuO-CeO2 catalyst could contribute to the irreversible desorption of CO at lower temperatures and inhibit the adsorption of H2 on the catalytic surface, and benefit the formation of formate species as well. Although the amounts of CO adsorption on Cu1 Mg1 Ce9 Odelta and Cu1 Ba1 Ce9 Odelta catalysts were much more than other catalysts at lower temperatures, they were mainly desorbed in the reversible form, which had no contribution to the selective CO oxidation.

摘要

CuO-CeO2系列催化剂是富氢气体中选择性CO氧化的有效催化剂。采用原位漫反射傅里叶变换红外光谱(原位DRIFTS)技术研究了掺杂碱金属和碱土金属氧化物的CuO-CeO2催化剂上的吸附物种。结果表明,在CuO-CeO2催化剂上出现了一个归因于羰基物种的2106 cm-1处的吸收峰。在反应气氛中,该吸收峰的强度随温度升高先增加后降低。值得注意的是,CuO-CeO2催化剂的主要活性吸附位点是Cu+物种。在较低温度下,羰基物种以可逆形式从CuO-CeO2催化剂表面脱附,而在较高温度下它们主要以不可逆形式脱附。在还原的CuO-CeO2催化剂表面还出现了一个归因于孪晶Ce(OH)2基团的3660 cm-1处的尖锐峰。1568、2838和2948 cm-1处的峰归因于甲酸盐物种,以1257和1633 cm-1为中心的峰归属于碳酸盐物种。CO能与活性羟基物种反应生成甲酸盐物种。在较高温度下,甲酸盐物种的C-H键会断裂形成碳酸盐物种。这两种物种会在较高温度下降低CuO-CeO2催化剂的性能。此外,当温度高于180℃时,对于Cu1Li1Ce9Oδ催化剂,观察到归因于CO2和甲酸盐物种的较强红外峰,并且仍然存在一个归因于羰基物种的弱红外峰。结果表明,作为电子给体,在CuO-CeO2催化剂上掺杂Li2O有助于在较低温度下CO的不可逆脱附,并抑制H2在催化表面的吸附,同时也有利于甲酸盐物种的形成。尽管在较低温度下,Cu1Mg1Ce9Oδ和Cu1Ba1Ce9Oδ催化剂上的CO吸附量比其他催化剂多得多,但它们主要以可逆形式脱附,这对选择性CO氧化没有贡献。

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