Liu Fen, Chen Xiaohua, Jie Weiwei, Liu Yumeng, Li Claudia, Song Guoqiang, Gong Xia, Liu Qian, Qiu Mei, Ding Shunmin, Hu Feiyang, Gong Lei, Kawi Sibudjing
College of Chemistry and Materials, Jiangxi Agricultural University, No. 1101 Zhimin Avenue, Nanchang 330045, China.
Department of Chemical and Biomolecular Engineering, National University of Singapore, 4 Engineering Drive 4, 117585, Singapore.
J Colloid Interface Sci. 2024 Nov 15;674:778-790. doi: 10.1016/j.jcis.2024.06.110. Epub 2024 Jun 18.
The CO preferential oxidation reaction (CO-PROX) is an effective strategy to remove residual poisonous CO in proton exchange membrane fuel cells, in which oxygen vacancies play a critical role in CO adsorption and activation. Herein, a series of CuO/CeO catalysts derived from Ce-MOFs precursors were synthesized using different organic ligands via the hydrothermal method and the CO-PROX performance was investigated. The CuO/CeO-135 catalyst derived from homophthalic tricarboxylic acid (1,3,5-HBTC) exhibited superior catalytic performance with 100 % CO conversion at a relatively low temperature (T = 100 °C), with a wide reaction temperature range and excellent stability. The superior catalytic properties were attributed to the structural improvements provided by the 1,3,5-HBTC precursors and the promotional effects of oxygen vacancies. Additionally, in-situ Raman spectroscopy was performed to verify the dynamic roles of oxygen vacancies for CO adsorption and activation, while in-situ DRIFTS analysis revealed key intermediates in the CO-PROX reaction, shedding light on the mechanistic aspects of the catalytic process. This work not only demonstrates insights into the effective CuO/CeO catalysts for CO preferential oxidation, but also provides a feasible way to synthesize MOF-derived catalysts.
一氧化碳优先氧化反应（CO-PROX）是去除质子交换膜燃料电池中残留有毒一氧化碳的有效策略，其中氧空位在一氧化碳的吸附和活化中起着关键作用。在此，通过水热法使用不同的有机配体合成了一系列源自Ce-MOFs前驱体的CuO/CeO催化剂，并研究了其CO-PROX性能。源自均苯三甲酸（1,3,5-HBTC）的CuO/CeO-135催化剂在相对较低的温度（T = 100°C）下表现出优异的催化性能，CO转化率达100%，具有较宽的反应温度范围和出色的稳定性。优异的催化性能归因于1,3,5-HBTC前驱体提供的结构改进以及氧空位的促进作用。此外，进行了原位拉曼光谱以验证氧空位对一氧化碳吸附和活化的动态作用，而原位漫反射红外傅里叶变换光谱分析揭示了CO-PROX反应中的关键中间体，阐明了催化过程的机理方面。这项工作不仅展示了对用于一氧化碳优先氧化的有效CuO/CeO催化剂的见解，还提供了一种合成MOF衍生催化剂的可行方法。
