Interpretation of H(2)-TPR from Cu-CHA Using First-Principles Calculations

利用第一性原理计算对 Cu-CHA 的 H(2)-TPR 进行解释

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Abstract

Temperature-programmed reduction and oxidation are used to obtain information on the presence and abundance of different species in complex catalytic materials. The interpretation of the temperature-programmed reaction profiles is, however, often challenging. One example is H(2) temperature-programmed reduction (H(2)-TPR) of Cu-chabazite (Cu-CHA), which is a material used for ammonia assisted selective catalytic reduction of NO(x) (NH(3)-SCR). The TPR profiles of Cu-CHA consist generally of three main peaks. A peak at 220 °C is commonly assigned to ZCuOH, whereas peaks at 360 and 500 °C generally are assigned to Z(2)Cu, where Z represents an Al site. Here, we analyze H(2)-TPR over Cu-CHA by density functional theory calculations, microkinetic modeling, and TPR measurements of samples pretreated to have a dominant Cu species. We find that H(2) can react with Cu ions in oxidation state +2, whereas adsorption on Cu ions in +1 is endothermic. Kinetic modeling of the TPR profiles suggests that the 220 °C peak can be assigned to Z(2)CuOCu and ZCuOH, whereas the peaks at higher temperatures can be assigned to paired Z(2)Cu and Z(2)CuHOOHCu species (360 °C) or paired Z(2)Cu and Z(2)CuOOCu (500 °C). The results are in good agreement with the experiments and facilitate the interpretation of future TPR experiments.

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