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使用负载型钯合金催化剂从 CO 和 H 合成甲醇。

Methanol synthesis from CO and H using supported Pd alloy catalysts.

机构信息

Max Planck-Cardiff Centre on the Fundamentals of Heterogeneous Catalysis FUNCAT, Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK.

出版信息

Faraday Discuss. 2023 Jan 31;242(0):193-211. doi: 10.1039/d2fd00119e.

Abstract

A number of Pd based materials have been synthesised and evaluated as catalysts for the conversion of carbon dioxide and hydrogen to methanol, a useful platform chemical and hydrogen storage molecule. Monometallic Pd catalysts show poor methanol selectivity, but this is improved through the formation of Pd alloys, with both PdZn and PdGa alloys showing greatly enhanced methanol productivity compared with monometallic Pd/AlO and Pd/TiO catalysts. Catalyst characterisation shows that the 1 : 1 β-PdZn alloy is present in all Zn containing post-reaction samples, including PdZn/GaO, with the PdGa alloy formed for the Pd/GaO sample. The heat of mixing was calculated for a variety of alloy compositions with high values determined for both PdZn and PdGa alloys, at -0.6 eV per atom and -0.8 eV per atom, respectively. However, ZnO is more readily reduced than GaO, providing a possible explanation for the preferential formation of the PdZn alloy, rather than PdGa, when in the presence of GaO.

摘要

已经合成了许多基于钯的材料,并将其评估为将二氧化碳和氢气转化为甲醇的催化剂,甲醇是一种有用的平台化学品和储氢分子。单金属 Pd 催化剂对甲醇的选择性差,但通过形成 Pd 合金可以得到改善,与单金属 Pd/AlO 和 Pd/TiO 催化剂相比,PdZn 和 PdGa 合金的甲醇产率都大大提高。催化剂特性表明,所有含 Zn 的反应后样品中都存在 1∶1β-PdZn 合金,包括 PdZn/GaO,而 Pd/GaO 样品中则形成了 PdGa 合金。计算了各种合金组成的混合热,对于 PdZn 和 PdGa 合金,分别确定了较高的值,分别为每原子-0.6 eV 和每原子-0.8 eV。然而,ZnO 比 GaO 更容易还原,这为在存在 GaO 时优先形成 PdZn 合金而不是 PdGa 合金提供了一种可能的解释。

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