Noble metal modified copper-exchanged mordenite zeolite (Cu-ex-MOR) catalysts for catalyzing the methane efficient gas-phase synthesis methanol

IF 9 1区工程技术 Q1 ENERGY & FUELS

Energy Pub Date : 2024-05-08 DOI:10.1016/j.energy.2024.131595

Xuanlan Xie , Chang Li , Zhiheng Lu , Yishuang Wang , Wenqiang Yang , Mingqiang Chen , Wenzhi Li

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Abstract

Copper mordenite catalysts are key for methane oxidation to methanol, yet lack sufficient activity. In this paper, noble metal (Au, Ru, Pt and Pd) modified copper ion-exchanged mordenite catalysts were prepared by the ion-exchange method for further improving the methanol yield in the gas-phase continuous catalytic direct partial oxidation of methane to methanol reaction, and the role of noble metal doping on Cu-ex-MOR catalysts was investigated. Experimental results showed that the doping of Ru resulted in a significant increase in the methanol yield of Ru/Cu-ex-MOR catalyst to 157.36 μmol/g_cat/h compared to that of Cu-ex-MOR catalyst (12.89 μmol/g_cat/h). SEM, XRD, FT-IR, N₂ adsorption-desorption, XPS, NH₃-TPD and H₂-TPR results showed that Ru/Cu-ex-MOR had uniformly dispersed Ru elements and the largest number of surface acidic and oxidation sites, which facilitated the adsorption and activation of methane. Additionally, it was found by TEM, in situ FT-IR and DFT characterization that Ru played a role in stabilizing the Cu active sites, the adsorptive activation of water on the Ru site and the H-transfer process reduced the energy required for breaking C–H bond of CH₄ at the Cu active site, which significantly improved the methane activation capacity of the Ru/Cu-ex-MOR catalysts, resulting in higher methanol yields.

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贵金属改性铜换莫代沸石（Cu-ex-MOR）催化剂用于催化甲烷高效气相合成甲醇

铜莫来石催化剂是甲烷氧化制甲醇的关键催化剂，但缺乏足够的活性。本文采用离子交换法制备了贵金属（Au、Ru、Pt 和 Pd）修饰的铜离子交换莫代森催化剂，以进一步提高气相连续催化甲烷直接部分氧化制甲醇反应中的甲醇产率，并研究了贵金属掺杂对 Cu-ex-MOR 催化剂的作用。实验结果表明，与 Cu-ex-MOR 催化剂（12.89 μmol/gcat/h）相比，掺杂 Ru 使 Ru/Cu-ex-MOR 催化剂的甲醇产率显著提高，达到 157.36 μmol/gcat/h。扫描电镜、XRD、傅立叶变换红外光谱、N2 吸附-解吸、XPS、NH3-TPD 和 H2-TPR 结果表明，Ru/Cu-ex-MOR 具有均匀分散的 Ru 元素和最多的表面酸性和氧化位点，这有利于甲烷的吸附和活化。此外，通过 TEM、原位 FT-IR 和 DFT 表征发现，Ru 起到了稳定 Cu 活性位点的作用，水在 Ru 位点上的吸附活化和 H 转移过程降低了 Cu 活性位点上断裂 CH4 的 C-H 键所需的能量，这显著提高了 Ru/Cu-ex-MOR 催化剂的甲烷活化能力，从而获得更高的甲醇产率。

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来源期刊

Energy 工程技术-能源与燃料

CiteScore

15.30

自引率

14.40%

发文量

审稿时长

14.2 weeks

期刊介绍： Energy is a multidisciplinary, international journal that publishes research and analysis in the field of energy engineering. Our aim is to become a leading peer-reviewed platform and a trusted source of information for energy-related topics. The journal covers a range of areas including mechanical engineering, thermal sciences, and energy analysis. We are particularly interested in research on energy modelling, prediction, integrated energy systems, planning, and management. Additionally, we welcome papers on energy conservation, efficiency, biomass and bioenergy, renewable energy, electricity supply and demand, energy storage, buildings, and economic and policy issues. These topics should align with our broader multidisciplinary focus.