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铜掺杂钴锰尖晶石提高 CO 低温还原 NO 性能的研究:结构性能、性能和机理的探索。

Effect of Cu-Doped Co-Mn Spinel for Boosting Low-Temperature NO Reduction by CO: Exploring the Structural Properties, Performance, and Mechanisms.

机构信息

State Key Laboratory of Fine Chemicals, Key Laboratory of Industrial Ecology and Environmental Engineering (MOE), School of Environmental Science and Technology, Dalian University of Technology, Dalian 116024, China.

Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845, Australia.

出版信息

ACS Appl Mater Interfaces. 2023 Mar 8;15(9):11885-11894. doi: 10.1021/acsami.2c23120. Epub 2023 Feb 24.

Abstract

Cobalt-manganese spinel catalysts performed unsatisfactory activity at low-temperature and narrow reaction temperature window, which greatly limited the application in NO reduction by CO. Herein, we synthesize a series of Cu-doped CoMnO catalysts and apply to NO reduction by CO. The CuCoMnO exhibited superior catalytic performance, reaching 100% NO conversion and 80% N selectivity at 250 °C. Detailed structural analysis showed that the introduced Cu replaces some Co in tetrahedral coordination to induce a strong synergistic effect between different metals. This endows the catalyst with the promotion of both electron transfer and oxygen vacancy generation on the catalyst surface. Importantly, the reaction mechanism and pathway were further revealed by diffusion Fourier transform infrared spectroscopy (DRIFTS) and density functional theory (DFT) calculations. The results indicated that the cycle of oxygen vacancy mainly determines the catalytic activity of NO reduction by CO. Notably, Cu doping significantly lowered the energy barrier of the rate-determining step (*CO + O → *O + CO), facilitating the desorption of the CO and exposing the active sites for efficient NO reduction with CO. This work offers an effective way for designing the catalyst in NO reduction by CO and provides a reference for exploring the catalytic mechanism of the reaction.

摘要

尖晶石型钴锰催化剂在低温下活性不佳,反应温度窗口较窄,这极大地限制了其在 CO 还原 NO 中的应用。在此,我们合成了一系列铜掺杂的 CoMnO 催化剂,并将其应用于 CO 还原 NO。CuCoMnO 表现出优异的催化性能,在 250°C 时达到 100%的 NO 转化率和 80%的 N 选择性。详细的结构分析表明,引入的 Cu 取代了一些四面体配位的 Co,从而在不同金属之间产生了强烈的协同效应。这使得催化剂表面的电子转移和氧空位生成得到促进。重要的是,通过漫反射傅里叶变换红外光谱(DRIFTS)和密度泛函理论(DFT)计算进一步揭示了反应机理和途径。结果表明,氧空位的循环主要决定了 CO 还原 NO 的催化活性。值得注意的是,Cu 掺杂显著降低了速率决定步骤(*CO + O → *O + CO)的能垒,促进了 CO 的脱附,并暴露了活性位,从而实现了高效的 CO 还原 NO。这项工作为 CO 还原 NO 催化剂的设计提供了一种有效途径,并为探索反应的催化机理提供了参考。

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