氯阴离子对CuO/CeO2/UiO-66催化CO-PROX反应活性的中毒效应及催化剂活化策略

IF 4.5 3区 材料科学 Q1 CHEMISTRY, APPLIED Microporous and Mesoporous Materials Pub Date : 2025-02-15 Epub Date: 2024-12-05 DOI:10.1016/j.micromeso.2024.113445
Carlos W. Dos Santos Moraes , P. Gómez Bernabéu , Katia J. Gómez Villegas , E. Guillén Bas , I. Martínez López , A. Davó Quiñonero , D. Fairén Jiménez , D. Lozano Castelló , A. Bueno López Prof.
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引用次数: 0

摘要

以ZrOCl2·8H2O为金属前驱体合成了UiO-66,制备了CuO/CeO2/UiO-66催化剂,并对其在富h2流中的优先CO氧化(CO- prox反应)进行了测试,该反应在燃料电池氢净化中具有实际意义。研究强调了UiO-66合成过程中残留的氯阴离子和DMF洗涤对CuO/CeO2/UiO-66催化性能的不利影响。开发了一种活化策略,包括在CO-PROX条件下在160°C下进行严格的水洗和热处理。这两个步骤都被认为是必要的,因为仅采用一个步骤不足以将氯含量降低到非中毒阈值。这种活化过程确实会影响UiO-66的结晶度和孔隙度,但通过获得功能齐全的催化剂是合理的。TEM图像证实了CuO/CeO2活性相在活化后和催化测试后在UiO-66基体上的均匀分散。使用CuO/CeO2/UiO-66催化剂在160°C下进行16小时的CO-PROX测试,一旦激活,在整个延长的长期实验中表现出稳定的性能。该研究为优化CuO/CeO2/UiO-66催化剂的CO-PROX应用提供了宝贵的见解。
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Poisoning effect of chlorine anions in the catalytic activity of CuO/CeO2/UiO-66 for CO-PROX reaction and strategy for catalyst activation
UiO-66 was synthesized using ZrOCl2·8H2O as metal precursor, and CuO/CeO2/UiO-66 catalysts were prepared and tested for preferential CO oxidation in H2-rich streams (CO-PROX reaction), a reaction of practical significance in hydrogen purification for fuel cells. The study highlights the detrimental effect of residual chlorine anions from UiO-66 synthesis and DMF washing on the catalytic performance of CuO/CeO2/UiO-66. An activation strategy involving rigorous water washing and thermal treatment at 160 °C under CO-PROX conditions was developed. Both steps were deemed necessary, as employing only one proved insufficient to reduce chlorine levels to non-poisoning thresholds. This activation procedure does compromise UiO-66 crystallinity and porosity, but it is justified by achieving a fully functional catalyst. TEM images confirm the uniform dispersion of the CuO/CeO2 active phase on the UiO-66 matrix post-activation and after catalytic testing. A 16-h CO-PROX test at 160 °C with the CuO/CeO2/UiO-66 catalyst, once activated, demonstrated stable performance throughout the extended long-term experiment. This research provides valuable insights into optimizing CuO/CeO2/UiO-66 catalysts for CO-PROX application.
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来源期刊
Microporous and Mesoporous Materials
Microporous and Mesoporous Materials 化学-材料科学:综合
CiteScore
10.70
自引率
5.80%
发文量
649
审稿时长
26 days
期刊介绍: Microporous and Mesoporous Materials covers novel and significant aspects of porous solids classified as either microporous (pore size up to 2 nm) or mesoporous (pore size 2 to 50 nm). The porosity should have a specific impact on the material properties or application. Typical examples are zeolites and zeolite-like materials, pillared materials, clathrasils and clathrates, carbon molecular sieves, ordered mesoporous materials, organic/inorganic porous hybrid materials, or porous metal oxides. Both natural and synthetic porous materials are within the scope of the journal. Topics which are particularly of interest include: All aspects of natural microporous and mesoporous solids The synthesis of crystalline or amorphous porous materials The physico-chemical characterization of microporous and mesoporous solids, especially spectroscopic and microscopic The modification of microporous and mesoporous solids, for example by ion exchange or solid-state reactions All topics related to diffusion of mobile species in the pores of microporous and mesoporous materials Adsorption (and other separation techniques) using microporous or mesoporous adsorbents Catalysis by microporous and mesoporous materials Host/guest interactions Theoretical chemistry and modelling of host/guest interactions All topics related to the application of microporous and mesoporous materials in industrial catalysis, separation technology, environmental protection, electrochemistry, membranes, sensors, optical devices, etc.
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