CeO2对抗烧结Au₲MgGa2O4催化剂用于水汽变换和催化燃烧反应的促进作用

引用本文: 任国庆, 裴广贤, 张景才, 李为臻. CeO₂对抗烧结Au₲MgGa₂O₄催化剂用于水汽变换和催化燃烧反应的促进作用[J]. 催化学报, 2019, 40(4): 600-608. doi: S1872-2067(19)63295-X shu

Citation: Guo-Qing Ren, Guang-Xian Pei, Jing-Cai Zhang, Wei-Zhen Li. Activity promotion of anti-sintering Au₲MgGa₂O₄ using ceria in the water gas shift reaction and catalytic combustion reactions[J]. Chinese Journal of Catalysis, 2019, 40(4): 600-608. doi: S1872-2067(19)63295-X shu

CeO₂对抗烧结Au₲MgGa₂O₄催化剂用于水汽变换和催化燃烧反应的促进作用

a 中国科学院大连化学物理研究所, 辽宁大连 116023;
b 中国科学院大学, 北京 100049;
c 中国科学院洁净能源创新研究院, 辽宁大连 116023
基金项目:
中国国家重点研发计划（2016YFA0202801）；国家自然科学基金（21403213，21673226）；中国科学院A类战略性先导科技专项"变革性洁净能源关键技术与示范"（XDA21040200）；中国科学院"百人计划".

摘要: 自上世纪八十年代在多相催化研究领域兴起纳米金催化淘金热以来，负载型纳米金催化剂的优越性和局限性都得到了广泛的研究.负载型纳米金催化剂活性强烈依赖于其晶粒尺寸和载体性质，一般认为，金纳米颗粒只有在一定的尺寸范围（2-5nm）且负载在"活性"载体表面才能发挥出其优异的催化活性.然而，小尺寸纳米金颗粒热稳定性差的弱点阻碍了其工业化应用的进程.因此，如何实现小尺寸金纳米颗粒的高温稳定以及构筑金与"活性"载体间有效的接触界面是发挥纳米金优异催化性能的关键.我们曾利用MgGa₂O₄尖晶石载体与金纳米颗粒形成金属-氧化物"异质孪晶"结构，从而实现了将~3nm的金颗粒稳定在块体金的熔点（1064℃）以上，为小尺寸纳米金的高温稳定提供了新的思路.但MgGa₂O₄尖晶石是一种非氧化还原性载体，对水分子或氧气分子的辅助活化作用较弱，因而限制了具有优异高温抗烧结性能的Au₲MgGa₂O₄催化剂在水汽变换和催化燃烧反应中的应用.
本文采用等体积浸渍法在高温800℃焙烧5h后的Au₲MgGa₂O₄-800℃-5h样品上进行CeO₂助剂的修饰，以提高其对水分子和氧气分子的活化能力.利用STEM，XRD和EDS-Mapping表征对CeO₂/[Au₲MgGa₂O₄-800℃-5h]样品进行结构分析，发现该样品中纳米Au具有优异的高温抗烧结性能，800℃焙烧5h并经CeO₂修饰后其颗粒尺寸仍保持在3.1nm左右，样品中CeO₂的晶粒尺寸约为6nm，且Au纳米颗粒与CeO₂助剂间形成了有效的接触界面.利用H₂-TPR和XPS表征对该样品的氧化还原性能及电子性质进行分析，发现CeO₂/[Au₲MgGa₂O₄-800℃-5h]样品中CeO₂的还原温度相比于CeO₂/MgGa₂O₄对比样品显著降低，XPS结果显示CeO₂添加后Au的化学价态由金属态变为氧化态，表明Au与CeO₂助剂间具有显著的电子转移.同时，CeO₂的添加显著提高了800℃老化后Au₲MgGa₂O₄催化水汽变换（CO转化率由~1.5%升到~34.0%，450℃）、甲烷燃烧（T₅₀降低80℃）和CO氧化（T₅₀降低100℃）等反应活性.为理解CeO₂对Au₲MgGa₂O₄的催化性能促进机制，我们选取水汽变换反应为例，利用DRIFTs表征发现CeO₂促进了反应物H₂O的活化，并结合小尺寸Au对CO的活化能力，从而使水汽变换反应顺利进行.
本文在MgGa₂O₄尖晶石稳定纳米金的基础上，利用具有优异氧传输性能的CeO₂作为助剂，提高了该催化剂对水分子和氧气分子的活化能力，从而获得了对水汽变换反应和催化燃烧反应具有高稳定性和高活性的CeO₂/[Au₲MgGa₂O₄]催化剂.这种"先稳定-后活化"的催化剂设计思路也为今后高稳定性、高催化活性的纳米金催化剂的设计和制备提供了借鉴.

关键词:

English

Activity promotion of anti-sintering Au₲MgGa₂O₄ using ceria in the water gas shift reaction and catalytic combustion reactions

a Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China;
b University of Chinese Academy of Sciences, Beijing 100049, China;
c Dalian National Laboratory for Clean Energy, CAS, Dalian 116023, Liaoning, China
Received Date: 26 November 2018
Revised Date: 03 January 2019
Fund Project:
This work was supported by the National Key R&D Program of China (2016YFA0202801), the National Natural Science Foundation of China (21403213, 21673226), the "Transformational Technologies for Clean Energy and Demonstration" Strategic Priority Research Program of the Chinese Academy of Sciences (XDA21040200), and the "Hundred Talents Programme" of the Chinese Academy of Sciences.

Abstract: Heterogeneous gold nanocatalysts have both inspired researchers with their unique catalytic performance and frustrated them due to the contradictions observed in their activities and stabilities. A recent breakthrough has shown that gold nanoparticles (NPs) can retain their catalytically active size over a MgGa₂O₄ spinel support upon sintering at high temperatures. Herein, we report the catalytic activity of anti-sintering Au₲MgGa₂O₄ for use in water gas shift reaction (WGSR) and catalytic combustion reactions, and the promoting effect of ceria. Upon adding ceria to 800℃-aged Au₲MgGa₂O₄, the CO conversion in the WGSR was increased from~1.5% to~34.0% at 450℃, and the "light-off" temperatures (T₅₀) for methane combustion and CO oxidation were decreased by~80 and~100℃, respectively. Characterizations using XRD, HAADF-STEM, EDS mapping, H₂-TPR, XPS, and DRIFTs confirmed the proximate contact of Au with ceria and their significant synergistic effect, which thereby combined the benefits of ceria toward the dissociation of H₂O or O₂ and the Au NPs toward activating CO or CH₄. These results show that this stepwise stabilization-activation strategy is efficient for rationally constructing stable and active gold nanocatalysts, which may open up possibilities for the wide application of gold nanocatalysts at elevated temperatures.

Key words:

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CeO₂对抗烧结Au₲MgGa₂O₄催化剂用于水汽变换和催化燃烧反应的促进作用

English

Activity promotion of anti-sintering Au₲MgGa₂O₄ using ceria in the water gas shift reaction and catalytic combustion reactions

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