AgAuPd/meso-Co3O4高效甲醇氧化催化剂

doi:10.1016/S1872-2067(18)63205-X

催化学报 ›› 2019, Vol. 40 ›› Issue (6): 837-848.DOI: 10.1016/S1872-2067(18)63205-X

• 第十一届全国环境催化与环境材料学术会议专栏 • 上一篇下一篇

AgAuPd/meso-Co₃O₄高效甲醇氧化催化剂

杨军, 刘雨溪, 邓积光, 赵星天, 张昆锋, 韩卓, 戴洪兴

北京工业大学环境与能源工程学院化学化工系, 绿色催化与分离北京市重点实验室, 区域大气复合污染防治北京市重点实验室, 先进功能材料教育部重点实验室, 催化化学与纳米科学实验室, 北京 100124

收稿日期:2018-10-27 修回日期:2018-11-26 出版日期:2019-06-18 发布日期:2019-04-26
通讯作者: 刘雨溪, 戴洪兴
基金资助:
国家自然科学基金（21677004，21876006，21622701）；国家高技术研究发展计划（863计划，2015AA034603）.

AgAuPd/meso-Co₃O₄:High-performance catalysts for methanol oxidation

Jun Yang, Yuxi Liu, Jiguang Deng, Xingtian Zhao, Kunfeng Zhang, Zhuo Han, Hongxing Dai

Beijing Key Laboratory for Green Catalysis and Separation, Key Laboratory of Beijing on Regional Air Pollution Control, Key Laboratory of Advanced Functional Materials, Education Ministry of China, Laboratory of Catalysis Chemistry and Nanoscience, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, China

Received:2018-10-27 Revised:2018-11-26 Online:2019-06-18 Published:2019-04-26
Contact: 10.1016/S1872-2067(18)63205-X
Supported by:
This work was supported by the National Natural Science Foundation of China (21677004, 21876006, and 21622701) and the National High Technology Research and Development Program of China (863 Program, 2015AA034603).

摘要/Abstract

摘要：

甲醇是重要的化工原料和溶剂，也是一种典型的挥发性有机物（VOCs），其排放会对人体和大气环境造成危害.迄今为止，最有效的消除低浓度VOCs的方法是催化氧化.该方法具有VOCs去除效率高、起燃温度低、设备简单且无二次污染等优点.众所周知，负载贵金属催化剂对VOCs氧化显示良好的低温活性，但反应气流中的水分会降低贵金属的催化性能.研究表明，与单一贵金属催化剂相比，贵金属合金催化剂不仅具有高的催化活性，而且还具有良好的水热稳定性.尽管已有文献报道了二元贵金属合金催化剂对VOCs的催化氧化，然而VOCs在三元贵金属合金上催化氧化的研究则较少.本文采用三维有序介孔结构的二氧化硅（KIT-6）硬模板法和聚乙烯醇保护的硼氢化钠还原法制备了0.68 wt% Ag_0.75Au_1.14Pd/meso-Co₃O₄，0.84 wt% Ag_0.54Au_2.29Pd/meso-Co₃O₄和0.93 wt% Ag_0.51Au_0.65Pd/meso-Co₃O₄三元贵金属合金催化剂以及0.28 wt% Ag/meso-Co₃O₄，0.35 wt% Au/meso-Co₃O₄和0.33 wt% Pd/meso-Co₃O₄单一贵金属催化剂.利用电感耦合等离子体-原子发射光谱（ICP-AES）、X射线衍射（XRD）、透射电子显微镜（TEM）、高角环形暗场-扫描透射电子显微镜（HAADF-STEM）、X射线光电子能谱（XPS）和氢气-程序升温还原（H₂-TPR）技术表征了催化剂的物化性质.催化剂的活性评价在固定床石英微型反应器中进行，反应气组成为0.1%甲醇+氧气+氮气（平衡气），甲醇/氧气摩尔比为1/200，空速约为80000mL g^–1 h^–1，利用气相色谱检测反应物和产物的浓度.
广角度XRD结果表明，meso-Co₃O₄具有立方晶相结构.XRD谱中未检测到Ag，Au和Pd的衍射峰，系贵金属负载量低且均匀分散在载体表面所致.贵金属粒径为2.8-4.5nm.小角度XRD和TEM结果表明，meso-Co₃O₄具有有序介孔结构.从HAADF-STEM照片可以观察到，0.68 wt% Ag_0.75Au_1.14Pd/meso-Co₃O₄中的贵金属形成了Ag-Au-Pd合金.BET结果显示，所制得催化剂的比表面积为115-120m²/g，孔径为5.7-6.0nm，孔容为0.15-0.16cm³/g.XPS结果表明，贵金属与载体之间较强的相互作用使0.68 wt% Ag_0.75Au_1.14Pd/meso-Co₃O₄具有最低的表面Co³⁺/Co²⁺摩尔比，从而使该催化剂表面拥有更多的氧空位，有利于吸附和活化氧气，提高表面吸附氧浓度，从而提高催化活性.0.68 wt% Ag_0.75Au_1.14Pd/meso-Co₃O₄具有最低的还原温度（即最好的低温还原性），有利于催化活性的提高.因此，高分散的Ag_0.75Au_1.14Pd纳米粒子、高的吸附氧浓度、优良的低温还原性以及载体与Ag_0.75Au_1.14Pd粒子之间强的相互作用是0.68Ag_0.75Au_1.14Pd/meso-Co₃O₄具有最高催化活性（当空速为80000mL g^–1 h^–1时，T_50%=100℃和T_90%=112℃）的主要原因.在反应温度为110℃和空速为80000mL g^–1 h^–1的条件下，向反应体系中分别引入3.0 vol%水蒸气和5.0 vol%二氧化碳，甲醇转化率分别下降6.0%和7.0%；当切断水和二氧化碳后，甲醇转化率均恢复到在无水和二氧化碳时的数值.因此，水和二氧化碳对该催化剂的失活是可逆的.换句话说，0.68 wt% Ag_0.75Au_1.14Pd/meso-Co₃O₄具有优良的水热稳定性和抗二氧化碳中毒能力.

关键词: 挥发性有机物, 介孔四氧化三钴, 负载贵金属催化剂, AgAuPd合金纳米粒子, 甲醇氧化

Abstract:

The meso-Co₃O₄ and Ag_xAu_yPd/meso-Co₃O₄ catalysts were prepared using the KIT-6-templating and polyvinyl alcohol-protected NaBH₄ reduction methods, respectively. Various techniques were used to characterize physicochemical properties of these materials. Catalytic performance of the samples was evaluated for methanol combustion. The cubically crystallized Co₃O₄ support displayed a three-dimensionally ordered mesoporous structure. The supported noble metal nanoparticles (NPs) possessed a surface area of 115-125 m²/g, with the noble NPs (average size=2.8-4.5 nm) being uniformly dispersed on the surface of meso-Co₃O₄. Among all of the samples, 0.68 wt% Ag_0.75Au_1.14Pd/meso-Co₃O₄ showed the highest catalytic activity (T_50%=100℃ and T_90% =112℃ at a space velocity of 80000 mL (g^-1 h^-1). The partial deactivation of the 0.68 wt% Ag_0.75Au_1.14Pd/meso-Co₃O₄ sample due to water vapor or carbon dioxide introduction was reversible. It is concluded that the good catalytic performance of 0.68 wt% Ag_0.75Au_1.14Pd/meso-Co₃O₄ was associated with its highly dispersed Ag_0.75Au_1.14Pd alloy NPs, high adsorbed oxygen species concentration, good low-temperature reducibility, and strong interaction between Ag_0.75Au_1.14Pd alloy NPs and meso-Co₃O₄.

Key words: Volatile organic compound, Mesoporous cobalt oxide, Supported noble metal catalyst, AgAuPd alloy nanoparticle, Methanol oxidation

杨军, 刘雨溪, 邓积光, 赵星天, 张昆锋, 韩卓, 戴洪兴. AgAuPd/meso-Co₃O₄高效甲醇氧化催化剂[J]. 催化学报, 2019, 40(6): 837-848.

Jun Yang, Yuxi Liu, Jiguang Deng, Xingtian Zhao, Kunfeng Zhang, Zhuo Han, Hongxing Dai. AgAuPd/meso-Co₃O₄:High-performance catalysts for methanol oxidation[J]. Chinese Journal of Catalysis, 2019, 40(6): 837-848.

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AgAuPd/meso-Co₃O₄高效甲醇氧化催化剂

AgAuPd/meso-Co₃O₄:High-performance catalysts for methanol oxidation

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