Pt/Co3O4/3DOM Al2O3:甲苯燃烧的高效催化剂

引用本文: 杨黄根, 邓积光, 刘雨溪, 谢少华, 徐鹏, 戴洪兴. Pt/Co₃O₄/3DOM Al₂O₃:甲苯燃烧的高效催化剂[J]. 催化学报, 2016, 37(6): 934-946. doi: 10.1016/S1872-2067(15)61095-6 shu

Citation: Huanggen Yang, Jiguang Deng, Yuxi Liu, Shaohua Xie, Peng Xu, Hongxing Dai. Pt/Co₃O₄/3DOM Al₂O₃: Highly effective catalysts for toluene combustion[J]. Chinese Journal of Catalysis, 2016, 37(6): 934-946. doi: 10.1016/S1872-2067(15)61095-6 shu

Pt/Co₃O₄/3DOM Al₂O₃:甲苯燃烧的高效催化剂

北京工业大学环境与能源工程学院化学化工系, 北京市绿色催化与分离重点实验室, 北京市区域大气污染控制重点实验室, 催化化学与纳米科学研究室, 北京 100124
基金项目:
北京市属高等学校创新团队建设提升计划.

国家高技术研究发展计划(863计划, 2015AA034603)

国家自然科学基金(21377008)

摘要: 与硫氧化物、氮氧化物、一氧化碳以及悬浮颗粒一样, 大部分挥发性有机物 (VOCs) 污染大气环境. 控制 VOCs 排放有多种方法, 其中催化氧化法是一种有效技术, 关键在于获得高效催化剂.
近年来, 负载过渡金属和贵金属催化剂因具有比单纯负载贵金属和单纯负载过渡金属氧化物更好的催化性能而备受关注. 在负载贵金属催化剂中, 高比表面积载体负载 Pt, Pd 或 Rh 催化剂得到广泛而深入的研究, 尽管这些催化剂成本较高, 但是其对 VOCs 氧化反应显示了很高的低温催化活性. 众所周知, 催化活性取决于贵金属和 VOCs 的种类, 不同负载贵金属催化剂对特定反应会表现出不同的催化活性. 负载 Pt 催化剂对长链碳氢化合物和芳香族化合物氧化反应表现出更高的活性. 相对于负载贵金属催化剂, 负载过渡金属氧化物催化剂不仅具有良好的氧化活性, 而且价格低廉. 迄今已发现许多过渡金属氧化物 (如 Co₃O₄, Cr₂O₃和 MnO₂等) 对典型 VOCs 氧化反应具有催化活性, 其中 Co₃O₄的催化活性尤为突出. 研究表明, Co₃O₄的性质和分散度是决定其性能的关键因素, 制备方法、载体性质和过渡金属氧化物负载量对 Co₃O₄的物化性质具有重要影响, 而且在负载 Pt 催化剂中添加金属氧化物能改善其催化性能. 尽管多孔氧化铝是一种常用的载体材料, 但目前尚无文献报道三维有序大孔-介孔氧化铝负载 Co₃O₄和 Pt 纳米粒子催化剂的制备及其对甲苯氧化反应的催化性能.
本文采用聚甲基丙烯酸甲酯微球胶晶模板法、等体积浸渍法和聚乙烯醇保护的硼氢化钠还原法制备了三维有序大孔-介孔 (3DOM Al₂O₃) 负载 Co₃O₄和 Pt (xPt/yCo₃O₄/3DOM Al₂O₃, Pt 的质量分数 (x%) 为 0-1.4%, Co₃O₄的质量分数 (y%) 为 0-9.2%) 纳米催化剂. 通过电感耦合等离子体原子发射光谱、X 射线衍射、氮气吸附-脱附、扫描电子显微镜、透射电子显微镜、选区电子衍射、X 射线光电子能谱及氢气程序升温还原等技术表征了催化剂的物化性质, 利用固定床微型石英反应器评价了催化剂对甲苯氧化反应的催化活性. 结果表明, xPt/yCo₃O₄/3DOMAl₂O₃催化剂具有多级孔结构 (大孔孔径为 180-200 nm, 介孔孔径为 4-6 nm), 比表面积为 94-102 m²/g. 粒径为 18.3 nm 的 Co₃O₄纳米粒子和粒径为 2.3-2.5 nm 的 Pt 纳米粒子均匀分散在 3DOM Al₂O₃表面. 在 xPt/yCo₃O₄/3DOM Al₂O₃催化剂中, 1.3Pt/8.9Co₃O₄/3DOM Al₂O₃拥有最高的 O_ads浓度、最好的低温还原性和最高的甲苯氧化反应催化活性 (当空速为 20000 mL g^-1 h^-1 时, 甲苯转化率达 90% 的反应温度为 160 ^oC). 基于催化剂的活性数据和结构表征, 我们认为, 1.3Pt/8.9Co₃O₄/3DOM Al₂O₃优异的催化性能与其高分散的 Pt 纳米粒子、高的 O_ads浓度、好的低温还原性、Pt 和 Co₃O₄纳米粒子间的强相互作用以及多级孔结构相关.

关键词:

English

Pt/Co₃O₄/3DOM Al₂O₃: Highly effective catalysts for toluene combustion

Beijing Key Laboratory for Green Catalysis and Separation, Key Laboratory of Beijing on Regional Air Pollution Control, and 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 Date: 29 January 2016
Revised Date: 19 March 2016
Fund Project:

This work was supported by the National High Technology Research and Development Program of China (863 Program, 2015AA034603), the National Natural Science Foundation of China (21377008), and Foundation on the Creative Research Team Construction Promotion Project of Beijing Municipal Institutions.

Abstract: Three-dimensionally ordered macro-/mesoporous alumina (3DOM Al₂O₃)-supported cobalt oxide and platinum nanocatalysts (xPt/yCo₃O₄/3DOM Al₂O₃, Pt mass fraction (x%) = 0-1.4%, Co₃O₄ mass fraction (y%) = 0-9.2%) were prepared using poly(methyl methacrylate) templating, incipient wetness impregnation and polyvinyl alcohol-protected reduction. The resulting xPt/yCo₃O₄/3DOM Al₂O₃ samples displayed a high-quality 3DOM architecture with macropores (180-200 nm in diameter) and mesopores (4-6 nm in diameter) together with surface areas in the range of 94 to 102 m²/g. Using these techniques, Co₃O₄ nanoparticles (NPs, 18.3 nm) were loaded on the 3DOM Al₂O₃ surface, after which Pt NPs (2.3-2.5 nm) were uniformly dispersed on the yCo₃O₄/3DOM Al₂O₃. The 1.3Pt/8.9Co₃O₄/3DOM Al₂O₃ exhibited the best performance for toluene oxidation, with a T_90% value (the temperature required to achieve 90% toluene conversion) of 160 ℃ at a space velocity of 20000 mL g^-1 h^-1. It is concluded that the excellent catalytic performance of the 1.3Pt/8.9Co₃O₄/3DOM Al₂O₃ is owing to well-dispersed Pt NPs, the high concentration of adsorbed oxygen species, good low-temperature reducibility, and strong interaction between the Pt and Co₃O₄ NPs, as well as the unique bimodal porous structure of the support.

Key words:

Three-dimensionally ordered macropore
/ Alumina-supported cobalt oxide catalyst
/ Supported platinum catalyst
/ Toluene combustion

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Pt/Co₃O₄/3DOM Al₂O₃:甲苯燃烧的高效催化剂

English

Pt/Co₃O₄/3DOM Al₂O₃: Highly effective catalysts for toluene combustion

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