Co3O4纳米催化剂催化CO的形貌效应:合成过程和催化活性

doi:10.1016/S1872-2067(16)62460-9

催化学报 ›› 2016, Vol. 37 ›› Issue (6): 908-922.DOI: 10.1016/S1872-2067(16)62460-9

Co₃O₄纳米催化剂催化CO的形貌效应:合成过程和催化活性

曾良鹏^a,b, 李孔斋^a,b, 黄樊^a,b, 祝星^a,b, 李宏程^a,b

a 昆明理工大学省部共建复杂有色金属资源清洁利用国家重点实验室, 云南昆明 650093;
b 昆明理工大学冶金与能源工程学院, 云南昆明 650093

收稿日期:2016-04-22 修回日期:2016-05-05 出版日期:2016-05-30 发布日期:2016-05-30
通讯作者: Kongzhai Li
基金资助:
国家自然科学基金(51374004, 51204083); 云南省后备人才培养基金(2012HB009, 2014HB006); 云南省应用基础研究计划(2014FB123); 金川公司校企合作项目(Jinchuan201115); 昆明理工大学人才培养计划(KKZ3201352038).

Effects of Co₃O₄ nanocatalyst morphology on CO oxidation: Synthesis process map and catalytic activity

Liangpeng Zeng^a,b, Kongzhai Li^a,b, Fan Huang^a,b, Xing Zhu^a,b, Hongcheng Li^a,b

a State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Kunming University of Science and Technology, Kunming 650093, Yunnan, China;
b Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, Yunnan, China

Received:2016-04-22 Revised:2016-05-05 Online:2016-05-30 Published:2016-05-30
Contact: Kongzhai Li
Supported by:
This work was supported by the National Natural Science Foundation of China (51374004, 51204083), the Candidate Talents Training Fund of Yunnan Province (2012HB009, 2014HB006), the Applied Basic Research Program of Yunnan Province (2014FB123), a School-Enterprise Cooperation Project from Jinchuan Corporation (Jinchuan 201115), and the Talents Training Program of Kunming University of Science and Technology (KKZ3201352038).

摘要/Abstract

摘要：

通过催化剂将CO转化为无毒气体仍然是目前减少CO污染的主要手段. 随着纳米技术的快速发展, 纳米催化剂因其在催化反应中呈现出的独特结构效应(如形貌效应、尺寸效应等)而受到人们的广泛关注. 已有大量研究表明, 纳米Co₃O₄作为一种非贵金属氧化物催化剂具有强烈的催化形貌效应, 展现出优异的CO低温催化活性. 因此, 通过合理的设计来调控催化剂粒子的形貌, 从而进一步改善催化剂的性能已成为近年来催化剂领域的重要研究方向. 对于Co₃O₄纳米催化剂的可控制备, 水热法具有反应温和、操作简便和产品形貌易控等特点. 早期的研究主要围绕于Co₃O₄形貌的可控合成以及不同形貌Co₃O₄催化剂对其催化活性产生的影响, 较少有对其形貌形成机制的报道. 特别是在水热反应中, 系统研究各反应参数对催化剂各异形貌的形成影响鲜有报道.
本文在前人的研究基础上, 重点研究了水热反应过程中各主要反应参数对产品形貌控制的影响, 绘制了一副不同形貌Co₃O₄材料的合成过程图, 并研究了Co₃O₄纳米催化剂催化CO氧化的形貌效应. 通过水热法先成功合成了三种不同形貌(纳米棒、纳米片和纳米立方)的碱式碳酸钴纳米粒子, 然后将其焙烧得到了Co₃O₄纳米粒子. 采用扫描电子显微镜(SEM), 透射电子显微镜(TEM), X射线粉末衍射仪(XRD), 程序升温还原(H₂-TPR和CO-TPR), 氮气吸附-脱附比表面积测试(BET), 氧气程序升温脱附(O₂-TPD), X射线光电子能谱(XPS) 等表征手段研究了不同反应参数对纳米碱式碳酸钴前驱体形貌形成的作用和各异形貌Co₃O₄纳米粒子在催化CO氧化反应中催化性能的差异及原因.
结果表明, Co₃O₄较好地继承了碱式碳酸钴的形貌, 在较低温度条件下(≤ 140 ℃), 钴源(CoCl₂或Co(NO₃)₂)是影响前驱体形貌的关键因素, 反应时间只对粒子的尺寸产生较大影响. 低温下, CoCl₂作为钴源易诱导生产纳米棒状碱式碳酸钴, 而Co(NO₃)₂则有利于纳米片状生成. 当温度高于140 ℃后, 无论何种钴源, 最终均制得纳米立方体. 表面活性剂CTAB对前驱体的均一性和粒子的分散性产生重要影响, 加入CTAB后得到的产品尺寸更均一, 形貌更加规整. 对比于其他两种形貌的样品, Co₃O₄纳米片显示出更好的CO催化氧化活性. XPS结果表明, 各形貌Co₃O₄纳米材料的表面组成存在明显差异, 活性物种Co³⁺含量的不同是影响催化活性差异的重要原因. Co₃O₄纳米片具有更多的Co³⁺活性位, 立方纳米Co₃O₄表面吸附氧含量较高, Co₃O₄纳米棒则暴露出相对更多的Co²⁺. 因此, 在三种形貌催化剂上CO氧化反应中, Co₃O₄纳米片表现出最优的催化活性, 纳米立方次之, 而纳米棒最差. H₂-TPR, CO-TPR和O₂-TPD等结果也表明, Co₃O₄纳米片拥有更强的还原性能和脱附氧能力, 其次是纳米立方Co₃O₄. 这与XPS结果一致, 证实了不同形貌Co₃O₄纳米催化剂上暴露活性位的数量和表面氧物种的不同是造成彼此间催化CO氧化活性差异的重要原因. 此外, 通过稳定性测试发现Co₃O₄纳米片具有较高的催化稳定性, 在水蒸气存在的情况下Co₃O₄纳米片逐渐失活, 但随后在干燥条件下其催化活性又逐渐得到恢复.

关键词: 四氧化三钴纳米催化剂, 合成过程地图, 形貌效应, 催化活性, 一氧化碳氧化

Abstract:

This study focuses on drawing a hydrothermal synthesis process map for Co₃O₄ nanoparticles with various morphologies and investigating the effects of Co₃O₄ nanocatalyst morphology on CO oxidation. A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies (i.e., nanorods, nanosheets, and nanocubes) were successfully synthesized, and Co₃O₄ nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors. The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures (≤ 140 ℃). Nanorods can be synthesized in CoCl₂ solution, while Co(NO₃)₂solution promotes the formation of nanosheets. Further increasing the synthesis temperature (higher than 140 ℃) results in the formation of nanocubes in either Co(NO₃)₂or CoCl₂ solution. The reaction time only affects the size of the obtained nanoparticles. The presence of CTAB could improve the uniformity and dispersion of particles. Co₃O₄ nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co³⁺ on the surface, much higher reducibility, and better oxygen desorption capacity.

Key words: Cobalt oxide nanocatalyst, Synthesis process map, Morphology effect, Catalytic activity, Carbon monoxide oxidation

曾良鹏, 李孔斋, 黄樊, 祝星, 李宏程. Co₃O₄纳米催化剂催化CO的形貌效应:合成过程和催化活性[J]. 催化学报, 2016, 37(6): 908-922.

Liangpeng Zeng, Kongzhai Li, Fan Huang, Xing Zhu, Hongcheng Li. Effects of Co₃O₄ nanocatalyst morphology on CO oxidation: Synthesis process map and catalytic activity[J]. Chinese Journal of Catalysis, 2016, 37(6): 908-922.

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Co₃O₄纳米催化剂催化CO的形貌效应:合成过程和催化活性

Effects of Co₃O₄ nanocatalyst morphology on CO oxidation: Synthesis process map and catalytic activity

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