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Structure-induced hollow Co3O4 nanoparticles with rich oxygen vacancies for efficient CO oxidation

结构诱导富集氧空位的空心Co3O4催化CO高效氧化

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Abstract

Co3O4 has been considered as one kind of promising catalysts for the oxidation of CO. According to the Mars-van Krevelen mechanism, oxygen vacancies of Co3O4 play a significant role in catalytic activity. Herein, we report a novel structure-induced strategy to develop hollow Co3O4 with rich oxygen vacancies for efficient oxidation of CO. Through a reduction-oxidation pyrolysis process, the metal-organic frameworks (MOFs) precursor (i.e., ZIF-67) is transformed into H-Co3O4@H-C, in which hollow Co3O4 (H-Co3O4) nanoparticles (NPs) are embedded in hollow carbon (H-C) shell. The hollow Co3O4 NPs feature rich oxygen vacancies and finish a complete conversion of CO at 130°C, which is much lower than that of solid Co3O4 (the temperature of full CO conversion T100=220°C). Besides, the hollow carbon shell could also reduce the diffusion resistance during the oxidation process. Benefiting from the unique hollow structures, H-Co3O4@H-C even shows comparable activity to noble metal catalysts under high weight hourly space velocities (WHSVs) up to 240,000 mL h−1 gcat.−1. Furthermore, the H-Co3O4@H-C catalyst also shows good durability with only a slight decline after the reaction has been operated for 24 h.

摘要

四氧化三钴(Co3O4)被认为是-种具有应用前景的CO氧化催化剂.根据Mars-van Krevelen机理, Co3O4的氧空位对提高催化活性起到非常重要的作用. 本文提出-种新颖的结构诱导策略以制备具有丰富氧空位的空心Co3O4, 实现高效CO氧化. 通过还原-氧化热解过程, 金属有机骨架前驱体(如ZIF-67)被转化成镶嵌有空心Co3O4颗粒的空心碳壳材料.空心Co3O4颗粒具有丰富的氧空位,在130°C时能催化CO完全氧化转化,远低于实心Co3O4材料的完全转化温度(220°C). 此外,空心碳壳结构可以降低氧化过程中的分子扩散阻力.得益于其独特的中空结构,H-Co3O4@H-C在高达240,000 mL h−1 gcat.−1的空速下显示出与贵金属催化剂相媲美的活性.此外, H-Co3O4@H-C催化剂也显示出良好的稳定性,反应24 h后活性才略微下降.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (21825802, 21576095 and 21436005), the Fundamental Research Funds for the Central Universities (2019PY11), the Science and Technology Program of Guangzhou (201804020009), the State Key Laboratory of Pulp and Paper Engineering (2017ZD04 and 2018TS03), and the Natural Science Foundation of Guangdong Province (2016A050502004 and 2017A030312005).

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Authors and Affiliations

  1. State Key Laboratory of Pulp and Paper Engineering, School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, China

    Zhijie Chen  (陈芝杰), Yajing Wang  (王亚晶), Qiannan Liang  (梁倩楠), Liyu Chen  (陈立宇), Weiteng Zhan  (詹伟腾) & Yingwei Li  (李映伟)

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  1. Zhijie Chen  (陈芝杰)
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  2. Yajing Wang  (王亚晶)
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  3. Qiannan Liang  (梁倩楠)
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  4. Liyu Chen  (陈立宇)
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  5. Weiteng Zhan  (詹伟腾)
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  6. Yingwei Li  (李映伟)
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Contributions

Li Y conceived the idea and designed the experiments; Chen Z synthesized the samples and performed most of the experiments; Wang Y, Liang Q, Chen L, and Zhan W participated in some characterization and/or reaction experiments and analyze the data; Chen Z and Li Y co-wrote the paper. All authors contributed to the general discussion.

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Correspondence to Yingwei Li  (李映伟).

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Supplementary information

Supporting data are available in the online version of the paper.

Conflict of interest

The authors declare that they have no conflict of interest.

Zhijie Chen received his BSc degree from South China University of Technology. He is currently a Master candidate with Prof. Yingwei Li at the School of Chemistry and Chemical Engineering, South China University of Technology, China. His current research focuses on the catalytic transformation of CO based on MOF-derived materials.

Yingwei Li received his BSc degree in 1998 and his PhD in 2003, both from Tsinghua University, and he then conducted postdoctoral work at the University of Calgary and the University of Michigan (Ann Arbor) from 2003 to 2007. He is currently a full professor at the School of Chemistry and Chemical Engineering, South China University of Technology. His research focuses on the design and synthesis of new MOF-based materials for heterogeneous catalysis.

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40843_2019_1178_MOESM1_ESM.pdf

Structure-induced hollow Co3O4 nanoparticles with defect-rich oxygen derived from MOFs for efficient CO oxidation reaction

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Chen, Z., Wang, Y., Liang, Q. et al. Structure-induced hollow Co3O4 nanoparticles with rich oxygen vacancies for efficient CO oxidation. Sci. China Mater. 63, 267–275 (2020). https://doi.org/10.1007/s40843-019-1178-5

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