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Controlling metallic Co0 in ZIF-67-derived N-C/Co composite catalysts for efficient photocatalytic CO2 reduction

调控ZIF-67衍生N-C/Co复合催化剂中的金属性Co0 实现高效光催化CO2还原

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Abstract

An efficient photocatalytic CO2 reduction has been reported in ZIF-67-derived-Co nanoparticles (NPs) encapsulated in nitrogen-doped carbon layers (N-C/Co). This work demonstrates that the pyrolysis temperature is crucial in tuning the grain size and components of metallic Co0 of N-C/Co composite catalysts, which optimizes their photocatalytic activities. Syntheses were conducted at 600, 700, and 800°C giving the N-C/Co-600, N-C/Co-700, and N-C/Co-800 samples, respectively. N-C layers can well wrap the Co NPs obtained at a low pyrolysis temperature (600°C) owing to their smaller grains than those of other samples. A high metallic Co0 content in the N-C/Co-600 sample can be attributed to the effective inhibition of surface oxidation. By contrast, the surface CoOx oxides in the N-C/Co-700 and N-C/Co-800 samples cover inside Co cores, inhibiting charge separation and transfer. As a result, the N-C/Co-600 sample yields the best photocatalytic activity. The carbon monoxide and hydrogen generation rates are as high as 1.62 × 104 and 2.01 × 104 µmol g−1 h−1, respectively. Additionally, the Co NPs make composite catalysts magnetic, enabling rapid and facile recovery of catalysts with the assistance of an external magnetic field. This work is expected to provide an instructive guideline for designing metal-organic framework-derived carbon/metal composite catalysts.

摘要

本文报道了由ZIF-67衍生而来的N掺杂C层包裹Co纳米颗粒(NC/Co)复合催化剂及其高效光催化CO2还原性能. 研究发现热解温度对 N-C/Co复合催化剂的晶粒尺寸和金属性Co0含量的调控具有关键作用, 并在此基础上优化了催化剂的光催化活性. 在较低热解温度(600°C)下 获得的Co纳米颗粒尺寸较小, 能够被N-C层良好保护, 从而有效抑制表 面氧化, 使得N-C/Co-600样品中具有更高含量的金属性Co0. 相反, NC/Co-700和N-C/Co-800样品中的表面氧化物CoOx覆盖了内部Co核, 不 利于电荷分离和迁移. 因此, N-C/Co-600样品表现出最佳的光催化活 性. CO和H2的产率分别高达1.62 × 104和2.01 × 104 µmol g−1 h−1. 另外, Co纳米颗粒使得复合催化剂具有磁性, 能够在外加磁场辅助下, 快速、 简易地分离回收. 本工作有望为MOF衍生碳/金属复合催化剂的设计提 供参考依据.

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Acknowledgements

This work was financially supported by the National Key Research and Development Program of China (2020YFA0710303) and the National Natural Science Foundation of China (51972061, U1905215 and 52072076).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Advanced Materials Technologies, College of Materials Science and Engineering, Fuzhou University, Fuzhou, 350108, China

    Fei-Fei Chen  (陈飞飞), Jianfeng Chen  (陈建丰), Ya-Nan Feng  (冯亚南), Lingyun Li  (李凌云) & Yan Yu  (于岩)

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  1. Fei-Fei Chen  (陈飞飞)
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  2. Jianfeng Chen  (陈建丰)
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  5. Yan Yu  (于岩)
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Contributions

Author contributions Chen FF and Chen J conducted the experiments; Chen FF wrote the manuscript; Feng YN contributed to data analysis; Li L and Yu Y conceived the idea of this work and revised the manuscript. All authors contributed to the general discussion.

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Correspondence to Lingyun Li  (李凌云) or Yan Yu  (于岩).

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Conflict of interest The authors declare that they have no conflict of interest.

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

Fei-Fei Chen received his BS degree in 2014 from Xiamen University and his PhD degree in 2019 from Shanghai Institute of Ceramics, Chinese Academy of Sciences. Currently, he is a lecturer at Fuzhou University. His research interests include photocatalytic CO2 reduction, water purification, ecological materials, low-dimensional inorganic nanostructures, and metal-organic framework-derived catalysts.

Jianfeng Chen received his BS degree in 2018 from Fujian Agriculture and Forestry University. Currently, he is an MS candidate under the supervision of Prof. Yan Yu at Fuzhou University. His research interests include photocatalytic CO2 reduction, metal-organic frameworks, and metal-organic framework-derived catalysts.

Lingyun Li received his BS degree in 2007 from Hefei University of Technology and his PhD degree in 2012 from Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. Currently, he is an associate professor at Fuzhou University. His research interests include optical materials, laser crystals, metal-organic frameworks, and environmental remediation.

Yan Yu received her BS, MS, and PhD degrees from Fuzhou University. She was a postdoctoral fellow in 2010–2013 at Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences. Currently, she is a professor at Fuzhou University. Her research interests include environmental remediation, water purification, ecological materials, photocatalytic CO2 reduction and H2 production.

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Chen, FF., Chen, J., Feng, YN. et al. Controlling metallic Co0 in ZIF-67-derived N-C/Co composite catalysts for efficient photocatalytic CO2 reduction. Sci. China Mater. 65, 413–421 (2022). https://doi.org/10.1007/s40843-021-1758-5

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