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Ionic-liquid-assisted synthesis of metal single-atom catalysts for benzene oxidation to phenol

离子液体辅助合成金属单原子催化剂用于苯氧化制苯酚

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Abstract

Ionic liquids (ILs) have the advantages of low cost, eco-friendliness, abundant heteroatoms, excellent solubility, and coordinated ability with metal ions. These features make ILs a suitable precursor for fabricating metal single-atom catalysts (SACs). Herein, we prepared various metal single atoms anchored on ultrathin N-doped nanosheets (denoted as Cu1/NC, Fe1/NC, Co1/NC, Ni1/NC, and Pd1/NC) by direct pyrolysis using ILs and g-C3N4 nanosheets as templates. Taking benzene oxidation to phenol with H2O2 as a model reaction to evaluate their catalytic performance and potential applications, Cu1/NC calcined at 1000°C (denoted as Cu1/NC-1000) exhibits the highest activity with a turnover frequency of about 200 h−1 in the first 1 h at 60°C, which is better than that of most metal SACs reported in the literature. High benzene conversion of 82% with high phenol selectivity of 96% and excellent recyclability were achieved using the Cu1/NC-1000 catalyst. This study provides an efficient general strategy for fabricating SACs using ILs for catalytic applications.

摘要

离子液体具有成本低、环境友好、杂原子丰富、溶解性好、与金属离子良好的配位能力等优点, 是一种理想的用于制备金属单原子催化剂的前驱体材料. 在本文中, 我们利用离子液体与金属的强配位能力, 以g-C3N4纳米片为结构模板, 合成了多种锚定在氮掺杂超薄碳纳米片上的金属单原子催化剂(分别简写为Cu1/NC、Fe1/NC、Co1/NC、Ni1/NC和Pd1/NC). 将上述金属单原子催化剂用于双氧水氧化苯制苯酚反应中, 1000°C煅烧得到的铜单原子催化剂(Cu1/NC-1000)表现出最高的活性, 60°C时反应1 h的转换频率(TOF)约为200 h−1, 优于文献报道的大多数金属单原子催化剂. 随着反应时间延长, 最终苯的转化率可达82%, 苯酚的选择性维持在96%. 此外, Cu1/NC-1000催化剂具有良好的循环稳定性. 本研究为制备单原子催化剂提供了一种新的有效的普适性策略.

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Acknowledgements

The authors acknowledge the financial support from the National Key R&D Program of China (2018YFA0208504 and 2018YFA0703503), the National Natural Science Foundation of China (21932006) and the Youth Innovation Promotion Association of CAS (2017049).

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Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences, Laboratory of Molecular Nanostructures and Nanotechnology, CAS Research/Education Center for Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Qikai Shen  (沈齐凯), Peipei Li  (李佩佩), Weiming Chen  (陈伟明), Hongqiang Jin  (晋红强), Jia Yu  (于珈), Lei Zhu  (朱磊), Zhucheng Yang  (杨翥成), Runqing Zhao  (赵润卿), Weiguo Song  (宋卫国) & Changyan Cao  (曹昌燕)

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Qikai Shen  (沈齐凯), Peipei Li  (李佩佩), Weiming Chen  (陈伟明), Hongqiang Jin  (晋红强), Jia Yu  (于珈), Lei Zhu  (朱磊), Zhucheng Yang  (杨翥成), Runqing Zhao  (赵润卿), Weiguo Song  (宋卫国) & Changyan Cao  (曹昌燕)

  3. Beijing Synchrotron Radiation Facility (BSRF), Institute of High Energy Physics, Chinese Academy of Science, Beijing, 100049, China

    Lirong Zheng  (郑黎荣)

Authors
  1. Qikai Shen  (沈齐凯)
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  2. Peipei Li  (李佩佩)
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  3. Weiming Chen  (陈伟明)
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  4. Hongqiang Jin  (晋红强)
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  5. Jia Yu  (于珈)
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  6. Lei Zhu  (朱磊)
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  7. Zhucheng Yang  (杨翥成)
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  8. Runqing Zhao  (赵润卿)
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  9. Lirong Zheng  (郑黎荣)
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  10. Weiguo Song  (宋卫国)
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  11. Changyan Cao  (曹昌燕)
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Contributions

Shen Q performed the experiments; Zheng L performed the XAFS characterization and analysis; Cao C and Song W designed the experiments; Shen Q, Cao C and Song W co-wrote the paper. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Lirong Zheng  (郑黎荣), Weiguo Song  (宋卫国) or Changyan Cao  (曹昌燕).

Additional information

Qikai Shen received his BSc degree from Shandong University in 2016. Currently, he is a PhD student under the supervision of Prof. Weiguo Song at the Institute of Chemistry, Chinese Academy of Sciences. His research interests are focused on the design and fabrication of single-atom catalysts for heterogeneous hydrogenation and oxidation catalysis.

Lirong Zheng obtained his PhD from the Institute of High Energy Physics (IHEP), Chinese Academy of Sciences in 2011. Since then, he has been working at the XAFS beamline of Beijing Synchrotron Radiation Facility at IHEP. His research interest is focused on the XAFS theory, method, data analysis, and applications.

Weiguo Song obtained his Bachelor’s degree from Peking University in 1992 and PhD from the University of Southern California in 2001. currently, he is a full professor at the Institute of Chemistry, Chinese Academy of Sciences. His current research interest mainly focuses on the synthesis of nanostructured materials and their applications in heavy metal-ion adsorption and nanocatalysis.

Changyan Cao obtained his PhD from Harbin Institute of Technology in 2011. Then, he worked as a postdoctor under the supervision of Prof. Weiguo Song at the Institute of Chemistry, Chinese Academy of Sciences. Currently, he is an associate professor in Prof. Weiguo Song’s group. His research interest mainly focuses on the design and controllable synthesis of nanocatalysts and single-atom catalysts for thermal catalysis.

Conflict of interest

The authors declare no conflict of interest.

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Shen, Q., Li, P., Chen, W. et al. Ionic-liquid-assisted synthesis of metal single-atom catalysts for benzene oxidation to phenol. Sci. China Mater. 65, 163–169 (2022). https://doi.org/10.1007/s40843-021-1734-x

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