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hcp-phased Ni nanoparticles with generic catalytic hydrogenation activities toward different functional groups

hcp晶相的Ni纳米颗粒对不同官能团的通用催化加氢活性

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Abstract

Catalytic hydrogenation is a vital industrial means to produce value-added fuels and fine chemicals, however, requiring highly efficient catalysts, especially the nonprecious ones. To date, the majority of high-performance industrial hydrogenation catalysts are made of precious metals-based materials, and any given catalyst could only be used to catalyze one or few specific reactions. Herein, we exemplify a crystal phase engineering approach to empower Ni nanoparticles (NPs) with superb intrinsic catalytic activities toward a wide spectrum of hydrogenation reactions. A facile pyrolysis approach is used to directly convert a Ni-imidazole MOF precursor into hexagonal close-packed (hcp)-phased Ni NPs on carbon support. The as-synthesized hcp-phased Ni NPs exhibit unprecedented hydrogenation catalytic activities in pure water towards nitro-, aldehyde-, ketone-, alkene- and N heterocyclic-compounds, outperforming the face-centered cubic (fcc)-Ni counterpart and the reported transition metals-based catalysts. The density functional theory calculations unveil that the presence of hcp-Ni boosts the intrinsic catalytic hydrogenation activity by coherently enhancing the substrate adsorption strength and lowering the reaction barrier energy of the rate-determining step. We anticipate that the crystal phase engineering design approach unveiled in this work would be adoptable to other types of reactions.

摘要

催化加氢是生产高附加值燃料和精细化学品的重要工业途径, 但需要高效的催化剂, 尤其是廉价的非贵金属催化剂. 迄今为止, 大多 数高性能催化加氢催化剂都是由贵金属材料制成, 并且这些催化剂都 只能用于催化一种或几种特定的反应. 在这里, 我们例证了一种晶相工 程方法, 其能赋予Ni纳米颗粒(NPs)卓越的、广谱的内在催化加氢活性. 这种负载于碳载体上含有hcp晶相的Ni NPs催化剂通过直接碳化热解 Ni咪唑MOF前驱体获得. 在纯水中, 含hcp相的Ni NPs对硝基、醛、 酮、烯烃和N杂环化合物表现出前所未有的加氢催化活性, 优于类似 物fcc-Ni和目前报道的其他过渡金属催化剂. 密度泛函理论计算表明, hcp-Ni通过增**底物吸附**度和降低速率决定步骤的反应势垒能共同 来提高内在催化氢化活性. 我们预计这项工作中揭示的晶相工程设计 方法将适用于其他类型的反应.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (51902311 and 51871209).

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Key Laboratory of Materials Physics, Centre for Environmental and Energy Nanomaterials, Anhui Key Laboratory of Nanomaterials and Nanotechnology, Institute of Solid State Physics, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei, 230031, China

    Yang Lv  (吕扬), Wanbing Gong  (龚万兵), Dongdong Wang  (汪东东), Chun Chen  (陈春), Guozhong Wang  (汪国忠), Haimin Zhang  (张海民) & Huijun Zhao  (赵惠军)

  2. School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology, Gardens Point Campus, Brisbane, QLD, 4001, Australia

    **n Mao  (冒鑫) & Aijun Du  (杜爱军)

  3. Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, 230026, China

    Wanbing Gong  (龚万兵) & Yue Lin  (林岳)

  4. Centre for Catalysis and Clean Energy, Griffith University, Gold Coast Campus, Queensland, 4222, Australia

    Porun Liu  (刘珀润) & Huijun Zhao  (赵惠军)

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  1. Yang Lv  (吕扬)
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  10. Aijun Du  (杜爱军)
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Contributions

Lv Y carried out the materials fabrication, characterizations and performance measurements, and wrote the initial manuscript; Mao X and Du A performed and guided theoretical analysis; Wang D, Chen C and Lin Y did some characterizations; Liu P, Wang G and Zhang H performed some data analysis; Gong W and Zhao H conceived and supervised this study, and revised the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Wanbing Gong  (龚万兵), Aijun Du  (杜爱军) or Huijun Zhao  (赵惠军).

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Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary information

Experimental details and supporting data are available in the online version of the paper.

Yang Lv received his MSc degree from the University of Science and Technology of China. He is working on the synthesis of novel nanomaterials for catalytic reactions.

**n Mao is now a PhD student under Prof. Aijun Du’s supervision at the School of Chemistry and Physics, Queensland University of Technology. His research interest mainly focuses on computational design of some nonprecious metal-based materials for energy conversion and storage processes, such as hydrogen evolution reactions, oxygen evolution/reduction reactions, and CO2 reduction reactions.

Wanbing Gong received his PhD degree from the University of Science and Technology of China in 2018. Then, he joined Hefei Institutes of Physical Science, Chinese Academy of Sciences as a postdoctor. He took a Research Associate Professor position at the University of Science and Technology of China in 2021. His current research interests focus on searching for new nonprecious catalytic materials and novel catalytic systems to meet the need of industries.

Aijun Du obtained his PhD in nuclear and particle physics (2002) from Fudan University, China. He worked at Australian Institute for Bioengineering and Nanotechnology, University of Queensland for nine years. He joined Queensland University of Technology in 2013 as an Associate Professor and was promoted to a full Professor in 2017. His research focuses on the development of innovative nanomaterials for clean energy, environmental and nanoelectronics applications.

Huijun Zhao obtained his PhD in chemistry (1994) from the University of Wollongong, Australia, and subsequently held Research Fellow/Senior Research Fellow positions at the University of Wollongong and University of Western Sydney. He took a Lecturer position at Griffith University and was promoted to Chair Professor of chemistry (2005). One of his current pursuits is to explore new means to unlock the catalytic powers of nonprecious materials for important reactions.

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Lv, Y., Mao, X., Gong, W. et al. hcp-phased Ni nanoparticles with generic catalytic hydrogenation activities toward different functional groups. Sci. China Mater. 65, 1252–1261 (2022). https://doi.org/10.1007/s40843-021-1860-x

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