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Oxygen modified CoP2 supported palladium nanoparticles as highly efficient catalyst for hydrolysis of ammonia borane

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Abstract

Ammonia borane (AB) is regarded as a promising chemical hydrogen-storage material due to its high hydrogen content, non-toxicity, and long-term stability under ambient temperature. However, constructing advanced catalysts to further promote the hydrogen production still remains a challenge for the hydrolysis of AB. Herein, we report a novel oxygen modified CoP2 (O-CoP2) material with dispersed palladium nanoparticles (Pd NPs) as a highly efficient and sustainable catalyst for AB hydrolysis. The modification of oxygen could optimize the catalytic synergy effect between CoP2 and Pd NPs, achieving enhanced catalytic activity with a turnover frequency (TOF) number of 532 min−1 and an activation energy (Ea) value of 16.79 kJ·mol−1. Meanwhile, reaction kinetic experiments prove that the activation of water is the rate-determining step (RDS). The water activation mechanism is revealed by quasi in-situ X-ray photoelectron spectroscopy (XPS) and in-situ X-ray absorption fine structure (XAFS) measurements. The activation of water leads to the production of -H and -OH groups, which are further adsorbed on the oxygen atoms in P-O bond and Pd atoms, respectively. In addition, density functional theory (DFT) calculations indicate that the introduced oxygen facilitates the adsorption and activation of water molecules. This novel modulation strategy successfully sheds new light on the development of advanced catalysts for hydrolysis of AB and beyond.

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Acknowledgements

The authors thank Prof. Jafu Chen and Dr. Yu Bai for help in structure and morphology characterization. The authors also appreciate the beamline BL14W1 in SSRF, BL10B, and BL11U in NSRL for synchrotron radiation measurements. The calculations were conducted on the supercomputing system in the Supercomputing Center of USTC. This work was financially supported by the National Key Research & Development Program of China (Nos. 2017YFA0700104, 2017YFA0403402, 2017YFA0403403, and 2019YFA0405601), the National Natural Science Foundation of China (Nos. 11875258, U1932213, U1932148, 21773222, 21872131, U1732272, U1832218, and U1932214), the Key Program of Research and Development of Hefei Science Center of Chinese Academy of Science (No. 2017HSC-KPRD001), the Fundamental Research Funds for the Central Universities (No. WK2060000016), Collaborative Innovation Program of Hefei Science Center, Chinese Academy of Science (No. 2019HSC-CIP009), Users with Excellence Program of Hefei Science Center, Chinese Academy of Science (Nos. 2018HSC-UE003 and 2019HSC-UE004), and the Youth Innovation Promotion Association, Chinese Academy of Science (No. 2020454).

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  1. Leijie Zhang and Jian Ye contributed equally to this work.

Authors and Affiliations

  1. National Synchrotron Radiation Laboratory, Department of Chemical Physics and Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, University of Science and Technology of China, Hefei, 230029, China

    Leijie Zhang, Jian Ye, Yi Tu, Qingyu Wang, Haibin Pan, Lihui Wu, Xusheng Zheng & Junfa Zhu

  2. School of Science, Anhui Agricultural University, Hefei, 230036, China

    Jian Ye

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  1. Leijie Zhang
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Correspondence to Xusheng Zheng or Junfa Zhu.

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Zhang, L., Ye, J., Tu, Y. et al. Oxygen modified CoP2 supported palladium nanoparticles as highly efficient catalyst for hydrolysis of ammonia borane. Nano Res. 15, 3034–3041 (2022). https://doi.org/10.1007/s12274-021-3941-7

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