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Amorphous nickel hydroxide shell tailors local chemical environment on platinum surface for alkaline hydrogen evolution reaction

Abstract

In analogy to natural enzymes, an elaborated design of catalytic systems with a specifically tailored local chemical environment could substantially improve reaction kinetics, effectively combat catalyst poisoning effect and boost catalyst lifetime under unfavourable reaction conditions. Here we report a unique design of ‘Ni(OH)2-clothed Pt-tetrapods’ with an amorphous Ni(OH)2 shell as a water dissociation catalyst and a proton conductive encapsulation layer to isolate the Pt core from bulk alkaline electrolyte while ensuring efficient proton supply to the active Pt sites. This design creates a favourable local chemical environment to result in acidic-like hydrogen evolution reaction kinetics with a lowest Tafel slope of 27 mV per decade and a record-high specific activity and mass activity in alkaline electrolyte. The proton conductive Ni(OH)2 shell can also effectively reject impurity ions and retard the Oswald ripening, endowing a high tolerance to solution impurities and exceptional long-term durability that is difficult to achieve in the naked Pt catalysts. The markedly improved hydrogen evolution reaction activity and durability in an alkaline medium promise an attractive catalyst material for alkaline water electrolysers and renewable chemical fuel generation.

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Fig. 1: ‘Ni(OH)2-clothed Pt-tetrapod’ with the proton conductive amorphous Ni(OH)2 to tailor local chemical environment on Pt surface for optimum HER in bulk alkaline electrolyte.
Fig. 2: Structural characterizations of Pttet@Ni(OH)2 nanocatalysts.
Fig. 3: Electrochemical characterizations of Pttet@Ni(OH)2 nanocatalysts.
Fig. 4: DFT calculations of the Pt@NiOxHy interface.
Fig. 5: Evaluation of HER activity and stability.

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Data availability

All data are available in the manuscript or Supplementary Information. The scripts for performing GCGA structure search and the DFT-optimized geometries are available in the Zenodo data repository at https://doi.org/10.5281/zenodo.7869311. Source data are provided with this paper.

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Acknowledgements

X.D. acknowledges support from the National Science Foundation award 1800580. Y.H. acknowledges partial support from the Office of Naval Research by the grant number N000141812155 and NewHydrogen, Inc. A.N.A. acknowledges support by DOE-BES grant DE-SC0019152. X.P. acknowledges the support from the National Science Foundation award DMR-1506535. J.D. acknowledges financial support from the Youth Innovation Promotion Association of the Chinese Academy of Sciences (Y2022006). HAADF imaging and EDS mapping were carried out using the JEOL Grand ARM in the Irvine Materials Research Institute at the University of California, Irvine. J.D. and T.H. acknowledge the support from Beijing Synchrotron Radiation Facility. A.N.A. acknowledges the computational and storage resources from the National Energy Research Scientific Computing Center (NERSC), a US Department of Energy Office of Science User Facility operated under contract no. DE-AC02-05CH11231.

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X.D. and Y.H. designed the research. C.W. performed the synthesis, most of the structural characterizations, and electrochemical tests. J.D. and T.H. performed the XAS measurement and analysed the EXAFS and XANES data. Z.Z. and A.N.A. conducted DFT calculations. S.W., H.P., J.H. and A.H.S. assisted in the synthesis. Z.L. and D.B. assisted in the SEM-EDS and X-ray diffraction analysis. M.X. conducted the aberration-corrected STEM characterization under the supervision of X.P. The paper was co-written by C.W., X.D., J.D., Z.Z., A.N.A. and Y.H. The research was supervised by X.D., Y.H. and A.N.A. All authors discussed the results and commented on the manuscript.

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Correspondence to Anastassia N. Alexandrova, Yu Huang or Xiangfeng Duan.

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Wan, C., Zhang, Z., Dong, J. et al. Amorphous nickel hydroxide shell tailors local chemical environment on platinum surface for alkaline hydrogen evolution reaction. Nat. Mater. 22, 1022–1029 (2023). https://doi.org/10.1038/s41563-023-01584-3

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