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Edge sites dominate the hydrogen evolution reaction on platinum nanocatalysts


Platinum nanocatalysts facilitate the hydrogen evolution reaction (HER) for renewable chemical fuel generation. These nanostructures encompass diverse surface sites, including (111) and (100) facets and edge sites between them. Identifying the exact active sites is essential for optimal catalyst design, but remains challenging. Here, combining electrical transport spectroscopy (ETS) with reactive force field (ReaxFF) calculations, we profile hydrogen adsorption on platinum nanowires and reveal two distinct peaks: one at 0.20 VRHE for (111) and (100) facets and one at 0.038 VRHE for edge sites. Concurrent ETS and cyclic voltammetry show that edge site adsorption coincides with the onset of the HER, indicating the critical role of edge sites. ReaxFF molecular dynamics calculations confirm lower activation barriers for the HER at edge sites, with two to four orders of magnitude higher turnover frequencies. ETS in alkaline media reveals substantially suppressed hydrogen adsorption on edge sites, contributing to the more sluggish HER kinetics. These findings resolve the elusive role of different sites on platinum surfaces, offering critical insights for HER catalyst design.

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Fig. 1: Experimental set-up of ETS probing PtNWs.
Fig. 2: In situ ETS study of PtNWs.
Fig. 3: Interfacial structures at various potentials and hydrogen coverages.
Fig. 4: Hydrogen adsorption behaviours on different sites of the PtNWs.
Fig. 5: Predicted reaction kinetics for seven possible Tafel reaction pathways.
Fig. 6: Comparison of HER kinetics in electrolytes of pH 1 and pH 13.

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Data availability

All of the data are available from the corresponding authors upon request. The simulation data are available from (ref. 45).


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X.D. acknowledges support from the National Science Foundation (award 1800580). Y.H. acknowledges gracious support from NewHydrogen. W.A.G. received support from the Liquid Sunlight Alliance, which is supported by the US Department of Energy (Fuels from Sunlight Hub, Office of Basic Energy Sciences, Office of Science) under award number DE-SC0021266. T.C. thanks the National Natural Science Foundation of China (22173066) and Priority Academic Program Development of Jiangsu Higher Education Institutions.

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X.D. conceived of the project. Y.H., W.A.G. and X.D. designed the research. Z.H. and A.H.S. conducted the experiments with assistance from G.Z., P.W., M.D., J.H., Z.W., S.W., J.C., B.P. and H.L. T.C. carried out the calculation. Y.H., X.D. and W.A.G. supervised the research. Z.H., T.C., A.H.S., Y.H., W.A.G. and X.D. wrote the paper with input from all authors.

Corresponding authors

Correspondence to Yu Huang, William A. Goddard III or Xiangfeng Duan.

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Nature Catalysis thanks Bin Liu, Graham Smith and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Schematic illustration of device fabrication.

(a) SiO2/Si substrate with pre-deposited gold electrodes. (b) The substrate was covered with a PMMA layer, and a window was opened on gold electrodes to form a template. (c) A Pt/NiO nanowires film was transferred onto the template and PMMA was then dissolved. (d) After acid treatment, a PMMA layer was coated on device, and a window was then opened to expose nanowires.

Extended Data Fig. 2 The characterization of as-synthesized Pt/NiO core/shell nanowires.

(a, b) TEM images (a) and size analysis (b) of Pt/NiO core/shell nanowires.

Extended Data Fig. 3 Removal of surface NiO and surface ligands from Pt/NiO NWs.

(a) Cyclic voltammetry of as-synthesized Pt/NiO NWs, partially activated Pt/NiO NWs (NiO was partially leached by 100 cycles of cyclic voltammetry (CV) in N2-saturated 0.1M HClO4 solution (1.1V to 0.05V versus RHE)) and fully activated PtNWs (NiO was fully leached). The absence of Ni2+/Ni3+ redox peaks in fully activated PtNWs confirms no Ni species on PtNW surface. (b) FTIR spectrum of pure oleylamine, as synthesized Pt/NiO NWs and acid leached Pt NWs. The pink vertical lines highlight the characteristic oleylamine peaks.

Extended Data Fig. 4 Structural characterizations of PtNWs.

High resolution TEM images (a–c) and HAADF-STEM images (d–f) of cross-section of PtNWs after 150 cycles of CV activation.

Extended Data Fig. 5 Correlation between derivative conductance change and CV current.

Derivative conductance change as a function of CV current at each potential. Red line is linear fitting of results at potential from 0.50VRHE to 0.17VRHE.

Extended Data Fig. 6 ETS studies of different batches of activated PtNWs (from Pt/NiO nanowires).

(ac) Conductance change (black curve) and corresponding derivative conductance change (red curve) of devices fabricated with different batches of PtNWs measured over potential range of −0.1V −0.6V (vs. RHE) in 0.1M HClO4 solution.

Extended Data Fig. 7 Characterization and on-chip CV and ETS study of alternative PtNWs.

(a) TEM image of the alternative PtNWs synthesized using a synthetic method with no Ni or other metal species added (denoted as P-PtNWs). (b) Size analysis of the P-PtNWs showed an average diameter of 1.11±0.19nm. (c) Derivative of conductance change and CV profile in the entire hydrogen adsorption region, highlighting the Hopd peak coincides with the rapid increase of HER current at 0.04 VRHE.

Extended Data Fig. 8 ETS studies of alternative PtNWs.

(ac) Conductance change (black curve) and corresponding derivative conductance change (red curve) of devices fabricated with different batches of P-PtNWs measured over potential range of −0.1V −0.6V (vs. RHE) in 0.1M HClO4 solution.

Extended Data Fig. 9 Snapshots of interfacial structure of nanowires of different size at −0.052VRHE.

Interfacial structure of two neighboring Pt(111) and Pt(100) surface [Pt(111)/Pt(100)], two neighboring Pt(111) and Pt(111) surface [Pt(111)/Pt(111)], and cross-section of PtNW with diameter of (a) 1.4nm, (b) 2nm, and (c) 2.5nm.

Extended Data Table 1 Comparison of hydrogen binding energies (HBEs) of different sites between ReaxFF and DFT

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Huang, Z., Cheng, T., Shah, A.H. et al. Edge sites dominate the hydrogen evolution reaction on platinum nanocatalysts. Nat Catal (2024).

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