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Cited by 3Electrocatalysts for Energy ConversionHydrogen Storage and MaterialsCO2 Reduction Techniques and Catalysts

Synergistic High Entropy and Inductive Effects in Aerogels Accelerate pH‐Universal Hydrogen Evolution

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Sui, Nicole L. D., Li, Yinghao, Sun, Yuntong, Yoshida, Takefumi, Ariga‐Miwa, Hiroko, Uruga, Tomoya, Zhang, Zhongqi, Long, Xiaojiang +3 more·2026·Small
DOI 10.1002/smll.202512101
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Abstract

Abstract The development of electrocatalysts that function efficiently across the full pH range remains a significant challenge for the hydrogen evolution reaction (HER). Herein, this study reports a class of high‐entropy aerogel alloys with remarkable pH‐universal HER performance. The excellent electrocatalytic activity arises from the synergistic contributions of three key features: (i) a highly porous architecture that exposes abundant active sites; (ii) high‐entropy effects that promote diverse catalytic sites; and (iii) strong inductive effects that optimize hydrogen adsorption/desorption and enhance water activation at active sites. Electrochemical measurements reveal that the best‐performing X‐La (X = PtPdRuOs) aerogel achieves low overpotentials of 2.3, 28.8, and 25.3 mV at 10 mA cm −2 in 1.0 m HClO 4 , PBS, and KOH, respectively. This study presents a promising design strategy for developing HER catalysts with robust activity across diverse pH environments.

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Crossref · 10.1002/smll.202512101

Cites

45 of 45 references verified0 citation errors · 0 not checkable

Statistics

Nothing to recompute.

Claims the paper makes

2 of 10 cited sources checked · 0 supported · 1 flagged · accuracy not yet measured

  • Findingown data

    X-Mn nanoparticle comprises 4 layers with Pt3, Ru3, Os3, and Mn3 clusters as the first layer and Pd3 in the other 3 layers.

    “Whereas each X-Mn nanoparticle comprises 4 layers with Pt 3 , Ru 3 , Os 3 , and Mn 3 clusters as the first layer and Pd 3 in the other 3 layers (Figure 2b).”
    Quote in the paperSubstantial claim
  • Findingown data

    EXAFS fitting confirmed that HEAA nanoparticles comprise discrete metal clusters rather than atomically dispersed metal atoms.

    “Extended X-ray absorption fine structure (EXAFS) fitting further confirmed that the HEAA nanoparticles comprise discrete metal clusters rather than atomically dispersed metal atoms (Figure 2; Figures S13-S16 and Tables S3-S19).”
    Quote in the paperSubstantial claim
  • Findingown data

    X-La contains structural defects such as atomic steps, amorphous sites, and large-angle grain boundaries.

    “The aberration-corrected TEM (ACTEM) further reveals structural defects, such as atomic steps, amorphous sites, and large-angle grain boundaries in X-La”
    Quote in the paperSubstantial claim
  • Findingown data

    EDX analysis confirms uniform dispersion of Pt, Pd, Ru, Os, and La in X-La.

    “Energy-dispersive X-ray (EDX) analysis confirms uniform dispersion of Pt, Pd, Ru, Os, and La in X-La (Figure 1d; Figure S5 and Tables S1 and S2).”
    Quote in the paperSubstantial claim
  • Findingown data

    Ru K-edge spectra remained relatively unchanged across all samples, suggesting consistent oxidation states for Ru.

    “In contrast, the Ru K-edge spectra remained relatively unchanged across all the samples, suggesting consistent oxidation states for Ru (Figure 1j).”
    Quote in the paperNot a substantial claim
  • May combine two claims. 26
  • Classified as probably not a substantial claim. 2

  • May combine two claims.

    Findingown data

    DOS calculations reveal that all samples exhibit metallic behavior, as demonstrated by electronic states crossing the Fermi level, suggesting that these HEA clusters possess excellent electrical conductivity to facilitate electron migration and transport.

    “The density of states (DOS) calculations reveal that all samples exhibit metallic behavior, as demonstrated by the presence of electronic states crossing the Fermi level, suggesting that these HEA clusters possess excellent electrical conductivity to facilitate electron migration and transport (Figure 5b) [35,36].”
    Quote in the paperSubstantial claim2 of 2 sources checked
    • cites [35] 35. L. Chai, Z. Hu, X. Wang, et al., "Stringing Bimetallic Metal-Organic Framework-Derived Cobalt Phosphide Composite for High-Efficiency Overall Water Splitting," Advanced Science 7 (2020): 1903195, https://doi. org/10.1002/advs.201903195. source

      Split into 2 atoms — 0 confirmed, 1 partially supported, 0 disputed, 0 misattributed, 1 unverifiable. Expand the claim to see per-atom verdicts.

      Experimental — accuracy not yet measured
    • cites [36] 36. H. Huang, Y. Zhao, Y. Bai, F. Li, Y. Zhang, and Y. Chen, "Conductive Metal-Organic Frameworks With Extra Metallic Sites as an Efficient Electrocatalyst for the Hydrogen Evolution Reaction," Advanced Science 7 (2020): 2000012, https://doi.org/10.1002/advs.202000012. source

      Split into 2 atoms — 0 confirmed, 1 partially supported, 1 disputed, 0 misattributed, 0 unverifiable. Expand the claim to see per-atom verdicts.

      Checked by a reasoning model — may be wrong.

      Experimental — accuracy not yet measured

  • Probably not a substantial claim: may not pass S3 (load-bearing). May combine two claims.

    Findingown data

    Among the five quaternary samples, the w/o La sample possesses the most distinct diffraction peak, with the highest signal-to-noise ratio, indicating the highest degree of crystallographic order.

    “Interestingly, among the five quaternary samples, the w/o La sample possesses the most distinct diffraction peak, with the highest signal-to-noise ratio, indicating the highest degree of crystallographic order (Figure S7).”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    The X-La sample has a high specific surface area of 85 m2/g with an average pore diameter of 14.1 nm.

    “Particularly, Brunauer-Emmett-Teller (BET) shows that the X-La sample has a high specific surface area of 85 m 2 /g with an average pore diameter of 14.1 nm (Figure S3).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    X-La nanoparticle consists of Pt3, Pd9, Ru6, Os6, and La3 nanoclusters, arranged in four distinct layers.

    “In particular, X-La nanoparticle consists of Pt 3 , Pd 9 , Ru 6 , Os 6 , and La 3 nanoclusters, arranged in four distinct layers (Figure 2a).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    In X-Mn, the Mn3 cluster is only connected to a Pt3 cluster, showing Pt─Mn bonds at 0.248 nm and CN Pt-Mn = 1.

    “Whereby, the Mn 3 cluster was only connected to a Pt 3 cluster, showing Pt─Mn bonds at 0.248 nm and CN Pt-Mn = 1 (Tables S8-S11).”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    In X-La, the La3 cluster can be connected to a Pt3, a Ru6, or an Os6 cluster, showing Pt─La bonds at 0.323 nm (CN Pt-La: 1), Ru─La bonds at 0.342 nm (CN Ru-La: 1), and Os─La bonds at 0.327 nm (CN Os-La: 1).

    “Particularly, the La 3 cluster could be connected to a Pt 3 , a Ru 6 , or an Os 6 cluster, showing Pt─La bonds at 0.323 nm (CN Pt-La : 1), Ru─La bonds at 0.342 nm (CN Ru-La : 1), and Os─La bonds at 0.327 nm (CN Os-La : 1) (Tables S4-S7).”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    In 1.0 M HClO4, X-La displays the best HER performance with an overpotential of 2.3 and 11.5 mV at 10 mA cm-2 and 100 mA cm-2, respectively, significantly outperforming commercial Pt/C (η10 = 16 mV).

    “In 1.0 m HClO 4 , the X-La displays the best HER performance with an outstanding overpotential of 2.3 and 11.5 mV at 10 mA cm -2 (η 10 ) and 100 mA cm -2 , respectively, significantly outperforming commercial Pt/C (η 10 = 16 mV) (Figure 3a).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    In X-In, In─Pd bonds are at 0.311 nm (CN In-Pd: 2) and In─Os bonds at 0.314 nm (CN In-Os: 3).

    “In─Pd bonds at 0.311 nm (CN In-Pd : 2) and In─Os bonds at 0.314 nm (CN In-Os : 3) (Tables S17-S20).”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    The Tafel slope of the w/o Pt sample (73.5 mV dec-1) was much larger than those of the other Pt-containing samples [w/o Pd (24.8), w/o Ru (29.8), w/o Os (24.5), and w/o La (20.8)], indicating that inclusion of Pt facilitates a shift from the slower Volmer-Heyrovsky pathway to the more efficient Volmer-Tafel pathway.

    “The Tafel slope of the w/o Pt sample (73.5 mV dec -1 ) was also much larger than those of the other Pt-containing samples [w/o Pd (24.8 mV dec -1 ), w/o Ru (29.8 mV dec -1 ), w/o Os (24.5 mV dec -1 ), and w/o La (20.8 mV dec -1 )], indicating that the inclusion of Pt facilitates a shift from the slower Volmer-Heyrovsky pathway to the more efficient Volmer-Tafel pathway (Figure S28b).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    The Tafel slopes follow the order X-La (13.5 mV dec-1) < X-Mn (33.7 mV dec-1) < X-Zn (41 mV dec-1) < X-In (64 mV dec-1), with X-La and X-Mn following the Volmer-Tafel mechanism, while X-Zn and X-In follow the slower Volmer-Heyrovsky pathway.

    “The Tafel slopes follow the same order as overpotentials: X-La (13.5 mV dec -1 ) < X-Mn (33.7 mV dec -1 ) < X-Zn (41 mV dec -1 ) < X-In (64 mV dec -1 ), with the X-La and X-Mn following the Volmer-Tafel mechanism, while the X-Zn and X-In follow the slower Volmer-Heyrovsky pathway.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    In X-Zn, Zn3 may be connected to a Pd6 and a Ru3 cluster, showing Zn─Pd bonds at 0.268 nm (CN Zn-Pd: 1) and Ru─Zn bonds at 0.253 nm (CN Ru-Zn: 1).

    “The Zn 3 may be connected to a Pd 6 and a Ru 3 cluster, showing Zn─Pd bonds at 0.268 nm (CN Zn-Pd : 1) and Ru─Zn bonds at 0.253 nm (CN Ru-Zn : 1).(Tables S12-S16).”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    In 1.0 M HClO4, the η10 values of the HEAA samples increased in the order X-La (2.3 mV) < X-Mn (3.7 mV) < X-Zn (6.5 mV) < X-In (9.2 mV), correlating with decreasing electronegativity difference among the constituent elements.

    “Particularly, the η 10 values of the HEAA samples increased in the order of X-La (2.3 mV) < X-Mn (3.7 mV) < X-Zn (6.5 mV) < X-In (9.2 mV), correlating with decreasing electronegativity difference among the constituent elements.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    In 1.0 M HClO4, the activity of the w/o Pt sample (39.3 mV) exceeds that of w/o Pd (5.75 mV), w/o Ru (3.05 mV), w/o Os (6.25 mV), and w/o La (6.55 mV), suggesting that Pt plays a dominant role in acidic HER catalysis.

    “In 1.0 m HClO 4 , the activity of the w/o Pt (39.3 mV) exceeds that of the w/o Pd (5.75 mV), w/o Ru (3.05 mV), w/o Os (6.25 mV), and w/o La (6.55 mV), suggesting that Pt plays a dominant role in acidic HER catalysis, as evidenced by the significantly higher overpotential observed for the w/o Pt sample compared to X-La (Figure S28a).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    X-La shows negligible degradation after 5000 cyclic voltammetry cycles and 20 h of continuous operation.

    “Stability tests further confirmed the robustness of X-La, showing negligible degradation after 5000 cyclic voltammetry (CV) cycles and 20 h of continuous operation (Figure 3e,f).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    X-Zn nanoparticle has 2 layers, with Pt3, Pd3, Ru3, Os3, and Zn3 forming the first layer and Pt3, Pd3, and Os3 in the second layer.

    “While an X-Zn nanoparticle has 2 layers, with Pt 3 , Pd 3 , Ru 3 , Os 3 , and Zn 3 forming the first layer and Pt 3 , Pd 3 , and Os 3 in the second layer (Figure 2c).”
    Quote in the paperNot a substantial claim

  • Probably not a substantial claim: may not pass S3 (load-bearing).

    Findingown data

    X-In nanoparticle consists of 3 layers.

    “Conversely, an X-In nanoparticle consists of 3 layers (Figure 2d).”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    The Tafel slope of X-La (13.5 mV dec-1) is the smallest, indicating that X-La possesses the fastest reaction kinetics.

    “The Tafel slope of X-La (13.5 mV dec -1 ) is also the smallest, exhibiting that the X-La sample possesses the fastest reaction kinetics (Figure 3b).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    The ECSA of X-La in 1.0 M HClO4 was 1.88 times, 2.67 times, and 3.79 times higher than that of X-Mn, X-Zn, and X-In, respectively.

    “The electrochemically active surface area (ECSA) of the X-La sample in 1.0 m HClO 4 was found to be 1.88 times, 2.67 times, and 3.79 times higher than that of X-Mn, X-Zn, and X-In, respectively (Table S27).”
    Quote in the paperNot a substantial claim

  • May combine two claims.

    Findingown data

    Tafel slope analysis in 1.0 M PBS and 1.0 M KOH revealed a consistent trend of X-La < X-Mn < X-Zn < X-In, with all samples following the Volmer-Heyrovsky mechanism.

    “The Tafel slope analysis revealed a consistent trend of X-La < X-Mn < X-Zn < X-In across both electrolytes, with all samples following the Volmer-Heyrovsky mechanism (Figure 4c).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Findingown data

    The most favorable ΔE_H2O values were found at the Pt-site in X-La, the Pt-site in X-Mn, the Os-site in X-Zn, and the Ru-site in X-In, with corresponding adsorption energies of -1.449, -1.083, -0.617, and -0.561 eV, respectively.

    “The most favorable ΔE H2O values were found at the Pt-site in X-La, the Pt-site in X-Mn, the Os-site in X-Zn, and the Ru-site in X-In, with corresponding adsorption energies of -1.449, -1.083, -0.617, and -0.561 eV, respectively (Figure 5e; Figures S36-S39).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationown data

    The excellent electrocatalytic activity of HEAAs arises from synergistic contributions of three key features: a highly porous architecture exposing abundant active sites, high-entropy effects promoting diverse catalytic sites, and strong inductive effects optimizing hydrogen adsorption/desorption and enhancing water activation at active sites.

    “The excellent electrocatalytic activity arises from the synergistic contributions of three key features: (i) a highly porous architecture that exposes abundant active sites; (ii) high-entropy effects that promote diverse catalytic sites; and (iii) strong inductive effects that optimize hydrogen adsorption/desorption and enhance water activation at active sites.”
    • Also stated in: § 3 Discussion · plain
      “The excellent electrocatalytic performance was attributed to the synergistic contributions of three key features.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationcitation

    These structural defects can function as active sites and facilitate the adsorption and activation of hydrogen intermediates.

    “all of which can function as active sites and facilitate the adsorption and activation of hydrogen intermediates”
    Quote in the paperSubstantial claim0 of 2 sources checked
    • cites [31] 31. L. Hou, Z. Li, H. Jang, et al., "Grain Boundary Tailors the Local Chemical Environment on Iridium Surface for Alkaline Electrocat- alytic Hydrogen Evolution," Angewandte Chemie International Edition 63 (2024): 202315633, https://doi.org/10.1002/anie.202315633. source
    • cites [32] 32. P. Prabhu and J.-M. Lee, "Influencing Electrocatalytic Processes Through Topographically Disordered Atomic Sites," Chem Catalysis 3 (2023): 100621, https://doi.org/10.1016/j.checat.2023.100621. source

  • May combine two claims.

    Interpretationcitation

    Lattice distortion suppresses long-range order but can stabilize local atomic arrangements, potentially improving the structural durability of active sites on the catalyst surface.

    “Such lattice distortion suppresses long-range order, but it can stabilize local atomic arrangements, potentially improving the structural durability of active sites on the catalyst surface [34].”
    Quote in the paperNot a substantial claim0 of 1 sources checked
    • cites [34] 34. H. Fu, H. Huang, Y. Chen, et al., "Lattice-Strained Metallic Aerogels as Efficient and Anti-Poisoning Electrocatalysts for Oxygen Reduction Reaction," Chemsuschem 17 (2024): 202301221, https://doi.org/10.1002/ cssc.202301221. source

  • May combine two claims.

    Interpretationown data

    Stronger inductive effects enhance hydrogen adsorption thermodynamics, contributing to improved HER catalytic activity, consistent with the experimental results.

    “This suggests that stronger inductive effects enhance hydrogen adsorption thermodynamics, contributing to improved HER catalytic activity, consistent with the experimental results (Figure 5d).”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationown data

    Both electrochemical and theoretical results reveal that stronger inductive effects significantly improve electrocatalytic performance by optimizing hydrogen adsorption and desorption behavior and enhancing water adsorption on active sites.

    “Both electrochemical and theoretical results reveal that stronger inductive effects significantly improve electrocatalytic performance by optimizing hydrogen adsorption and desorption behavior and enhancing water adsorption on active sites.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationown data

    The sequential decrease in ΔE_H2O from X-La to X-Mn to X-Zn to X-In correlates with the experimentally observed trend in HER activity under neutral and alkaline conditions, further confirming the critical role of water adsorption energetics.

    “This sequential decrease in ΔE H2O from X-La to X-Mn to X-Zn to X-In correlates with the experimentally observed trend in HER activity under neutral and alkaline conditions, further confirming the critical role of water adsorption energetics.”
    Quote in the paperSubstantial claim

  • May combine two claims.

    Interpretationown data

    The orchestrated interplay of a porous architecture, high-entropy effects, and inductive tuning maximizes the number of exposed active sites, facilitates charge transfer and redistribution, and stabilizes key reaction intermediates, thereby enhancing electrocatalytic HER.

    “Specifically, the orchestrated interplay of a porous architecture, high-entropy effects, and inductive tuning maximizes the number of exposed active sites, facilitates charge transfer and redistribution, and stabilizes key reaction intermediates, thereby enhancing electrocatalytic HER.”
    Quote in the paperSubstantial claim
27 of 27

  • The paper relies on this without support.

    In neutral and alkaline conditions, the activity of current HER catalysts is limited primarily by additional energy barriers associated with water dissociation.

    “While current catalysts display excellent HER performance in acidic media, their activity in neutral and alkaline conditions is typically limited, primarily due to the additional energy barriers associated with water dissociation.”

  • The paper relies on this without support.

    High-entropy alloy catalysts can facilitate efficient multi-step HER, particularly by enhancing water dissociation under neutral and alkaline environments.

    “To overcome this issue, high-entropy alloy catalysts offering a broad spectrum of active sites for different reactants and reaction intermediates present a promising platform to facilitate efficient multi-step HER, particularly by enhancing water dissociation under neutral and alkaline environments.”
2 of 2

Self-check

Percentages, sums and reported differences re-computed from the paper’s own numbers.

Each contradiction between two passages listed here was confirmed by an independent check.

  • Acidic HER activity is described in the opposite direction from the overpotentials

    Minor

    The w/o Pt sample has the highest listed overpotential among these variants, yet its activity is said to exceed theirs. The paper also treats its higher overpotential as evidence that removing Pt impairs performance.

1 of 1

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Authors
Sui, N. L. D., Li, Y., Sun, Y., Yoshida, T., Ariga‐Miwa, H., Uruga, T., Zhang, Z., Long, X., Wang, G., Iwasawa, Y., & Lee, J.
Affiliations
  • Nanyang Technological University (SG)
  • University of Electro-Communications (JP)
  • Innovation Research Center for Fuel Cells and Hydrogen The University of Electro‐Communications Chofu Tokyo Japan
  • SPring-8 (JP)
  • Yangtze Normal University (CN)
Corresponding author
  • Wang, Guangzhao
  • Iwasawa, Yasuhiro
  • Lee, Jong‐Min
ORCID
Venue
Small
Publisher
Wiley
Published
2025-12-29
Volume
22
Issue
10
Pages
e12101-e12101
ISSN
  • 1613-6810 (ISSN-L)
  • 1613-6829
DOI
10.1002/smll.202512101
OpenAlex
W7117460332
Semantic Scholar
d57c0a794f5c51d0789cc1dc33cb58cda92f921d
Cited by
3
References
37
Citations by year
2026: 3
FWCI
0.42
Type
journal article
Language
en
Open access
Licence
Locations
  • Small (publishedVersion)
  • PubMed (publishedVersion)
  • DR-NTU (Nanyang Technological University) (submittedVersion)
Topics
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
  • Physical Sciences › Materials Science › Materials Chemistry › Hydrogen Storage and Materials
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
Keywords
hydrogen evolution reaction, high-entropy alloys, aerogels, pH-universal electrocatalysts, inductive effects, lanthanum doping, water activation, hydrogen adsorption, porous architecture, electrocatalyst design

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