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Cited by 200Electrocatalysts for Energy ConversionCO2 Reduction Techniques and CatalystsHydrogen Storage and Materials

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Bixbyite-type Ln2O3 as promoters of metallic Ni for alkaline electrocatalytic hydrogen evolution

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Sun, Hongming, Yan, Zhenhua, Tian, Caiying, Li, Cha, Feng, Xin, Huang, Rong, Lan, Yinghui, Chen, Jing, Li, Cheng-Peng, Zhang, Zhihong, Du, Miao·2022·Nature Communications
DOI 10.1038/s41467-022-31561-4PMC PMC9256667
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Abstract

The active-site density, intrinsic activity, and durability of Ni-based catalysts are critical to their application in industrial alkaline water electrolysis. This work develops a kind of promoters, the bixbyite-type lanthanide metal sesquioxides (Ln 2 O 3 ), which can be implanted into metallic Ni by selective high-temperature reduction to achieve highly efficient Ni/Ln 2 O 3 hybrid electrocatalysts toward hydrogen evolution reaction. The screened Ni/Yb 2 O 3 catalyst shows the low overpotential (20.0 mV at 10 mA cm −2 ), low Tafel slope (44.6 mV dec −1 ), and excellent long-term durability (360 h at 500 mA cm −2 ), significantly outperforming the metallic Ni and benchmark Pt/C catalysts. The remarkable hydrogen evolution activity and stability of Ni/Yb 2 O 3 are attributed to that the Yb 2 O 3 promoter with high oxophilicity and thermodynamic stability can greatly enlarge the active-site density, reduce the energy barrier of water dissociation, optimize the free energy of hydrogen adsorption, and avoid the oxidation corrosion of Ni.

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  • Traditional supports on the micrometer scale are usually not compatible with catalysts on the nanoscale and therefore do not contribute considerably to the intrinsic catalytic activity.

    “traditional supports on the micrometer scale are usually not compatible with the catalysts on the nanoscale and therefore do not contribute considerably to the intrinsic catalytic activity.”

    From An energy-saving support made of silver nanowire aerogel for hydrogen evolution reaction (2023) · cites this paper as [30]

    The Results section reports that a strongly coupled Ni/Yb2O3 interface improves catalytic activity and that Ni sites far from the interface have low activity. It does not say that traditional micrometer-scale supports are usually incompatible with nanoscale catalysts or generally make little contribution to intrinsic activity; searches for those size and support terms did not establish that broader claim. No page numbers are available in our copy. (LLM, conf=0.78)

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Research works printed but not linked: 65

  1. Lu, B. et al. Ruthenium atomically dispersed in carbon outperforms platinum toward hydrogen evolution in alkaline media. Nat. Commun. 10, 631 (2019). · DOI · Paper page
  2. Zang, Y. et al. Tuning orbital orientation endows molybdenum disulfide with exceptional alkaline hydrogen evolution capability. Nat. Commun. 10, 1217 (2019). · DOI
  3. Kou, T. et al. Carbon doping switching on the hydrogen adsorption activity of NiO for hydrogen evolution reaction. Nat. Commun. 11, 590 (2020). · DOI
  4. Gong, M., Wang, D. Y., Chen, C. C., Hwang, B. J. & Dai, H. A mini review on nickel-based electrocatalysts for alkaline hydrogen evolution reaction. Nano Res. 9, 28–46 (2015). · DOI
  5. Zhao, L. et al. Steering elementary steps towards efficient alkaline hydrogen evolution via size-dependent Ni/NiO nanoscale heterosurfaces. Natl Sci. Rev. 7, 27–36 (2020). · DOI
  6. Li, Y. et al. Implanting Ni–O–VOx sites into Cu-doped Ni for low-overpotential alkaline hydrogen evolution. Nat. Commun. 11, 2720 (2020). · DOI
  7. Hall, D. S., Bock, C. & MacDougall, R. R. The electrochemistry of metallic nickel: oxides, hydroxides, hydrides and alkaline hydrogen evolution. J. Electrochem. Soc. 160, 235 (2013). · DOI
  8. Gong, M. et al. Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis. Nat. Commun. 5, 4695 (2014). · DOI
  9. Gong, M. et al. Blending Cr2O3 into a NiO–Ni electrocatalyst for sustained water splitting. Angew. Chem. Int. Ed. 54, 11989–11993 (2015). · DOI
  10. Lao, M. et al. Platinum/nickel bicarbonate heterostructures towards accelerated hydrogen evolution under alkaline conditions. Angew. Chem. Int. Ed. 58, 5432–5437 (2019). · DOI
  11. Lu, K. et al. LixNiO/Ni Heterostructure with strong basic lattice oxygen enables electrocatalytic hydrogen evolution with Pt-like activity. J. Am. Chem. Soc. 142, 12613–12619 (2020). · DOI
  12. Ruqia, B. & Choi, S. Catalytic surface specificity on Pt and Pt-Ni(OH)2 electrodes for the hydrogen evolution reaction in alkaline electrolytes and their nano-scaled electro-catalysts. ChemSusChem 11, 2643–2653 (2018). · DOI
  13. Xue, S. et al. Enhancing the hydrogen evolution reaction activity of platinum electrodes in alkaline media using nickel-iron clusters. Angew. Chem. Int. Ed. 59, 10934–10938 (2020). · DOI
  14. Luo, Y. et al. Two-dimensional MoS2 confined Co(OH)2 electrocatalysts for hydrogen evolution in alkaline electrolytes. ACS Nano 12, 4565–4573 (2018). · DOI
  15. Xiao, X. et al. In situ growth of Ru nanoparticles on (Fe,Ni)(OH)2 to boost hydrogen evolution activity at high current density in alkaline media. Small Methods 4, 1900796 (2020). · DOI
  16. Dai, L. et al. Ultrathin Ni(0)-embedded Ni(OH)2 heterostructured nanosheets with enhanced electrochemical overall water splitting. Adv. Mater. 32, 1906915 (2020). · DOI
  17. Huang, J. et al. Boosting hydrogen transfer during Volmer reaction at oxides/metal nanocomposites for efficient alkaline hydrogen evolution. ACS Energy Lett. 4, 3002–3010 (2019). · DOI
  18. Hu, C. et al. In situ electrochemical production of ultrathin nickel nanosheets for hydrogen evolution electrocatalysis. Chem 3, 122–133 (2017). · DOI
  19. Wang, J. et al. The application of CeO2-based materials in electrocatalysis. J. Mater. Chem. A 7, 17675–17702 (2019). · DOI
  20. Li, Q. et al. A review on CeO2-based electrocatalyst and photocatalyst in energy conversion. Adv. Energy Sustain. Res. 2, 200063 (2021).
  21. Wu, K., Sun, L. D. & Yan, C. H. Recent progress in well-controlled synthesis of ceria-based nanocatalysts towards enhanced catalytic performance. Adv. Energy Mater. 6, 1600501 (2016). · DOI
  22. Yang, F. et al. Boosting hydrogen oxidation activity of Ni in alkaline media through oxygen-vacancy-rich CeO2/Ni heterostructures. Angew. Chem. Int. Ed. 58, 14179–14183 (2019). · DOI
  23. Xia, J. et al. Efficient optimization of electron/oxygen pathway by constructing ceria/hydroxide interface for highly active oxygen evolution reaction. Adv. Funct. Mater. 30, 1908367 (2020). · DOI
  24. Sivanantham, A., Ganesan, P. & Shanmugam, S. A synergistic effect of Co and CeO2 in nitrogen-doped carbon nanostructure for the enhanced oxygen electrode activity and stability. Appl. Catal. B-Environ. 237, 1148–1159 (2018). · DOI
  25. Xu, H., Wang, A. L., Tong, Y. & Li, G. R. Enhanced catalytic activity and stability of Pt/CeO2/PANI hybrid hollow nanorod arrays for methanol electro-oxidation. ACS Catal. 6, 5198–5206 (2016). · DOI
  26. Rezvani, A. et al. CO2 reduction to methanol on Au/CeO2 catalysts: mechanistic insights from activation/deactivation and SSITKA measurements. ACS Catal. 10, 3580–3594 (2020). · DOI
  27. Lv, C. et al. An amorphous noble-metal-free electrocatalyst that enables nitrogen fixation under ambient conditions. Angew. Chem. Int. Ed. 57, 6073–6076 (2018). · DOI
  28. Weng, Z. et al. Metal/oxide interface nanostructures generated by surface segregation for electrocatalysis. Nano Lett. 15, 7704–7710 (2015). · DOI · Paper page
  29. Yang, L., Liu, R. & Jiao, L. Electronic redistribution: construction and modulation of interface engineering on CoP for enhancing overall water splitting. Adv. Funct. Mater. 30, 1909618 (2020). · DOI
  30. Zhang, R. et al. Selective phosphidation: an effective strategy toward CoP/CeO2 interface engineering for superior alkaline hydrogen evolution electrocatalysis. J. Mater. Chem. A 6, 1985–1990 (2018). · DOI
  31. Sun, H. et al. Coupling NiCo alloy and CeO2 to enhance electrocatalytic hydrogen evolution in alkaline solution. Adv. Sustain. Syst. 4, 2000122 (2020). · DOI
  32. Pavlik, A. III, Ushakov, S. V., Navrotsky, A., Benmore, C. J. & Weber, R. J. K. Structure and thermal expansion of Lu2O3 and Yb2O3 up to the melting points. J. Nucl. Mater. 495, 385–391 (2017). · DOI
  33. Yan, Z. et al. Anion insertion enhanced electrodeposition of robust metal hydroxide/ oxide electrodes for oxygen evolution. Nat. Commun. 9, 2373 (2018). · DOI
  34. Sun, H. et al. Superhydrophilic amorphous Co-B-P nanosheet electrocatalysts with Pt-like activity and durability for the hydrogen evolution reaction. J. Mater. Chem. A 6, 22062–22069 (2018). · DOI
  35. Wang, J. et al. Non-precious-metal catalysts for alkaline water electrolysis: operando characterizations, theoretical calculations, and recent advances. Chem. Soc. Rev. 49, 9154–9196 (2020). · DOI
  36. Wang, X. et al. Strategies for design of electrocatalysts for hydrogen evolution under alkaline conditions. Mater. Today 36, 125–138 (2020). · DOI · Paper page
  37. Hu, C., Zhang, L. & Gong, J. Recent progress made in the mechanism comprehension and design of electrocatalysts for alkaline water splitting. Energy Environ. Sci. 12, 2620–2645 (2019). · DOI
  38. Nikolic, V. M. et al. Kinetics of hydrogen evolution reaction in alkaline electrolysis on a Ni cathode in the presence of Ni–Co–Mo based ionic activators. Appl. Catal. B-Environ. 179, 88–94 (2015). · DOI
  39. Xie, C. et al. In-situ phase transition of WO3 boosting electron and hydrogen transfer for enhancing hydrogen evolution on Pt. Nano Energy 71, 104653 (2020). · DOI · Paper page
  40. Mao, B. et al. Identifying the transfer kinetics of adsorbed hydroxyl as a descriptor. Angew. Chem. Int. Ed. 59, 15232–15237 (2020). · DOI
  41. Subbaraman, R. et al. Trends in activity for the water electrolyser reactions on 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts. Nat. Mater. 11, 550–557 (2012). · DOI · Paper page
  42. Wei, C. et al. Surface composition dependent ligand effect in tuning the activity of nickel-copper bimetallic electrocatalysts toward hydrogen evolution in alkaline. J. Am. Chem. Soc. 142, 7765–7775 (2020). · DOI
  43. Kim, J. et al. Tailoring binding abilities by incorporating oxophilic transition metals on 3D nanostructured Ni arrays for accelerated alkaline hydrogen evolution reaction. J. Am. Chem. Soc. 143, 1399–1408 (2021). · DOI
  44. Carrasco, J. et al. In situ and theoretical studies for the dissociation of water on an active Ni/CeO2 catalyst: importance of strong metal-support interactions for the cleavage of O–H bonds. Angew. Chem. Int. Ed. 54, 3917–3921 (2015). · DOI
  45. Liu, Z. et al. Ambient pressure XPS and IRRAS investigation of ethanol steam reforming on Ni–CeO2(111) catalysts: an in situ study of C–C and O–H bond scission. Phys. Chem. Chem. Phys. 54, 16621–16628 (2016). · DOI
  46. Chen, X. et al. Boosting electrocatalytic oxygen evolution by cation defect modulation via electrochemical etching. CCS Chem. 3, 675–685 (2020). · DOI
  47. Duan, Y. et al. Bimetallic nickel–molybdenum–tungsten nanoalloys for high-efficiency hydrogen oxidation catalysis in alkaline electrolytes. Nat. Commun. 11, 4789 (2020). · DOI
  48. Guo, Y. et al. Low-temperature CO2 methanation over CeO2-supported Ru single atoms, nanoclusters, and nanoparticles competitively tuned by strong metal–support interactions and H-spillover effect. ACS Catal. 8, 6203–6215 (2018). · DOI
  49. Resasco, J. et al. Uniformity is key in defining structure–function relationships for atomically dispersed metal catalysts: the case of Pt/CeO2. J. Am. Chem. Soc. 142, 169–184 (2020). · DOI
  50. Sun, H. et al. Self-supported transition-metal-based electrocatalysts for hydrogen and oxygen evolution. Adv. Mater. 32, 1806326 (2020). · DOI
  51. Sun, H. et al. Porous multishelled Ni2P hollow microspheres as active electrocatalyst for hydrogen and oxygen evolution. Chem. Mater. 29, 8539–8547 (2017). · DOI
  52. Obata, K. & Takanabe, K. A permselective CeOx coating improves the stability of oxygen evolution electrocatalysts. Angew. Chem. Int. Ed. 57, 1616–1620 (2018). · DOI
  53. Wang, T., Gao, X. & Jiao, L. Ni2P/NiMoP heterostructure as a bifunctional electrocatalyst for energy-saving hydrogen production. eScience 1, 67–74 (2021).
  54. He, Q. et al. Achieving efficient alkaline hydrogen evolution reaction over a Ni5P4 catalyst incorporating single-atomic Ru sites. Adv. Mater. 32, 1906972 (2020). · DOI
  55. Jiang, X. et al. Heterostructure of Ru2P/WO3/NPC synergistically promotes H2O dissociation for improved hydrogen evolution. Angew. Chem. Int. Ed. 60, 4110–4116 (2021). · DOI
  56. Sun, Y. et al. Modulating electronic structure of metal-organic frameworks by introducing atomically dispersed Ru for efficient hydrogen evolution. Nat. Commun. 12, 1369 (2021). · DOI
  57. Sun, L. et al. Modification of the intermediate binding energies on Ni/Ni3N heterostructure for enhanced alkaline hydrogen oxidation reaction. Adv. Funct. Mater. 31, 2106156 (2021). · DOI
  58. Lykhach, Y. et al. Counting electrons on supported nanoparticles. Nat. Mater. 15, 284–288 (2016). · DOI
  59. Huang, J. et al. The underlying molecular mechanism of fence engineering to break the activity-stability trade-off of catalysts. Angew. Chem. Int. Ed. 61, e202114899 (2022). · DOI
  60. Soares, D. E., Kleinke, M. U., Torriani, I. & Teschke, O. Deactivation mechanism of nickel cathodes in alkaline media. Int. J. Hydrog. Energy 7, 573–578 (1994). · DOI
  61. Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996). · DOI · Paper page
  62. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994). · DOI · Paper page
  63. Hammer, B., Hansen, L. B. & Nørskov, J. K. Improved adsorption energetics within density-functional theory using revised Perdew–Burke–Ernzerhof functionals. Phys. Rev. B 59, 7413–7421 (1999). · DOI · Paper page
  64. Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976). · DOI · Paper page
  65. Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000). · DOI

Cited by

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Metadata

Authors
Sun, H., Yan, Z., Tian, C., Li, C., Feng, X., Huang, R., Lan, Y., Chen, J., Li, C.-P., Zhang, Z., & Du, M.
Affiliations
  • Tianjin Normal University (CN)
  • Nankai University (CN)
  • Zhengzhou University of Light Industry (CN)
Corresponding author
  • Li, Cha
  • Li, Cheng-Peng
  • Du, Miao
ORCID
Venue
Nature Communications
Publisher
Springer Science and Business Media LLC
Published
2022-07-05
Volume
13
Issue
1
Pages
3857-3857
ISSN
2041-1723 (ISSN-L)
DOI
10.1038/s41467-022-31561-4
PMC
PMC9256667
OpenAlex
W4283819947
Cited by
200
References
4
Citations by year
2026: 33 · 2025: 51 · 2024: 62 · 2023: 49 · 2022: 5
FWCI
7.52
Type
journal article
Language
en
Open access
Licence
Locations
  • Nature Communications (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • RePEc: Research Papers in Economics (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
Funders
  • National Natural Science Foundation of China (52101268)
  • The Science & Technology Development Fund of Tianjin Education Commission for Higher Education
Topics
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Electrocatalysts for Energy Conversion
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
  • Physical Sciences › Materials Science › Materials Chemistry › Hydrogen Storage and Materials
Keywords
nickel-based electrocatalysts, alkaline hydrogen evolution reaction, water electrolysis, high-temperature reduction, active site density, oxophilicity, hydrogen adsorption free energy, catalyst stability, platinum-free electrocatalysts

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