Cited by 670Electrocatalysts for Energy ConversionCO2 Reduction Techniques and CatalystsHydrogen Storage and Materials

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Single platinum atoms embedded in nanoporous cobalt selenide as electrocatalyst for accelerating hydrogen evolution reaction

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Abstract

Abstract Designing efficient electrocatalysts for hydrogen evolution reaction is significant for renewable and sustainable energy conversion. Here, we report single-atom platinum decorated nanoporous Co0.85Se (Pt/np-Co0.85Se) as efficient electrocatalysts for hydrogen evolution. The achieved Pt/np-Co0.85Se shows high catalytic performance with a near-zero onset overpotential, a low Tafel slope of 35 mV dec−1, and a high turnover frequency of 3.93 s−1 at −100 mV in neutral media, outperforming commercial Pt/C catalyst and other reported transition-metal-based compounds. Operando X-ray absorption spectroscopy studies combined with density functional theory calculations indicate that single-atom platinum in Pt/np-Co0.85Se not only can optimize surface states of Co0.85Se active centers under realistic working conditions, but also can significantly reduce energy barriers of water dissociation and improve adsorption/desorption behavior of hydrogen, which synergistically promote thermodynamics and kinetics. This work opens up further opportunities for local electronic structures tuning of electrocatalysts to effectively manipulate its catalytic properties by an atomic-level engineering strategy.

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Crossref · 10.1038/s41467-019-09765-y

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Figures

Fig. 1 Fabrication and structural characterization of Pt/np-Co0.85Se. a Schematic illustration of the fabrication procedure. b X-ray diffraction (XRD) patterns of np-Co0.85Se and Pt/np-Co0.85Se. c SEM image of Pt/np-Co0.85Se. Inset shows the microstructure of cross-section of Pt/np-Co0.85Se. d, e HAADF-STEM images of Pt/np-Co0.85Se. f Line-scanning intensity profile obtained from the area highlighted with red rectangles in regions A and B in e. g The STEM-EDX elemental mapping of Pt/np-Co0.85Se. Scale bars: c 500 nm, inset: 20 µm. d 2 nm. e 1 nm. g 10 nm
Fig. 1 Fabrication and structural characterization of Pt/np-Co0.85Se. a Schematic illustration of the fabrication procedure. b X-ray diffraction (XRD) patterns of np-Co0.85Se and Pt/np-Co0.85Se. c SEM image of Pt/np-Co0.85Se. Inset shows the microstructure of cross-section of Pt/np-Co0.85Se. d, e HAADF-STEM images of Pt/np-Co0.85Se. f Line-scanning intensity profile obtained from the area highlighted with red rectangles in regions A and B in e. g The STEM-EDX elemental mapping of Pt/np-Co0.85Se. Scale bars: c 500 nm, inset: 20 µm. d 2 nm. e 1 nm. g 10 nmCC BY · PubMed Central
Fig. 2 X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) characterizations. a XPS spectra of Pt/np-Co0.85Se and commercial Pt/C in Pt 4f regions. b The normalized XANES at the Pt L3-edge of Pt foil, commercial Pt/C, PtO2, and Pt/np-Co0.85Se. The inset shows the average oxidation state of Pt in Pt/np-Co0.85Se. c Corresponding FT-EXAFS spectra from b. d The normalized XANES spectra at the Se K-edge of np-Co0.85Se and Pt/np-Co0.85Se. e Corresponding FT-EXAFS spectra from d. f The normalized XANES spectra at the Co K-edge of np-Co0.85Se and Pt/np-Co0.85Se. g Corresponding FT-EXAFS spectra from f
Fig. 2 X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) characterizations. a XPS spectra of Pt/np-Co0.85Se and commercial Pt/C in Pt 4f regions. b The normalized XANES at the Pt L3-edge of Pt foil, commercial Pt/C, PtO2, and Pt/np-Co0.85Se. The inset shows the average oxidation state of Pt in Pt/np-Co0.85Se. c Corresponding FT-EXAFS spectra from b. d The normalized XANES spectra at the Se K-edge of np-Co0.85Se and Pt/np-Co0.85Se. e Corresponding FT-EXAFS spectra from d. f The normalized XANES spectra at the Co K-edge of np-Co0.85Se and Pt/np-Co0.85Se. g Corresponding FT-EXAFS spectra from fCC BY · PubMed Central
Fig. 3 Electrochemical hydrogen evolution reaction (HER) performance. a HER polarization curves of np-Co0.85Se, Pt/np-Co0.85Se and Pt/C. b Corresponding to Tafel plots of the presented data in a. c Corresponding to onset potential at −1 mA cm−2 of the presented data in a. d The mass activity of Pt/np-Co0.85Se and state-of-the-art Pt/C. e Comparison of merit with respect to both kinetics (Tafel slope) and activity (the overpotential required to achieve −10 mA cm−2), with references all measured in neutral medium. f TOF values of Pt/np-Co0.85Se (red dot), together with previous reported HER electrocatalysts at −100 mV vs. RHE. g Faradaic efficiency of Pt/np-Co0.85Se at different applied potentials. h The detail of hydrogen Faradaic efficiency measurement. i Accelerated HER polarization curves of Pt/np-Co0.85Se. j Current density vs. time (i–t) curves of Pt/np-Co0.85Se recorded for 40 h s at −50 mV vs. RHE
Fig. 3 Electrochemical hydrogen evolution reaction (HER) performance. a HER polarization curves of np-Co0.85Se, Pt/np-Co0.85Se and Pt/C. b Corresponding to Tafel plots of the presented data in a. c Corresponding to onset potential at −1 mA cm−2 of the presented data in a. d The mass activity of Pt/np-Co0.85Se and state-of-the-art Pt/C. e Comparison of merit with respect to both kinetics (Tafel slope) and activity (the overpotential required to achieve −10 mA cm−2), with references all measured in neutral medium. f TOF values of Pt/np-Co0.85Se (red dot), together with previous reported HER electrocatalysts at −100 mV vs. RHE. g Faradaic efficiency of Pt/np-Co0.85Se at different applied potentials. h The detail of hydrogen Faradaic efficiency measurement. i Accelerated HER polarization curves of Pt/np-Co0.85Se. j Current density vs. time (i–t) curves of Pt/np-Co0.85Se recorded for 40 h s at −50 mV vs. RHECC BY · PubMed Central
Fig. 4 In situ and operando X-ray absorption spectroscopy (XAS) characterizations. a, b Co K-edge XANES of a np-Co0.85Se and b Pt/np-Co0.85Se from OCV to −0.2 V (vs. RHE) in 1.0 M PBS. c, d First-order derivatives of the XANES spectra of c np-Co0.85Se and d Pt/np-Co0.85Se. e, f FT-EXAFS spectra of e np-Co0.85Se and f Pt/np-Co0.85Se. g Schematic illustration of the hydrogen evolution reaction (HER) mechanism determined by in situ and operando XAS analysis of Pt/np-Co0.85Se in neutral media
Fig. 4 In situ and operando X-ray absorption spectroscopy (XAS) characterizations. a, b Co K-edge XANES of a np-Co0.85Se and b Pt/np-Co0.85Se from OCV to −0.2 V (vs. RHE) in 1.0 M PBS. c, d First-order derivatives of the XANES spectra of c np-Co0.85Se and d Pt/np-Co0.85Se. e, f FT-EXAFS spectra of e np-Co0.85Se and f Pt/np-Co0.85Se. g Schematic illustration of the hydrogen evolution reaction (HER) mechanism determined by in situ and operando XAS analysis of Pt/np-Co0.85Se in neutral mediaCC BY · PubMed Central
Fig. 5 Density functional theory (DFT) calculations. a Calculated spin density distribution in the Co0.85Se supercell before and after Pt atoms doping. The blue and yellow balls refer to Co and Se atoms. Yellow and cyan isosurfaces represent positive and negative spin densities (0.005 e/Å3), respectively. b Calculated DOS of Co0.85Se and Pt/Co0.85Se. c Calculated adsorption free energy diagrams for the Volmer step on the as-built np-Co0.85Se, Pt (111) and Pt/Co0.85Se models. d Free energy diagrams for hydrogen adsorption at different active sites of Co0.85Se (004), Pt (111), and Pt/Co0.85Se (004)
Fig. 5 Density functional theory (DFT) calculations. a Calculated spin density distribution in the Co0.85Se supercell before and after Pt atoms doping. The blue and yellow balls refer to Co and Se atoms. Yellow and cyan isosurfaces represent positive and negative spin densities (0.005 e/Å3), respectively. b Calculated DOS of Co0.85Se and Pt/Co0.85Se. c Calculated adsorption free energy diagrams for the Volmer step on the as-built np-Co0.85Se, Pt (111) and Pt/Co0.85Se models. d Free energy diagrams for hydrogen adsorption at different active sites of Co0.85Se (004), Pt (111), and Pt/Co0.85Se (004)CC BY · PubMed Central

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Metadata

Authors
Jiang, K., Liu, B., Luo, M., Ning, S., Peng, M., Zhao, Y., Lu, Y.-R., Chan, T.-S., de Groot, F. M. F., & Tan, Y.
Affiliations
  • Hunan University (CN)
  • Stockholm University (SE)
  • Shanghai Polytechnic University (CN)
  • National University of Singapore (SG)
  • National Synchrotron Radiation Research Center (TW)
  • Utrecht University (NL)
Corresponding author
Tan, Yongwen
Venue
Nature Communications
Published
2019-04-15
Volume
10
Issue
1
Pages
1743-1743
ISSN
2041-1723 (ISSN-L)
OpenAlex
W2939140644
Cited by
670
References
55
Citations by year
2026: 33 · 2025: 87 · 2024: 88 · 2023: 100 · 2022: 127 · 2021: 125 · 2020: 93 · 2019: 17
FWCI
19.26
Type
journal article
Language
en
Open access
Locations
  • Nature Communications (publishedVersion, cc-by)
  • Europe PMC (PubMed Central) (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • National University of Singapore (submittedVersion, cc-by)
  • RePEc: Research Papers in Economics (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion)
  • Utrecht University Repository (Utrecht University) (submittedVersion, other-oa)
Funders
  • National Natural Science Foundation of China (51771072)
  • Hunan University (71860007)
  • State Key Laboratory of Advanced Design and Manufacturing for Vehicle Body (71860007)
  • Fundamental Research Funds for the Central Universities
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
platinum single atoms, hydrogen evolution reaction, electrocatalysts, water dissociation, hydrogen sorption, surface states, local electronic structure, media neutrality, Pt/C comparison

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