Atomic Sulfur Filling Oxygen Vacancies Optimizes H Absorption and Boosts the Hydrogen Evolution Reaction in Alkaline Media

Jing Jin; Jie Yin; Hongbo Liu; Bolong Huang; Yang Hu; Hong Zhang; Mingzi Sun; Yong Peng; Pinxian Xi; Chun Hua Yan

doi:10.1002/anie.202104055

Atomic Sulfur Filling Oxygen Vacancies Optimizes H Absorption and Boosts the Hydrogen Evolution Reaction in Alkaline Media

Jing Jin, Jie Yin, Hongbo Liu, Bolong Huang (Corresponding Author), Yang Hu, Hong Zhang, Mingzi Sun, Yong Peng, Pinxian Xi, Chun Hua Yan

Research output: Journal article publication › Journal article › Academic research › peer-review

184 Citations (Scopus)

Abstract

The hydrogen evolution reaction (HER) usually has sluggish kinetics in alkaline solution due to the difficulty in forming binding protons. Herein we report an electrocatalyst in which sulfur atoms are doping in the oxygen vacancies (V_O) of inverse spinel NiFe₂O₄ (S-NiFe₂O₄) to create active sites with enhanced electron transfer capability. This electrocatalyst has an ultralow overpotential of 61 mV at the current density of 10 mA cm⁻² and long-term stability of 60 h at 1.0 Acm⁻² in 1.0 M KOH media. In situ Raman spectroscopy revealed that S sites adsorb hydrogen adatom (H*) and in situ form S-H*, which favor the production of hydrogen and boosts HER in alkaline solution. DFT calculations further verified that S introduction lowered the energy barrier of H₂O dissociation. Both experimental and theoretical investigations confirmed S atoms are active sites of the S-NiFe₂O₄.

Original language	English
Pages (from-to)	14117-14123
Number of pages	7
Journal	Angewandte Chemie - International Edition
Volume	60
Issue number	25
DOIs	https://doi.org/10.1002/anie.202104055
Publication status	Published - 14 Jun 2021

Keywords

electrocatalysis
H* intermediate
hydrogen evolution reaction
sulfur
surface reconstruction

ASJC Scopus subject areas

Catalysis
General Chemistry

More information

10.1002/anie.202104055

http://hdl.handle.net/10397/95278

Cite this

@article{0181e83e0327421c9ee4fa8f7b1a6e60,

title = "Atomic Sulfur Filling Oxygen Vacancies Optimizes H Absorption and Boosts the Hydrogen Evolution Reaction in Alkaline Media",

abstract = "The hydrogen evolution reaction (HER) usually has sluggish kinetics in alkaline solution due to the difficulty in forming binding protons. Herein we report an electrocatalyst in which sulfur atoms are doping in the oxygen vacancies (VO) of inverse spinel NiFe2O4 (S-NiFe2O4) to create active sites with enhanced electron transfer capability. This electrocatalyst has an ultralow overpotential of 61 mV at the current density of 10 mA cm−2 and long-term stability of 60 h at 1.0 Acm−2 in 1.0 M KOH media. In situ Raman spectroscopy revealed that S sites adsorb hydrogen adatom (H*) and in situ form S-H*, which favor the production of hydrogen and boosts HER in alkaline solution. DFT calculations further verified that S introduction lowered the energy barrier of H2O dissociation. Both experimental and theoretical investigations confirmed S atoms are active sites of the S-NiFe2O4.",

keywords = "electrocatalysis, H* intermediate, hydrogen evolution reaction, sulfur, surface reconstruction",

author = "Jing Jin and Jie Yin and Hongbo Liu and Bolong Huang and Yang Hu and Hong Zhang and Mingzi Sun and Yong Peng and Pinxian Xi and Yan, {Chun Hua}",

note = "Funding Information: We acknowledge support from the National Natural Science Foundation of China (No. 21931001 and 21922105), Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province (2019ZX‐04), and the 111 Project (B20027). B.H. acknowledges the support of the Natural Science Foundation of China (NSFC) (No. 21771156), and the Early Career Scheme (ECS) fund (Grant No. PolyU 253026/16P) from the Research Grant Council (RGC) in Hong Kong. J.Y. acknowledges the support of the National Postdoctoral Program for Innovative Talents (BX20200157). Publisher Copyright: {\textcopyright} 2021 Wiley-VCH GmbH",

year = "2021",

month = jun,

day = "14",

doi = "10.1002/anie.202104055",

language = "English",

volume = "60",

pages = "14117--14123",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "25",

}

TY - JOUR

T1 - Atomic Sulfur Filling Oxygen Vacancies Optimizes H Absorption and Boosts the Hydrogen Evolution Reaction in Alkaline Media

AU - Jin, Jing

AU - Yin, Jie

AU - Liu, Hongbo

AU - Huang, Bolong

AU - Hu, Yang

AU - Zhang, Hong

AU - Sun, Mingzi

AU - Peng, Yong

AU - Xi, Pinxian

AU - Yan, Chun Hua

N1 - Funding Information: We acknowledge support from the National Natural Science Foundation of China (No. 21931001 and 21922105), Special Fund Project of Guiding Scientific and Technological Innovation Development of Gansu Province (2019ZX‐04), and the 111 Project (B20027). B.H. acknowledges the support of the Natural Science Foundation of China (NSFC) (No. 21771156), and the Early Career Scheme (ECS) fund (Grant No. PolyU 253026/16P) from the Research Grant Council (RGC) in Hong Kong. J.Y. acknowledges the support of the National Postdoctoral Program for Innovative Talents (BX20200157). Publisher Copyright: © 2021 Wiley-VCH GmbH

PY - 2021/6/14

Y1 - 2021/6/14

N2 - The hydrogen evolution reaction (HER) usually has sluggish kinetics in alkaline solution due to the difficulty in forming binding protons. Herein we report an electrocatalyst in which sulfur atoms are doping in the oxygen vacancies (VO) of inverse spinel NiFe2O4 (S-NiFe2O4) to create active sites with enhanced electron transfer capability. This electrocatalyst has an ultralow overpotential of 61 mV at the current density of 10 mA cm−2 and long-term stability of 60 h at 1.0 Acm−2 in 1.0 M KOH media. In situ Raman spectroscopy revealed that S sites adsorb hydrogen adatom (H*) and in situ form S-H*, which favor the production of hydrogen and boosts HER in alkaline solution. DFT calculations further verified that S introduction lowered the energy barrier of H2O dissociation. Both experimental and theoretical investigations confirmed S atoms are active sites of the S-NiFe2O4.

AB - The hydrogen evolution reaction (HER) usually has sluggish kinetics in alkaline solution due to the difficulty in forming binding protons. Herein we report an electrocatalyst in which sulfur atoms are doping in the oxygen vacancies (VO) of inverse spinel NiFe2O4 (S-NiFe2O4) to create active sites with enhanced electron transfer capability. This electrocatalyst has an ultralow overpotential of 61 mV at the current density of 10 mA cm−2 and long-term stability of 60 h at 1.0 Acm−2 in 1.0 M KOH media. In situ Raman spectroscopy revealed that S sites adsorb hydrogen adatom (H*) and in situ form S-H*, which favor the production of hydrogen and boosts HER in alkaline solution. DFT calculations further verified that S introduction lowered the energy barrier of H2O dissociation. Both experimental and theoretical investigations confirmed S atoms are active sites of the S-NiFe2O4.

KW - electrocatalysis

KW - H intermediate

KW - hydrogen evolution reaction

KW - sulfur

KW - surface reconstruction

UR - http://www.scopus.com/inward/record.url?scp=85105230082&partnerID=8YFLogxK

U2 - 10.1002/anie.202104055

DO - 10.1002/anie.202104055

M3 - Journal article

AN - SCOPUS:85105230082

SN - 1433-7851

VL - 60

SP - 14117

EP - 14123

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 25

ER -

Atomic Sulfur Filling Oxygen Vacancies Optimizes H Absorption and Boosts the Hydrogen Evolution Reaction in Alkaline Media

Abstract

Keywords

ASJC Scopus subject areas

More information

Other files and links

Fingerprint

Cite this