skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

Abstract

Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm –2 and 100 mA cm –2 at overpotentials of 48 mV and 109 mV, respectively. Lastly, phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.

Authors:
 [1];  [2];  [3];  [1];  [1];  [1];  [1];  [2];  [1];  [1]
  1. Yale Univ., West Haven, CT (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Peking Univ., Beijing (China)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1245394
Alternate Identifier(s):
OSTI ID: 1247983
Report Number(s):
BNL-111954-2016-JA; BNL-112075-2016-JA
Journal ID: ISSN 2041-1723; R&D Project: MA453MAEA; VT1201000
Grant/Contract Number:  
SC00112704
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal Issue: 12; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; chemical sciences; catalysis; materials science; nanotechnology; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Liu, Wen, Hu, Enyuan, Jiang, Hong, Xiang, Yingjie, Weng, Zhe, Li, Min, Fan, Qi, Yu, Xiqian, Altman, Eric I., and Wang, Hailiang. A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide. United States: N. p., 2016. Web. doi:10.1038/ncomms10771.
Liu, Wen, Hu, Enyuan, Jiang, Hong, Xiang, Yingjie, Weng, Zhe, Li, Min, Fan, Qi, Yu, Xiqian, Altman, Eric I., & Wang, Hailiang. A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide. United States. doi:10.1038/ncomms10771.
Liu, Wen, Hu, Enyuan, Jiang, Hong, Xiang, Yingjie, Weng, Zhe, Li, Min, Fan, Qi, Yu, Xiqian, Altman, Eric I., and Wang, Hailiang. Fri . "A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide". United States. doi:10.1038/ncomms10771. https://www.osti.gov/servlets/purl/1245394.
@article{osti_1245394,
title = {A highly-active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide},
author = {Liu, Wen and Hu, Enyuan and Jiang, Hong and Xiang, Yingjie and Weng, Zhe and Li, Min and Fan, Qi and Yu, Xiqian and Altman, Eric I. and Wang, Hailiang},
abstractNote = {Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm–2 and 100 mA cm–2 at overpotentials of 48 mV and 109 mV, respectively. Lastly, phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.},
doi = {10.1038/ncomms10771},
journal = {Nature Communications},
number = 12,
volume = 7,
place = {United States},
year = {2016},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 72 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Sustainable Hydrogen Production
journal, August 2004


Hydrogen as an energy carrier: Prospects and challenges
journal, June 2012


Recent advances in layered transition metal dichalcogenides for hydrogen evolution reaction
journal, January 2014

  • Yang, Jieun; Shin, Hyeon Suk
  • J. Mater. Chem. A, Vol. 2, Issue 17
  • DOI: 10.1039/C3TA14151A

Earth-abundant inorganic electrocatalysts and their nanostructures for energy conversion applications
journal, January 2014

  • Faber, Matthew S.; Jin, Song
  • Energy Environ. Sci., Vol. 7, Issue 11
  • DOI: 10.1039/C4EE01760A

Noble metal-free hydrogen evolution catalysts for water splitting
journal, January 2015

  • Zou, Xiaoxin; Zhang, Yu
  • Chemical Society Reviews, Vol. 44, Issue 15
  • DOI: 10.1039/C4CS00448E

Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts
journal, July 2007

  • Jaramillo, T. F.; Jorgensen, K. P.; Bonde, J.
  • Science, Vol. 317, Issue 5834, p. 100-102
  • DOI: 10.1126/science.1141483

Molybdenum sulfides—efficient and viable materials for electro - and photoelectrocatalytic hydrogen evolution
journal, January 2012

  • Laursen, Anders B.; Kegnæs, Søren; Dahl, Søren
  • Energy & Environmental Science, Vol. 5, Issue 2
  • DOI: 10.1039/c2ee02618j

Enhanced catalytic activity in strained chemically exfoliated WS2 nanosheets for hydrogen evolution
journal, July 2013

  • Voiry, Damien; Yamaguchi, Hisato; Li, Junwen
  • Nature Materials, Vol. 12, Issue 9
  • DOI: 10.1038/nmat3700

MoSe 2 and WSe 2 Nanofilms with Vertically Aligned Molecular Layers on Curved and Rough Surfaces
journal, June 2013

  • Wang, Haotian; Kong, Desheng; Johanes, Petr
  • Nano Letters, Vol. 13, Issue 7
  • DOI: 10.1021/nl401944f

CoSe 2 Nanoparticles Grown on Carbon Fiber Paper: An Efficient and Stable Electrocatalyst for Hydrogen Evolution Reaction
journal, March 2014

  • Kong, Desheng; Wang, Haotian; Lu, Zhiyi
  • Journal of the American Chemical Society, Vol. 136, Issue 13
  • DOI: 10.1021/ja501497n

Amorphous Molybdenum Phosphide Nanoparticles for Electrocatalytic Hydrogen Evolution
journal, August 2014

  • McEnaney, Joshua M.; Crompton, J. Chance; Callejas, Juan F.
  • Chemistry of Materials, Vol. 26, Issue 16
  • DOI: 10.1021/cm502035s

A Cost-Effective 3D Hydrogen Evolution Cathode with High Catalytic Activity: FeP Nanowire Array as the Active Phase
journal, September 2014

  • Jiang, Ping; Liu, Qian; Liang, Yanhui
  • Angewandte Chemie International Edition, Vol. 53, Issue 47
  • DOI: 10.1002/anie.201406848

Carbon Nanotubes Decorated with CoP Nanocrystals: A Highly Active Non-Noble-Metal Nanohybrid Electrocatalyst for Hydrogen Evolution
journal, May 2014

  • Liu, Qian; Tian, Jingqi; Cui, Wei
  • Angewandte Chemie International Edition, Vol. 53, Issue 26
  • DOI: 10.1002/anie.201404161

Local atomic structure modulations activate metal oxide as electrocatalyst for hydrogen evolution in acidic water
journal, August 2015

  • Li, Yu Hang; Liu, Peng Fei; Pan, Lin Feng
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9064

Phosphorus-Modified Tungsten Nitride/Reduced Graphene Oxide as a High-Performance, Non-Noble-Metal Electrocatalyst for the Hydrogen Evolution Reaction
journal, March 2015

  • Yan, Haijing; Tian, Chungui; Wang, Lei
  • Angewandte Chemie International Edition, Vol. 54, Issue 21
  • DOI: 10.1002/anie.201501419

Synthesis of MoS2 and MoSe2 Films with Vertically Aligned Layers
journal, February 2013

  • Kong, Desheng; Wang, Haotian; Cha, Judy J.
  • Nano Letters, Vol. 13, Issue 3, p. 1341-1347
  • DOI: 10.1021/nl400258t

MoS2 Nanoparticles Grown on Graphene An Advanced Catalyst for the Hydrogen Evolution Reaction
journal, May 2011

  • Li, Yanguang; Wang, Hailiang; Xie, Liming
  • Journal of the American Chemical Society, Vol. 133, Issue 19, p. 7296-7299
  • DOI: 10.1021/ja201269b

Edge-Oriented MoS 2 Nanoporous Films as Flexible Electrodes for Hydrogen Evolution Reactions and Supercapacitor Devices
journal, October 2014


Conducting MoS 2 Nanosheets as Catalysts for Hydrogen Evolution Reaction
journal, November 2013

  • Voiry, Damien; Salehi, Maryam; Silva, Rafael
  • Nano Letters, Vol. 13, Issue 12
  • DOI: 10.1021/nl403661s

Amorphous Molybdenum Sulfides as Hydrogen Evolution Catalysts
journal, July 2014

  • Morales-Guio, Carlos G.; Hu, Xile
  • Accounts of Chemical Research, Vol. 47, Issue 8
  • DOI: 10.1021/ar5002022

Molybdenum Phosphosulfide: An Active, Acid-Stable, Earth-Abundant Catalyst for the Hydrogen Evolution Reaction
journal, October 2014

  • Kibsgaard, Jakob; Jaramillo, Thomas F.
  • Angewandte Chemie International Edition, Vol. 53, Issue 52
  • DOI: 10.1002/anie.201408222

Triggering the electrocatalytic hydrogen evolution activity of the inert two-dimensional MoS 2 surface via single-atom metal doping
journal, January 2015

  • Deng, Jiao; Li, Haobo; Xiao, Jianping
  • Energy & Environmental Science, Vol. 8, Issue 5
  • DOI: 10.1039/C5EE00751H

Electrochemical tuning of vertically aligned MoS2 nanofilms and its application in improving hydrogen evolution reaction
journal, November 2013

  • Wang, H.; Lu, Z.; Xu, S.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 49
  • DOI: 10.1073/pnas.1316792110

Electrochemically Fabricated Polypyrrole and MoS x Copolymer Films as a Highly Active Hydrogen Evolution Electrocatalyst
journal, March 2014

  • Wang, Tanyuan; Zhuo, Junqiao; Du, Kuangzhou
  • Advanced Materials, Vol. 26, Issue 22
  • DOI: 10.1002/adma.201400265

An efficient molybdenum disulfide/cobalt diselenide hybrid catalyst for electrochemical hydrogen generation
journal, January 2015

  • Gao, Min-Rui; Liang, Jin-Xia; Zheng, Ya-Rong
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms6982

Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide
journal, September 2015

  • Cabán-Acevedo, Miguel; Stone, Michael L.; Schmidt, J. R.
  • Nature Materials, Vol. 14, Issue 12
  • DOI: 10.1038/nmat4410

Highly Crystallized Cubic Cattierite CoS 2 for Electrochemically Hydrogen Evolution over Wide pH Range from 0 to 14
journal, December 2014


High-Performance Electrocatalysis Using Metallic Cobalt Pyrite (CoS 2 ) Micro- and Nanostructures
journal, June 2014

  • Faber, Matthew S.; Dziedzic, Rafal; Lukowski, Mark A.
  • Journal of the American Chemical Society, Vol. 136, Issue 28
  • DOI: 10.1021/ja504099w

Light scattering and ir measurements in XS 2 pryite‐type compounds
journal, May 1976

  • Anastassakis, E.; Perry, C. H.
  • The Journal of Chemical Physics, Vol. 64, Issue 9
  • DOI: 10.1063/1.432711

Raman studies of nearly half-metallic ferromagnetic CoS 2
journal, September 2014


Improved electrochemical performance of CoS 2 –MWCNT nanocomposites for sodium-ion batteries
journal, January 2015

  • Shadike, Zulipiya; Cao, Ming-Hui; Ding, Fei
  • Chemical Communications, Vol. 51, Issue 52
  • DOI: 10.1039/C5CC02564H

CoP nanoparticles deposited on reduced graphene oxide sheets as an active electrocatalyst for the hydrogen evolution reaction
journal, January 2015

  • Ma, Lianbo; Shen, Xiaoping; Zhou, Hu
  • Journal of Materials Chemistry A, Vol. 3, Issue 10
  • DOI: 10.1039/C4TA06458E

Synthesis of FeP 2 /C nanohybrids and their performance for hydrogen evolution reaction
journal, January 2015

  • Jiang, Jun; Wang, Chunde; Zhang, Jiajia
  • Journal of Materials Chemistry A, Vol. 3, Issue 2
  • DOI: 10.1039/C4TA04758C

Tungsten Phosphide Nanorod Arrays Directly Grown on Carbon Cloth: A Highly Efficient and Stable Hydrogen Evolution Cathode at All pH Values
journal, December 2014

  • Pu, Zonghua; Liu, Qian; Asiri, Abdullah M.
  • ACS Applied Materials & Interfaces, Vol. 6, Issue 24
  • DOI: 10.1021/am5060178

Synthesizing Nanoparticles of Co-P-Se compounds as Electrocatalysts for the Hydrogen Evolution Reaction
journal, May 2015


Kinetic criteria for the mechanism of the hydrogen evolution reaction
journal, February 1986


Ternary Hybrid Material for High-Performance Lithium–Sulfur Battery
journal, September 2015

  • Fan, Qi; Liu, Wen; Weng, Zhe
  • Journal of the American Chemical Society, Vol. 137, Issue 40
  • DOI: 10.1021/jacs.5b07071

Metal/Oxide Interface Nanostructures Generated by Surface Segregation for Electrocatalysis
journal, October 2015


First-row transition metal dichalcogenide catalysts for hydrogen evolution reaction
journal, January 2013

  • Kong, Desheng; Cha, Judy J.; Wang, Haotian
  • Energy & Environmental Science, Vol. 6, Issue 12
  • DOI: 10.1039/c3ee42413h

A metallic CoS 2 nanopyramid array grown on 3D carbon fiber paper as an excellent electrocatalyst for hydrogen evolution
journal, January 2015

  • Zhang, Haichuan; Li, Yingjie; Zhang, Guoxin
  • Journal of Materials Chemistry A, Vol. 3, Issue 12
  • DOI: 10.1039/C5TA00707K

CoSe 2 Nanowires Array as a 3D Electrode for Highly Efficient Electrochemical Hydrogen Evolution
journal, February 2015

  • Liu, Qian; Shi, Jinle; Hu, Jianming
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 7
  • DOI: 10.1021/am509185x

Fe K-EDGE X-RAY ABSORPTION (XANES/EXAFS) SPECTROSCOPIC STUDY OF THE NONSTOICHIOMETRIC SrFe1−xSnxO3−y SYSTEM
journal, September 1998


Transition metal pyrite dichalcogenides. High-pressure synthesis and correlation of properties
journal, November 1968

  • Bither, Tom A.; Bouchard, R. J.; Cloud, W. H.
  • Inorganic Chemistry, Vol. 7, Issue 11
  • DOI: 10.1021/ic50069a008

Sulfur K x‐ray absorption spectra of FeS, FeS 2 , and Fe 2 S 3
journal, January 1981

  • Sugiura, Chikara
  • The Journal of Chemical Physics, Vol. 74, Issue 1
  • DOI: 10.1063/1.440876

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Density-functional theory and strong interactions: Orbital ordering in Mott-Hubbard insulators
journal, August 1995


Electronic properties of random alloys: Special quasirandom structures
journal, November 1990


    Works referencing / citing this record:

    Doping-induced structural phase transition in cobalt diselenide enables enhanced hydrogen evolution catalysis
    journal, June 2018


    In Situ Electrochemical Investigation of Acidic Pressure Oxidation of Pyrite at 160–240°C
    journal, January 2018

    • Cui, Can; Li, Heping; Lin, Sen
    • Journal of The Electrochemical Society, Vol. 165, Issue 5
    • DOI: 10.1149/2.0081807jes