Operando Spectroscopic Analysis of an Amorphous Cobalt Sulfide Hydrogen Evolution Electrocatalyst

被引:347
作者
Kornienko, Nikolay [1 ]
Resasco, Joaquin [2 ]
Becknell, Nigel [1 ]
Jian, Chang-Ming [1 ]
Liu, Yi-Sheng [3 ]
Nie, Kaiqi [3 ,4 ,5 ]
Sun, Xuhui [4 ,5 ]
Guo, Jinghua [3 ]
Leone, Stephen R. [1 ,6 ,7 ]
Yang, Peidong [1 ,8 ,9 ]
机构
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
[2] Univ Calif Berkeley, Dept Chem Engn, Berkeley, CA 94720 USA
[3] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Adv Light Source, Berkeley, CA 94720 USA
[4] Soochow Univ, Western Univ Ctr Synchrotron Radiat Res, Inst Funct Nano & Soft Mat FUNSOM, Suzhou 215123, Peoples R China
[5] Soochow Univ, Collaborat Innovat Ctr Suzhou Nano Sci & Technol, Suzhou 215123, Peoples R China
[6] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Div Chem Sci, Berkeley, CA 94720 USA
[7] Univ Calif Berkeley, Dept Phys, Berkeley, CA 94720 USA
[8] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Div Mat Sci, Berkeley, CA 94720 USA
[9] Kavli Energy Nanosci Inst, Berkeley, CA 94720 USA
基金
美国国家科学基金会;
关键词
X-RAY-ABSORPTION; TRANSITION-METAL COMPOUNDS; ENHANCED RAMAN-SCATTERING; EDGE XANES SPECTROSCOPY; SULFUR K-EDGE; ELECTRONIC-STRUCTURE; HYDRODESULFURIZATION CATALYSTS; PHOSPHIDE NANOPARTICLES; OXYGEN REDUCTION; WATER OXIDATION;
D O I
10.1021/jacs.5b03545
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The generation of chemical fuel in the form of molecular H-2 via the electrolysis of water is regarded to be a promising approach to convert incident solar power into an energy storage medium. Highly efficient and cost-effective catalysts are required to make such an approach practical on a large scale. Recently, a number of amorphous hydrogen evolution reaction (HER) catalysts have emerged that show promise in terms of scalability and reactivity, yet remain poorly understood. In this work, we utilize Raman Spectroscopy and X-ray absorption spectroscopy (XAS) as a tool to elucidate the structure and function of an amorphous cobalt sulfide (CoSx) catalyst. Ex situ measurements reveal that the as-deposited CoSx catalyst is composed of small clusters in which the cobalt is surrounded by both sulfur and oxygen.,Operando experiments, performed while the CoSx is catalyzing the HER, yield a molecular model in which cobalt is in an octahedral CoS2-like state where the cobalt center is predominantly surrounded by a first shell Of sulfur atoms, which, in turn, are preferentially exposed to electrolyte relative to bulk CoS2. We surmise that these CoS2-like clusters form under cathodic polarization and expose a high density of catalytically active sulfur sites for the HER.
引用
收藏
页码:7448 / 7455
页数:8
相关论文
共 85 条
  • [21] Earth-Abundant Metal Pyrites (FeS2, CoS2, NiS2, and Their Alloys) for Highly Efficient Hydrogen Evolution and Polysulfide Reduction Electrocatalysis
    Faber, Matthew S.
    Lukowski, Mark A.
    Ding, Qi
    Kaiser, Nicholas S.
    Jin, Song
    [J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2014, 118 (37) : 21347 - 21356
  • [22] High-Performance Electrocatalysis Using Metallic Cobalt Pyrite (CoS2) Micro- and Nanostructures
    Faber, Matthew S.
    Dziedzic, Rafal
    Lukowski, Mark A.
    Kaiser, Nicholas S.
    Ding, Qi
    Jin, Song
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (28) : 10053 - 10061
  • [23] Farrell SP, 2002, AM MINERAL, V87, P1321
  • [24] Energy and environment policy case for a global project on artificial photosynthesis
    Faunce, Thomas A.
    Lubitz, Wolfgang
    Rutherford, A. W. Bill
    MacFarlane, Douglas R.
    Moore, Gary F.
    Yang, Peidong
    Nocera, Daniel G.
    Moore, Tom A.
    Gregory, Duncan H.
    Fukuzumi, Shunichi
    Yoon, Kyung Byung
    Armstrong, Fraser A.
    Wasielewski, Michael R.
    Styring, Stenbjorn
    [J]. ENERGY & ENVIRONMENTAL SCIENCE, 2013, 6 (03) : 695 - 698
  • [25] Sulfur K-edge xanes spectroscopy:: Chemical state and content of sulfur in silicate glasses
    Fleet, ME
    Liu, XY
    Harmer, SL
    King, PL
    [J]. CANADIAN MINERALOGIST, 2005, 43 : 1605 - 1618
  • [26] High-resolution spectroscopy of CoS (X4Δi):: Examining 3d transition-metal sulfide bonds -: art. no. 164312
    Flory, MA
    McLamarrah, SK
    Ziurys, LM
    [J]. JOURNAL OF CHEMICAL PHYSICS, 2005, 123 (16)
  • [27] SOLID-STATE SYNTHESIS AND CHARACTERIZATION OF MODEL HYDRODESULFURIZATION CATALYSTS
    GARCIA, MAV
    LINDNER, J
    SACHDEV, A
    SCHWANK, J
    [J]. JOURNAL OF CATALYSIS, 1989, 119 (02) : 388 - 399
  • [28] Compositional dependence of the Raman lineshapes in GaSxSe1-x layered mixed crystals
    Gasanly, NM
    [J]. JOURNAL OF RAMAN SPECTROSCOPY, 2005, 36 (09) : 879 - 883
  • [29] In Situ X-ray Absorption Spectroscopy Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction
    Gorlin, Yelena
    Lassalle-Kaiser, Benedikt
    Benck, Jesse D.
    Gul, Sheraz
    Webb, Samuel M.
    Yachandra, Vittal K.
    Yano, Junko
    Jaramillo, Thomas F.
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (23) : 8525 - 8534
  • [30] Raman Spectroscopy of nanomaterials: How spectra relate to disorder, particle size and mechanical properties
    Gouadec, Gwenael
    Colomban, Philippe
    [J]. PROGRESS IN CRYSTAL GROWTH AND CHARACTERIZATION OF MATERIALS, 2007, 53 (01) : 1 - 56