Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: A scanning probe investigation of the role of surface motifs in the behavior of p-WSe2 photocathodes

Abstract

The spatial variation in the photoelectrochemical performance for the reduction of an aqueous one-electron redox couple, Ru(NH3)63+/2+, and for the evolution of H2(g) from 0.5 M H2SO4(aq) at the surface of bare or Pt-decorated p-type WSe2 photocathodes has been investigated in situ using scanning photocurrent microscopy (SPCM). The measurements revealed significant differences in the charge-collection performance (quantified by the values of external quantum yields, Φext) on various macroscopic terraces. Local spectral response measurements indicated a variation in the local electronic structure among the terraces, which was consistent with a non-uniform spatial distribution of sub-band-gap states within the crystals. The photoconversion efficiencies of Pt-decorated p-WSe2 photocathodes were greater for the evolution of H2(g) from 0.5 M H2SO4 than for the reduction of Ru(NH3)63+/2+, and terraces that exhibited relatively low values of Φext for the reduction of Ru(NH3)63+/2+ could in some cases yield values of Φext for the evolution of H2(g) comparable to the values of Φext yielded by the highest-performing terraces. In conclusion, although the spatial resolution of the techniques used in this work frequently did not result in observation of the effect of edge sites on photocurrent efficiency, some edge effects were observed in the measurements; however the observed edgemore » effects differed among edges, and did not appear to determine the performance of the electrodes.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [4];  [4];  [5];  [4];  [6];  [7];  [5];  [8];  [9]
+ Show Author Affiliations
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering; California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering
  3. Columbia Univ., New York, NY (United States). Dept. of Chemical Engineering; National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research. Materials Measurement Lab.
  4. California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP); California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Engineering and Applied Science
  5. California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP)
  6. Bruker Nano Surfaces, Goleta, CA (United States)
  7. Univ. of California, Irvine, CA (United States). Dept. of Chemistry and Department of Chemical Engineering and Materials Science
  8. California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP); California Inst. of Technology (CalTech), Pasadena, CA (United States). Molecular Materials Research Center, Beckman Inst.
  9. California Inst. of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering; California Inst. of Technology (CalTech), Pasadena, CA (United States). Joint Center for Artificial Photosynthesis (JCAP); California Inst. of Technology (CalTech), Pasadena, CA (United States). Molecular Materials Research Center, Beckman Inst.; California Inst. of Technology (CalTech), Pasadena, CA (United States). Kavli Nanoscience Inst.
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office (HFTO)
OSTI Identifier:
1436126
Grant/Contract Number:  
SC0004993; FG02-03ER15483
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Velazquez, Jesus M., John, Jimmy, Esposito, Daniel V., Pieterick, Adam, Pala, Ragip, Sun, Guofeng, Zhou, Xinghao, Huang, Zhuangqun, Ardo, Shane, Soriaga, Manuel P., Brunschwig, Bruce S., and Lewis, Nathan S. A scanning probe investigation of the role of surface motifs in the behavior of p-WSe2 photocathodes. United States: N. p., 2015. Web. doi:10.1039/c5ee02530c.
Copy to clipboard
Velazquez, Jesus M., John, Jimmy, Esposito, Daniel V., Pieterick, Adam, Pala, Ragip, Sun, Guofeng, Zhou, Xinghao, Huang, Zhuangqun, Ardo, Shane, Soriaga, Manuel P., Brunschwig, Bruce S., & Lewis, Nathan S. A scanning probe investigation of the role of surface motifs in the behavior of p-WSe2 photocathodes. United States. https://doi.org/10.1039/c5ee02530c
Copy to clipboard
Velazquez, Jesus M., John, Jimmy, Esposito, Daniel V., Pieterick, Adam, Pala, Ragip, Sun, Guofeng, Zhou, Xinghao, Huang, Zhuangqun, Ardo, Shane, Soriaga, Manuel P., Brunschwig, Bruce S., and Lewis, Nathan S. Thu . "A scanning probe investigation of the role of surface motifs in the behavior of p-WSe2 photocathodes". United States. https://doi.org/10.1039/c5ee02530c. https://www.osti.gov/servlets/purl/1436126.
Copy to clipboard
@article{osti_1436126,
title = {A scanning probe investigation of the role of surface motifs in the behavior of p-WSe2 photocathodes},
author = {Velazquez, Jesus M. and John, Jimmy and Esposito, Daniel V. and Pieterick, Adam and Pala, Ragip and Sun, Guofeng and Zhou, Xinghao and Huang, Zhuangqun and Ardo, Shane and Soriaga, Manuel P. and Brunschwig, Bruce S. and Lewis, Nathan S.},
abstractNote = {The spatial variation in the photoelectrochemical performance for the reduction of an aqueous one-electron redox couple, Ru(NH3)63+/2+, and for the evolution of H2(g) from 0.5 M H2SO4(aq) at the surface of bare or Pt-decorated p-type WSe2 photocathodes has been investigated in situ using scanning photocurrent microscopy (SPCM). The measurements revealed significant differences in the charge-collection performance (quantified by the values of external quantum yields, Φext) on various macroscopic terraces. Local spectral response measurements indicated a variation in the local electronic structure among the terraces, which was consistent with a non-uniform spatial distribution of sub-band-gap states within the crystals. The photoconversion efficiencies of Pt-decorated p-WSe2 photocathodes were greater for the evolution of H2(g) from 0.5 M H2SO4 than for the reduction of Ru(NH3)63+/2+, and terraces that exhibited relatively low values of Φext for the reduction of Ru(NH3)63+/2+ could in some cases yield values of Φext for the evolution of H2(g) comparable to the values of Φext yielded by the highest-performing terraces. In conclusion, although the spatial resolution of the techniques used in this work frequently did not result in observation of the effect of edge sites on photocurrent efficiency, some edge effects were observed in the measurements; however the observed edge effects differed among edges, and did not appear to determine the performance of the electrodes.},
doi = {10.1039/c5ee02530c},
journal = {Energy & Environmental Science},
number = 1,
volume = 9,
place = {United States},
year = {Thu Oct 08 00:00:00 EDT 2015},
month = {Thu Oct 08 00:00:00 EDT 2015}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/c5ee02530c
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 32 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Self-assembled 2D WSe2 thin films for photoelectrochemical hydrogen production
journal, July 2015

  • Yu, Xiaoyun; Prévot, Mathieu S.; Guijarro, Néstor
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8596

Controlled Scalable Synthesis of Uniform, High-Quality Monolayer and Few-layer MoS2 Films
journal, May 2013

  • Yu, Yifei; Li, Chun; Liu, Yi
  • Scientific Reports, Vol. 3, Issue 1
  • DOI: 10.1038/srep01866

Preparation of WSe 2 surfaces with high photoactivity
journal, January 1992

Charge Collection Microscopy on p-WSe[sub 2]: Recombination Sites and Minority Carrier Diffusion Length
journal, January 1982

  • Lewerenz, H. J.
  • Journal of The Electrochemical Society, Vol. 129, Issue 2
  • DOI: 10.1149/1.2123871

Selective Adsorption of Thiol Molecules at Sulfur Vacancies on MoS 2 (0001), Followed by Vacancy Repair via S–C Dissociation
journal, October 2012

  • Makarova, Marina; Okawa, Yuji; Aono, Masakazu
  • The Journal of Physical Chemistry C, Vol. 116, Issue 42
  • DOI: 10.1021/jp307267h

Defect-Dominated Doping and Contact Resistance in MoS 2
journal, February 2014

  • McDonnell, Stephen; Addou, Rafik; Buie, Creighton
  • ACS Nano, Vol. 8, Issue 3
  • DOI: 10.1021/nn500044q

Photoelectrochemistry of WSe[sub 2] Electrodes
journal, January 1984

  • Lewerenz, H. J.
  • Journal of The Electrochemical Society, Vol. 131, Issue 1
  • DOI: 10.1149/1.2115467

Hydrogen Evolution from Pt/Ru-Coated p-Type WSe 2 Photocathodes
journal, December 2012

  • McKone, James R.; Pieterick, Adam P.; Gray, Harry B.
  • Journal of the American Chemical Society, Vol. 135, Issue 1
  • DOI: 10.1021/ja308581g

Heteroepitaxial growth of layered transition metal dichalcogenides on sulfur‐terminated GaAs{111} surfaces
journal, January 1990

  • Ueno, Keiji; Shimada, Toshihiro; Saiki, Koichiro
  • Applied Physics Letters, Vol. 56, Issue 4
  • DOI: 10.1063/1.102817

Electronic State Formation by Surface Atom Removal on a MoS$_{2}$ Surface
journal, June 2012

  • Kodama, Nagisa; Hasegawa, Tsuyoshi; Tsuruoka, Tohru
  • Japanese Journal of Applied Physics, Vol. 51
  • DOI: 10.1143/JJAP.51.06FF07

Methods for comparing the performance of energy-conversion systems for use in solar fuels and solar electricity generation
journal, January 2015

  • Coridan, Robert H.; Nielander, Adam C.; Francis, Sonja A.
  • Energy & Environmental Science, Vol. 8, Issue 10
  • DOI: 10.1039/C5EE00777A

Operando Synthesis of Macroporous Molybdenum Diselenide Films for Electrocatalysis of the Hydrogen-Evolution Reaction
journal, July 2014

  • Saadi, Fadl H.; Carim, Azhar I.; Velazquez, Jesus M.
  • ACS Catalysis, Vol. 4, Issue 9
  • DOI: 10.1021/cs500412u

Bridging the Gap Between Bulk and Nanostructured Photoelectrodes: The Impact of Surface States on the Electrocatalytic and Photoelectrochemical Properties of MoS 2
journal, May 2013

  • Chen, Zhebo; Forman, Arnold J.; Jaramillo, Thomas F.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 19
  • DOI: 10.1021/jp311375k

WSe 2 : Optical and electrical properties as related to surface passivation of recombination centers
journal, August 1989

Defect control of hydrogenation activity of molybdenum sulfide catalyst
journal, December 1976

Photoelectrochemistry and Photovoltaics of Layered Semiconductors
book, January 1992

Polycrystalline WSe[sub 2] Photoelectrodes
journal, January 1982

  • Ginley, D. S.
  • Journal of The Electrochemical Society, Vol. 129, Issue 1
  • DOI: 10.1149/1.2123736

Impact of intrinsic atomic defects on the electronic structure of MoS 2 monolayers
journal, August 2014

The WSe2/Tungsten-Oxide Interface: Structure and Photoluminescence
journal, May 1993

  • Tenne, R.; Eherman, K.; Mahalu, D.
  • Berichte der Bunsengesellschaft für physikalische Chemie, Vol. 97, Issue 5
  • DOI: 10.1002/bbpc.19930970510

Passivation of recombination centers in n ‐WSe 2 yields high efficiency (>14%) photoelectrochemical cell
journal, October 1985

  • Tenne, R.; Wold, A.
  • Applied Physics Letters, Vol. 47, Issue 7
  • DOI: 10.1063/1.96066

Surface defects on n-MoSe2 electrodes used in photoelectrochemical solar cells
journal, December 1983

Vertical Heterostructures of Layered Metal Chalcogenides by van der Waals Epitaxy
journal, May 2014

  • Zhang, Xingwang; Meng, Fei; Christianson, Jeffrey R.
  • Nano Letters, Vol. 14, Issue 6
  • DOI: 10.1021/nl501000k

Relationship between surface morphology and solar conversion efficiency of tungsten diselenide photoanodes
journal, March 1980

  • Lewerenz, H. J.; Heller, A.; DiSalvo, F. J.
  • Journal of the American Chemical Society, Vol. 102, Issue 6
  • DOI: 10.1021/ja00526a019

Solar Water Splitting Cells
journal, November 2010

  • Walter, Michael G.; Warren, Emily L.; McKone, James R.
  • Chemical Reviews, Vol. 110, Issue 11, p. 6446-6473
  • DOI: 10.1021/cr1002326

Synthesis and hydrogen-evolution activity of tungsten selenide thin films deposited on tungsten foils
journal, March 2014

Evaluation and reduction of efficiency losses at tungsten diselenide photoanodes
journal, January 1980

  • Parkinson, Bruce A.; Furtak, Thomas E.; Canfield, Duane
  • Faraday Discussions of the Chemical Society, Vol. 70
  • DOI: 10.1039/dc9807000233

Semiconductor Electrodes. 44. Photoelectrochemistry at Polycrystalline p-Type WSe[sub 2] Films
journal, January 1982

  • Abruna, Hector D.
  • Journal of The Electrochemical Society, Vol. 129, Issue 3
  • DOI: 10.1149/1.2123949

Hydrodesulfurization activity and electronic properties of molybdenum sulfide catalyst
journal, July 1974

Schottky-barrier formation on a covalent semiconductor without Fermi-level pinning: The metal- MoS 2 (0001) interface
journal, July 1987

  • Lince, Jeffrey R.; Carré, David J.; Fleischauer, Paul D.
  • Physical Review B, Vol. 36, Issue 3
  • DOI: 10.1103/PhysRevB.36.1647

Hydrogen Oxidation and Evolution Reaction Kinetics on Platinum: Acid vs Alkaline Electrolytes
journal, January 2010

  • Sheng, Wenchao; Gasteiger, Hubert A.; Shao-Horn, Yang
  • Journal of The Electrochemical Society, Vol. 157, Issue 11
  • DOI: 10.1149/1.3483106

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

The optical properties of single crystals of WSe2 and MoTe2
journal, September 1963

The high-efficiency (17.1%) WSe 2 photo-electrochemical solar cell
journal, June 1988

Efficient and stable photoelectrochemical cells constructed with WSe2 and MoSe2 photoanodes
journal, March 1981

Passivation of recombination centers on the WSe 2 surface
journal, July 1988

Controlled photocorrosion of tungsten diselenide: influence of molecular oxygen
journal, October 1990

  • Mahalu, D.; Peisach, M.; Jaegermann, W.
  • The Journal of Physical Chemistry, Vol. 94, Issue 21
  • DOI: 10.1021/j100384a005
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Interaction between H 2 O, N 2 , CO, NO, NO 2 and N 2 O molecules and a defective WSe 2 monolayer
    journal, January 2017

    • Ma, Dongwei; Ma, Benyuan; Lu, Zhiwen
    • Physical Chemistry Chemical Physics, Vol. 19, Issue 38
    • DOI: 10.1039/c7cp04351a

    Depletion layer controls photocatalytic hydrogen evolution with p-type gallium phosphide particles
    journal, January 2019

    • Zhao, Zeqiong; Willard, Emma J.; Dominguez, Julius R.
    • Journal of Materials Chemistry A, Vol. 7, Issue 30
    • DOI: 10.1039/c9ta05879f

    Two-Dimensional Material Molybdenum Disulfides as Electrocatalysts for Hydrogen Evolution
    journal, September 2017

    Strategies for enhancing the photocurrent, photovoltage, and stability of photoelectrodes for photoelectrochemical water splitting
    text, January 2019

    • Wooseok, Yang,; Ramanujam, Prabhakar, Rajiv; Jeiwan, Tan,
    • Royal Society of Chemistry
    • DOI: 10.5167/uzh-183873
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: