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Title: A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes

Abstract

Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. We demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co 3 O 4 /Co(OH) 2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. Furthermore, these films comprise compact and continuous nanocrystalline Co 3 O 4 spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH) 2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p + n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]; ORCiD logo [2];  [2];  [3]; ORCiD logo [4];  [5];  [5];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Chemical Sciences Division
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis, Molecular Biophysics and Integrated Bioimaging
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry, Materials Science Division
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1379751
Grant/Contract Number:  
AC02-05CH11231; SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 16; Journal Issue: 3; Journal ID: ISSN 1476-1122
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; electrocatalysts; electronic materials; photocatalysis; synthesis and processing

Citation Formats

Yang, Jinhui, Cooper, Jason K., Toma, Francesca M., Walczak, Karl A., Favaro, Marco, Beeman, Jeffrey W., Hess, Lucas H., Wang, Cheng, Zhu, Chenhui, Gul, Sheraz, Yano, Junko, Kisielowski, Christian, Schwartzberg, Adam, and Sharp, Ian D. A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes. United States: N. p., 2016. Web. doi:10.1038/nmat4794.
Yang, Jinhui, Cooper, Jason K., Toma, Francesca M., Walczak, Karl A., Favaro, Marco, Beeman, Jeffrey W., Hess, Lucas H., Wang, Cheng, Zhu, Chenhui, Gul, Sheraz, Yano, Junko, Kisielowski, Christian, Schwartzberg, Adam, & Sharp, Ian D. A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes. United States. doi:10.1038/nmat4794.
Yang, Jinhui, Cooper, Jason K., Toma, Francesca M., Walczak, Karl A., Favaro, Marco, Beeman, Jeffrey W., Hess, Lucas H., Wang, Cheng, Zhu, Chenhui, Gul, Sheraz, Yano, Junko, Kisielowski, Christian, Schwartzberg, Adam, and Sharp, Ian D. Mon . "A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes". United States. doi:10.1038/nmat4794. https://www.osti.gov/servlets/purl/1379751.
@article{osti_1379751,
title = {A multifunctional biphasic water splitting catalyst tailored for integration with high-performance semiconductor photoanodes},
author = {Yang, Jinhui and Cooper, Jason K. and Toma, Francesca M. and Walczak, Karl A. and Favaro, Marco and Beeman, Jeffrey W. and Hess, Lucas H. and Wang, Cheng and Zhu, Chenhui and Gul, Sheraz and Yano, Junko and Kisielowski, Christian and Schwartzberg, Adam and Sharp, Ian D.},
abstractNote = {Artificial photosystems are advanced by the development of conformal catalytic materials that promote desired chemical transformations, while also maintaining stability and minimizing parasitic light absorption for integration on surfaces of semiconductor light absorbers. We demonstrate that multifunctional, nanoscale catalysts that enable high-performance photoelectrochemical energy conversion can be engineered by plasma-enhanced atomic layer deposition. The collective properties of tailored Co 3 O 4 /Co(OH) 2 thin films simultaneously provide high activity for water splitting, permit efficient interfacial charge transport from semiconductor substrates, and enhance durability of chemically sensitive interfaces. Furthermore, these films comprise compact and continuous nanocrystalline Co 3 O 4 spinel that is impervious to phase transformation and impermeable to ions, thereby providing effective protection of the underlying substrate. Moreover, a secondary phase of structurally disordered and chemically labile Co(OH) 2 is introduced to ensure a high concentration of catalytically active sites. Application of this coating to photovoltaic p + n-Si junctions yields best reported performance characteristics for crystalline Si photoanodes.},
doi = {10.1038/nmat4794},
journal = {Nature Materials},
number = 3,
volume = 16,
place = {United States},
year = {2016},
month = {11}
}

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Works referenced in this record:

Benchmarking Hydrogen Evolving Reaction and Oxygen Evolving Reaction Electrocatalysts for Solar Water Splitting Devices
journal, March 2015

  • McCrory, Charles C. L.; Jung, Suho; Ferrer, Ivonne M.
  • Journal of the American Chemical Society, Vol. 137, Issue 13
  • DOI: 10.1021/ja510442p

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Unification of Catalytic Water Oxidation and Oxygen Reduction Reactions: Amorphous Beat Crystalline Cobalt Iron Oxides
journal, December 2014

  • Indra, Arindam; Menezes, Prashanth W.; Sahraie, Nastaran Ranjbar
  • Journal of the American Chemical Society, Vol. 136, Issue 50
  • DOI: 10.1021/ja509348t

Reversible amorphization and the catalytically active state of crystalline Co3O4 during oxygen evolution
journal, October 2015

  • Bergmann, Arno; Martinez-Moreno, Elias; Teschner, Detre
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9625

Structure and Valency of a Cobalt−Phosphate Water Oxidation Catalyst Determined by in Situ X-ray Spectroscopy
journal, October 2010

  • Kanan, Matthew W.; Yano, Junko; Surendranath, Yogesh
  • Journal of the American Chemical Society, Vol. 132, Issue 39
  • DOI: 10.1021/ja1023767

Efficient and Sustained Photoelectrochemical Water Oxidation by Cobalt Oxide/Silicon Photoanodes with Nanotextured Interfaces
journal, April 2014

  • Yang, Jinhui; Walczak, Karl; Anzenberg, Eitan
  • Journal of the American Chemical Society, Vol. 136, Issue 17
  • DOI: 10.1021/ja501513t

A Photocleavable Rapamycin Conjugate for Spatiotemporal Control of Small GTPase Activity
journal, January 2011

  • Umeda, Nobuhiro; Ueno, Tasuku; Pohlmeyer, Christopher
  • Journal of the American Chemical Society, Vol. 133, Issue 1
  • DOI: 10.1021/ja108258d

An electrodeposited inhomogeneous metal–insulator–semiconductor junction for efficient photoelectrochemical water oxidation
journal, September 2015

  • Hill, James C.; Landers, Alan T.; Switzer, Jay A.
  • Nature Materials, Vol. 14, Issue 11
  • DOI: 10.1038/nmat4408

Composite photoanodes for photoelectrochemical solar water splitting
journal, January 2010

  • Sun, Jianwei; Zhong, Diane K.; Gamelin, Daniel R.
  • Energy & Environmental Science, Vol. 3, Issue 9
  • DOI: 10.1039/c0ee00030b

Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst
journal, February 2014

  • Zhang, Miao; de Respinis, Moreno; Frei, Heinz
  • Nature Chemistry, Vol. 6, Issue 4
  • DOI: 10.1038/nchem.1874

Cobalt-Oxide-Based Materials as Water Oxidation Catalyst: Recent Progress and Challenges
journal, September 2014

  • Deng, Xiaohui; Tüysüz, Harun
  • ACS Catalysis, Vol. 4, Issue 10
  • DOI: 10.1021/cs500713d

Protection of p + -n-Si Photoanodes by Sputter-Deposited Ir/IrO x Thin Films
journal, May 2014

  • Mei, Bastian; Seger, Brian; Pedersen, Thomas
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 11
  • DOI: 10.1021/jz500865g

Mechanistic Studies of the Oxygen Evolution Reaction by a Cobalt-Phosphate Catalyst at Neutral pH
journal, November 2010

  • Surendranath, Yogesh; Kanan, Matthew W.; Nocera, Daniel G.
  • Journal of the American Chemical Society, Vol. 132, Issue 46
  • DOI: 10.1021/ja106102b

In Situ Observation of Surface Species on Iridium Oxide Nanoparticles during the Oxygen Evolution Reaction
journal, May 2014

  • Sanchez Casalongue, Hernan G.; Ng, May Ling; Kaya, Sarp
  • Angewandte Chemie International Edition, Vol. 53, Issue 28
  • DOI: 10.1002/anie.201402311

An Optocatalytic Model for Semiconductor–Catalyst Water-Splitting Photoelectrodes Based on In Situ Optical Measurements on Operational Catalysts
journal, March 2013

  • Trotochaud, Lena; Mills, Thomas J.; Boettcher, Shannon W.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 6
  • DOI: 10.1021/jz4002604

Real-time sub- Å ngstrom imaging of reversible and irreversible conformations in rhodium catalysts and graphene
journal, July 2013


Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies
journal, January 2016

  • Kim, Wooyul; McClure, Beth Anne; Edri, Eran
  • Chemical Society Reviews, Vol. 45, Issue 11
  • DOI: 10.1039/C6CS00062B

Imaging columns of the light elements carbon, nitrogen and oxygen with sub Ångstrom resolution
journal, November 2001


High-Performance Silicon Photoanodes Passivated with Ultrathin Nickel Films for Water Oxidation
journal, November 2013


Design principles for maximizing photovoltage in metal-oxide-protected water-splitting photoanodes
journal, October 2015

  • Scheuermann, Andrew G.; Lawrence, John P.; Kemp, Kyle W.
  • Nature Materials, Vol. 15, Issue 1
  • DOI: 10.1038/nmat4451

Remote Plasma Atomic Layer Deposition of Co3O4 Thin Films
journal, January 2011

  • Donders, M. E.; Knoops, H. C. M.; van, M. C. M.
  • Journal of The Electrochemical Society, Vol. 158, Issue 4
  • DOI: 10.1149/1.3552616

Plasma-Assisted Atomic Layer Deposition: Basics, Opportunities, and Challenges
journal, September 2011

  • Profijt, H. B.; Potts, S. E.; van de Sanden, M. C. M.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 29, Issue 5
  • DOI: 10.1116/1.3609974

Efficient solar water splitting by enhanced charge separation in a bismuth vanadate-silicon tandem photoelectrode
journal, July 2013

  • Abdi, Fatwa F.; Han, Lihao; Smets, Arno H. M.
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3195

Benchmarking Heterogeneous Electrocatalysts for the Oxygen Evolution Reaction
journal, October 2013

  • McCrory, Charles C. L.; Jung, Suho; Peters, Jonas C.
  • Journal of the American Chemical Society, Vol. 135, Issue 45
  • DOI: 10.1021/ja407115p

In Operando Identification of Geometrical-Site-Dependent Water Oxidation Activity of Spinel Co 3 O 4
journal, December 2015

  • Wang, Hsin-Yi; Hung, Sung-Fu; Chen, Han-Yi
  • Journal of the American Chemical Society, Vol. 138, Issue 1
  • DOI: 10.1021/jacs.5b10525

Atomic layer-deposited tunnel oxide stabilizes silicon photoanodes for water oxidation
journal, June 2011

  • Chen, Yi Wei; Prange, Jonathan D.; Dühnen, Simon
  • Nature Materials, Vol. 10, Issue 7
  • DOI: 10.1038/nmat3047

Identification of Highly Active Fe Sites in (Ni,Fe)OOH for Electrocatalytic Water Splitting
journal, January 2015

  • Friebel, Daniel; Louie, Mary W.; Bajdich, Michal
  • Journal of the American Chemical Society, Vol. 137, Issue 3
  • DOI: 10.1021/ja511559d

Cobalt–Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts: The Role of Structure and Composition on Activity, Stability, and Mechanism
journal, March 2015

  • Burke, Michaela S.; Kast, Matthew G.; Trotochaud, Lena
  • Journal of the American Chemical Society, Vol. 137, Issue 10
  • DOI: 10.1021/jacs.5b00281

Heterogeneous Water Oxidation: Surface Activity versus Amorphization Activation in Cobalt Phosphate Catalysts
journal, January 2015

  • González-Flores, Diego; Sánchez, Irene; Zaharieva, Ivelina
  • Angewandte Chemie International Edition, Vol. 54, Issue 8
  • DOI: 10.1002/anie.201409333

Amorphous TiO2 coatings stabilize Si, GaAs, and GaP photoanodes for efficient water oxidation
journal, May 2014


Electrodeposition of Crystalline Co 3 O 4 —A Catalyst for the Oxygen Evolution Reaction
journal, September 2012

  • Koza, Jakub A.; He, Zhen; Miller, Andrew S.
  • Chemistry of Materials, Vol. 24, Issue 18
  • DOI: 10.1021/cm3012205

Atomic Layer Deposition: An Overview
journal, January 2010

  • George, Steven M.
  • Chemical Reviews, Vol. 110, Issue 1, p. 111-131
  • DOI: 10.1021/cr900056b

Electrochemical Water Oxidation with Cobalt-Based Electrocatalysts from pH 0–14: The Thermodynamic Basis for Catalyst Structure, Stability, and Activity
journal, August 2011

  • Gerken, James B.; McAlpin, J. Gregory; Chen, Jamie Y. C.
  • Journal of the American Chemical Society, Vol. 133, Issue 36
  • DOI: 10.1021/ja205647m

Artificial photosynthesis for solar water-splitting
journal, July 2012

  • Tachibana, Yasuhiro; Vayssieres, Lionel; Durrant, James R.
  • Nature Photonics, Vol. 6, Issue 8
  • DOI: 10.1038/nphoton.2012.175

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

Water oxidation by amorphous cobalt-based oxides: in situ tracking of redox transitions and mode of catalysis
journal, January 2015

  • Risch, Marcel; Ringleb, Franziska; Kohlhoff, Mike
  • Energy & Environmental Science, Vol. 8, Issue 2
  • DOI: 10.1039/C4EE03004D

Deposition of β-Co(OH) 2 Films by Electrochemical Reduction of Tris(ethylenediamine)cobalt(III) in Alkaline Solution
journal, April 2013

  • Koza, Jakub A.; Hull, Caleb M.; Liu, Ying-Chau
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm400579k

Atomic Layer Deposition of a Submonolayer Catalyst for the Enhanced Photoelectrochemical Performance of Water Oxidation with Hematite
journal, February 2013

  • Riha, Shannon C.; Klahr, Benjamin M.; Tyo, Eric C.
  • ACS Nano, Vol. 7, Issue 3
  • DOI: 10.1021/nn305639z

Solution-Cast Metal Oxide Thin Film Electrocatalysts for Oxygen Evolution
journal, October 2012

  • Trotochaud, Lena; Ranney, James K.; Williams, Kerisha N.
  • Journal of the American Chemical Society, Vol. 134, Issue 41
  • DOI: 10.1021/ja307507a

p-Type Transparent Conducting Oxide/n-Type Semiconductor Heterojunctions for Efficient and Stable Solar Water Oxidation
journal, July 2015

  • Chen, Le; Yang, Jinhui; Klaus, Shannon
  • Journal of the American Chemical Society, Vol. 137, Issue 30
  • DOI: 10.1021/jacs.5b03536

Enhanced Activity of Gold-Supported Cobalt Oxide for the Electrochemical Evolution of Oxygen
journal, April 2011

  • Yeo, Boon Siang; Bell, Alexis T.
  • Journal of the American Chemical Society, Vol. 133, Issue 14
  • DOI: 10.1021/ja200559j

Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni
journal, January 2011

  • Biesinger, Mark C.; Payne, Brad P.; Grosvenor, Andrew P.
  • Applied Surface Science, Vol. 257, Issue 7, p. 2717-2730
  • DOI: 10.1016/j.apsusc.2010.10.051

Structure Sensitivity of the Oxygen Evolution Reaction Catalyzed by Cobalt(II,III) Oxide
journal, November 2015

  • Plaisance, Craig P.; van Santen, Rutger A.
  • Journal of the American Chemical Society, Vol. 137, Issue 46
  • DOI: 10.1021/jacs.5b07779

570 mV photovoltage, stabilized n-Si/CoO x heterojunction photoanodes fabricated using atomic layer deposition
journal, January 2016

  • Zhou, Xinghao; Liu, Rui; Sun, Ke
  • Energy & Environmental Science, Vol. 9, Issue 3
  • DOI: 10.1039/C5EE03655K

Detection of Single Atoms and Buried Defects in Three Dimensions by Aberration-Corrected Electron Microscope with 0.5-Å Information Limit
journal, September 2008


    Works referencing / citing this record:

    Carbon dioxide electroreduction to C2 products over copper-cuprous oxide derived from electrosynthesized copper complex
    journal, August 2019


    Suppressing Photoinduced Charge Recombination via the Lorentz Force in a Photocatalytic System
    journal, July 2019


    Metal–organic framework-derived integrated nanoarrays for overall water splitting
    journal, January 2018

    • Guan, Cao; Wu, Haijun; Ren, Weina
    • Journal of Materials Chemistry A, Vol. 6, Issue 19
    • DOI: 10.1039/c8ta02528b

    Suppressing Photoinduced Charge Recombination via the Lorentz Force in a Photocatalytic System
    journal, July 2019


    Carbon dioxide electroreduction to C2 products over copper-cuprous oxide derived from electrosynthesized copper complex
    journal, August 2019


    Metal–organic framework-derived integrated nanoarrays for overall water splitting
    journal, January 2018

    • Guan, Cao; Wu, Haijun; Ren, Weina
    • Journal of Materials Chemistry A, Vol. 6, Issue 19
    • DOI: 10.1039/c8ta02528b