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Title: End-On Bound Iridium Dinuclear Heterogeneous Catalysts on WO3 for Solar Water Oxidation

Abstract

Heterogeneous catalysts with atomically defined active centers hold great promise for high-performance applications. Among them, catalysts featuring active moieties with more than one metal atom are important for chemical reactions that require synergistic effects but are rarer than single atom catalysts (SACs). The difficulty in synthesizing such catalysts has been a key challenge. Recent progress in preparing dinuclear heterogeneous catalysts (DHCs) from homogeneous molecular precursors has provided an effective route to address this challenge. Nevertheless, only side-on bound DHCs, where both metal atoms are affixed to the supporting substrate, have been reported. The competing end-on binding mode, where only one metal atom is attached to the substrate and the other metal atom is dangling, has been missing. Here, we report the first observation that end-on binding is indeed possible for Ir DHCs supported on WO3. Unambiguous evidence supporting the binding mode was obtained by in situ diffuse reflectance infrared Fourier transform spectroscopy and high-angle annular dark-field scanning transmission electron microscopy. Density functional theory calculations provide additional support for the binding mode, as well as insights into how end-on bound DHCs may be beneficial for solar water oxidation reactions. The results have important implications for future studies of highly effective heterogeneousmore » catalysts for complex chemical reactions.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [1]; ORCiD logo [1];  [3];  [1];  [5];  [4]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]
+ Show Author Affiliations
  1. Boston College, Chestnut Hill, MA (United States). Dept. of Chemistry. Merkert Chemistry Center
  2. Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering and Materials Science
  3. Yale Univ., New Haven, CT (United States). Yale Energy Sciences Inst. Dept. of Chemistry
  4. Tufts Univ., Medford, MA (United States). Dept. of Chemical and Biological Engineering
  5. Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering and Materials Science. Dept. of Physics and Astronomy
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Tufts Univ., Medford, MA (United States); Univ. of California, Irvine, CA (United States); Boston College, Chestnut Hill, MA (United States); Yale Univ., New Haven, CT (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1498669
Grant/Contract Number:  
FG02-05ER15730; SC0001059; FG02-05ER46237; CBET 1703663; 1703655
Resource Type:
Accepted Manuscript
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 4; Journal Issue: 9; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhao, Yanyan, Yan, Xingxu, Yang, Ke R., Cao, Sufeng, Dong, Qi, Thorne, James E., Materna, Kelly L., Zhu, Shasha, Pan, Xiaoqing, Flytzani-Stephanopoulos, Maria, Brudvig, Gary W., Batista, Victor S., and Wang, Dunwei. End-On Bound Iridium Dinuclear Heterogeneous Catalysts on WO3 for Solar Water Oxidation. United States: N. p., 2018. Web. doi:10.1021/acscentsci.8b00335.
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Zhao, Yanyan, Yan, Xingxu, Yang, Ke R., Cao, Sufeng, Dong, Qi, Thorne, James E., Materna, Kelly L., Zhu, Shasha, Pan, Xiaoqing, Flytzani-Stephanopoulos, Maria, Brudvig, Gary W., Batista, Victor S., & Wang, Dunwei. End-On Bound Iridium Dinuclear Heterogeneous Catalysts on WO3 for Solar Water Oxidation. United States. doi:10.1021/acscentsci.8b00335.
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Zhao, Yanyan, Yan, Xingxu, Yang, Ke R., Cao, Sufeng, Dong, Qi, Thorne, James E., Materna, Kelly L., Zhu, Shasha, Pan, Xiaoqing, Flytzani-Stephanopoulos, Maria, Brudvig, Gary W., Batista, Victor S., and Wang, Dunwei. Wed . "End-On Bound Iridium Dinuclear Heterogeneous Catalysts on WO3 for Solar Water Oxidation". United States. doi:10.1021/acscentsci.8b00335. https://www.osti.gov/servlets/purl/1498669.
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@article{osti_1498669,
title = {End-On Bound Iridium Dinuclear Heterogeneous Catalysts on WO3 for Solar Water Oxidation},
author = {Zhao, Yanyan and Yan, Xingxu and Yang, Ke R. and Cao, Sufeng and Dong, Qi and Thorne, James E. and Materna, Kelly L. and Zhu, Shasha and Pan, Xiaoqing and Flytzani-Stephanopoulos, Maria and Brudvig, Gary W. and Batista, Victor S. and Wang, Dunwei},
abstractNote = {Heterogeneous catalysts with atomically defined active centers hold great promise for high-performance applications. Among them, catalysts featuring active moieties with more than one metal atom are important for chemical reactions that require synergistic effects but are rarer than single atom catalysts (SACs). The difficulty in synthesizing such catalysts has been a key challenge. Recent progress in preparing dinuclear heterogeneous catalysts (DHCs) from homogeneous molecular precursors has provided an effective route to address this challenge. Nevertheless, only side-on bound DHCs, where both metal atoms are affixed to the supporting substrate, have been reported. The competing end-on binding mode, where only one metal atom is attached to the substrate and the other metal atom is dangling, has been missing. Here, we report the first observation that end-on binding is indeed possible for Ir DHCs supported on WO3. Unambiguous evidence supporting the binding mode was obtained by in situ diffuse reflectance infrared Fourier transform spectroscopy and high-angle annular dark-field scanning transmission electron microscopy. Density functional theory calculations provide additional support for the binding mode, as well as insights into how end-on bound DHCs may be beneficial for solar water oxidation reactions. The results have important implications for future studies of highly effective heterogeneous catalysts for complex chemical reactions.},
doi = {10.1021/acscentsci.8b00335},
journal = {ACS Central Science},
number = 9,
volume = 4,
place = {United States},
year = {2018},
month = {7}
}
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Journal Article:
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DOI:  10.1021/acscentsci.8b00335
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Cited by: 20 works
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Figures / Tables:

Figure 1 Figure 1: Schematics of our synthesis strategy for side-on and end-on bound DHCs. Starting from molecular dinuclear precursors, the catalyst is first adsorbed onto a substrate, and then the organic ligands are removed by photochemical treatments. The binding mode is defined by the structure of the substrate. When dual bindingmore » sites with the suitable density and distance are available (such as on Fe2O3, panel A), a side-on mode is preferred. Otherwise, the end-on mode is preferred (such as on WO3, panel B).« less
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Works referencing / citing this record:

Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis
journal, January 2019

  • Bartlett, Stuart A.; Sackville, Emma V.; Gibson, Emma K.
  • Chemical Communications, Vol. 55, Issue 54
  • DOI: 10.1039/c9cc02088h

Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis
journal, January 2019

  • Bartlett, Stuart A.; Sackville, Emma V.; Gibson, Emma K.
  • Chemical Communications, Vol. 55, Issue 54
  • DOI: 10.1039/c9cc02088h

Water Oxidation Catalysts for Artificial Photosynthesis
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Hybrid Photoelectrochemical Water Splitting Systems: From Interface Design to System Assembly
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Atom‐by‐Atom Resolution of Structure–Function Relations over Low‐Nuclearity Metal Catalysts
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  • Vorobyeva, Evgeniya; Fako, Edvin; Chen, Zupeng
  • Angewandte Chemie, Vol. 131, Issue 26
  • DOI: 10.1002/ange.201902136

Atom‐by‐Atom Resolution of Structure–Function Relations over Low‐Nuclearity Metal Catalysts
journal, June 2019

  • Vorobyeva, Evgeniya; Fako, Edvin; Chen, Zupeng
  • Angewandte Chemie International Edition, Vol. 58, Issue 26
  • DOI: 10.1002/anie.201902136

Recent Advances in the Development of Molecular Catalyst‐Based Anodes for Water Oxidation toward Artificial Photosynthesis
journal, November 2018

  • Zahran, Zaki N.; Tsubonouchi, Yuta; Mohamed, Eman A.
  • ChemSusChem, Vol. 12, Issue 9
  • DOI: 10.1002/cssc.201802795

Mono‐/Multinuclear Water Oxidation Catalysts
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Highly reversible photochromism in composite WO3/nanocellulose films
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Fuels and energy carriers from single-site catalysts prepared via surface organometallic chemistry
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Thin film photoelectrodes for solar water splitting
journal, January 2019

  • He, Yumin; Hamann, Thomas; Wang, Dunwei
  • Chemical Society Reviews, Vol. 48, Issue 7
  • DOI: 10.1039/c8cs00868j

Artificial photosynthesis: opportunities and challenges of molecular catalysts
journal, January 2019

  • Zhang, Biaobiao; Sun, Licheng
  • Chemical Society Reviews, Vol. 48, Issue 7
  • DOI: 10.1039/c8cs00897c

Energy transfer on a two-dimensional antenna enhances the photocatalytic activity of CO 2 reduction by metal–organic layers
journal, January 2019

  • Hu, Xuefu; Chen, Peican; Zhang, Cankun
  • Chemical Communications, Vol. 55, Issue 65
  • DOI: 10.1039/c9cc04594e

Selectivity of H 2 O 2 and O 2 by water oxidation on metal oxide surfaces
journal, January 2019

  • Zhu, Shasha; Zhao, Yanyan; He, Yumin
  • The Journal of Chemical Physics, Vol. 150, Issue 4
  • DOI: 10.1063/1.5046886

Surface chemistry and photoelectrochemistry—Case study on tantalum nitride
journal, October 2019

  • He, Yumin; Chen, Rong; Fa, Wenjun
  • The Journal of Chemical Physics, Vol. 151, Issue 13
  • DOI: 10.1063/1.5122996
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