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

Journal Article · · ACS Central Science
 [1];  [2];  [3];  [4];  [5];  [5];  [3];  [5];  [6];  [4];  [3];  [3];  [5]
  1. Boston College, Chestnut Hill, MA (United States). Dept. of Chemistry. Merkert Chemistry Center; Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, United States
  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. Boston College, Chestnut Hill, MA (United States). Dept. of Chemistry. Merkert Chemistry Center
  6. Univ. of California, Irvine, CA (United States). Dept. of Chemical Engineering and Materials Science. Dept. of Physics and Astronomy
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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.
Research Organization:
Boston College, Chestnut Hill, MA (United States); 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); Yale Univ., New Haven, CT (United States)
Sponsoring Organization:
National Science Foundation (NSF) (United States); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
FG02-05ER15730; FG02-05ER46237; SC0001059
OSTI ID:
1498669
Journal Information:
ACS Central Science, Journal Name: ACS Central Science Journal Issue: 9 Vol. 4; ISSN 2374-7943
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (16)

Water Oxidation Catalysts for Artificial Photosynthesis journal July 2019
Hybrid Photoelectrochemical Water Splitting Systems: From Interface Design to System Assembly journal June 2019
Atom‐by‐Atom Resolution of Structure–Function Relations over Low‐Nuclearity Metal Catalysts journal May 2019
Atom‐by‐Atom Resolution of Structure–Function Relations over Low‐Nuclearity Metal Catalysts journal June 2019
Recent Advances in the Development of Molecular Catalyst‐Based Anodes for Water Oxidation toward Artificial Photosynthesis journal November 2018
Mono‐/Multinuclear Water Oxidation Catalysts journal June 2019
Enhanced Photoelectrochemical Performance of WO 3 ‐Based Composite Photoanode Coupled with Carbon Quantum Dots and NiFe Layered Double Hydroxide journal September 2019
Highly reversible photochromism in composite WO3/nanocellulose films journal September 2019
Fuels and energy carriers from single-site catalysts prepared via surface organometallic chemistry journal November 2019
Immobilization of a molecular cobalt cubane catalyst on porous BiVO 4 via electrochemical polymerization for efficient and stable photoelectrochemical water oxidation journal January 2019
Thin film photoelectrodes for solar water splitting journal January 2019
Artificial photosynthesis: opportunities and challenges of molecular catalysts journal January 2019
Evidence for tetranuclear bis-μ-oxo cubane species in molecular iridium-based water oxidation catalysts from XAS analysis journal January 2019
Energy transfer on a two-dimensional antenna enhances the photocatalytic activity of CO 2 reduction by metal–organic layers journal January 2019
Selectivity of H 2 O 2 and O 2 by water oxidation on metal oxide surfaces journal January 2019
Surface chemistry and photoelectrochemistry—Case study on tantalum nitride journal October 2019

Figures / Tables (4)

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Stable iridium dinuclear heterogeneous catalysts supported on metal-oxide substrate for solar water oxidation
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY