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Chromophore-Catalyst Assembly for Water Oxidation Prepared by Atomic Layer Deposition

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [1];  [1];  [1];  [2];  [1];  [1];  [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States)
  2. Univ. of North Carolina, Chapel Hill, NC (United States); Daegu Univ. (Korea)
+ Show Author Affiliations
Visible-light-driven water splitting was explored in a dye sensitized photoelectrosynthesis cell (DSPEC) based on a photoanode with a phosphonic acid-derivatized donor–π–acceptor (D–π–A) organic chromophore, 1, and the water oxidation catalyst [Ru(bda)(4-O(CH2)3P(O3H2)2-pyr)2], 2, (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate). The photoanode was prepared by using a layering strategy beginning with the organic dye anchored to an FTO|core/shell electrode, atomic layer deposition (ALD) of a thin layer (<1 nm) of TiO2, and catalyst binding through phosphonate linkage to the TiO2 layer. Device performance was evaluated by photocurrent measurements for core/shell photoanodes, with either SnO2 or nanoITO core materials, in acetate-buffered, aqueous solutions at pH 4.6 or 5.7. The absolute magnitudes of photocurrent changes with the core material, TiO2 spacer layer thickness, or pH, observed photocurrents were 2.5-fold higher in the presence of catalyst. The findings of transient absorption measurements and DFT calculations reflect that electron injection by the photoexcited organic dye is ultrafast promoted by electronic interactions enabled by orientation of the dye’s molecular orbitals on the electrode surface. Rapid injection is followed by recombination with the oxidized dye which is 95% complete by 1.5 ns. While chromophore decomposition limits the efficiency of the DSPEC devices toward O2 production, the flexibility of the strategy presented here offers a new approach to photoanode design.
Research Organization:
Univ. of North Carolina, Chapel Hill, NC (United States). Energy Frontier Research Center (EFRC) Center for Solar Fuels (UNC EFRC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0001011
OSTI ID:
1469971
Journal Information:
ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 44 Vol. 9; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (9)

A Noble-Metal-Free Heterogeneous Photosensitizer-Relay Catalyst Triad That Catalyzes Water Oxidation under Visible Light journal December 2018
A Robust, Precious‐Metal‐Free Dye‐Sensitized Photoanode for Water Oxidation: A Nanosecond‐Long Excited‐State Lifetime through a Prussian Blue Analogue journal February 2020
Innenrücktitelbild: A Robust, Precious‐Metal‐Free Dye‐Sensitized Photoanode for Water Oxidation: A Nanosecond‐Long Excited‐State Lifetime through a Prussian Blue Analogue (Angew. Chem. 10/2020) journal February 2020
A Noble‐Metal‐Free Heterogeneous Photosensitizer‐Relay Catalyst Triad That Catalyzes Water Oxidation under Visible Light journal November 2018
A Robust, Precious‐Metal‐Free Dye‐Sensitized Photoanode for Water Oxidation: A Nanosecond‐Long Excited‐State Lifetime through a Prussian Blue Analogue journal February 2020
Inside Back Cover: A Robust, Precious‐Metal‐Free Dye‐Sensitized Photoanode for Water Oxidation: A Nanosecond‐Long Excited‐State Lifetime through a Prussian Blue Analogue (Angew. Chem. Int. Ed. 10/2020) journal February 2020
Ultrathin oxide layers for nanoscale integration of molecular light absorbers, catalysts, and complete artificial photosystems journal January 2019
Stabilized photoanodes for water oxidation by integration of organic dyes, water oxidation catalysts, and electron-transfer mediators journal August 2018
Inorganic Photochemistry and Solar Energy Harvesting: Current Developments and Challenges to Solar Fuel Production journal January 2019

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Related Subjects

14 SOLAR ENERGY
36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
42 ENGINEERING
D−π−A organic dye
artificial photosynthesis
core/shell
dye sensitized photoelectrosynthesis cell
electron transfer
transient absorption
water splitting