Heterobinuclear Light Absorber Coupled to Molecular Wire for Charge Transport across Ultrathin Silica Membrane for Artificial Photosynthesis
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Coupling of robust, all-inorganic heterobinuclear light absorbers to metal oxide catalysts for water oxidation across an ultrathin product-separating silica membrane requires charge transfer through organic molecular wires embedded in the silica. A synthetic approach for assembling the bimetallic units on the silica surface is introduced that is compatible with the presence of encapsulated organic molecules. Accurate selection and fine tuning of the concentration of embedded conducting wires are enabled by a two-step method consisting of surface attachment of a tripodal anchor, trimethoxysilyl aniline, followed by attachment of p-oligo(phenylene vinylene) through amide linkage. Each step of the assembly process was monitored and characterized by a combination of Fourier transform infrared, Fourier transform-Raman, and UV-vis spectroscopy techniques. Hole transfer was observed from transient CoIII, formed by TiIVOCoII → TiIIIOCoIII charge transfer excitation of the chromophore, to p-oligo(phenylene vinylene) molecule within the 8 ns width of the photolysis laser pulse by transient optical absorption spectroscopy of the wire radical cation. The rectifying property of the light absorber-wire assembly enabled by appropriate selection of redox potentials of metals and embedded wire obviates the need for a molecularly defined linkage between the components. Combined with the previously observed ultrafast hole injection from the embedded wires to Co oxide catalyst, the result implies visible-light-induced hole transfer from visible-light-excited binuclear light absorber to water oxidation catalyst across the silica separation membrane in a few nanoseconds or faster. Finally, demonstration and understanding of this interfacial charge-transfer step is critical for developing nanoscale core-shell architectures for complete photosynthetic cycles.
- Research Organization:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
- Grant/Contract Number:
- AC02-05CH11231; KA 4403/1-1
- OSTI ID:
- 1786329
- Journal Information:
- ACS Applied Materials and Interfaces, Vol. 10, Issue 37; ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)Copyright Statement
- Country of Publication:
- United States
- Language:
- English
Ultrathin Amorphous Silica Membrane Enhances Proton Transfer across Solid‐to‐Solid Interfaces of Stacked Metal Oxide Nanolayers while Blocking Oxygen
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journal | February 2020 |
Ultrathin oxide layers for nanoscale integration of molecular light absorbers, catalysts, and complete artificial photosystems
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journal | January 2019 |
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