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Title: Structure and Orientation of Molecular Wires Embedded in Ultrathin Silica Membrane for Artificial Photosynthesis Elucidated by Polarized FT-IRRAS

Abstract

Surface sensitive infrared spectroscopic methods are employed for elucidating the structure and orientation of charge conducting molecular wires of type oligo(p-phenylenevinylene) covalently anchored on an ultrathin planar Co oxide catalyst surface and embedded in a few nanometer thick amorphous silica membrane. Comparison of polarized FT-IRRAS with nonpolarized grazing angle ATR FT-IR spectra of nanolayer samples supported on a flat Pt surface and transmission spectra of powder samples showed distinct intensity differences for molecular in-plane and out-of-plane modes that reveal the spatial orientation with respect to the oxide surface. All observations support an upright orientation of the molecular wire axis, which is further confirmed by comparison with IRRAS measurements of physisorbed, horizontally positioned wire molecules. The structural integrity of the molecules is maintained after embedding in the silica membrane by plasma-enhanced atomic layer deposition at 40 °C. The results provide the first spectroscopic evidence of perpendicular orientation of the wire molecules. The complementary surface sensitive infrared measurements by FT-IRRAS and grazing angle ATR FT-IR constitute a powerful approach for elucidating the structure and orientation of surface-anchored molecules and the integrity upon casting into oxide layers such as silica for developing artificial photosystems. Use of the nanolayer construct in IRRAS spectroelectrochemical cellmore » configuration will enable in situ monitoring of the structural and orientation integrity of the silica embedded molecular wires under the sustained electron and proton flux conditions of photocatalytic operation.« less

Authors:
 [1];  [1]; ORCiD logo [1]
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  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division; Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
OSTI Identifier:
1560608
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 123; Journal Issue: 31; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Katsoukis, Georgios, Jo, Won Jun, and Frei, Heinz. Structure and Orientation of Molecular Wires Embedded in Ultrathin Silica Membrane for Artificial Photosynthesis Elucidated by Polarized FT-IRRAS. United States: N. p., 2019. Web. doi:10.1021/acs.jpcc.9b02523.
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Katsoukis, Georgios, Jo, Won Jun, & Frei, Heinz. Structure and Orientation of Molecular Wires Embedded in Ultrathin Silica Membrane for Artificial Photosynthesis Elucidated by Polarized FT-IRRAS. United States. https://doi.org/10.1021/acs.jpcc.9b02523
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Katsoukis, Georgios, Jo, Won Jun, and Frei, Heinz. Thu . "Structure and Orientation of Molecular Wires Embedded in Ultrathin Silica Membrane for Artificial Photosynthesis Elucidated by Polarized FT-IRRAS". United States. https://doi.org/10.1021/acs.jpcc.9b02523. https://www.osti.gov/servlets/purl/1560608.
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@article{osti_1560608,
title = {Structure and Orientation of Molecular Wires Embedded in Ultrathin Silica Membrane for Artificial Photosynthesis Elucidated by Polarized FT-IRRAS},
author = {Katsoukis, Georgios and Jo, Won Jun and Frei, Heinz},
abstractNote = {Surface sensitive infrared spectroscopic methods are employed for elucidating the structure and orientation of charge conducting molecular wires of type oligo(p-phenylenevinylene) covalently anchored on an ultrathin planar Co oxide catalyst surface and embedded in a few nanometer thick amorphous silica membrane. Comparison of polarized FT-IRRAS with nonpolarized grazing angle ATR FT-IR spectra of nanolayer samples supported on a flat Pt surface and transmission spectra of powder samples showed distinct intensity differences for molecular in-plane and out-of-plane modes that reveal the spatial orientation with respect to the oxide surface. All observations support an upright orientation of the molecular wire axis, which is further confirmed by comparison with IRRAS measurements of physisorbed, horizontally positioned wire molecules. The structural integrity of the molecules is maintained after embedding in the silica membrane by plasma-enhanced atomic layer deposition at 40 °C. The results provide the first spectroscopic evidence of perpendicular orientation of the wire molecules. The complementary surface sensitive infrared measurements by FT-IRRAS and grazing angle ATR FT-IR constitute a powerful approach for elucidating the structure and orientation of surface-anchored molecules and the integrity upon casting into oxide layers such as silica for developing artificial photosystems. Use of the nanolayer construct in IRRAS spectroelectrochemical cell configuration will enable in situ monitoring of the structural and orientation integrity of the silica embedded molecular wires under the sustained electron and proton flux conditions of photocatalytic operation.},
doi = {10.1021/acs.jpcc.9b02523},
journal = {Journal of Physical Chemistry. C},
number = 31,
volume = 123,
place = {United States},
year = {Thu Jul 18 00:00:00 EDT 2019},
month = {Thu Jul 18 00:00:00 EDT 2019}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.9b02523
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Cited by: 6 works
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Figures / Tables:

Figure 1 Figure 1: Sample geometry for FT-IRRAS (left) and GATR FT-IR measurement configurations (right) for a Si/Pt/Co3O4 sample with PV3 embedded in SiO2.
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Works referenced in this record:

Visible Light-Induced Hole Injection into Rectifying Molecular Wires Anchored on Co 3 O 4 and SiO 2 Nanoparticles
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Heterobinuclear Light Absorber Coupled to Molecular Wire for Charge Transport across Ultrathin Silica Membrane for Artificial Photosynthesis
journal, August 2018

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Ultrathin oxide layers for nanoscale integration of molecular light absorbers, catalysts, and complete artificial photosystems
journal, January 2019

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  • The Journal of Chemical Physics, Vol. 150, Issue 4
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Ultrafast Charge Transfer between Light Absorber and Co 3 O 4 Water Oxidation Catalyst across Molecular Wires Embedded in Silica Membrane
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    Works referencing / citing this record:

    Ultrathin Amorphous Silica Membrane Enhances Proton Transfer across Solid‐to‐Solid Interfaces of Stacked Metal Oxide Nanolayers while Blocking Oxygen
    journal, February 2020

    • Jo, Won Jun; Katsoukis, Georgios; Frei, Heinz
    • Advanced Functional Materials, Vol. 30, Issue 12
    • DOI: 10.1002/adfm.201909262
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      Figures / Tables found in this record:

      Figure 1 (p. 32)figure
      Figure 2 (p. 33)figure
      Figure 3 (p. 34)figure
      Figure 4 (p. 35)figure
      Figure 5 (p. 36)figure
      Figure 6 (p. 37)figure
      Figure 7 (p. 38)figure
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