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Dual-Band Electrochromism in Hydrous Tungsten Oxide
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    Dual-Band Electrochromism in Hydrous Tungsten Oxide
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    ACS Photonics

    Cite this: ACS Photonics 2023, 10, 9, 3409–3418
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    https://doi.org/10.1021/acsphotonics.3c00921
    Published September 1, 2023
    Copyright © 2023 American Chemical Society

    Abstract

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    The independent modulation of visible and near-infrared light by a single material, termed dual-band electrochromism, is highly desirable for smart windows to enhance the energy efficiency of buildings. Tungsten oxides are commercially important electrochromic materials, exhibiting reversible visible and near-infrared absorption when electrochemically reduced in an electrolyte containing small cations or protons. The presence of structural water in tungsten oxides has been associated with faster electrochromic switching speeds. Here, we find that WO3·H2O, a crystalline hydrate, exhibits dual-band electrochromism unlike the anhydrous WO3. This provides a heretofore unexplored route to tune the electrochromic response of tungsten oxides. Absorption of near-infrared light is achieved at low Li+/e injection, followed by the absorption of visible light at higher Li+/e injection as a result of an electrochemically induced phase transition. We propose that the dual-band modulation is possible due to the more open structure of WO3·H2O as compared to WO3. This facilitates a more extended solid-solution Li+ insertion regime that benefits the modulation of near-infrared radiation via plasmon absorption. Higher degrees of Li+/e insertion lead to polaronic absorption associated with localized charge storage. These results inform how structural factors influence the electrochemically induced spectral response of transition-metal oxides and the important role of structural water beyond optical switching speed.

    Copyright © 2023 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsphotonics.3c00921.

    • The data underlying this study (cyclic voltammetry, X-ray diffraction, Raman spectroscopy, scanning electron microscopy, spectroelectrochemistry, and DFT calculations) are openly available in Zenodo at https://doi.org/10.5281/zenodo.8087655.

    • Survey of literature (Table S1); Pawley refinements of GIXRD patterns of thin films of WO3·H2O, WO3, and the pristine FTO glass substrate (Figure S1); structural characterization (Table S2); DFT-optimized lattice parameters (Table S3); Raman spectroscopy of WO3·H2O and WO3 (Figure S2); laser profilometry of WO3·H2O and WO3 (Figure S3); optical transmittance of WO3·H2O and WO3 (Figures S4 and S5); cyclic voltammetry of WO3·H2O and WO3 (Figures S6, S7, and S10); total charge passed for WO3·H2O and WO3 (Figure S8); areal capacity and coulombic efficiency of WO3·H2O and WO3 (Figure S9); coloration efficiency of WO3·H2O and WO3 (Figure S11); calculated transmittance spectra for WO3 and WO3·H2O (Figures S12 and S13); and calculated joint density of states of WO3·H2O and WO3 (Figure S14) (PDF)

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    Cited By

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    This article is cited by 2 publications.

    1. Benjamin Z. Zydlewski, Delia J. Milliron. Dual-Band Electrochromic Devices Utilizing Niobium Oxide Nanocrystals. ACS Applied Materials & Interfaces 2024, 16 (19) , 24920-24928. https://doi.org/10.1021/acsami.4c02997
    2. Xiaohui Sun, Dong Wang, Wei Wu, Xueying Zhao, Xuyang Zhang, Bo Wang, Xianhui Rong, Guohua Wu, Xiangwei Wang. Amorphous and Crystalline Ti-Doped WO3·2H2O for Dual-Band Electrochromic Smart Windows. ACS Sustainable Chemistry & Engineering 2024, 12 (14) , 5459-5467. https://doi.org/10.1021/acssuschemeng.3c07679

    ACS Photonics

    Cite this: ACS Photonics 2023, 10, 9, 3409–3418
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsphotonics.3c00921
    Published September 1, 2023
    Copyright © 2023 American Chemical Society

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