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Photoelectrochemical Performance of the Ag(III)-Based Oxygen-Evolving Catalyst

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Dipartimento di Chimica, Università degli Studi di Torino, via Pietro Giuria 5, 10125 Torino, Italy
*E-mail: [email protected]. Tel.: +39 011 670 8449. Fax: +39 011 670 5242.
Cite this: ACS Appl. Mater. Interfaces 2017, 9, 28, 23800–23809
Publication Date (Web):June 29, 2017
https://doi.org/10.1021/acsami.7b05901
Copyright © 2017 American Chemical Society
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Abstract

We report the electrosynthesis of a water oxidation catalyst based on Ag oxides (AgCat). The deposited AgCat is composed of mixed valence crystalline Ag oxides with the presence of particle aggregates whose size is ∼1 μm. This catalyst, coupled with TiO2 and hematite, and under photoelectrochemical conditions, substantially increases photocurrents in a wide range of applied potentials compared with bare and Co-Pi-modified photocatalysts. AgCat can sustain current densities comparable with other water oxidation catalysts. Dark bulk electrolysis demonstrated that AgCat is stable and can sustain high turnover number in operative conditions. Oxygen evolution from water occurs in mild conditions: pH = 2–13, room temperature and pressure, and moderate overpotentials (600 mV) compatible with the coupling with semiconducting oxides as sensitizers. Using hematite in sustained electrolysis O2 production is significant, both in the dark and under irradiation, after an initial slow induction time in which modification of surface species occurs.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.7b05901.

  • pH-Eh diagrams for Ag in the presence of sulfate; optimization of the current density as a function of electrosynthesis time and potential obtained through an experimental design approach, chronopotentiometry, and cyclic voltammetry of pristine TiO2 electrodes; anodic LSV of TiO2-Co-Pi; linear sweep voltammetry and O2 production rates of electrodeposited α-Fe2O3, α-Fe2O3(PRED), and α-Fe2O3(PRED)-Co-Pi in the dark and under irradiation; current density and O2 evolution rate as functions of the time for α-Fe2O3(PRED); O2 production rate and faradaic efficiency in the dark and under irradiation for bare and AgCat-modified α-Fe2O3 electrodes; LSVs and ATR-FTIR spectra of α-Fe2O3(PRED) electrodes; LSV of AgCat on ITO; and overpotential values for water oxidation and photocurrent density for TiO2 and hematite electrodes (PDF)

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