An Operando X-ray Absorption Spectroscopy Study of a NiCu-TiO2 Photocatalyst for H-2 Evolution

Spanu D, Minguzzi A, Recchia S, Shahvaranfard F, Tomanec O, Zboril R, Schmuki P, Ghigna P, Altomare M (2020)

Publication Type: Journal article

Publication year: 2020

Journal

ACS Catalysis American Chemical Society

Book Volume: 10

Pages Range: 8293-8302

Journal Issue: 15

DOI: 10.1021/acscatal.0c01373

Abstract

Cu- or Ni-decorated semiconductors represent a potential low-cost alternative to noble-metal-modified photocatalysts. Even more effective are bimetallic NiCu nanoparticles, which can provide a remarkable photocatalytic H-2 evolution enhancement compared to single-element Cu or Ni systems. The main concern of such alloyed co-catalysts is their activity with respect to alteration of their elemental composition and oxidation state over reaction time. Ex situ characterization techniques provide controversial interpretations of the co-catalytic role of the individual elements. Hypotheses such as the in situ reduction of "native" Ni or Cu species during photocatalysis, the oxidation of metallic Cu or Ni into oxides or hydroxides, or the formation of p-n junctions or core/shell structures have been proposed. Herein, we present an operando X-ray absorption spectroscopy study of a NiCu-TiO2 system under UV light illumination in ethanol-water solutions, i.e., under photocatalytic H-2 evolution conditions. The experimental approach allows for monitoring in real time chemical changes that take place in the co-catalyst under intermittent illumination, i.e., under light on-off cycles. We show that while Ni and Cu are partially oxidized in the as-formed NiCu co-catalyst (air-formed surface oxides or hydroxides) and undergo partial dissolution in the liquid phase under dark conditions, such Ni and Cu oxidized and dissolved species are reduced/redeposited as a bimetallic NiCu phase at the TiO2 surface under illumination. The dissolution/redeposition mechanism is triggered by TiO2 conduction band electrons. We not only prove a UV-light-induced healing of the NiCu co-catalyst but also unambiguously demonstrate that the species responsible for the strongly enhanced photocatalytic H-2 evolution of NiCu nanoparticles are the metallic states of Ni and Cu.

Authors with CRIS profile

Fahimeh Shahvaranfard Lehrstuhl für Werkstoffwissenschaften (Korrosion und Oberflächentechnik) Patrik Schmuki Lehrstuhl für Werkstoffwissenschaften (Korrosion und Oberflächentechnik) Marco Altomare Lehrstuhl für Werkstoffwissenschaften (Korrosion und Oberflächentechnik)

Involved external institutions

Palacky University Olomouc / Univerzita Palackého v Olomouci CZ Czech Republic (CZ) Università degli Studi di Pavia IT Italy (IT) Università degli studi di Milano IT Italy (IT) University of Insubria / Università degli Studi dell'Insubria IT Italy (IT)

How to cite

APA:

Spanu, D., Minguzzi, A., Recchia, S., Shahvaranfard, F., Tomanec, O., Zboril, R.,... Altomare, M. (2020). An Operando X-ray Absorption Spectroscopy Study of a NiCu-TiO2 Photocatalyst for H-2 Evolution. ACS Catalysis, 10(15), 8293-8302. https://dx.doi.org/10.1021/acscatal.0c01373

MLA:

Spanu, Davide, et al. "An Operando X-ray Absorption Spectroscopy Study of a NiCu-TiO2 Photocatalyst for H-2 Evolution." ACS Catalysis 10.15 (2020): 8293-8302.

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