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 H2 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 H2 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 H2 evolution of NiCu nanoparticles are the metallic states of Ni and Cu.

An Operando X-ray Absorption Spectroscopy Study of a NiCu−TiO2 Photocatalyst for H2 Evolution / D. Spanu, A. Minguzzi, S. Recchia, F. Shahvardanfard, O. Tomanec, R. Zboril, P. Schmuki, P. Ghigna, M. Altomare. - In: ACS CATALYSIS. - ISSN 2155-5435. - 10:15(2020 Jul), pp. 8293-8302. [10.1021/acscatal.0c01373]

An Operando X-ray Absorption Spectroscopy Study of a NiCu−TiO2 Photocatalyst for H2 Evolution

A. Minguzzi;M. Altomare
2020

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 H2 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 H2 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 H2 evolution of NiCu nanoparticles are the metallic states of Ni and Cu.
Settore CHIM/02 - Chimica Fisica
lug-2020
Article (author)
File in questo prodotto:
File Dimensione Formato  
60-ACSCat_NiCuTiO2_XASpdf.pdf

accesso riservato

Tipologia: Publisher's version/PDF
Dimensione 3.57 MB
Formato Adobe PDF
3.57 MB Adobe PDF   Visualizza/Apri   Richiedi una copia
ms_R2.pdf

accesso aperto

Tipologia: Pre-print (manoscritto inviato all'editore)
Dimensione 1.22 MB
Formato Adobe PDF
1.22 MB Adobe PDF Visualizza/Apri
Pubblicazioni consigliate

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2434/752737
Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 49
  • ???jsp.display-item.citation.isi??? 47
social impact