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Facet-engineered TiO₂ drives photocatalytic activity and stability of supported noble metal clusters during H₂ evolution.

ABSTRACT: Metal clusters supported on TiO₂ are widely used in many photocatalytic applications, including pollution control and production of solar fuels. Besides high photoactivity, stability during the photoreaction is another essential quality of high-performance photocatalysts, however systematic studies on this attribute are absent for metal clusters supported on TiO₂. Here we have studied, both experimentally and with first-principles simulation methods, the stability of Pt, Pd and Au clusters prepared by ball milling on nanoshaped anatase nanoparticles preferentially exposing {001} (plates) and {101} (bipyramids) facets during the photogeneration of hydrogen. It is found that Pt/TiO₂ exhibits superior stability than Pd/TiO₂ and Au/TiO₂, and that {001} facet-based photocatalysts always are more stable than their {101} analogous regardless of the considered metal species. The loss of stability associated with cluster sintering, which is facilitated by the transfer of photoexcited carriers from the metal species to the neighbouring Ti and O atoms, most significantly and detrimentally affects the H₂-evolution photoactivity.

SUBMITTER: Chen Y

PROVIDER: S-EPMC10547715 | biostudies-literature | 2023 Oct

REPOSITORIES: biostudies-literature

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Facet-engineered TiO2 drives photocatalytic activity and stability of supported noble metal clusters during H2 evolution.

Chen Yufen Y Soler Lluís L Cazorla Claudio C Oliveras Jana J Bastús Neus G NG Puntes Víctor F VF Llorca Jordi J

Nature communications 20231003 1

Metal clusters supported on TiO2 are widely used in many photocatalytic applications, including pollution control and production of solar fuels. Besides high photoactivity, stability during the photoreaction is another essential quality of high-performance photocatalysts, however systematic studies on this attribute are absent for metal clusters supported on TiO2. Here we have studied, both experimentally and with first-principles simulation methods, the stability of Pt, Pd ...[more]

PMID: 37789037

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Project description:A series of facet-engineered TiO2/BaFe12O19 composites were synthesized through hydrothermal growth of both phases and subsequent deposition of the different, faceted TiO2 nanoparticles onto BaFe12O19 microplates. The well-defined geometry of the composite and uniaxial magnetic anisotropy of the ferrite allowed alternate interfaces between both phases and fixed the orientation between the TiO2 crystal structure and the remanent magnetic field within BaFe12O19. The morphology and crystal structure of the composites were confirmed by a combination of scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses together with the detailed study of BaFe12O19 electronic and magnetic properties. The photocatalytic activity and magnetic field effect were studied in the reaction of phenol degradation for TiO2/BaFe12O19 and composites of BaFe12O19 covered with a SiO2 protective layer and TiO2. The observed differences in phenol degradation are associated with electron transfer and the contribution of the magnetic field. All obtained magnetic composite materials can be easily separated in an external magnetic field, with efficiencies exceeding 95%, and recycled without significant loss of photocatalytic activity. The highest activity was observed for the composite of BaFe12O19 with TiO2 exposing {1 0 1} facets. However, to prevent electron transfer within the composite structure, this photocatalyst material was additionally coated with a protective SiO2 layer. Furthermore, TiO2 exposing {1 0 0} facets exhibited significant synergy with the BaFe12O19 magnetic field, leading to 2 times higher photocatalytic activity when ferrite was magnetized before the process. The photoluminescence emission study suggests that for this particular combination, the built-in magnetic field of the ferrite suppressed the recombination of the photogenerated charge carriers. Ultimately, possible effects of complex electro/magnetic interactions within the magnetic photocatalyst are shown and discussed for the first time, including the anisotropic properties of both phases.

Dataset Information

Facet-engineered TiO₂ drives photocatalytic activity and stability of supported noble metal clusters during H₂ evolution.

Publications

Facet-engineered TiO<sub>2</sub> drives photocatalytic activity and stability of supported noble metal clusters during H<sub>2</sub> evolution.

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