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. 2024 Sep 1;31(Pt 5):1071-1077.
doi: 10.1107/S1600577524004788. Epub 2024 Jul 15.

In situ photodeposition of ultra-small palladium particles on TiO2

Elizaveta Kozyr  1 , Sara Martí-Sánchez  2 , Alina Skorynina  3 , Jordi Arbiol  2 , Carlos Escudero  3 , Lorenzo Mino  1 , Aram Bugaev  4
Affiliations

In situ photodeposition of ultra-small palladium particles on TiO2

Elizaveta Kozyr et al. J Synchrotron Radiat. .

Abstract

In situ and operando investigation of photocatalysts plays a fundamental role in understanding the processes of active phase formation and the mechanisms of catalytic reactions, which is crucial for the rational design of more efficient materials. Using a custom-made operando photocatalytic cell, an in situ procedure to follow the formation steps of Pd/TiO2 photocatalyst by synchrotron-based X-ray absorption spectroscopy (XAS) is proposed. The procedure resulted in the formation of ∼1 nm Pd particles with a much narrower size distribution and homogeneous spreading over TiO2 support compared with the samples generated in a conventional batch reactor. The combination of in situ XAS spectroscopy with high-angle annular dark-field scanning transmission electron microscopy demonstrated the formation of single-atom Pd(0) sites on TiO2 as the initial step of the photodeposition process. Palladium hydride particles were observed for all investigated samples upon exposure to formic acid solutions.

Keywords: Pd/TiO2; XANES; operando spectroscopy; photocatalysis.

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Figures

Figure 1
Figure 1
Schematic (a) and photograph (b) of the operando photocatalytic cell.
Figure 2
Figure 2
XANES (a) and phase-uncorrected FT-EXAFS (b) data collected during in situ photodeposition of palladium on TiO2. Colored lines correspond to different irradiation times. Dashed black and gray lines correspond to the reference H2PdCl4 and Pd foil, respectively.
Figure 3
Figure 3
XANES (a) and phase-uncorrected FT-EXAFS (b) data for the sample, synthesized using a conventional batch procedure, in the initial state (black), after addition of water and formic acid to the photocatalytic cell (red) and after performing UV irradiation and removing the liquid (blue).
Figure 4
Figure 4
STEM characterization of the Pdinsitu sample. Low (a) and high (b) magnification HAADF-STEM images. (c) Histogram of Pd particle size distribution. (d) EDX elemental maps corresponding to the area shown in part (a).
Figure 5
Figure 5
STEM characterization of the Pdbatch sample. Low (a) and high (b) magnification HAADF-STEM images. (c) Histogram of Pd particle size distribution. (d) EDX elemental maps corresponding to the area shown in part (a).
See this image and copyright information in PMC

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