Hydrodechlorination of Diclofenac in an Aqueous Solution over Pd/ZrO2 and Pd/ZrO2SiO2 Catalysts

Pd/ZrO 2 and Pd/ZrO 2 SiO 2 catalysts prepared by wet impregnation and reduced with H 2 under mild (30°C, aqueous suspension) or harsh (320°C) conditions are compared in the hydrodechlorination of the microecotoxicant diclofenac (DCF) in an aqueous solution at 30°С. According to the TPR and XPS data...

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Veröffentlicht in:Moscow University chemistry bulletin 2024-06, Vol.79 (3), p.156-169
Hauptverfasser: Shishova, V. V., Lokteva, E. S., Maksimov, G. S., Maslakov, K. I., Kaplin, I. Yu, Maksimov, S. V., Golubina, E. V.
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Sprache:eng
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Zusammenfassung:Pd/ZrO 2 and Pd/ZrO 2 SiO 2 catalysts prepared by wet impregnation and reduced with H 2 under mild (30°C, aqueous suspension) or harsh (320°C) conditions are compared in the hydrodechlorination of the microecotoxicant diclofenac (DCF) in an aqueous solution at 30°С. According to the TPR and XPS data, the addition of SiO 2 to the support reduces the degree of metal-support interaction and facilitates the reduction of palladium. Despite the lower Pd 0 fraction, the Pd/ZrO 2 catalyst is more active in the batch reactor: after reduction at 320°С, it slightly, and after mild reduction, significantly (7 times), exceeds Pd/ZrO 2 SiO 2 in catalytic activity. XRD and TEM show a wider size distribution of palladium nanoparticles in the Pd/ZrO 2 sample, while low-temperature N 2 adsorption, XPS, and TPR demonstrated better accessibility of palladium on the Pd/ZrO 2 surface due to the reduced decoration by the support components and increased pore size. These features explain the increased activity of Pd/ZrO 2 . Testing in the flow system demonstrated higher DCF conversion in the presence of catalysts reduced at 320°C and higher stability of Pd/ZrO 2 SiO 2 compared to Pd/ZrO 2 . The stability is ensured by the increased reducibility of Pd 2+ with H 2 and by the developed surface of Pd/ZrO 2 SiO 2 , which prevents deactivation under the action of HCl released in hydrodechlorination.
ISSN:0027-1314
1935-0260
DOI:10.3103/S0027131424700123