Size-dependent strong metal-support interaction modulation of Pt/CoFe2O4 catalysts

doi:10.1016/S1872-2067(24)60208-1

Abstract

Abstract:

Supported metal catalysts are the backbone of heterogeneous catalysis, playing a crucial role in the modern chemical industry. Metal-support interactions (MSIs) are known important in determining the catalytic performance of supported metal catalysts. This is particularly true for single-atom catalysts (SACs) and pseudo-single-atom catalysts (pseudo-SACs), where all metal atoms are dispersed on, and interact directly with the support. Consequently, the MSI of SACs and pseudo-SACs are theoretically more sensitive to modulation compared to that of traditional nanoparticle catalysts. In this work, we experimentally demonstrated this hypothesis by an observed size-dependent MSI modulation. We fabricated CoFe₂O₄ supported Pt pseudo-SACs and nanoparticle catalysts, followed by a straightforward water treatment process. It was found that the covalent strong metal-support interaction (CMSI) in pseudo-SACs can be weakened, leading to a significant activity improvement in methane combustion reaction. This finding aligns with our recent observation of CoFe₂O₄ supported Pt SACs. By contrast, the MSI in Pt nanoparticle catalyst was barely affected by the water treatment, giving rise to almost unchanged catalytic performance. This work highlights the critical role of metal size in determining the MSI modulation, offering a novel strategy for tuning the catalytic performance of SACs and pseudo-SACs by fine-tuning their MSIs.

Key words: Strong metal-support interaction, Single-atom catalyst, Pseudo-single-atom catalyst, Size dependence, Pt/CoFe₂O₄ catalyst

Yangyang Li, Jingyi Yang, Botao Qiao, Tao Zhang. Size-dependent strong metal-support interaction modulation of Pt/CoFe₂O₄ catalysts[J]. Chinese Journal of Catalysis, 2025, 69: 292-302.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60208-1

https://www.cjcatal.com/EN/Y2025/V69/I2/292

Figures/Tables 7

Fig. 1. (a,c) The AC-HAADF-STEM images of Ptn/CoFe2O4 and Ptn/CoFe2O4-w; (b,d) The size distribution of Ptn/CoFe2O4 and Ptn/CoFe2O4-w; (e,g) The TEM images of PtNP/CoFe2O4 and PtNP/CoFe2O4-w; (f,h) The size distribution of PtNP/CoFe2O4 and PtNP/CoFe2O4-w.

Fig. 2. (a,b) The CO-DRIFT spectra of Ptn/CoFe2O4 and PtNP/CoFe2O4 catalysts before and after water treatment. (c,d) The low temperature CO-DRIFT spectra of Ptn/CoFe2O4 and Ptn/CoFe2O4-w.

Fig. 3. The H2-TPR profile of CoFe2O4 (a), Ptn/CoFe2O4 (b), and PtNP/CoFe2O4 (c) before and after water treatment.

Fig. 4. The Pt 4f XPS spectra of Ptn/CoFe2O4 (a) and PtNP/CoFe2O4 (b) before and after water treatment.

Fig. 5. (a) Catalytic activity of methane combustion over Ptn/CoFe2O4 and PtNP/CoFe2O4 before and after water treatment. (b) The CH4-TPSR over Ptn/CoFe2O4 and Ptn/CoFe2O4-w. (c) CO oxidation of Ptn/CoFe2O4 and Ptn/CoFe2O4-w.

Fig. 6. (a) CH4 conversion profile of stability test of Ptn/CoFe2O4-w at 350 °C with water soak treatment. (b) The stability test of Ptn/CoFe2O4 at 350 °C with or without 2 vol% or 10 vol% steam. The reaction conditions: 0.5 vol%CH4, 20 vol%O2, and balanced with N2, GHSV = 39600 mL/(gcat·h).

Fig. 7. The 18O2 isotope labeling experiments of Ptn/CoFe2O4 (a) and PtNP/CoFe2O4 (b) before and after water treatment. The reaction conditions: 0.5 vol% CH4, 20 vol% 18O2/16O2, and He balanced, GHSV = 36000 mL/(gcat·h).

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Size-dependent strong metal-support interaction modulation of Pt/CoFe₂O₄ catalysts

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