In-situ adaptive evolution of rhodium oxide clusters into single atoms via mobile rhodium-adsorbate intermediates

doi:10.1016/S1872-2067(23)64426-2

Abstract

Abstract:

It is a common phenomenon for supported metal catalysts to undergo thermally-induced or adsorbate-induced reconstruction. Great efforts have been devoted to making these reconstruction adaptive to the reaction environment instead of deactivation. Herein, we reported the evolution of initially inactive RhO_x clusters on Al₂O₃ into the formation of catalytically active oxygen vacancies and Rh single atoms via mobile Rh-CO intermediates during hydroformylation of propene. The activated catalyst exhibited a high specific activity of 3.0 × 10⁴ mol mol_Rh^-1 h^-1 towards hydroformylation reaction. Mechanistic studies revealed the evolution paths. Specially, RhO_x clusters were reduced by CO to form oxygen vacancy where the surrounding unsaturated Rh atoms enabled the chemisorption of CO*. Rh atoms that were ejected from RhO_x clusters diffused on Al₂O₃ supports to generate Rh single atom via the formation of carbonyl or geminal dicarbonyl species. Meanwhile, the Rh atoms on clusters were also leached to the solution by the adsorbed CO molecules, followed by partial re-adsorption on the support. This work not only offers an efficient catalyst for propene hydroformylation, but also advances the understandings of dynamic evolution of catalysts.

Key words: Propene hydroformylation, Dynamic evolution, Cluster, Single atom, Reconstruction

Zhengtian Pu, Haibin Yin, Xinlong Ma, Jin Zhao, Jie Zeng. In-situ adaptive evolution of rhodium oxide clusters into single atoms via mobile rhodium-adsorbate intermediates[J]. Chinese Journal of Catalysis, 2023, 48: 247-257.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64426-2

https://www.cjcatal.com/EN/Y2023/V48/I5/247

Figures/Tables 4

Fig. 1. Catalytic properties of Rh/Al2O3 during hydroformylation reaction. (a) Time courses of fresh Rh/Al2O3 and spent Rh/Al2O3. The black line refers to fresh Rh/Al2O3. The red line refers to spent Rh/Al2O3. (b) Product yields of butyraldehyde and isobutyraldehyde over fresh Rh/Al2O3 after different pre-treatments. (c) Specific activities over activated Rh/Al2O3 at different temperatures. (d) Stability tests of activated Rh/Al2O3. Dash line represents to ideal stability. Reaction conditions: 10 mg of catalyst, 10 mL of toluene, 4 bar of propene (6.00 mmol), 30 bar of CO/H2 (1:1). For panels (a), (b), and (d), the temperature was 110 °C. For panels (b), the reaction time was 0.5 h, while the error bar represents the standard deviation obtained from three independent tests. For panel (c), the mass of catalyst and reaction time was listed in Supplementary Table S5. For panel (d), the reaction time was 2 h.

Fig. 2. Structural characterizations. HAADF-STEM images of fresh (a) and activated (b) Rh/Al2O3. (c) Rh 3d XPS spectra of fresh Rh/Al2O3 and activated Rh/Al2O3. Rh K-edge XANES spectra (d) and Rh K-edge EXAFS in R space (e) of fresh Rh/Al2O3 and activated Rh/Al2O3, Rh foil and Rh2O3 were used as a reference. (f) EPR spectra of fresh Rh/Al2O3 after different periods of hydroformylation reaction. Al2O3 was used as a reference.

Fig. 3. Dynamic evolution of Rh/Al2O3 during activation. (a) CO-DRIFTS spectra for fresh Rh/Al2O3 after different in-situ pre-treatment. The samples were treated under corresponding gas and temperature for 30 min, followed by 10% CO/Ar absorption at 30 °C for 15 min, then switching to He to flow for 10 min. Finally, the spectra were obtained at 30 °C. (b) Temperature-and-gas-programming CO-DRIFTS spectra of fresh Rh/Al2O3. Temperature course was on the left (red axes). Rh K-edge XANES spectra (c), magnified absorption edge (d) and Rh K-edge (e) EXAFS in R space of Rh/Al2O3 after 10% CO/Ar treatment at 110 °C for different time. Rh foil and Rh2O3 were used as references.

Fig. 4. Rh trapping studies. CO-DRIFTS spectra for spent Rh/Al2O3 (a), in-situ Rh/Al2O3 (b), in-situ Rh/CeO2 (c), and spent CeO2+Rh/Al2O3 (d). The samples were treated under flowing air at 350 °C for 30 min and cooled down to 110 °C, followed by 10% CO/Ar adsorption for 15 min, then switching to He to flow for 10 min. Finally, the spectra were obtained at 110 °C. Different absorption signals were marked with different color. The region in light blue (Asym) refers to the symmetric stretching vibrations of geminal dicarbonyl Rh(I)-(CO)2 species. The region in blue (Aasym) refers to the asymmetric stretching vibrations of geminal dicarbonyl Rh(I)-(CO)2 species. The region in green (Alin) refers to the linear adsorption of CO.

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