Surface dynamics of Rh/Al2O3 during propane dehydrogenation

doi:10.1016/S1872-2067(24)60063-X

Abstract

Abstract:

The surface structures of heterogeneous catalysts significantly impact catalytic performance, especially for structure-sensitive reactions. In this study, we employed surface techniques such as low-energy ion scattering spectroscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy with CO as a probe (CO-FTIR) to investigate the surface dynamics of Rh/Al₂O₃ catalysts for propane dehydrogenation (PDH). We observed a notable induction process for PDH on Rh/Al₂O₃ catalysts, marked by significant variations in propane conversion, methane, and propylene selectivities. These changes were attributed to substantial coke formation. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy) and CO-FTIR revealed the coexistence of Rh nanoparticles, clusters, and single atoms on the surface. Through various dynamic quasi in-situ characterizations, we found that coke preferentially covered Rh clusters, thereby inhibiting C-C bond breaking and methane formation. Meanwhile, Rh single atoms were less affected by coke coverage and remained exposed as active and selective sites for PDH, favoring propylene production. This work underscores the sensitivity of PDH to the sizes of Rh species, with isolated Rh single atoms promoting propylene formation.

Key words: Propane dehydrogenation, Rhodium, Coke, Single atom, Quasi in-situ spectroscopy, Surface dynamics

Shuyi Li, Changle Mu, Nianqiu He, Jie Xu, Yanping Zheng, Mingshu Chen. Surface dynamics of Rh/Al₂O₃ during propane dehydrogenation[J]. Chinese Journal of Catalysis, 2024, 62: 145-155.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60063-X

https://www.cjcatal.com/EN/Y2024/V62/I7/145

Figures/Tables 8

Fig. 1. AC-HAADF-STEM images of Rh/Al2O3 catalysts with varying Rh loadings: 3% (a,b), 1% (c), 0.5% (d), 0.1% (e), and 0.03% (f). (Red circles: Rh clusters, yellow circles: Rh single atoms).

Fig. 2. (a) Model of a Rh/Al2O3 catalyst (yellow balls: metallic Rh atoms, purple balls: interfacial Rh atoms, green balls: Rh single atoms). XPS Rh 3d spectra of the Rh/Al2O3 catalysts: 3% (b), 1% (c), and 0.5% (d).

Fig. 3. Catalytic performance of Rh/Al2O3. (a) Propane conversion; (b) propylene selectivity; (c) methane selectivity; (d) ethene selectivity; (e) ethane selectivity; (f) carbon balance.

Fig. 4. Propane-pulse tests of 3% Rh/Al2O3 (a), 1% Rh/Al2O3 (b), 0.5% Rh/Al2O3 (c), 0.1% Rh/Al2O3 (d) and 0.03% Rh/Al2O3 (e). (f) The propane consumption amounts of the Rh/Al2O3.

Fig. 5. LEIS spectra (He+) of the Rh/Al2O3 catalysts before and after propane treatment. (a,b) 3% Rh/Al2O3; (c,d) 1% Rh/Al2O3. The spectra were adjusted to have a comparable peak height of O.

Fig. 6. CO-FTIR spectra of the Rh/Al2O3 catalysts: Models of CO adsorbed on Rh species (a), 3% Rh/Al2O3 (b), 1% Rh/Al2O3 (c), 0.5% Rh/Al2O3 (d), 0.1% Rh/Al2O3 (e), and 0.03% Rh/Al2O3 (f).

Fig. 7. (a) Schematic of surface dynamics of the Rh/Al2O3 catalysts before and after the induction process. (b) Adsorption types of propylene on the Rh species.

Fig. 8. (a) TPOC of the spent 3% Rh/Al2O3 (m/e = 18, 28, and 44 for H2O, CO, and CO2, respectively). (b) TPOC of the spent Rh/Al2O3 catalysts and the Al2O3 support (m/e = 44 for CO2). HAADF-STEM image (c) and TEM image (d) of the spent 3% Rh/Al2O3. (blue circle: coke, yellow circle: Rh clusters. Two Rh clusters inside the red circles were selected as a reference to prove that these two images were obtained in the same area.)

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Surface dynamics of Rh/Al₂O₃ during propane dehydrogenation

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