Probing active species for CO hydrogenation over ZnCr2O4 catalysts

doi:10.1016/S1872-2067(21)64008-1

Abstract

Abstract:

Oxide catalysts are increasingly employed for hydrogenation reactions, among which ZnCrO_x is a major catalyst for the oxide-zeolite (OXZEO) process and for the hydrogenation of C1 molecules in general. Owing to the complex nature of ternary oxides, the surface and catalytic properties of ZnCr₂O₄spinel have remained controversial for CO hydrogenation. Combining in-situ Fourier-transformed infrared spectroscopy and X-ray photoelectron spectroscopy, we examined the adsorption and reaction of CO/H₂ on the ZnCr₂O₄ catalysts, which were pre-treated under oxidative or reductive conditions. The reduced ZnCr₂O₄ catalyst was found to expose more surface sites for CO adsorption/reaction than the oxidized ZnCr₂O₄ catalyst. Exposing the reduced ZnCr₂O₄ to H₂ at room temperature led to the formation of surface hydride species, which would transform into hydroxyl species at elevated temperatures. The reduced ZnCr₂O₄ surface exhibited much stronger interaction with CO and H₂ than ZnO and Cr₂O₃. Exposing the reduced ZnCr₂O₄ to the CO and H₂ (1:1) mixture gas led to the hydrogenation of CO. However, CO was oxidized by the hydroxyl species via the water-gas-shift reaction, whereas the hydrogenation of CO could only be achieved by surface hydride species on the reduced ZnCr₂O₄ to formyl or formate species at 373-473 K. Our study has thus shed light on the active species that control elementary reaction process of CO hydrogenation on complex oxide surfaces.

Key words: ZnCr₂O₄, Fourier-transformed infrared, spectroscopy, CO adsorption, Hydride, Hydroxyl

Yunjian Ling, Yihua Ran, Weipeng Shao, Na Li, Feng Jiao, Xiulian Pan, Qiang Fu, Zhi Liu, Fan Yang, Xinhe Bao. Probing active species for CO hydrogenation over ZnCr₂O₄ catalysts[J]. Chinese Journal of Catalysis, 2022, 43(8): 2017-2025.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)64008-1

https://www.cjcatal.com/EN/Y2022/V43/I8/2017

Figures/Tables 9

Fig. 1. TEM image (a), XRD pattern (b) and quasi-in-situ XPS spectra (c-e) of the ZnCr2O4 catalysts. XPS measurements compared the ZnCr2O4 catalyst pretreated in 1 mbar O2 at 673 K or 10 mbar H2 at 673 K by their Zn 2p (c), Cr 2p3/2 (d) and O 1s (e) spectra, respectively. (f) FT-IR background spectra of the oxidized and reduced ZnCr2O4 catalysts.

Fig. 2. (a) FT-IR spectra of the oxidized and reduced ZnCr2O4 catalysts exposed to 0.001 mbar CO at 120 K. (b) FT-IR spectra of oxidized ZnCr2O4 exposed to 0.001 mbar CO at 117 K, followed by UHV evacuation and the annealing at indicated temperatures from 133 to 313 K in UHV. (c) FT-IR spectra of reduced ZnCr2O4 exposed to 0.001 mbar CO at 114 K, followed by UHV evacuation and the annealing at indicated temperatures from 133 to 333 K in UHV.

Fig. 3. (a) FT-IR spectra of the oxidized and reduced ZnCr2O4 catalysts exposed to 10 mbar CO at room temperature. (b) FT-IR spectra of oxidized ZnCr2O4 exposed to 10 mbar CO at room temperature, followed by UHV evacuation and the annealing at indicated temperatures from 323 to 473 K in UHV. (c) FT-IR spectra of reduced ZnCr2O4 exposed to 10 mbar CO at room temperature, followed by UHV evacuation and the annealing at indicated temperatures from 323 to 873 K in UHV.

Fig. 4. (a) FT-IR spectra of oxidized and reduced ZnCr2O4 catalysts exposed to 12 mbar H2 and 1 bar H2 at room temperature, respectively. (b) FT-IR spectra of oxidized and reduced ZnCr2O4 catalysts exposed to 1 bar D2 at room temperature.

Fig. 5. FT-IR spectra of the reduced ZnCr2O4 catalyst exposed to 1 bar H2 (a) or 1 bar D2 (b) at room temperature, which is followed by UHV evacuation and the annealing at indicated temperatures from 373 to 873 K.

Fig. 6. FT-IR spectra of reduced ZnCr2O4 catalysts exposed to 2 mbar H2/CO (1:1) gas mixture at room temperature, followed by the annealing at 373 and 473 K, respectively.

Fig. 7. FT-IR spectra of reduced ZnCr2O4 and hydroxylated ZnCr2O4 catalysts exposed to 1 bar H2 (a) or 10 mbar CO (b) at room temperature. The hydroxylation was achieved by annealing the reduced ZnCr2O4 in 1 mbar H2 at 623 K.

Fig. 8. FT-IR spectra of hydroxyl-covered ZnCr2O4 catalyst exposed to 1 mbar CO at indicated temperatures from room temperature to 623 K (a,b) and hydride-covered ZnCr2O4 catalyst exposed to 1 mbar CO at indicated temperatures from room temperature to 523 K (c,d). The hydroxyl-covered ZnCr2O4 catalyst was prepared by annealing the reduced ZnCr2O4 in 1 mbar H2 at 623 K. The hydride-covered ZnCr2O4 catalyst was prepared by exposing the reduced ZnCr2O4 in 1 bar H2 at room temperature.

Fig. 9. Schematic diagram on the roles of hydride and hydroxyl species in their reactions with CO on ZnCr2O4.

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Probing active species for CO hydrogenation over ZnCr₂O₄ catalysts

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