Electronic perturbation-promoted interfacial pathway for facile C-H dissociation

doi:10.1016/S1872-2067(23)64575-9

Abstract

Abstract:

Interface has often played significant role in the behavior of metal-based catalysts during various heterogeneous reactions. Herein, we reported a novel interfacial pathway for propane dehydrogenation on Pt-GaO_x dual sites. The active ensemble, composing Pt particles and Ga₂O₃ clusters, facilitates the facile dissociation of C‒H bonds (energy barrier < 0.30 eV) through H-abstraction by O sites, coupled with alkyl stabilization on the Pt surface. Notably, the electronic perturbation of the Pt slab induces higher-lying O 2p states at the interface, accompanied by a substantial density of states around fermi level. This is in stark contrast to the O species present in Ga₂O₃ crystals or clusters alone, leading to an exceptionally strong affinity for H and a robust ability for C-H scission. The Pt/Ga-Al₂O₃ catalysts prepared with Pt nanoparticles decorated by Ga oxide exhibit superior performance compared to Pt/Al₂O₃ and PtSn/Al₂O₃ catalysts. This insight into interfacial catalysis contributes to a broader understanding of the origin of the high catalytic efficiency observed in metal-based catalysts.

Key words: Metal-based catalysts, C-H dissociation, Propane dehydrogenation, Electronic perturbation, Interfacial catalysis

Zhe Wang, Chunpeng Wang, Bing Lu, Zhirong Chen, Yong Wang, Shanjun Mao. Electronic perturbation-promoted interfacial pathway for facile C-H dissociation[J]. Chinese Journal of Catalysis, 2024, 56: 130-138.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64575-9

https://www.cjcatal.com/EN/Y2024/V56/I1/130

Figures/Tables 5

Fig. 1. HAADF-STEM images and corresponding particle size distribution of 2% Pt/Al2O3 (a) and 2% Pt/Ga-Al2O3 (b). (c,d) Aberration-corrected TEM image and corresponding EDX mapping of 2% Pt/Ga-Al2O3. (e) Pt 4d XPS spectra of 2% Pt/Al2O3 and 2% Pt/Ga-Al2O3. (f) Ga 2p XPS spectra of 2% Pt/Ga-Al2O3-cal (before reduction) and 2% Pt/Ga-Al2O3. (g) FT-IR of CO adsorbed on 2% Pt/Al2O3 and 2% Pt/Ga-Al2O3 at 30 °C (color code in structure models: cyan, Pt; red, O; grey, C). HRTEM and HAADF-STEM (with EDS line data) images of PtNP/Ga-Al2O3-cal (before reduction) (h,i) and PtNP/Ga-Al2O3 (j,k).

Fig. 2. (a) FT-IR of CO adsorbed on 2% Pt/Ga-Al2O3 reduced at different temperature (2% Pt/Ga-Al2O3-cal were catalysts without reduction; 2% Pt/Ga-Al2O3-cal and 2% Pt/Ga-Al2O3-cal denotes catalysts reduced at 200 °C and 300 °C, respectively; 2% Pt/Ga-Al2O3 means reduction at 550 °C, as shown in methods; color code in structure models: cyan, Pt; red, O; grey, C). (b) Proposed scheme for structure evolution of Ga-containing Pt catalysts during reduction process.

Fig. 3. (a) PDH performance of Pt-based catalysts with 2 wt% Pt loading. (b) HAADF-STEM image of 0.6% Pt/Ga-Al2O3; the scale bar corresponds to 10 nm. (c) FT-IR of adsorbed CO on 0.6% Pt/Al2O3 and 0.6% Pt/Ga-Al2O3 (color code in structure models: cyan, Pt; red, O; grey, C). (d) PDH performance of Pt-based catalysts with 0.6 wt% Pt loading. (e) Regeneration property of 0.6% Pt/Ga-Al2O3.

Fig. 4. The free energy profile along the corresponding pathway of propane dehydrogenation on Pt (111) and Ga2O3-Pt model (reaction pathway on Pt (111) plane was shown in Fig. S12; color code in structure models: cyan, Pt; light brown, Ga; red, O; grey, C; white, H).

Fig. 5. (a) Charge density difference of propane dissociated adsorption on Ga2O3-Pt model (yellow and cyan areas means charge depletion and accumulation, respectively, with 0.003 e/?3 isosurface value; light grey, light green, red, brown and white balls denote Pt, Ga, O, C and H atoms, respectively. According to the charge analysis, H bonded to O site lose about 0.62 electron). (b) The reaction (Er) and activation (Ea) energy of the C-H bond (in methylene) dissociation on various active sites. (c) Bader charge of adsorbed H and C3H7 on Pt-O dual sites of different catalyst models. (d) The relationship between C-H activation energy and adsorption energy of H. (e) O 2p partial density of states (pDOS) of various O sites for H adsorption in C-H dissociation. (f) Charge density difference upon Ga2O3 decoration on Pt (111).

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