Modulation of the cobalt species state on zincosilicate to maximize propane dehydrogenation to propylene

doi:10.1016/S1872-2067(24)60133-6

Chinese Journal of Catalysis ›› 2024, Vol. 66: 168-180.DOI: 10.1016/S1872-2067(24)60133-6

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Modulation of the cobalt species state on zincosilicate to maximize propane dehydrogenation to propylene

Hao Liu^a^,¹, Bingxian Chu^c^,¹, Tianxiang Chen^d^,¹, Jie Zhou^a, Lihui Dong^c, Tsz Woon Benedict Lo^d, Bin Li^c^,^*(), Xiaohui He^a^,^e^,^*(), Hongbing Ji^a^,^b^,^*()

^aKey Laboratory of Bioinorganic and Synthetic Chemistry of Ministry of Education, Fine Chemical Industry Research Institute, School of Chemistry, IGCME, Sun Yat-sen University, Guangzhou 510275, Guangdong, China
^bState Key Laboratory Breeding Base of Green-Chemical Synthesis Technology, Institute of Green Petroleum Processing and Light Hydrocarbon Conversion, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
^cGuangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology, School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, Guangxi, China
^dState Key Laboratory of Chemical Biology and Drug Discovery, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hunghom, Hong Kong, China
^eGuangdong Technology Research Center for Synthesis and Separation of Thermosensitive Chemicals, Guangzhou 510275, Guangdong, China

Received:2024-06-14 Accepted:2024-08-31 Online:2024-11-18 Published:2024-11-10
Contact: *E-mail: binli@gxu.edu.cn (B. Li),hexiaohui@mail.sysu.edu.cn (X. He),jihb@mail.sysu.edu.cn (H. Ji).
About author:¹Contributed equally to this work.
Supported by:
National Key Research and Development Program Nanotechnology Specific Project(2020YFA0210902);Guangdong Natural Science Funds for Distinguished Young Scholar(2022B1515020035);National Natural Science Foundation of China(22078371);National Natural Science Foundation of China(U22A20428);National Natural Science Foundation of China(21938001);National Natural Science Foundation of China(22422815);Science and Technology Innovation Teams of Shanxi Province(202304051001007)

Abstract

Abstract:

Dispersing metals from nanoparticles into clusters or single atoms often exhibits unique properties such as the inhibition of structure-sensitive side reactions. Here, we reported the use of ion exchange (IE) methods and direct hydrogen reduction to achieve high dispersion of Co species on zincosilicate. The obtained 2Co/Zn-4-IE catalyst achieved an initial propane conversion of 41.4% at a temperature of 550 °C in a 25% propane and 75% nitrogen atmosphere for propane dehydrogenation. Visualization of the presence of Co species within specific rings (alpha-α, beta-β and delta-δ) was obtained by aberration-corrected scanning transmission electron microscopy. A series of Fourier transform infrared spectra confirmed the anchoring of Co by specific hydroxyl groups in zincosilicate and the specific coordination environment of Co and its presence in the rings essentially as a single site. The framework Zn for the modulation of the microenvironment and the presence of Co species as Lewis acid active sites (Co-O₄) was also supported by density functional theory calculations.

Key words: Zincosilicate zeolite, Anchoring effect, Microenvironment modification, Isolated Co site, Propane dehydrogenation

Hao Liu, Bingxian Chu, Tianxiang Chen, Jie Zhou, Lihui Dong, Tsz Woon Benedict Lo, Bin Li, Xiaohui He, Hongbing Ji. Modulation of the cobalt species state on zincosilicate to maximize propane dehydrogenation to propylene[J]. Chinese Journal of Catalysis, 2024, 66: 168-180.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60133-6

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Figures/Tables 8

Fig. 1. Electron microscopy analyses of the 2Co/Zn-4-IE with a Co actual content of 1.0 wt% (after H2 reduction, 550 °C). (a,b) Low-resolution HAADF-STEM images. (c,e) AC-STEM images of the 2Co/Zn-4-IE framework are taken along the two main crystallographic axes. (d,f) Structure of the MFI-type framework. (g) AC-STEM image of 2Co/Zn-4-IE along the straight 10-MR channel (i.e., the [010] axis). (h-j) The rectangular regions in Fig. 1(g) are enlarged to reveal the different positions of Co species within the different rings (α, β, and γ). (k) AC-STEM images and elemental mappings for Si, O, Zn, and Co.

Fig. 2. (a-c) Co 2p and Zn 2p spectra of different samples (H2 represents the sample reduced in a H2 at 550 °C for 1 h; R represents the sample reacted in a 25% propane atmosphere at 550 °C for 8.5 h). Fits of the FT Co K-edge EXAFS spectra of 2Co/Zn-4-IE-H2 (d), 1Co/Zn-4-IWI-H2 (e) and 2Co/Zn-4-IE-R (f). Fits of the FT Zn K-edge EXAFS spectra of 2Co/Zn-4-IE-H2 (g), 1Co/Zn-4-IWI-H2 (h) and 2Co/Zn-4-IE-R (i).

Fig. 3. Co 2p spectra of 2Co/Zn-4-IE (a) and 1Co/Zn-4-IWI (b) (the sample were reduced in situ in H2 at 550 °C for 1 h). It is worth mentioning that in situ XPS was first collected at room temperature and then collected again after 1 h of in situ warming and reduction, allowing for a more realistic state of the Co species.

Fig. 4. (a-c) FT-IR spectra of Zn-4, 1Co/Zn-4-IWI and 2Co/Zn-4-IE are recorded after NO adsorption. (d) H2-TPR curves of 1Co/Zn-4-IWI and 2Co/Zn-4-IE. (e) FT-IR spectra of different samples. (f) UV-vis-NIR spectra of Zn-4, 2Co/Zn-4-IE and 2Co/Zn-4-IE-H2 (Zn-4 and 2Co/Zn-4-IE are dehydrated at 400 °C under vacuum). (g) Different rings of Co species present in zeolite channels (α,β,γ). (h) UV-vis-NIR spectra of (0.5-4)Co/Zn-4-IE (these samples are dehydrated at 400 °C under vacuum). (i) Rietveld refinement of SXRD data and the corresponding refined crystal structure of Co/Zn-4-IE-H2.

Fig. 5. FT-IR spectra of Zn-4 (a), 1Co/Zn-4-IWI (b) and 2Co/Zn-4-IE (c) are recorded after CD3CN adsorption and desorption at different temperatures. (d-g) Pyridine-adsorbed FT-IR spectra and corresponding numbers of acid sites at different temperatures. (h) NH3-TPD curves. (i) DRIFTS spectra of -OH groups.

Fig. 6. (a) PDH performance over various catalysts. (b) PDH performance of 2Co/Zn-4-IE under various WHSV. (c) PDH performance of 2Co/Zn-4-IE at different temperatures and reaction atmospheres, pure C3H8, WHSV=8.5 h-1 (unless otherwise specified). (d,e) PDH performance over 2Co/Zn-4-IE after 10 (350 °C for 4 h) or 6 (450 °C for 1 h) regeneration cycles. (f) Productivity of C3H6 versus deactivation rate for the catalysts in this work compared with other Co-based catalysts.

Fig. 7. (a) Optimized structure of 2Co/Zn-4-IE by DFT calculations with relative energy shown in eV. (Si: green; Zn: silvery; O: red; Co: blue). Lower energy indicates greater stability and a higher probability of existence. (b) PDOS analysis for the framework O atom surrounding Zn sites. (c) PDOS analysis for Co and surrounding O atom. (d) -COHP of O 2p-Co 3d interaction curves. (e) PDOS of Co, H and C atoms in *H + *C3H7 adsorbed on Co-Zn-CSU. (f) COHP on H 1s-Co 3d interaction and H 1s - C 2p interaction. Here, both H and C are in the methylene group of *C3H7.

Fig. 8. The calculated energy profiles along the minimum energy pathways and the optimized intermediates upon PDH reaction with the reduced 2Co/Zn-4-IE. blue, silvery, red, brown, green, and white spheres represent Co, Zn, O, C, Si, and H atoms, respectively.

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Modulation of the cobalt species state on zincosilicate to maximize propane dehydrogenation to propylene

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