CO2-promoted ethylbenzene dehydrogenation catalyzed by zeolite-encaged single chromium sites

doi:10.1016/S1872-2067(24)60241-X

Abstract

Abstract:

The selective activation of C-H bonds is pivotal in catalysis for converting hydrocarbons into value-added chemicals. Ethylbenzene dehydrogenation to styrene is crucial process to produce polystyrene and its derivatives used in synthetic materials. Herein, K-Cr@Y with zeolite-encaged isolated O=Cr(VI)=O species modified by extraframework potassium ions is constructed, showing remarkable performance in CO₂-promoted ethylbenzene dehydrogenation with initial ethylbenzene conversion of 66% and styrene selectivity of 96%, outperforming other M-Cr@Y catalysts (M = Li, Na, Rb, Cs). Extraframework potassium ions can modulate the electron density of zeolite-encaged Cr(VI) species and therefore facilitate C-H bond activation in ethylbenzene molecules. The gradual reduction of zeolite-encaged O=Cr(VI)=O to less active Cr(IV)=O species by dihydrogen during ethylbenzene dehydrogenation is evidenced by comprehensive characterization results, and Cr(IV)=O can be re-oxidized to O=Cr(VI)=O species upon simple calcination regeneration. The results from in situ DRIFT spectroscopy elucidate the critical promotion role of CO₂ in ethylbenzene dehydrogenation over K-Cr@Y by retarding the over-reduction of zeolite-encaged Cr species to inactive Cr(III) species and suppressing coke deposition. This study advances the rational design of non-noble metal catalysts for CO₂-promoted ethylbenzene dehydrogenation with zeolite-encaged high valence transition metal ions modulated by extraframework cations.

Key words: C-H bond activation, CO₂-promoted ethylbenzene dehydrogenation, K-Cr@Y, O=Cr(VI)=O, Cr(IV)=O

Jian Dang, Xin Deng, Weijie Li, Di Yang, Guangjun Wu, Landong Li. CO₂-promoted ethylbenzene dehydrogenation catalyzed by zeolite-encaged single chromium sites[J]. Chinese Journal of Catalysis, 2025, 71: 158-168.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60241-X

https://www.cjcatal.com/EN/Y2025/V71/I4/158

Figures/Tables 6

Fig. 1. Ethylbenzene dehydrogenation over M-Cr@Y. EB conversion (A) and ST selectivity (B) in CO2-promoted EB dehydrogenation reaction over M-Cr@Y catalysts. (C) TPSR curves of CO2-promoted EB dehydrogenation over K-Cr@Y catalyst. Reaction conditions: 100 mg catalyst, 101 kPa, 1.2% EB, He as balance gas, total flow rate = 10 mL/min, CO2/EB = 10/1, WHSV =0.31 h-1. (D) Product distribution in CO2-promoted EB dehydrogenation reaction over K-Cr@Y catalyst. Reaction conditions: 100 mg catalyst, 101 kPa, 823 K, 1.2% EB, N2 as balance gas, total flow rate = 10 mL/min, CO2/EB = 10/1, WHSV =0.31 h-1.

Fig. 2. Structural characterization of K-Cr@Y zeolite. (A) Cr K-edge XANES spectra of Cr foil, Cr2O3, CrO2, Na2CrO4 and K-Cr@Y. (B) FT k2-weighted EXAFS and fitting spectra of Cr foil, Cr2O3, Na2CrO4 and K-Cr@Y. (C) WT EXAFS spectra of Cr foil, Cr2O3, Na2CrO4 and K-Cr@Y. (D) STEM image of K-Cr@Y along the orientation of [110]. (E) High-magnification Cs-corrected HADDF STEM image of K-Cr@Y viewed along the orientation of [110] as well as the schematic model on the same projection. (F) Enlarged high contrast STEM images of K-Cr@Y. Scale bar: 1 nm, Cr atoms marked by yellow dash circle.

Fig. 3. Optimization of ethylbenzene dehydrogenation over K-Cr@Y catalyst. (A) CO2-promoted EB dehydrogenation reactivity over K-Cr@Y under different ratios of CO2/EB. Reaction conditions: 100 mg K-Cr@Y, 101 kPa, 823 K, 1.2% EB, N2 as balance gas, total flow rate = 10 mL/min, CO2/EB = x/1 (x = 0, 1, 10, 20, 30, 50). (B) CO2-promoted EB dehydrogenation reactivity over K-Cr@Y under different reaction temperatures. Reaction conditions: 100 mg K-Cr@Y catalyst, 101 kPa, 1.2% EB, N2 as balance gas, total flow rate = 10 mL/min, CO2/EB = 10/ 1. CO2-promoted EB dehydrogenation performance (C) and ST formation rate (D) over K-Cr@Y under different flow rates. Reaction conditions: 100 mg K-Cr@Y, 101 kPa, 823 K, 1.2% EB, N2 as balance gas, total flow rate = x mL/min (x = 10, 20, 30, 50), CO2/EB = 10/1, WHSV= 0.31 to 1.56 h-1. (E) Comparison of various catalysts in EB dehydrogenation in terms of ST selectivity and ST formation rate.

Fig. 4. Stability and recyclability of K-Cr@Y catalyst in ethylbenzene dehydrogenation. (A) Durability and recyclability tests of K-Cr@Y catalyst in CO2-promoted EB dehydrogenation. Reaction conditions: 100 mg K-Cr@Y catalyst, 101 kPa, 1.2% EB, 823 K, N2 as balance gas, total flow rate = 10 mL/min, CO2/EB = 10/1, WHSV =0.31 h-1. (B) Cr K-edge XANES spectra of K-Cr@Y-fresh, K-Cr@Y-used and CrO2. (C) FT k2-weighted EXAFS and fitting spectra of K-Cr@Y-fresh, K-Cr@Y-used and CrO2. (D) FTIR spectra of CO adsorption on K-Cr@Y-used sample after CO adsorption and He purging. (E) Cr 2p XPS of K-Cr@Y-fresh, K-Cr@Y-used and K-Cr@Y-regenerated catalysts. (F) H2-TPR curves of K-Cr@Y-fresh, K-Cr@Y-used and K-Cr@Y-regenerated catalysts.

Fig. 5. Reaction mechanism of EB dehydrogenation over K-Cr@Y catalyst. (A) TPSR profiles of EB-D scrambling over M-Cr@Y catalysts. Reaction conditions: 100 mg catalyst, 101 kPa, 1.2% EB, 2%D2 in N2, total flow rate = 10 mL/min, CO2/EB = 10/1. (B) In situ DRIFT spectra of CO2-promoted EB dehydrogenation over K-Cr@Y catalyst. Reaction conditions: 30 mg K-Cr@Y catalyst, 101 kPa, 1.2%EB, 823 K, N2 as balance gas, total flow rate = 20 mL/min, CO2/EB = 10(0)/1. (C) In situ DRIFT spectra of introducing ST to K-Cr@Y. Reaction conditions: 30 mg K-Cr@Y catalyst, 101 kPa, 0.8% ST, 823 K, N2 = 20 mL/min. (D) In situ DRIFT spectra of CO2-promoted EB dehydrogenation over Cs-Cr@Y catalyst. Reaction conditions: 30 mg Cs-Cr@Y catalyst, 101 kPa, 1.2% EB, 823 K, N2 as balance gas, total flow rate = 20 mL/min, CO2/EB = 10(0)/1.

Scheme 1. Graphical representation of dynamic Cr species in K-Cr@Y under the conditions of CO2-promoted EB dehydrogenation and catalytic regeneration.

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CO₂-promoted ethylbenzene dehydrogenation catalyzed by zeolite-encaged single chromium sites

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