Diffusion-acidity cooperative effect in ZnZrOx/SAPO-34 tandem catalysts for enhanced CO2-to-propylene conversion

doi:10.1016/S1872-2067(26)65189-3

Abstract

Abstract:

Achieving carbon neutrality requires the development of rational catalytic strategies for efficient CO₂ utilization, particularly toward propylene, which global demand continues to increase. Herein, a diffusion-acidity cooperative effect strategy is proposed and implemented using ZnZrO_x/SAPO-34 tandem catalysts to enhance propylene selectivity in CO₂ hydrogenation. Compared with a ZnZrO_x/conventional SAPO-34 catalyst, which exhibits 29.4% propylene selectivity among hydrocarbons, the optimized ZnZrO_x/SAPO-34 system delivers a CO₂ conversion of 19.2% with a substantially improved propylene selectivity of 52.6%, further rising to 57.4% at higher gas hourly space velocity. The results reveal that accelerating molecular diffusion within SAPO-34 promotes the rapid transport and transformation of hydrogenated intermediates formed on ZnZrO_x, thereby suppressing undesired secondary hydrogenation pathways. Simultaneously, an increased content of strong Brönsted acid sites associated with Si(0Si,4Al) and Si(1Si,3Al) facilitates selective propylene formation. These findings suggest diffusion-acidity cooperative effect as a possible design principle for efficient CO₂-to-propylene conversion over ZnZrO_x/SAPO-34.

Key words: CO₂ hydrogenation, Tandem process, C-C coupling, Light olefins, Propylene selectivity1. Introduction

Donghang Chen, Junchen Liu, Wei Deng, Biao Gao, Yifu Wang, Motonori Watanabe, Tatsumi Ishihara, Limin Guo. Diffusion-acidity cooperative effect in ZnZrO_x/SAPO-34 tandem catalysts for enhanced CO₂-to-propylene conversion[J]. Chinese Journal of Catalysis, 2026, 90: 145-157.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65189-3

https://www.cjcatal.com/EN/Y2026/V90/I11/145

Figures/Tables 7

Fig. 1. XRD pattern (a), N2 sorption isotherm (b), HRTEM image (c), aberration-corrected scanning TEM-high-angle annular dark-field images and element distribution (d) of the ZnZrOx catalyst. (e) Zn LMM Auger spectra for ZnZrOx and ZnO. (f) XPS spectra of Zr 3d for ZnZrOx catalysts and ZrO2.

Fig. 2. (a) Schematic illustration of the diffusion enhancement strategy. (b) Intra-diffusion rates of methanol in SAPO-34 zeolites with different morphologies. (c) Intra-diffusion rates of propylene in SAPO-34 zeolites with different morphologies. (d) CO2 hydrogenation performance and product selectivity of the three ZnZrOx/SAPO-34 catalysts under reaction conditions of 370 °C, 3 MPa, and 6000 mL/(g·h).

Fig. 3. NH3-TPD profiles (a), 31P MAS NMR spectra (b), 27Al MAS NMR spectra (c), 1H MAS NMR spectra (d), and 29Si MAS NMR spectra (e) of the SAPO-34-COM, SAPO-34-NS, and SAPO-34-NS-BE samples. (f) Schematic illustration of the changes of acid sites.

Fig. 4. (a) Relationship between propylene selectivity and Si/Al ratio. (b) Comparison of propylene selectivity between different strategies (based on ZnZrOx/SAPO-34-COM). CO2 hydrogenation performance and product selectivity of ZnZrOx/SAPO-34-NS-BE at different reaction temperatures (3 MPa, 6000 mL/(g·h)) (c), at various GHSVs (370 °C, 3 MPa) (d), at different reaction pressures (370 °C, 6000 mL/(g·h)) (e). (f) Propylene selectivity among hydrocarbon products over ZnZrOx/SAPO-34-NS-BE at varying GHSVs and pressures. (g) Comparison of the catalytic performance in this work with previously reported catalysts. (h) Diffusion-acidity cooperative effect applied in other metal oxide catalysts.

Fig. 5. (a) In-situ DRIFTS spectra of CO2 hydrogenation. In-situ DRIFTS spectra collected after switching off the CO2 feed (b) and temporal evolutions of formate and methoxy species (c) over ZnZrOx/SAPO-34-COM. (d) In-situ DRIFTS spectra of CO2 hydrogenation. In-situ DRIFTS spectra collected after switching off the CO2 feed (e), and temporal evolutions of formate and methoxy species (f) over ZnZrOx/SAPO-34-NS-BE (300 °C and 0.1 MPa).

Fig. 6. (a) Stability test of ZnZrOx/SAPO-34-COM over 60 h on stream. (b) Stability test of ZnZrOx/SAPO-34-NS-BE over 60 h on stream. (c) TGA results of the samples after the 60 h stability tests. Stability test of ZnZrOx/SAPO-34-NS-BE over 150 h on stream (d), and TGA results (e) of the samples after the 150 h stability tests.

Fig. 7. Schematic illustration of the proposed reaction mechanism of CO2 hydrogenation over the ZnZrOx/SAPO-34.

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Diffusion-acidity cooperative effect in ZnZrO_x/SAPO-34 tandem catalysts for enhanced CO₂-to-propylene conversion

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