Engineering catalytic microenvironments for enhancing ethylene production in CO2 capture and in-situ oxidative dehydrogenation of ethane

doi:10.1016/S1872-2067(26)65101-7

Abstract

Abstract:

The integrated CO₂ capture and conversion through oxidative dehydrogenation of ethane (iCCC-ODHE) utilizes the captured CO₂ as a mild oxidant to promote value-added ethylene production. Nevertheless, it is still trapped by low efficiency owing to little understandings about the synergistic interaction between the CO₂ capture and catalytic ODHE. Herein, we focus on exploring the contributions of local catalytic environments to the iCCC-ODHE performance through tailoring the catalyst itself and the proximity-governed effect. The Co-ZSM-5 catalysts are developed to achieve a selective cleavage of the C-H bond over the C-C bond in C₂H₆ through modulating the relative concentration of Co²⁺. When coupling the optimized Co-ZSM-5 catalyst with the CO₂ adsorbent Ca₄MgO₅ by adjusting packing configurations in a fixed bed, a superior iCCC-ODHE performance with an excellent CO₂ capture capacity of 10.8 mmol g_adsorbent^‒1 and a remarkable C₂H₄ yield of 45.4% is achieved at 650 °C in the granule-stacking configuration. Consistently, the density functional theory calculations reveal the pathway of these abnormal phenomena that the low local CO₂ concentration around catalytic sites, corresponding to a relatively far proximity distance, shows a significant effect on decreasing the reaction energy of selective cleavage of the first C-H bond in C₂H₆. Meanwhile, the produced *H species can be consumed by the following adsorbed *CO₂, facilitating the shift of reaction equilibrium forwardly for the formation of C₂H₄ and CO. Therefore, this insight into the local catalytic environment provides a promising iCCC-ODHE strategy toward carbon neutrality.

Key words: CO₂ capture, Oxidative dehydrogenation of ethane, Co-ZSM-5/Ca₄MgO₅ dual functional materials, Local catalytic environment, C-H/C-C bonds selective cleavage

Zihao Gao, Kai Huang, Qingling Xu, Xin Wang, Zhicheng Liu, Bin Shao, Jun Hu. Engineering catalytic microenvironments for enhancing ethylene production in CO₂ capture and in-situ oxidative dehydrogenation of ethane[J]. Chinese Journal of Catalysis, 2026, 88: 322-334.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65101-7

https://www.cjcatal.com/EN/Y2026/V88/I9/322

Figures/Tables 5

Fig. 1. Schematic diagram of fixed-bed reactor of iCCC-ODHE.

Fig. 2. (a) XRD patterns of H-ZSM-5 and Co-ZSM-5-x. (b) FTIR results of H-ZSM-5, Co-ZSM-5-1.5 and Co-ZSM-5-4.5. (c) UV-vis DRS spectra of Co-ZSM-5-1.5 and Co-ZSM-5-4.5. (d) HADDF-STEM image of Co-ZSM-5-1.5 catalyst. (e) AC-STEM image of Co-ZSM-5-1.5. Note that the white circles indicate single cobalt atoms, and the green circles highlight adjacent clusters of single-atom sites. (f) HADDF-STEM image of Co-ZSM-5-4.5 catalyst. (g) HRTEM image of the Co3O4 particles at the surface of Co-ZSM-5-4.5. XPS spectra (h), H2-TPR results and the calculated H2 consumption based on the reduction peak area in insert (i), and NH3-TPD results (j) of H-ZSM-5, Co-ZSM-5-1.5, and Co-ZSM-5-4.5. SEM image (k) and EDS mapping images (l) of Ca4MgO5. (m) Ten adsorption-desorption cycles of Ca4MgO5 (Adsorption at 650 °C, 50 mL min-1 of 20 vol% CO2; Desorption at 700 °C, 50 mL min-1 of N2).

Fig. 3. (a) Typical outflow curve of iCCC-ODHE process, (b) C2H4 and CO productions on Co-ZSM-5-1.5 and Co-ZSM-5-4.5, respectively. (c) Integration configurations of Ca4MgO5 and Co-ZSM-5-1.5 of granule-stacking, and powder-mixing. Effect of integration configurations of granule-stacking and powder-mixing on the space time yield of (d) C2H4 and (e) CO. Note that the default reaction conditions were 650 °C, 50 mL min-1 of 20 vol% CO2 for CO2 capture; 650 °C, 80 mL min-1 of 5 vol% C2H6 for ODHE. In-situ DRIFTS spectra under 20 vol% of CO2 (f), and 5 vol% of ethane (g). (h) Peak intensities evolution of HCOO* form (f) and *COOH signal from (h).

Fig. 4. Proposed mechanisms of Path 1: Low local CO2 concentration (a), Path 2: High local CO2 concentration (b), and Path 3: ethane dehydrogenation under high local CO2 concentration (c). (d) Energy profiles of above three pathways.

Fig. 5. The effect of cobalt loading of the catalyst (a), the capture and conversion temperature (b), and the WHSV (c) on the iCCC-ODHE performance. (d) 10 cyclic tests of iCCC-ODHE; Note that the default reaction conditions were isothermally at 650 °C, 50 mL min-1 of 20 vol% CO2 for CO2 capture; 80 mL min-1 of 5 vol% C2H6 for ODHE conversion.

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Engineering catalytic microenvironments for enhancing ethylene production in CO₂ capture and in-situ oxidative dehydrogenation of ethane

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