Utilizing CO2 as a mild oxidant for oxidative dehydrogenation of ethane (ODHE) is an attractive way of recycling this greenhouse contaminant. Typically, CO2 capture and conversion processes are performed in separate beds, however, combining these processes into one bed incurs advantages of lower thermal gradient and reduced energy costs. This study formulated the first generation of structured dual-functional materials (DFMs) by directly 3D printing metal-oxide-CaO/ZSM-5 inks into monolithic contactors. Specifically, we 3D-printed monoliths with V, Ga, Ni, or Ti dopants to perform metal screening and determine which metal generates the best structured DFM for combined CO2 capture and utilization in ODHE. The samples were vigorously characterized by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), N2 physisorption, NH3-temperature programmed desorption (NH3-TPD), H2-temperature programmed reduction (H2-TPR), energy dispersive spectroscopy (EDS), and Pyridine Fourier Transform Infrared Spectroscopy (Py-FTIR). Their CO2 capture/ODHE performances were assessed with CO2 adsorption at 600 °C and ODHE of 25 mL/min 7% C2H6 at 700 °C. The combined adsorption/catalysis experiments indicated that the best performance was observed in V-CaO/ZSM-5 which achieved a staggeringly high CO2 capture (5.4 mmol/g), 65.2% CO2 conversion, 36.5% C2H6 conversion, 98% C2H4 selectivity, and 35.8% C2H4 yield as well as zero thermal cracking after 40 min-on-stream. This performance exceeded that of any previously reported material for combined CO2 capture and ODHE utilization, indicating this novel printing method can generate DFMs with exceptional potential for combined CO2 capture and utilization processes.


Chemical and Biochemical Engineering


National Science Foundation, Grant CBET-1802049

Keywords and Phrases

Additive manufacturing; Combined CO Capture/Conversion 2; Dual functional adsorbent/Catalyst Monoliths; Ethylene production

International Standard Serial Number (ISSN)


Document Type

Article - Journal

Document Version

Final Version

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© 2023 Elsevier, All rights reserved.

Publication Date

01 Mar 2022