Developing routes of utilizing CO2 emissions is important for long-term environmental preservation, as storing such emissions underground will eventually become unsustainable. One way of utilizing CO2 emissions is as a light-oxidant feedstock for oxidative dehydrogenation of propane (ODHP) to propylene. However, the adsorption and reaction steps typically occur at widely different temperatures, meaning that the thermal gradients – and by extension process energy requirements – are often unreasonably high. In recent years, dual-functional materials (DFMs) – i.e., materials comprised of a high temperature adsorbent phase alongside a heterogeneous catalyst – have been employed for combined CO2 adsorption and utilization over one material within a single bed using a reduced thermal gradient. However, these materials have never been formed into practical contactors and have never been applied to ODHP applications. Therefore, in this study we manufactured the first-generation of DFM adsorbent/catalyst monoliths, comprised of CaO (adsorbent) and M@ZSM-5 (M = V-, Ga-, Ti-, or Ni-oxide) heterogeneous catalysts, using our novel direct metal-oxide 3D printing technique. The monoliths were vigorously characterized using N2 physisorption, C3H8-DRIFTS, NH3-TPD, Py-FTIR, H2-TPR, XRD, XPS, and elemental mapping and were assessed for CO2 capture/ODHP utilization at 600–700 ºC. The adsorption/catalysis experiments revealed that these materials can perform both processes effectively at 600 ºC, with reduced propylene yield at higher temperature, which eliminated the need for a thermal gradient between the adsorption and catalysis steps. Between the various samples, the Ti-doped monolith generated the best balance of CO2 conversion (76%) and propylene selectivity (39%), due to the high dispersion of TiO2, favorable redox properties and controlled acidity of the dopant. However, it was also found that varying the metal dopant could be used to control the heuristics of CO2/C3H8 conversion, C3H6 selectivity, and C3H6 yield, meaning that the manufacturing process outlined herein represents a promising way of tuning the chemical properties of structured DFM adsorbent/catalyst materials. More importantly, this study establishes a promising proof-of-concept for 3D printing as a facile means of structuring these exciting composite materials and expands DFMs to the previously unexplored application of ODHP.


Chemical and Biochemical Engineering


National Science Foundation, Grant CBET-1802049

Keywords and Phrases

3D printing; Direct CO capture-utilization 2; Dual-functional adsorbent-catalyst materials; oxidative propane dehydrogenation

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 Apr 2022