Carbon capture, utilization, and storage (CCUS) technologies are pivotal for transitioning to a net-zero economy by 2050. In particular, conversion of captured CO2 to marketable chemicals and fuels appears to be a sustainable approach to not only curb greenhouse emissions but also transform wastes like CO2 into useful products through storage of renewable energy in chemical bonds. Bifunctional materials (BFMs) composed of adsorbents and catalysts have shown promise in reactive capture and conversion of CO2 at high temperatures. In this study, we extend the application of 3D printing technology to formulate a novel set of BFMs composed of CaO and Ce1-xCoxNiO3 perovskite-type oxide catalysts for the dual-purpose use of capturing CO2 and reforming CH4 for H2 production. Three honeycomb monoliths composed of equal amounts of adsorbent and catalyst constituents with varied Ce1-xCox ratios were 3D printed to assess the role of cobalt on catalytic properties and overall performance. The samples were vigorously characterized using X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), N2 physisorption, X-ray photoelectron spectroscopy (XPS), H2-TPR, in situ CO2 adsorption/desorption XRD, and NH3-TPD. Results showed that the Ce1-xCox ratios ─x = 0.25, 0.50, and 0.75─did not affect crystallinity, texture, or metal dispersion. However, a higher cobalt content reduced reducibility, CO2 adsorption/desorption reversibility, and oxygen species availability. Assessing the structured BFM monoliths via combined CO2 capture and CH4 reforming in the temperature range 500-700 °C revealed that such differences in physiochemical properties lowered H2 and CO yields at higher cobalt loading, leading to best catalytic performance in Ce0.75Co0.25NiO3/Ca sample that achieved 77% CO2 conversion, 94% CH4 conversion, 61% H2 yield, and 2.30 H2/CO ratio at 700 °C. The stability of this BFM was assessed across five adsorption/reaction cycles, showing only marginal losses in the H2/CO yield. Thus, these findings successfully expand the use of 3D printing to unexplored perovskite-based BFMs and demonstrate an important proof-of-concept for their use in combined CO2 capture and utilization in H2 production processes.


Chemical and Biochemical Engineering

Publication Status

Open Access


National Science Foundation, Grant NSF CBET-2316143

Keywords and Phrases

bifunctional materials; hydrogen production; methane dry reforming; reactive capture of CO 2; structured monolith

International Standard Serial Number (ISSN)


Document Type

Article - Journal

Document Version

Final Version

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© 2024 American Chemical Society, All rights reserved.

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Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 License.

Publication Date

22 Jan 2024