Application of Solid-Supported Amines for Thermocatalytic Reactive CO₂ Capture

Reactive CO₂ capture (RCC) is a promising strategy for process intensification of carbon capture and conversion for production of low-carbon fuels and chemicals. As state-of-the-art sorbent materials in point source and direct air capture systems, solid-supported amines are a natural choice to pair with supported CO₂ hydrogenation catalysts (e.g., metallic nanoparticles) for developing high-capacity sorbent-catalyst materials for use in RCC. In this Perspective, we summarize the relevant literature combining solid-supported amines with metallic nanoparticles for thermocatalytic RCC and detail two of our own case studies using RCC to synthesize methane and methanol. Our observations suggest that the temperature mismatch between CO₂ desorption and reaction, along with potential catalyst site poisoning by grafted aminosilanes, is a significant obstacle to realizing the potential of amine-based RCC materials in the decarbonization of chemical production. This stands in contrast to literature detailing successful RCC using liquid amines and solid catalysts, which may benefit from more favorable mass transfer dynamics, as well as early stage reports into RCC solid-phase amine-Pd materials, whose findings we were not able to replicate. More judicious reaction selection and synthetic design strategies to match materials with process conditions offer alternative pathways for future research.. Authors: McNeary, W. Wilson [National Renewable Energy Laboratory (NREL), Golden, CO (United States)] (ORCID:0000000183395121); Ellebracht, Nathan C. [Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)] (ORCID:0000000168154936); Jue, Melinda L. [Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)] (ORCID:0000000268642419); Rasmussen, Mathew J. [National Renewable Energy Laboratory (NREL), Golden, CO (United States)]; Crawford, James M. [Montana State Univ., Bozeman, MT (United States)] (ORCID:0000000336146055). DOE Contract: AC36-08GO28308; AC52-07NA27344. Subjects: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Materials science,Energy,Chemistry; carbon capture; carbon conversion; direct air capture; process intensification; reactive capture