Support Pore Structure and Composition Strongly Influence the Direct Air Capture of CO(2) on Supported Amines

[Image: see text] A variety of amine-impregnated porous solid sorbents for direct air capture (DAC) of CO(2) have been developed, yet the effect of amine-solid support interactions on the CO(2) adsorption behavior is still poorly understood. When tetraethylenepentamine (TEPA) is impregnated on two different supports, commercial γ-Al(2)O(3) and MIL-101(Cr), they show different trends in CO(2) sorption when the temperature (−20 to 25 °C) and humidity (0–70% RH) of the simulated air stream are varied. In situ IR spectroscopy is used to probe the mechanism of CO(2) sorption on the two supported amine materials, with weak chemisorption (formation of carbamic acid) being the dominant pathway over MIL-101(Cr)-supported TEPA and strong chemisorption (formation of carbamate) occurring over γ-Al(2)O(3)-supported TEPA. Formation of both carbamic acid and carbamate species is enhanced over the supported TEPA materials under humid conditions, with the most significant enhancement observed at −20 °C. However, while equilibrium H(2)O sorption is high at cold temperatures (e.g., −20 °C), the effect of humidity on a practical cyclic DAC process is expected to be minimal due to slow H(2)O uptake kinetics. This work suggests that the CO(2) capture mechanisms of impregnated amines can be controlled by adjusting the degree of amine-solid support interaction and that H(2)O adsorption behavior is strongly affected by the properties of the support materials. Thus, proper selection of solid support materials for amine impregnation will be important for achieving optimized DAC performance under varied deployment conditions, such as cold (e.g., −20 °C) or ambient temperature (e.g., 25 °C) operations.