Three primary amine materials functionalized onto mesoporous silica with low, medium, and high surface amine coverages are prepared and evaluated for binary CO2/H2O adsorption under dilute conditions. Enhancement of amine efficiency due to humid adsorption is most pronounced for low surface amine coverage materials. In situ FT-IR spectra of adsorbed CO2 on these materials suggest this enhancement may be associated with the formation of bicarbonate species during adsorption on materials with low surface amine coverage, though such species are not observed on high surface coverage materials. On the materials with the lowest amine loading, bicarbonate is observed on longer time scales of adsorption, but only after spectral contributions from rapidly forming alkylammonium carbamate species are removed. This is the first time that direct evidence for bicarbonate formation, which is known to occur in liquid aqueous amine solutions, has been presented for CO2 adsorption on solid amine adsorbents.

Composites of poly(ethylenimine) (PEI) and mesoporous silica are effective, reversible adsorbents for CO2, both from flue gas and in direct air-capture applications. The morphology of the PEI within the silica can strongly impact the overall carbon capture efficiency and rate of saturation. Here, we directly probe the spatial distribution of the supported polymer through small-angle neutron scattering (SANS). Combined with textural characterization from physisorption analysis, the data indicate that PEI first forms a thin conformal coating on the pore walls, but all additional polymer aggregates into plug(s) that grow along the pore axis. This model is consistent with observed trends in amine-efficiency (CO2/N binding ratio) and pore size distributions, and points to a trade-off between achieving high chemical accessibility of the amine binding sites, which are inaccessible when they strongly interact with the silica, and high accessibility for mass transport, which can be hampered by diffusion through PEI plugs. We illustrate this design principle by demonstrating higher CO2 capacity and uptake rate for PEI supported in a hydrophobically modified silica, which exhibits repulsive interactions with the PEI, freeing up binding sites.

Studies on aminopolymer/oxide composite materials for direct CO capture from air have often focused on the prototypical poly(ethylenimine) (PEI) as the aminopolymer. However, it is known that PEI will oxidatively degrade at elevated temperatures. This degradation has been ascribed to the presence of secondary amines, which, when oxidized, lose their CO capture capacity. Here, we demonstrate the use of small molecule poly(propylenimine) (PPI) in linear and dendritic architectures supported in silica as adsorbent materials for direct CO capture from air. Regardless of amine loading or aminopolymer architecture, the PPI-based sorbents are found to be more efficient for CO capture than PEI-based sorbents. Moreover, PPI is found to be more resistant to oxidative degradation than PEI, even while containing secondary amines, as supported by FTIR, NMR, and ESI-MS studies. These results suggest that PPI-based CO sorbents may allow for longer sorbent working lifetimes due to an increased tolerance to sorbent regeneration conditions and suggest that the presence of secondary amines may not mean that all aminopolymers will oxidatively degrade.

Supported amines are promising candidate adsorbents for the removal of CO2 from flue gases and directly from ambient air. The incorporation of additives into polymeric amines such as poly(ethylenimine) (PEI) supported on mesoporous oxides is an effective strategy to improve the performance of the materials. Here, several practical aspects of this strategy are addressed with regards to direct air capture. The influence of three additives (CTAB, PEG200, PEG1000) was systematically explored under dry simulated air capture conditions (400 ppm of CO2, 30 °C). With SBA-15 as a model support for poly(ethylenimine) (PEI), the nature of the additive induced heterogeneities in the deposition of organic on the interior and exterior of the particles, an important consideration for future scale up to practical systems. The PEG200 additive increased the observed thermodynamic performance (∼60% increase in amine efficiency) of the adsorbents regardless of the PEI content, while the other molecules had less positive effects. A threshold PEG200/PEI value was identified at which the diffusional limitations of CO2 within the materials were nearly eliminated. The threshold PEG/PEI ratio may have physical origin in the interactions between PEI and PEG, as the optimal ratio corresponded to nearly equimolar OH/reactive (1°, 2°) amine ratios. The strategy is shown to be robust to the characteristics of the host support, as PEG200 improved the amine efficiency of PEI when supported on two varieties of mesoporous γ-alumina with PEI.

Poly(ethyleneimine)-impregnated sorbents are prepared using a hierarchical silica support with bimodal meso-/macroporosity. The sorbents behave unexpectedly during CO 2 adsorption from simulated air and flue gases (400 ppm and 10% CO 2 ) at a fixed temperature, as compared to systems built on commonly studied mesoporous materials. The results demonstrate that (i) impregnation methods influence the efficacy of sorption performance and (ii) the sorbents show almost similar uptake capacities under 400 ppm and 10% dry CO 2 at 30 °C, exhibiting step-like CO 2 adsorption isotherms. These unusual observations are rationalized via control experiments and a hypothesized sorption mechanism. While the sorption performance near room temperature is unexpectedly identical under 400 ppm and 10% CO 2 conditions, there is an optimal temperature at each gas concentration where the uptake is maximized. The maximum sorption capacities are 2.6 and 4.1 mmol CO 2 /g sorbent at the optimized sorption temperatures using 400 ppm and 10% dry CO 2 , respectively. The presence of water vapor under 400 ppm CO 2 conditions further improves the sorption capacity to 3.4 mmol/g sorbent, which is the highest capacity under direct air capture conditions among known amine sorbents impregnated with a similar polymer, to the best of our knowledge.