Distribution and Transport of CO2 in Hyperbranched Poly(ethylenimine)-Loaded MCM-41: A Molecular Dynamics Simulation Approach.

Fossil fuel use is accelerating climate change, driving the need for efficient CO2 capture technologies. Solid adsorption-based direct air capture (DAC) of CO2 has emerged as a promising mode for CO2 removal from the atmosphere due to its potential for scalability. Sorbents based on porous supports incorporating oligomeric amines in their pore spaces are widely studied. In this study, we investigate the intermolecular interactions and adsorption of CO2 and H2O molecules in hyperbranched poly(ethylenimine) (HB-PEI) functionalized MCM-41 systems to understand the distribution and transport of CO2 and H2O molecules. Density Functional Theory (DFT) is employed to compute the binding energies of CO2 and H2O molecules with HB-PEI and MCM-41 and to develop force field parameters for molecular dynamics (MD) simulations. The MD simulations are performed to examine the distribution and transport of CO2 and H2O molecules as a function of the HB-PEI content. The study finds that an HB-PEI content of approximately 34 wt % is thermodynamically favorable, with an upper limit of HB-PEI loading between 45 and 50 wt %. The distribution of CO2 and H2O molecules is primarily determined by their adsorptive binding energies, for which H2O molecules dominate the occupation of binding sites due to their strong affinity with silanol groups on MCM-41 and amine groups of HB-PEI. The HB-PEI content has a considerable impact on the diffusion of CO2 and H2O molecules. Furthermore, a larger number of water molecules (higher relative humidity) reduces the correlation of CO2 with the MCM-41 pore surface while enhancing the correlation of CO2 with the amine groups of the HB-PEI. Overall, the presence of H2O molecules increases the CO2 correlation with the amine groups and also the CO2 transport within HB-PEI-loaded MCM-41, meaning that the presence of H2O enhances the CO2 capture in the HB-PEI-loaded MCM-41. These findings are consistent with experimental observations of the impact of increasing humidity on CO2 capture while providing new, molecular-level explanations for the macroscopic experimental findings.

Contributions of CO2, O2, and H2O to the Oxidative Stability of Solid Amine Direct Air Capture Sorbents at Intermediate Temperature.

Aminopolymer-based sorbents are preferred materials for extraction of CO2 from ambient air [direct air capture (DAC) of CO2] owing to their high CO2 adsorption capacity and selectivity at ultra-dilute conditions. While those adsorptive properties are important, the stability of a sorbent is a key element in developing high-performing, cost-effective, and long-lasting sorbents that can be deployed at scale. Along with process upsets, environmental components such as CO2, O2, and H2O may contribute to long-term sorbent instability. As such, unraveling the complex effects of such atmospheric components on the sorbent lifetime as they appear in the environment is a critical step to understanding sorbent deactivation mechanisms and designing more effective sorbents and processes. Here, a poly(ethylenimine) (PEI)/Al2O3 sorbent is assessed over continuous and cyclic dry and humid conditions to determine the effect of the copresence of CO2 and O2 on stability at an intermediate temperature of 70 °C. Thermogravimetric and elemental analyses in combination with in situ horizontal attenuated total reflection infrared (HATR-IR) spectroscopy are performed to measure the extent of deactivation, elemental content, and molecular level changes in the sorbent due to deactivation. The thermal/thermogravimetric analysis results reveal that incorporating CO2 with O2 accelerates sorbent deactivation using these sorbents in dry and humid conditions compared to that using CO2-free air in similar conditions. The in situ HATR-IR spectroscopy results of PEI/Al2O3 sorbent deactivation under a CO2-air environment show the formation of primary amine species in higher quantity (compared to that in conditions without O2 or CO2), which arises due to the C-N bond cleavage at secondary amines due to oxidative degradation. We hypothesize that the formation of bound CO2 species such as carbamic acids catalyzes C-N cleavage reactions in the oxidative degradation pathway by shuttling protons, resulting in a low activation energy barrier for degradation, as probed by metadynamics simulations. In the cyclic experiment after 30 cycles, results show a gradual loss in stability (dry: 29%, humid: 52%) under CO2-containing air (0.04% CO2/21% O2 balance N2). However, the loss in capacity during cyclic studies is significantly less than that during continuous deactivation, as expected.

Insights into the Oxidative Degradation Mechanism of Solid Amine Sorbents for CO2 Capture from Air: Roles of Atmospheric Water.

Direct air capture (DAC) processes for extraction of CO2 from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al2 O3 , is explored in detail. By combining CO2 adsorption measurements, oxidative degradation rates, elemental analyses, solid-state NMR and in situ IR spectroscopic analysis in conjunction with 18 O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. We demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.

Distribution and Transport of CO2 in Hydrated Hyperbranched Poly(ethylenimine) Membranes: A Molecular Dynamics Simulation Approach.

Hyperbranched poly(ethylenimine) (HB-PEI) has been distinguished as a promising candidate for carbon dioxide (CO2) capture. In this study, we investigate the distribution and transport of CO2 molecules in a HB-PEI membrane at various hydration levels using molecular dynamics (MD) simulations. For this, model structures consisting of amorphous HB-PEI membranes with CO2 molecules are equilibrated at various hydration levels. Under dry conditions, the primary and secondary amines are highly associated with CO2, indicating that they would participate in CO2 capture via the carbamate formation mechanism. Under hydrated conditions, the pair correlations of CO2 with the primary and secondary amines are reduced. This result suggests that the carbamate formation mechanism is less prevalent compared to dry conditions, which is also supported by CO2 residence time analysis. However, in the presence of water molecules, it is found that the CO2 molecules can be associated with both amine groups and water molecules, which would enable the tertiary amine as well as the primary and secondary amines to capture CO2 molecules via the bicarbonate formation mechanism. Through our MD simulation results, the feasibilities of different CO2 capture pathways in HB-PEI membranes are demonstrated at the molecular level.

Effect of Extended Aging and Oxidation on Linear Poly(propylenimine)-Mesoporous Silica Composites for CO2 Capture from Simulated Air and Flue Gas Streams.

Physical aging or degradation of amine-containing polymers and supported amine adsorbents is a critical issue that could limit the practical application of such materials for CO2 capture. However, to date, there is a scarcity of studies that evaluate the long-term stability of amine-based sorbents without the exclusive use of accelerated aging tests. Here, we demonstrate that extended aging (∼2 years) of linear poly(propylenimine) (LPPI) confined in mesoporous silica (SBA-15) supports does not drastically impact the CO2 adsorption performance under simulated flue gas (10% CO2) and direct air capture (DAC, 400 ppm CO2) conditions, although the behavior of the aged sorbents and polymers in the two CO2 concentration regimes differs. The sorbents made with aged LPPI have modestly decreased CO2 uptake performance (≲20% lower) compared to the fresh polymers, with overall good CO2 cycling performance. The data indicate that only slow degradation occurs under the deployed ambient storage conditions. Even after extended aging, the LPPI-based sorbents preserved their ability to display stable temperature-swing cycling performance. In parallel, the impact of blending LPPI polymers of different number-average molecular weights, Mn, is evaluated, seeking to understand its impact on adsorbent performance. The results demonstrate that the blends of two Mn aged LPPI give similar CO2 adsorption performance to adsorbents made from a single-Mn LPPI, suggesting that molecular weight will not negatively impact adsorbent performance in the studied Mn range. After an accelerated oxidation experiment, the aged LPPI sorbents retained a larger portion of the samples' original performance when cycling under simulated flue gas conditions than under DAC conditions. However, in each case, the oxidized sorbents could be cycled repeatedly with consistent uptake performance. Overall, these first of their kind extended aging tests suggest that LPPI-based amine adsorbents offer promise for long-term, stable use in carbon capture applications.

Linking Silica Support Morphology to the Dynamics of Aminopolymers in Composites.

A combined computational and experimental approach is used to elucidate the effect of silica support morphology on polymer dynamics and CO2 adsorption capacities in aminopolymer/silica composites. Simulations are based on coarse-grained molecular dynamics simulations of aminopolymer composites where a branched aminopolymer, representing poly(ethylenimine) (PEI), is impregnated into different silica mesoporous supports. The morphology of the mesoporous supports varies from hexagonally packed cylindrical pores representing SBA-15, double gyroids representing KIT-6 and MCM-48, and cagelike structures representing SBA-16. In parallel, composites of PEI and the silica supports SBA-15, KIT-6, MCM-48, and SBA-16 are synthesized and characterized, including measuring their CO2 uptake. Simulations predict that a 3D pore morphology, such as those of KIT-6, MCM-48, and SBA-16, will have faster segmental mobility and have lower probability of primary amine and surface silanol associations, which should translate to higher CO2 uptake in comparison to a 2D pore morphology such as that of SBA-15. Indeed, it is found that KIT-6 has higher CO2 uptake than SBA-15 at equivalent PEI loading, even though both supports have similar surface area and pore volume. However, this is not the case for the MCM-48 support, which has smaller pores, and SBA-16, whose pore structure rapidly degrades after PEI impregnation.

Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO2 Capture Applications: A Quasielastic Neutron Scattering Study.

Composite gas sorbents, formed from an active polymer phase and a porous support, are promising materials for the separation of acid gases from a variety of gas streams. Significant changes in sorption performance (capacity, rate, stability etc.) can be achieved by tuning the properties of the polymer and the nature of interactions between polymer and support. Here we utilize quasielastic neutron scattering (QENS) and coarse-grained molecular dynamics (MD) simulations to characterize the dynamic behavior of the most commonly reported polymer in such materials, poly(ethylenimine) (PEI), both in bulk form and when supported in a mesoporous silica framework. The polymer chain dynamics (rotational and translational diffusion) are characterized using two neutron backscattering spectrometers that have overlapping time scales, ranging from picoseconds to a few nanoseconds. Two modes of motion are detected for the PEI molecule in QENS. At low energy transfers, a "slow process" on the time scale of ∼200 ps is found and attributed to jump-mediated, center-of-mass diffusion. A second, "fast process" at ∼20 ps scale is also found and is attributed to a locally confined, jump-diffusion. Characteristic data (time scale and spectral weight) of these processes are compared to those characterized by MD, and reasonable agreement is found. For the nanopore-confined PEI, we observe a significant reduction in the time scale of polymer motion as compared to the bulk. The impacts of silica surface functionalization and of polymer fill fraction in the silica pores (controlling the portion of polymer molecules in contact with the pore walls), are both studied in detail. Hydrophobic functionalization of the silica leads to an increase of the PEI mobility above that in native silanol-terminated silica, but the dynamics are still slower than those in bulk PEI. Sorbents with faster PEI dynamics are also found to be more efficient for CO2 capture, possibly because sorption sites are more accessible than those in systems with slower PEI dynamics. Thus, this work supports the existence of a link between the affinity of the support for PEI and the accessibility of active sorbent functional groups.

Design of Aminopolymer Structure to Enhance Performance and Stability of CO2 Sorbents: Poly(propylenimine) vs Poly(ethylenimine).

Studies on aminopolymer/oxide composite materials for direct CO2 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 CO2 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 CO2 capture from air. Regardless of amine loading or aminopolymer architecture, the PPI-based sorbents are found to be more efficient for CO2 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 CO2 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.

Poly(ethylenimine)-Functionalized Monolithic Alumina Honeycomb Adsorbents for CO2 Capture from Air.

The development of practical and effective gas-solid contactors is an important area in the development of CO2 capture technologies. Target CO2 capture applications, such as postcombustion carbon capture and sequestration (CCS) from power plant flue gases or CO2 extraction directly from ambient air (DAC), require high flow rates of gas to be processed at low cost. Extruded monolithic honeycomb structures, such as those employed in the catalytic converters of automobiles, have excellent potential as structured contactors for CO2 adsorption applications because of the low pressure drop imposed on fluid moving through the straight channels of such structures. Here, we report the impregnation of poly(ethylenimine) (PEI), an effective aminopolymer reported commonly for CO2 separation, into extruded monolithic alumina to form structured CO2 sorbents. These structured sorbents are first prepared on a small scale, characterized thoroughly, and compared with powder sorbents with a similar composition. Despite consistent differences observed in the filling of mesopores with PEI between the monolithic and powder sorbents, their performance in CO2 adsorption is similar across a range of PEI contents. A larger monolithic cylinder (1 inch diameter, 4 inch length) is evaluated under conditions closer to those that might be used in large-scale applications and shows a similar performance to the smaller monoliths and powders tested initially. This larger structure is evaluated over five cycles of CO2 adsorption and steam desorption and demonstrates a volumetric capacity of 350 molCO2 m-3monolith and an equilibration time of 350 min under a 0.4 m s(-1) linear flow velocity through the monolith channels using 400 ppm CO2 in N2 as the adsorption gas at 30 °C. This volumetric capacity surpasses that of a similar technology considered previously, which suggested that CO2 could be removed from air at an operating cost as low as $100 per ton.

Unraveling the Dynamics of Aminopolymer/Silica Composites.

The structure and dynamics of a model branched polymer was investigated through molecular dynamics simulations and neutron scattering experiments. The polymer confinement, monomer concentration, and solvent quality were varied in the simulations and detailed comparisons between the calculated structural and dynamical properties of the unconfined polymer and those confined within an adsorbing and nonadsorbing cylindrical pore, representing the silica based structural support of the composite, were made. The simulations show a direct relationship in the structure of the polymer and the nonmonotonic dynamics as a function of monomer concentration within an adsorbing cylindrical pore. However, the nonmonotonic behavior disappears for the case of the branched polymer within a nonadsorbing cylindrical pore. Overall, the simulation results are in good agreement with quasi-elastic neutron scattering (QENS) studies of branched poly(ethylenimine) in mesoporous silica (SBA-15) of comparable size, suggesting an approach that can be a useful guide for understanding how to tune porous polymer composites for enhancing desired dynamical and structural behavior targeting carbon dioxide adsorption.

Characterization of a Mixture of CO2 Adsorption Products in Hyperbranched Aminosilica Adsorbents by (13)C Solid-State NMR.

Hyperbranched amine polymers (HAS) grown from the mesoporous silica SBA-15 (hereafter "SBA-15-HAS") exhibit large capacities for CO2 adsorption. We have used static in situ and magic-angle spinning (MAS) ex situ (13)C nuclear magnetic resonance (NMR) to examine the adsorption of CO2 by SBA-15-HAS. (13)C NMR distinguishes the signal of gas-phase (13)CO2 from that of the chemisorbed species. HAS polymers possess primary, secondary, and tertiary amines, leading to multiple chemisorption reaction outcomes, including carbamate (RnNCOO(-)), carbamic acid (RnNCOOH), and bicarbonate (HCO3(-)) moieties. Carbamates and bicarbonate fall within a small (13)C chemical shift range (162-166 ppm), and a mixture was observed including carbamic acid and carbamate, the former disappearing upon evacuation of the sample. By examining the (13)C-(14)N dipolar coupling through low-field (B0 = 3 T) (13)C{(1)H} cross-polarization MAS NMR, carbamate is confirmed through splitting of the (13)C resonance. A third species that is either bicarbonate or a second carbamate is evident from bimodal T2 decay times of the ∼163 ppm peak, indicating the presence of two species comprising that single resonance. The mixture of products suggests that (1) the presence of amines and water leads to bicarbonate being present and/or (2) the multiple types of amine sites in HAS permit formation of chemically distinct carbamates.

Role of Additives in Composite PEI/Oxide CO2 Adsorbents: Enhancement in the Amine Efficiency of Supported PEI by PEG in CO2 Capture from Simulated Ambient Air.

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.

An efficient low-temperature route to nitrogen-doping and activation of mesoporous carbons for CO2 capture.

An innovative strategy for post-synthesis nitrogen-doping of mesoporous carbons (MCs) with high yields (>90%) at low temperatures (230-380 °C) by using a strong base, sodium amide (NaNH2), was developed. The as-prepared N-doped MCs exhibit a significantly enhanced CO2 adsorption performance in terms of capacity and selectivity when compared to their parent MCs.

Interrogating the Carbon and Oxygen K-Edge NEXAFS of a CO2-Dosed Hyperbranched Aminosilica.

Using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, we shed light on the nature of the interaction between CO2 and the amine moieties in a hyperbranched aminosilica (HAS) material, a porous aminosilica composite with great potential for postcombustion carbon capture applications. We show that after dosing a pristine (annealed) HAS sample with CO2, the C K-edge NEXAFS spectrum presents a new π* resonance at 289.9 eV, which can be attributed to the formation of a C═O (carbonyl) bond. Additional analyses of the O K-edge using model samples containing carbamate, carbonate, and bicarbonate functional groups as reference demonstrate a carbamate bonding mechanism for the chemical adsorption of CO2 by the HAS material under the conditions employed. These findings show the capability of the C and O K-edge NEXAFS technique to identify CO2-adsorbate species despite the high concentration of C and O atoms inherently present in the sample (prior to CO2 dosing) and the significant similarities between the possible adsorbates.

Probing the Role of Zr Addition versus Textural Properties in Enhancement of CO2 Adsorption Performance in Silica/PEI Composite Sorbents.

Polymeric amines such as poly(ethylenimine) (PEI) supported on mesoporous oxides are promising candidate adsorbents for CO2 capture processes. An important aspect to the design and optimization of these materials is a fundamental understanding of how the properties of the oxide support such as pore structure, particle morphology, and surface properties affect the efficiency of the guest polymer in its interactions with CO2. Previously, the efficiency of impregnated PEI to adsorb CO2 was shown to increase upon the addition of Zr as a surface modifier in SBA-15. However, the efficacy of this method to tune the adsorption performance has not been explored in materials of differing textural and morphological nature. Here, these issues are directly addressed via the preparation of an array of SBA-15 support materials with varying textural and morphological properties, as well as varying content of zirconium doped into the material. Zirconium is incorporated into the SBA-15 either during the synthesis of the SBA-15, or postsynthetically via deposition of Zr species onto pure-silica SBA-15. The method of Zr incorporation alters the textural and morphological properties of the parent SBA-15 in different ways. Importantly, the CO2 capacity of SBA-15 impregnated with PEI increases by a maximum of ∼60% with the quantity of doped Zr for a "standard" SBA-15 containing significant microporosity, while no increase in the CO2 capacity is observed upon Zr incorporation for an SBA-15 with reduced microporosity and a larger pore size, pore volume, and particle size. Finally, adsorbents supported on SBA-15 with controlled particle morphology show only modest increases in CO2 capacity upon inclusion of Zr to the silica framework. The data demonstrate that the textural and morphological properties of the support have a more significant impact on the ability of PEI to capture CO2 than the support surface composition.

Linking CO2 Sorption Performance to Polymer Morphology in Aminopolymer/Silica Composites through Neutron Scattering.

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.

Post-grafting amination of alkyl halide-functionalized silica for applications in catalysis, adsorption, and 15N NMR spectroscopy.

An anhydrous synthesis of aminosilica materials from alkyl halide-functionalized mesoporous SBA-15 silica by post-grafting amination is introduced for applications in CO2 adsorption, cooperative catalysis, and (15)N solid-state NMR spectroscopy. The synthesis is demonstrated to convert terminal alkyl halide-functionalized silica materials containing Cl, Br, and I to primary alkylamines using anhydrous ammonia in a high-pressure reactor. The benefits of the post-grafting amination procedure include (i) use of anhydrous isotopically labeled ammonia, (15)NH3, to create aminosilica materials that can be investigated using (15)N solid-state NMR to elucidate potential intermediates and surface species in CO2 adsorption processes and catalysis, (ii) similar CO2 uptake in experiments extracting CO2 from dry simulated air experiments, and (iii) improved activity in acid-base bifunctional catalysis compared to traditional amine-grafted materials. The effects of the type of halide, the initial halide loading, and the total reaction time on the conversion of the halides to primary amines are explored. Physical and chemical characterizations of the materials show that the textural properties of the silica are unaffected by the reaction conditions and that quantitative conversion to primary amines is achieved even at short reaction times and high initial alkyl halide loadings. Additionally, preliminary (15)N solid-state NMR experiments indicate formation of nitrogen-containing species and demonstrate that the synthesis can be used to create materials useful for investigating surface species by NMR spectroscopy. The differences between the materials prepared via post-grafting amination vs traditional aminosilane grafting are attributed to the slightly increased spacing of the amines synthesized by amination because the alkylhalosilanes are initially better spaced on the silica surface after grafting, whereas the aminosilanes likely cluster to a greater extent when grafted on the silica surface. A slight increase in amine spacing allows for more effective amine-silanol interactions in cooperative catalysis without reducing the amine efficiency in CO2 uptake under the conditions used here.

Steam induced structural changes of a poly(ethylenimine) impregnated γ-alumina sorbent for CO2 extraction from ambient air.

Poly(ethylenimine) (PEI) impregnated mesoporous γ-alumina sorbents are utilized for CO2 adsorption from dry and humid simulated ambient air, and the sorbents are regenerated under an environment of flowing steam for times ranging from 5 min to 24 h of continuous exposure. The sorbents are compared on the basis of equilibrium CO2 capacities from simulated air at 400 ppm of CO2, 50% relative humidity, and 30 °C as well as their physiochemical characterization by means of X-ray diffraction (XRD), (27)Al NMR spectroscopy, IR spectroscopy, Raman spectroscopy, N2 physisorption, and elemental analysis. The sorbents retain better than 90% of the initial equilibrium capacity of ∼1.7 mmol/g at steam exposure times up to 12 h; however, PEI leaching reduced the capacity of the sorbent to 0.66 mmol/g after 24 h of continuous treatment. It is demonstrated that the γ-alumina support partially hydrates to form a boehmite crystal phase at steam times of 90 min and longer but that this phase transition occurs predominately between 90 min and 12 h of steam treatment, slowing at longer times of 12 and 24 h of treatment. Evidence is presented to suggest that the presence of boehmite on the sorbent surface does not significantly alter the amine efficiency of impregnated PEI. The collected results suggest that γ-alumina/PEI composite materials are promising sorbents for CO2 capture from ambient air with regeneration in flowing steam.

Effect of Amine Surface Coverage on the Co-Adsorption of CO2 and Water: Spectral Deconvolution of Adsorbed Species.

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.