Improving the direct air capture capacity of grafted amines via thermal treatment.

This study investigates the effects of elevated temperature thermal treatments on the direct air capture of CO2 by aminosilane-grafted SBA-15 silica sorbents. Exposing samples to high temperatures (200-250 °C compared to 80-120 °C) in an inert environment resulted in improved CO2 capacity (5-21%) that was sustained over multiple adsorption/desorption cycles.

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.

Enhanced hydrogen bonding via epoxide-functionalization restricts mobility in poly(ethylenimine) for CO2 capture.

Free energy sampling, deep potential molecular dynamics, and characterizations provide insights into the impact of epoxide-functionalization on the hydrogen bonding and mobility of poly(ethylenimine), a promising CO2 sorbent. These findings rationalize the anti-degradation effects of epoxide functionalization and open up new avenues for designing more durable CO2 sorbents.

Probing the Kinetic Origin of Varying Oxidative Stability of Ethyl- vs. Propyl-spaced Amines for Direct Air Capture.

Amine-based adsorbents are promising for direct air capture of CO2 , yet oxidative degradation remains a key unmitigated risk hindering wide-scale deployment. Borrowing wisdom from the basic auto-oxidation scheme, insights are gained into the underlying degradation mechanisms of polyamines by quantum chemical, advanced sampling simulations, adsorbent synthesis, and accelerated degradation experiments. The reaction kinetics of polyamines are contrasted with that of typical aliphatic polymers and they elucidate for the first time the critical role of aminoalkyl hydroperoxide decomposition in the oxidative degradation of amino-oligomers. The experimentally observed variation in oxidative stability of polyamines with different backbone structures is explained by the relationship between the local chemical structure and the free energy barrier of aminoalkyl hydroperoxide decomposition, suggesting that its energetics can be used as a descriptor to screen and design new polyamines with improved stability. The developed computational capability sheds light on radical-induced degradation chemistry of other organic functional materials.

Unblocking a rigid purine MOF for kinetic separation of xylenes.

The separation of xylene isomers still remains an industrially challenging task. Here, porous purine-based metal-organic frameworks (MOFs) have been synthesized and studied for their potential in xylene separations. In particular, Zn(purine)I showed excellent para-xylene/ortho-xylene separation capability with a diffusion selectivity of 6 and high equilibrium adsorption selectivity as indicated by coadsorption experiments. This high selectivity is attributed to the shape and size of the channel aperture within the rigid framework of Zn(purine)I.

Efficient Hydrogen Delivery for Microbial Electrosynthesis via 3D-Printed Cathodes.

The efficient delivery of electrochemically in situ produced H2 can be a key advantage of microbial electrosynthesis over traditional gas fermentation. However, the technical details of how to supply large amounts of electric current per volume in a biocompatible manner remain unresolved. Here, we explored for the first time the flexibility of complex 3D-printed custom electrodes to fine tune H2 delivery during microbial electrosynthesis. Using a model system for H2-mediated electromethanogenesis comprised of 3D fabricated carbon aerogel cathodes plated with nickel-molybdenum and Methanococcus maripaludis, we showed that novel 3D-printed cathodes facilitated sustained and efficient electromethanogenesis from electricity and CO2 at an unprecedented volumetric production rate of 2.2 L CH4 /L catholyte /day and at a coulombic efficiency of 99%. Importantly, our experiments revealed that the efficiency of this process strongly depends on the current density. At identical total current supplied, larger surface area cathodes enabled higher methane production and minimized escape of H2. Specifically, low current density (<1 mA/cm2) enabled by high surface area cathodes was found to be critical for fast start-up times of the microbial culture, stable steady state performance, and high coulombic efficiencies. Our data demonstrate that 3D-printing of electrodes presents a promising design tool to mitigate effects of bubble formation and local pH gradients within the boundary layer and, thus, resolve key critical limitations for in situ electron delivery in microbial electrosynthesis.

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.

Oxidatively-Stable Linear Poly(propylenimine)-Containing Adsorbents for CO2 Capture from Ultradilute Streams.

Aminopolymer-based solid sorbents have been widely investigated for the capture of CO2 from dilute streams such as flue gas or ambient air. However, the oxidative stability of the widely studied aminopolymer, poly(ethylenimine) (PEI), is limited, causing it to lose its CO2 capture capacity after exposure to oxygen at elevated temperatures. Here, we demonstrate the use of linear poly(propylenimine) (PPI), synthesized through a simple cationic ring-opening polymerization, as a more oxidatively stable alternative to PEI with high CO2 capacity and amine efficiency. The performance of linear PPI/SBA-15 composites was investigated over a range of CO2 capture conditions (CO2 partial pressure, adsorption temperature) to examine the tradeoff between adsorption capacity and sorption-site accessibility, which was expected to be more limited in linear polymers relative to the prototypical hyperbranched PEI. Linear PPI/SBA-15 composites were more efficient at CO2 capture and retained 65-83 % of their CO2 capacity after exposure to a harsh oxidative treatment, compared to 20-40 % retention for linear PEI. Additionally, we demonstrated long-term stability of linear PPI sorbents over 50 adsorption/desorption cycles with no loss in performance. Combined with other strategies for improving the oxidative stability and adsorption kinetics, linear PPI may play a role as a component of stable solid adsorbents in commercial applications for CO2 capture.

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.

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.

Adsorption Microcalorimetry of CO2 in Confined Aminopolymers.

Aminopolymers confined within mesoporous supports have shown promise as materials for direct capture of CO2 from ambient air. In spite of this, relatively little is known about the energetics of CO2 binding in these materials, and the limited calorimetric studies published to date have focused on materials made using molecular aminosilanes rather than amine polymers. In this work, poly(ethylenimine) (PEI) is impregnated within mesoporous SBA-15, and the heats of CO2 adsorption at 30 °C are investigated using a Tian-Calvet calorimeter with emphasis on the role of PEI loading and CO2 pressure in the compositional region relevant to direct capture of CO2 from ambient air. In parallel, CO2 uptakes of these materials are measured using multiple complementary approaches, including both volumetric and gravimetric methods, and distinct changes in uptake as a function of CO2 pressure and amine loading are observed. The CO2 sorption behavior is directly linked to textural data describing the porosity and PEI distribution in the materials.

Controlling Catalytic Selectivity via Adsorbate Orientation on the Surface: From Furfural Deoxygenation to Reactions of Epoxides.

Specificity to desired reaction products is the key challenge in designing solid catalysts for reactions involving addition or removal of oxygen to/from organic reactants. This challenge is especially acute for reactions involving multifunctional compounds such as biomass-derived aromatic molecules (e.g., furfural) and functional epoxides (e.g., 1-epoxy-3-butene). Recent surface-level studies have shown that there is a relationship between adsorbate surface orientation and reaction selectivity in the hydrogenation pathways of aromatic oxygenates and the ring-opening or ring-closing pathways of epoxides. Control of the orientation of reaction intermediates on catalytic surfaces by modifying the surface or near-surface environment has been shown to be a promising method of affecting catalytic selectivity for reactions of multifunctional molecules. In this Perspective, we review recent model studies aimed at understanding the surface chemistry for these reactions and studies that utilize this insight to rationally design supported catalysts.

PIM-1 as a Solution-Processable "Molecular Basket" for CO2 Capture from Dilute Sources.

Rising atmospheric CO2 levels have triggered recent research into the science of amine materials supported on hard, porous materials such as mesoporous silica or alumina. While such materials can give high CO2 uptakes and good sorption kinetics, they are difficult to utilize in practical applications due to difficulty in contacting large volumes of CO2-laden gases with powder materials without significant pressure drops or sorbent attrition. Here, we describe a simple approach based on the impregnation of a permanently microporous polymer, PIM-1, with poly(ethylene imine) (PEI), removing the need for use of the hard oxide. PEI/PIM-1 composites demonstrate comparable performance to more traditionally studied oxide sorbents, with the benefit that PIM-1 is soluble in common solvents, making it eminently more viable for processing into morphologies that can facilitate heat and mass transfer and fabrication into low pressure drop contactors. In addition to adsorption studies performed on a variety of PEI/PIM-1 architectures, spin diffusion NMR studies were performed to suggest that PEI is well-dispersed within the PIM-1, allowing for rapid CO2 adsorption.

Hydrogen exposure effects on Pt/Al2O3 catalysts coated with thiolate monolayers.

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was used to examine the effect of thermal treatment of self-assembled monolayers (SAMs) produced from various thiols (1-hexanethiol, 1-decanethiol, 1-octadecanethiol, 1,6-hexanedithiol, 1,10-decanedithiol, 1,2-benzenedithiol) on a 5 wt % Pt/Al2O3 catalyst. Catalysts were characterized during heating and cooling between 290 and 553 K in both the presence and absence of H2. Overall, the behavior of thiols on Pt/Al2O3 in an inert He environment was similar to the behavior reported in other works on Au, although in the case of the Pt catalyst, C-H bond dissociation in the thiols was apparent at high temperatures. Under H2 flow, however, markedly different behavior was observed; in particular, conformational order was observed to increase with increasing temperature, up to temperatures as high as 500 K for octadecanethiol-coated catalysts. The effects of H2 exposure are much less pronounced for alkanedithiol-coated catalysts. 1,2-Benzenedithiol was found to undergo partial hydrogenation under H2, indicating that hydrogenating reaction conditions can also influence the chemical structure of the monolayer on active metals, such as Pt. The differences in thiolate structure caused by high-temperature exposure to hydrogen were found to have a significant effect on the rate and selectivity for hydrogenation of prenal, indicating that such effects may be broadly important in the use of thiolate-promoted catalysts for hydrogenation reactions.

Synergistic Effects of Alloying and Thiolate Modification in Furfural Hydrogenation over Cu-Based Catalysts.

Control of bimetallic surface composition and surface modification with self-assembled monolayers (SAMs) represent two methods for modifying catalyst activity and selectivity. However, possible synergistic effects of employing these strategies in concert have not been previously explored. We investigated the effects of modifying Cu/Al2O3 catalysts by alloying with Ni and modifying with octadecanethiol (C18) SAMs, using furfural hydrogenation as a probe reaction. Incorporation of small amounts of Ni (Cu4Ni) improved catalytic activity while slightly reducing hydrogenation selectivity. Further incorporation of Ni resulted in high rates for decarbonylation and ring-opening. Modification of the Cu4Ni catalyst with C18-SAMs resulted in improvement in both the activity and hydrogenation selectivity. X-ray photoelectron spectroscopy experiments on bimetallic thin films and density functional theory calculations revealed that the C18-SAM kinetically stabilized Cu at the surface under hydrogenation conditions. These results indicate that thiolate monolayers can be used to control surface bimetallic composition to improve catalytic performance.

Directing reaction pathways by catalyst active-site selection using self-assembled monolayers.

One key route for controlling reaction selectivity in heterogeneous catalysis is to prepare catalysts that exhibit only specific types of sites required for desired product formation. Here we show that alkanethiolate self-assembled monolayers with varying surface densities can be used to tune selectivity to desired hydrogenation and hydrodeoxygenation products during the reaction of furfural on supported palladium catalysts. Vibrational spectroscopic studies demonstrate that the selectivity improvement is achieved by controlling the availability of specific sites for the hydrogenation of furfural on supported palladium catalysts through the selection of an appropriate alkanethiolate. Increasing self-assembled monolayer density by controlling the steric bulk of the organic tail ligand restricts adsorption on terrace sites and dramatically increases selectivity to desired products furfuryl alcohol and methylfuran. This technique of active-site selection simultaneously serves both to enhance selectivity and provide insight into the reaction mechanism.