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DOE OSTI2025

Reactive CO 2 capture and mineralization of magnesium hydroxide to produce hydromagnesite with inherent solvent regeneration

Valorization of multiple low value streams including CO 2 emissions and magnesium-hydroxide bearing mine tailings to produce magnesium carbonate through reactive CO 2 capture and mineralization provides a less explored opportunity to manage several gigatons of CO 2 emissions. To resolve the feasibility of converting magnesium hydroxide to magnesium carbonate through reactive CO 2 capture and mineralization, CO 2 capture solvents such as sodium glycinate are harnessed to capture CO 2 and react directly with Mg(OH) 2 to produce hydromagnesite (Mg 5 [(CO 3 )4(OH) 2 ]·4H 2 O). This approach eliminates the energy-intensive step of producing high purity CO 2 associated with regenerating the solvent, and redissolving CO 2 to produce magnesium carbonate. Interestingly, while temperatures below 50 °C facilitate CO 2 capture, the mineralization kinetics are slow. However, at higher temperatures, accelerated carbon mineralization is favored by the faster kinetics of Mg(OH) 2 dissolution and precipitation of magnesium carbonate. Reacting Mg(OH) 2 at 90 °C with 15 wt% solids in the presence of 2.5 M sodium glycinate after 3 hours under well-stirred conditions results in an extent of carbon mineralization of 75.5%. The theoretical maximum extent of carbon mineralization when hydromagnesite is formed is 80%. Pre-loading CO 2 on the solvent is also an effective approach to ensure that sufficient CO2 is available for reactive CO 2 capture and mineralization, particularly when dilute CO 2 and N 2 mixtures are used. Higher extents of carbon mineralization are associated with an increase in the particle size and a reduction in the cumulative pore volume. These insights unlock the feasibility of harnessing reactive CO 2 capture and mineralization as a pathway to convert magnesium-hydroxide bearing resources into industrially relevant magnesium carbonate products.

Reactive CO2↗

DOE OSTI2020

Electrocatalytic CO 2 reduction on earth abundant 2D Mo 2 C and Ti 3 C 2 MXenes

Mo 2 C and Ti 3 C 2 MXenes were investigated as earth-abundant electrocatalyts for the CO 2 reduction reaction (CO 2 RR). Mo 2 C and Ti 3 C 2 exhibited faradaic efficiencies of 90% (250 mV overpotential) and 65% (650 mV overpotential), respectively, for the reduction of CO 2 to CO in acetonitrile using an ionic liquid electrolyte. The use of ionic liquid 1-ethyl-2-methylimidazolium tetrafluoroborate as an electrolyte in organic solvent suppressed the competing hydrogen evolution reaction. Density functional theory (DFT) calculations suggested that the catalytic active sites are oxygen vacancy sites on both MXene surfaces. Also, a spontaneous dissociation of adsorbed COOH species to a water molecule and adsorbed CO on Mo 2 C promote the CO 2 RR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Compact Absorber Technology Leads to Significant Reduction in the Cost of Point Source CO 2 Capture

The size of columns in traditional absorption-based processes for CO 2 capture contributes significantly to the overall capital cost. A demonstrated method to reduce the cost of point source CO 2 capture, focusing on reducing the absorber height by increasing the liquid-to-gas reaction contact area and decreasing the CO 2 diffusion resistance without increasing gas-side pressure drop is presented along with techno-economic analysis results. Bench-scale tests on the unique Compact Absorber showed overall CO 2 mass transfer enhancement of varying degrees compared to a traditional packed column for similar process conditions, demonstrating that a 60+% reduction in size of a typical post-combustion absorber with a packing height of 70-100 ft and total height of 150-180 ft can be achieved. The techno-economic analysis showed significant cost reductions when the Compact Absorber is combined with other transformative aspects of the University of Kentucky Institute for Decarbonization and Energy Advancement point source CO 2 capture process compared to the U.S. Department of Energy National Energy Technology Laboratory pertinent reference case for pulverized coal plants with CO 2 capture. Here, a levelized cost of electricity excluding CO 2 transportation and storage of $\$95.6$/MWh was estimated, which is a 9% reduction, with a total capital cost contribution of $45/MWh, which is a 12% reduction. Additionally, a breakeven CO 2 sales price also referred to as the cost of CO 2 capture, of $36.70/tonne was estimated when the UK hindered primary amine solvent is used, which is a 20% reduction compared to the reference case.

CO2 capture↗

DOE OSTI2026

CO 2 Sorption in Moisture Swing Anion Exchange Resins for Direct Air Capture: Experimental Isotherm Determination and Modeling

Moisture swing (MS) sorption is a promising direct air capture (DAC) technology to achieve negative CO 2 emissions and counter global warming. Here, in this study, MS CO 2 sorption in a model MS sorbent, IRA900, was investigated. IRA900 is a macroporous commercial strong-base anion exchange resin (AER) with quaternary ammonium functional groups. A rigorous CO 2 desorption process was developed to desorb all CO 2 from the sample and obtain CO 2 sorption isotherms as a function of relative humidity, CO 2 partial pressure, and temperature. CO 2 sorption increased with decreasing relative humidity, decreasing temperature, and increasing CO 2 partial pressure. Remarkably, the total CO 2 uptake from the sorption isotherms matched the ion exchange capacity (IEC) of the material, suggesting a stoichiometry of one CO 2 molecule reacting per active site. An isotherm model for CO 2 sorption starting with empty sorption sites (i.e., with the AER in the OH – form) described the experimental data well, supporting the hypothesis that the bicarbonate-loaded AER fully unloaded to the OH – state following rigorous CO 2 desorption. CO 2 sorption kinetics were studied, and carbon diffusion coefficients were estimated as a function of %RH and CO 2 partial pressure. Overall, this study provides a roadmap for the systematic evaluation of MS CO 2 DAC materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

DOE OSTI2025

Editors’ Choice—Rapid Deactivation Convolutes Electrochemical CO 2 Reduction Selectivity Measurements on Gold Rotating Ring Disk Electrodes

Voltammetric measurements of electrochemical CO 2 reduction reaction (CO 2 RR) selectivity on rotating ring disk electrodes (RRDE) are a rapid and sensitive method for quantifying an electrocatalyst’s selectivity, i.e. faradaic efficiency (FE). This method has been applied to polycrystalline Au electrocatalysts where a Au disk electrode catalyzes both the CO 2 RR and hydrogen evolution reaction while the concentric Au ring electrode selectively senses CO by oxidizing CO back to CO 2 . Such measurements enabled fundamental mechanistic studies but suffer from poor inter-laboratory reproducibility. This work identifies causes of variability in RRDE selectivity measurements by comparing protocols with different electrochemical methods, reagent purities, and glassware cleaning procedures. We observed FE CO decrease by 56% during 5 min chronoamperometry measurements, a phenomenon that is not readily apparent in voltammetric scans due to their dynamic nature. Electroplating of electrolyte impurities onto the disk and ring surfaces were identified as a major contributor to Au deactivation. Additionally, the oxygen reduction reaction may lead to higher disk currents in inadequately purged electrolytes, causing an apparent underestimation of FE CO at low overpotentials. Lastly, we propose operational bounds for CO 2 RR selectivity measurements on Au using the RRDE method and provide suggestions on steps for improving the accuracy of this technique.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Tailoring Interfaces for Enhanced Methanol Production from Photoelectrochemical CO 2 Reduction

Efficient and stable photoelectrochemical reduction of CO 2 into highly reduced liquid fuels remains a formidable challenge, which requires an innovative semiconductor/catalyst interface to tackle. In this study, we introduce a strategy involving the fabrication of a silicon micropillar array structure coated with a superhydrophobic fluorinated carbon layer for the photoelectrochemical conversion of CO 2 into methanol. The pillars increase the electrode surface area, improve catalyst loading and adhesion without compromising light absorption, and help confine gaseous intermediates near the catalyst surface. The superhydrophobic coating passivates parasitic side reactions and further enhances local accumulation of reaction intermediates. Upon one-electron reduction of the molecular catalyst, the semiconductor–catalyst interface changes from adaptive to buried junctions, providing a sufficient thermodynamic driving force for CO 2 reduction. These structures together create a unique microenvironment for effective reduction of CO 2 to methanol, leading to a remarkable Faradaic efficiency reaching 20% together with a partial current density of 3.4 mA cm –2 , surpassing the previous record based on planar silicon photoelectrodes by a notable factor of 17. Furthermore, this work demonstrates a new pathway for enhancing photoelectrocatalytic CO 2 reduction through meticulous interface and microenvironment tailoring and sets a benchmark for both Faradaic efficiency and current density in solar liquid fuel production.

14 SOLAR ENERGY↗

DOE OSTI2024

An experimental investigation on the CO 2 storage capacity of the composite confining system

Assuring secure containment of stored CO 2 is of paramount importance—for climate change mitigation, for permitting, and for reassuring the public. Regional seals, such as those sealing petroleum accumulations, have proven to be effective for securing CO 2 . However, the goal of permanent sequestration can also be satisfied with “composite confining systems” consisting of multiple, possibly discontinuous flow barriers that, in aggregate, create a system with very high permeability anisotropy and effectively retard the vertical migration of CO 2 . This study focuses on investigating the barrier characteristics necessary for effective containment of CO 2 , using both physical flow experiments and modified invasion percolation simulations. The simulations are calibrated to the physical experiments and are used to further extend the analysis. Results show that for a composite confining system, a) even barriers with low capillary entry pressure contrast to the underlying flow unit can divert rising CO 2 ; b) curved or anticlinal barrier topography can enhance CO 2 trapping; c) fining-upward gradations make little difference to barrier effectiveness or CO 2 retention; d) longer barriers retain more CO 2 regardless of barrier topography. Finally, field-scale simulations have demonstrated the importance of barrier length for increasing CO 2 storage capacity. Furthermore, the results presented can be used to inform the development of new screening criteria for characterization and effectiveness of composite confining systems.

58 GEOSCIENCES↗

DOE OSTI2022

Engineering Catalyst–Electrolyte Microenvironments to Optimize the Activity and Selectivity for the Electrochemical Reduction of CO 2 on Cu and Ag

We report the electrochemical reduction of carbon dioxide (CO 2 R) driven by renewably generated electricity (e.g., solar and wind) offers a promising means for reusing the CO 2 released during the production of cement, steel, and aluminum as well as the production of ammonia and methanol. If CO 2 could be removed from the atmosphere at acceptable costs (i.e., <$100/t of CO 2 ), then CO 2 R could be used to produce carbon-containing chemicals and fuels in a fully sustainable manner. Economic considerations dictate that CO 2 R current densities must be in the range of 0.1 to 1 A/cm 2 and selectivity toward the targeted product must be high in order to minimize separation costs. Industrially relevant operating conditions can be achieved by using gas diffusion electrodes (GDEs) to maximize the transport of species to and from the cathode and combining such electrodes with a solid-electrolyte membrane by eliminating the ohmic losses associated with liquid electrolytes. Additionally, high product selectivity can be attained by careful tuning of the microenvironment near the catalyst surface (e.g., the pH, the concentrations of CO 2 and H 2 O, and the identities of the cations in the double layer adjacent to the catalyst surface).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Liquid–Solid Boundaries Dominate Activity of CO 2 Reduction on Gas-Diffusion Electrodes

Electrochemical CO 2 electrolysis to produce hydrocarbon fuels or material feedstocks offers a renewable alternative to fossilized carbon sources. Gas-diffusion electrodes (GDEs), composed of solid electrocatalysts on porous supports positioned near the interface of a conducting electrolyte and CO 2 gas, have been able to demonstrate the substantial current densities needed for future commercialization. These higher reaction rates have often been ascribed to the presence of a three-phase interface, where solid, liquid, and gas provide electrons, water, and CO 2 , respectively. Conversely, mechanistic work on electrochemical reactions implicates a fully two-phase reaction interface, where gas molecules reach the electrocatalyst’s surface by dissolution and diffusion through the electrolyte. Because the discrepancy between an atomistic three-phase versus two-phase reaction has substantial implications for the design of catalysts, gas-diffusion layers, and cell architectures, the nuances of nomenclatures and governing phenomena surrounding the three-phase-region require clarification. In this paper we outline the macro, micro, and atomistic phenomena occurring within a gas-diffusion electrode to provide a focused discussion on the architecture of the often-discussed three-phase region for CO 2 electrolysis. From this information, we comment on the outlook for the broader CO 2 electroreduction GDE cell architecture.

CO2 reduction↗

DOE OSTI2023

Intrinsic thermal expansion and tunability of thermal expansion coefficient in Ni-substituted Co 2 V 2 O 7

Abstract Framework oxide materials are well-known for exhibiting not only negative thermal expansion (NTE), but also demonstrating thermal expansion that can be controlled using composition as a tuning parameter. In this work, we study the intrinsic thermal expansion properties of Co 2 V 2 O 7 , which has shown bulk linear NTE, and attempt to understand how substituting Ni 2+ for Co 2+ will affect the thermal expansion. The isomorphic solid solution is synthesized through solid-state methods and characterized using x-ray diffraction (XRD), diffuse reflectance spectroscopy, and neutron diffraction. The size difference between Ni 2+ and Co 2+ as well as the polyhedral volume of each Co 2+ metal coordination environment in the crystal structure allows Ni 2+ to partially be directed toward one crystallographic site over the other. Variable temperature synchrotron XRD data are employed to understand intrinsic thermal expansion. Across the solid solution, no intrinsic NTE is observed at the microscopic level, yet a degree of tunability in the thermal expansion coefficient with Ni substitution is demonstrated. The disparities between the intrinsic and bulk thermal expansion properties suggest that a morphological mechanism may have resulted in NTE in the bulk.

Materials Science↗

DOE OSTI2023

One-Pot Synthesis of Melamine Formaldehyde Resin-Derived N-Doped Porous Carbon for CO 2 Capture Application

The design and synthesis of porous carbons for CO 2 adsorption have attracted tremendous interest owing to the ever-soaring concerns regarding climate change and global warming. Herein, for the first time, nitrogen-rich porous carbon was prepared with chemical activation (KOH) of commercial melamine formaldehyde resin (MF) in a single step. It has been shown that the porosity parameters of the as-prepared carbons were successfully tuned by controlling the activating temperature and adjusting the amount of KOH. Thus, as-prepared N-rich porous carbon shows a large surface area of 1658 m 2 /g and a high N content of 16.07 wt%. Benefiting from the unique physical and textural features, the optimal sample depicted a CO 2 uptake of up to 4.95 and 3.30 mmol/g at 0 and 25 °C under 1 bar of pressure. More importantly, as-prepared adsorbents show great CO 2 selectivity over N 2 and outstanding recyclability, which was prominently important for CO 2 capture from the flue gases in practical application. An in-depth analysis illustrated that the synergetic effect of textural properties and surface nitrogen decoration mainly determined the CO 2 capture performance. However, the textural properties of carbons play a more important role than surface functionalities in deciding CO 2 uptake. In view of cost-effective synthesis, outstanding textural activity, and the high adsorption capacity together with good selectivity, this advanced approach becomes valid and convenient in fabricating a unique highly efficient N-rich carbon adsorbent for CO 2 uptake and separation from flue gases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Codesign of an integrated metal–insulator–semiconductor photocathode for photoelectrochemical reduction of CO 2 to ethylene

Photoelectrochemical carbon-dioxide reduction (PEC CO 2 R) is a potentially attractive means for producing chemicals and fuels using sunlight, water, and carbon dioxide; however, this technology is in its infancy. To date, most studies of PEC CO 2 R have reported products containing one carbon atom (C 1 products) but the production of valuable products containing two or more carbons (C 2+ products), such as ethylene, ethanol, etc., is rarely demonstrated. Metal–semiconductor–insulator (MIS) photocathode/catalyst structures offer a promising approach for this purpose, since they integrate the functions of light absorption, charge separation, and catalysis. In this study, we have investigated a Cu/TiO 2 /p-Si photocathode/catalyst structure with the aim of establishing the effects of semiconductor–insulator interactions on the performance of the photocathode and the influence of the direction of illumination of the MIS structure on the total current density and the distribution of products formed by on the Cu catalyst. Here, we have also examined the influence of ionomer coatings deposited on the Cu surface on the total current density and the distribution of products formed. A major finding is that for a fixed Cu potential the distribution of products formed by PEC CO 2 R are the same, irrespective of the direction of illumination, and are identical to those obtained by electrochemical reduction of CO 2 (EC CO 2 R). Another important finding is that the total current density and the faradaic efficiency to ethylene are enhanced significantly by deposition of a thin bilayer of Sustainion/Nafion onto the surface of the Cu.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Enhancing CO 2 Transport Across a PEEK‐Ionene Membrane and Water‐Lean Solvent Interface

Abstract Efficient direct air capture (DAC) of CO 2 will require strategies to deal with the relatively low concentration in the atmosphere. One such strategy is to employ the combination of a CO 2 ‐selective membrane coupled with a CO 2 capture solvent acting as a draw solution. Here, the interactions between a leading water‐lean carbon‐capture solvent, a polyether ether ketone (PEEK)‐ionene membrane, CO 2 , and combinations were probed using advanced NMR techniques coupled with advanced simulations. We identify the speciation and dynamics of the solvent, membrane, and CO 2 , presenting spectroscopic evidence of CO 2 diffusion through benzylic regions within the PEEK‐ionene membrane, not spaces in the ionic lattice as expected. Our results demonstrate that water‐lean capture solvents provide a thermodynamic and kinetic funnel to draw CO 2 from the air through the membrane and into the bulk solvent, thus enhancing the performance of the membrane. The reaction between the carbon‐capture solvent and CO 2 produces carbamic acid, disrupting interactions between the imidazolium (Im + ) cations and the bistriflimide anions within the PEEK‐ionene membrane, thereby creating structural changes through which CO 2 can diffuse more readily. Consequently, this restructuring results in CO 2 diffusion at the interface that is faster than CO 2 diffusion in the bulk carbon‐capture solvent.

Walter, Eric D.↗

DOE OSTI2022

Contrasting responses of woody and grassland ecosystems to increased CO 2 as water supply varies

Experiments show that elevated atmospheric CO 2 (eCO 2 ) often enhances plant photosynthesis and productivity, yet this effect varies substantially and may be climate sensitive. Understanding if, where and how water supply regulates CO 2 enhancement is critical for projecting terrestrial responses to increasing atmospheric CO 2 and climate change. Here, using data from 14 long-term ecosystem-scale CO 2 experiments, we show that the eCO 2 enhancement of annual aboveground net primary productivity is sensitive to annual precipitation and that this sensitivity differs between woody and grassland ecosystems. During wetter years, CO 2 enhancement increases in woody ecosystems but declines in grass-dominated systems. Consistent with this difference, woody ecosystems can increase leaf area index in wetter years more effectively under eCO 2 than can grassland ecosystems. Overall, and across different precipitation regimes, woody systems had markedly stronger CO 2 enhancement (24%) than grasslands (13%). Finally, we developed an empirical relationship to quantify aboveground net primary productivity enhancement on the basis of changes in leaf area index, providing a new approach for evaluating eCO 2 impacts on the productivity of terrestrial ecosystems.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2022

Regenerable solvents mediate accelerated low temperature CO 2 capture and carbon mineralization of ash and nano-scale calcium carbonate formation

The dual need to remove CO 2 from our emissions and treat alkaline industrial residues such as ash materials motivate the design of innovative pathways to simultaneously capture and convert CO 2 into mineralized carbonates. Direct carbon mineralization is one approach that addresses the need to simultaneously treat alkaline industrial residues and mineralize CO 2 emissions. Low CO 2 solubility in water and slow kinetics at ambient temperature have challenged the direct carbon mineralization of alkaline industrial residues. Here, to address these challenges, the use of CO 2 capture solvents that enhance CO 2 solubility and facilitate accelerated carbon mineralization of fly ash at temperatures below 90 °C is investigated. Calcium carbonate formation results in the inherent regeneration of the solvent. The carbon mineralization extents of non-calcium carbonate content in fly ash were 50% and 51% and in waste ash were 58% and 62% in 2.5 M sodium glycinate and 30 wt% MEA solutions, respectively. The experiments were performed at 50 °C for 3 hours with CO 2 partial pressure of 1 atm in a continuously stirred slurry environment with 15 wt.% solid. Furthermore, nanoscale CaCO 3 is successfully synthesized from dissolved calcium using CO 2 -loaded sodium glycinate and surfactants such as CTAB (Cetyl Trimethyl Ammonium Bromide). Surfactants such as CTAB bind to the calcium carbonate surface and regulate the growth of calcium carbonate particles. These innovative approaches demonstrate the feasibility of directly storing CO 2 in fly ash and waste ash as calcium carbonate and producing nanoscale calcium carbonate using regenerable CO 2 capture solvents.

42 ENGINEERING↗

DOE OSTI2025

Impact of salinity on morphology, growth, and pigment profiles of Scenedesmus obliquus HTB1 under ambient air and elevated CO 2 (10 %) conditions

Certain microalgal species, such as Scenedesmus obliquus strain HTB1, thrive under high CO 2 concentrations, making them promising for carbon sequestration to mitigate climate change. Isolated from the Baltimore Inner Harbor, HTB1 grows faster with 10 % CO 2 than with ambient air. To investigate its responses to salinity and elevated CO 2 , two experiments were conducted. In the first, HTB1 was cultured at seven different salinities (0, 17.5, 20, 22.5, 25, 27.5, and 30 ppt) (parts per thousand) under ambient air. Higher salinity caused cell shrinkage, color changes from green to pale white, reduced pigments like zeaxanthin, lutein, and chlorophyll b, but increased canthaxanthin. Growth declined significantly above 22.5 ppt. The second experiment compared HTB1's response to salinity (0, 10, 20 ppt) under air and 10 % CO 2 . Cultures under 10 % CO 2 showed minimal color changes, while those under air shifted from green to brown, with salinity having less inhibitory effects on growth under elevated CO 2 . Interestingly, lutein and canthaxanthin levels rose with salinity in 10 % CO 2 . These findings indicate that elevated CO 2 mitigates salt stress in HTB1, reducing its impact on growth and promoting adaptive pigment changes. This study sheds light on how salinity and CO 2 interact to influence HTB1's morphology, growth, and pigment composition, enhancing our understanding of its resilience and potential applications.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2025

Integrated CO 2 capture and hydrogenation in presence of Ru–Na 2 ZrO 3 : An in-situ study

Integrated CO 2 capture and conversion (ICCC) by hydrogenation is a promising strategy to utilize carbon dioxide and this work add to the effort to elucidate the catalytic hydrogenation mechanism using Ru based dual functional materials (DFM). Ru-Na 2 ZrO 3 DFMs, obtained through different wet methods, were evaluated for the first time and the relationship between Ru and support systematically investigated. The thermally stable and cyclable Ru-Na 2 ZrO 3 -a (obtained without filtration step) exhibited CO 2 conversion of 80% and a higher yield of CO at 400°C compared to previously tested DFM, while the Na depleted/Zr rich Ru-Na 2 ZrO 3 -b resulted in 90% selectivity to CH 4 with yield of 1.11 mmol/g at the same temperature. The in-situ experiments have provided conclusive evidence showing that CO 2 hydrogenation on the two Ru DFMs is fundamentally different. In Ru-Na 2 ZrO 3 -a, the monoclinic Na 2 ZrO 3 support acted as the active centre (not as promoter) for CO 2 bridging binding and hydrogenation to CH 4 at the metal-support interface through associative formate pathway with limited further reduction to methane due to lack of H 2 spillover from the small and well dispersed Ru NPs, which results in CO desorption. Conversely, abundant clusters of larger Ru NPs in Ru-Na 2 ZrO 3 -b, led to CH 4 production due to co-existent Ru on-top direct dissociation of CO 2 (preferential) and monodentate formate adsorption and further methanation. Alkali zirconates doped metals, and their synthesis method could thus play a crucial role in designing tuneable heterogeneous catalysis in C 1 chemistry, which could significantly benefit the environment by lowering CO 2 levels, encouraging cleaner industrial practices, supporting a circular economy, and converting waste CO 2 into valuable products.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Investigation of the Effect of Framework Flexibility on CO 2 Adsorption in SIFSIX-3-Cu Using a Machine-Learned Force Field

Metal–organic frameworks (MOFs) offer promise as selective CO 2 sorbents, but successful MOF sorbent materials need high CO 2 binding affinity and selectivity for CO 2 over water. This work focuses on the use of machine-learned force fields (MLFFs) to model CO 2 adsorption in flexible MOFs, with a focus on SIFSIX-3-Cu, an anion-pillared MOF known for its high CO 2 affinity. A preliminary high-throughput screening of over 900 anion-pillared MOFs was performed using rigid UFF+DDEC6 force fields to predict zero-loading heats of adsorption for CO 2 and H 2 O. SIFSIX-3-Cu was selected for further computational study due to its predicted CO 2 heat of adsorption and experimental relevance. A DeePMD-based MLFF was trained to reproduce DFT (PBE+D3) energies and forces, with an iterative sampling scheme combining molecular dynamics, geometry optimization, random geometric insertion, and NVT Monte Carlo-based configuration generation to capture both attractive and repulsive regions of the potential energy surface. Flexibility of the MOF was explicitly included, contrasting with previous models that approximated the MOF as rigid. Hybrid Monte Carlo/molecular dynamics (MC/MD) simulations with the MLFF produced CO 2 adsorption isotherms in good agreement with experimental data at direct air capture (DAC) pressures (e.g., 40 Pa), in contrast to previous overestimations of CO 2 sorption by models with rigid structures. Bond and angle histogram analysis showed that MOF flexibility increased the variance of fluorine–fluorine diagonal distances at adsorption sites, resulting in a lower predicted sorption for flexible, asymmetric SIFSIX-3-Cu pore geometries compared to the rigid, symmetric DFT-optimized SIFSIX-3-Cu pore geometry. A detailed description of flexibility afforded by the MLFF resulted in an accurately predicted CO 2 uptake (0.88 mmol/g) at low pressure (40 Pa) compared to the experimentally measured value (1.24 mmol/g). In conclusion, these results underscore the importance of including framework flexibility when modeling adsorption phenomena in MOFs, particularly for low-pressure applications.

adsorption↗