Direct Air Capture Of CO2 Research Articles

Hierarchical ion interactions in the direct air capture of CO2 at air/aqueous interfaces.

The direct air capture (DAC) of CO2 using aqueous solvents is plagued by slow kinetics and interfacial barriers that limit effectiveness in combating climate change. Functionalizing air/aqueous surfaces with charged amphiphiles shows promise in accelerating DAC; however, insight into these interfaces and how they evolve in time remains poorly understood. Specifically, competitive ion interactions between DAC reagents and reaction products feedback onto the interfacial structure, thereby modulating interfacial chemical composition and overall function. In this work, we probe the role of glycine amino acid anions (Gly-), an effective CO2 capture reagent, that promotes the organization of cationic oligomers at air/aqueous interfaces. These surfaces are probed with vibrational sum frequency generation spectroscopy and molecular dynamics simulations. Our findings demonstrate that the competition for surface sites between Gly- and captured carbonaceous anions (HCO3-, CO32-, carbamates) drives changes in surface hydration, which in turn tunes oligomer ordering. This phenomenon is related to a hierarchical ordering of anions at the surface that are electrostatically attracted to the surface and their ability to compete for interfacial water. These results point to new ways to tune interfaces for DAC via stratification of ions based on relative surface propensities and specific ion effects.

Enhancing adsorbent performance for direct air capture of CO2 by in-situ amine-grafting of layered double hydroxides

The development of efficient and cost-effective CO2 adsorbents is crucial for carbon capture from ultradilute conditions. Amine-grafted mesoporous materials prepared by silane chemical reactions are well-known CO2 adsorbents with high thermal stabilities, but their capacities for direct air capture (DAC) are usually restricted by low amine loadings and CO2 capture capacity. Herein, we present an in-situ amine grafting method that enables high amine loadings by in-situ grafting initial ultrathin LDHs nanosheets in an organic solvent. For in-situ triamine grafted Mg2Al-CO3 LDH (IN-TRI-LDH) amine loading is boosted to 5.91mmol N g−1 and ultimately achieving a remarkable adsorption capacity of 0.98 mmol g−1 at 25°C and 400 ppm CO2, nearly double that of the amine-LDHs grafted through a conventional two-step process. A further 22 % enhancement of the CO2 capacity is observed under 20 RH%. In addition, IN-TRI-LDH maintains a working capacity of 0.85 mmol g−1 at a low desorption temperature of 70 °C. A 50 adsorption–desorption cyclic test under simulated humid DAC conditions shows minimal performance degradation. Such a sufficient working capacity and low desorption temperature reduces the thermal energy consumption to 2.27 GJ t−1 at a desorption temperature of 40 °C.

Region specific economic model for solid sorbent direct air capture using geothermal energy resources (S-DAC-GT)

Low temperature geothermal resources, ranging from 80° to 120 °C, may substantially lower both the cost and the CO2 emissions footprint of CO2 direct air capture (DAC) systems. This paper provides a model for determining a region-specific economic analysis for DAC with solid sorbent (S-DAC) using geothermal resources (S-DAC-GT).This paper provides a methodology and program for calculating estimated cost and carbon emissions for potential S-DAC facilities on a region-specific basis. The paper outlines the necessary region-specific characteristics required as parameters for the techno-economic model. The region-specific characteristics are then applied to an S-DAC energy and cost model based on existing literature to calculate the levelized cost per tonne of CO2 captured and stored. Further, the model provides a reasonable approximation of the carbon intensity of the S-DAC-GT system. These calculations allow selecting and prioritizing regions appropriate for potential S-DAC-GT facilities operating at a scale of ∼1 Mt CO2 captured and stored per year.This paper presents a novel approach that addresses several gaps in current DAC techno-economic analyses found in literature. First, the model is highly customizable, allowing the user to apply their own proprietary sorbent properties and region specific parameters to determine precise costs and carbon emissions for their hypothetical S-DAC-GT facility. Second, the overwhelming majority of DAC techno-economic analyses in literature assume away variability of ambient conditions, presuming stable temperature and humidity during operations. This paper directly integrates these large local ambient effects on sorbent performance and evaluates S-DAC-GT costs and carbon emissions based on specific and variable conditions dictated by the user. Third, the flexibility of the model allows the user to rapidly compare S-DAC-GT costs and carbon emissions in different user selected regions, with custom sorbent characteristics. The model provides visualizations of the sensitivity of S-DAC-GT costs and carbon emissions to different parameters and provides visualizations of the cost and carbon emissions due to variability in ambient conditions.Existing techno-economic analyses are either region agnostic or constrain their results to a specific region. The novelty of this paper and its model is the deeper technical and economic analysis of using geothermal energy as the thermal resource, coupled with customizability and visualizations that enable accelerated differentiation of S-DAC-GT costs and carbon intensity by region.

A Comparative Review of Post-Combustion Capture and Direct Air Capture of CO2

Mitigating anthropogenic CO2 emissions has been a subject of incredible urgency in recent years. Carbon capture and storage (CCS) has emerged as a promising means of cutting emissions, with post-combustion capture and direct air capture (DAC) both gaining traction as methods of offsetting emissions from point sources and the ambient atmosphere. Each of these carbon capture methods rely on absorbent or adsorbent materials to function, whose properties can vastly impact capture performance. In this work, 14 materials are analyzed, with qualitative descriptions and performance data of each material based on existing review papers and representative case studies being presented. The review highlights limitations in the field in standardizing the reporting of experimental data, complicating the direct comparison of different materials’ efficacies. While no single CCS technology is found to be unequivocally superior, the promising performances of certain materials in earlier stages of development emphasize the importance of investing further in emerging post-combustion capture materials. This study concludes that CCS technologies are a necessary tool in ultimately reaching net zero emissions due to their role in neutralizing sectors resistant to decarbonization, but they should not be relied upon to substitute the transition to renewable energy, as the prevention of emissions should take priority over the abatement of emissions.

Thermodynamic efficiency of membrane separation of dilute gas: Estimation for CO2 direct air capture application

Gas separation technology is crucial for addressing environmental issues like CO2 capture to mitigate climate change. While membrane separation is often cited for its efficiency, accurate estimations are scarce. We present estimations based on classical thermodynamics for very lean CO2 composition (400 ppm), revealing rich details in simple systems and deriving guiding principles. Our main conclusion emphasizes the critical necessity of a high membrane separation ratio, and we discuss candidates for achieving this goal.

Diverse decarbonization pathways under near cost-optimal futures

Energy system optimization models offer insights into energy and emissions futures through least-cost optimization. However, real-world energy systems often deviate from deterministic scenarios, necessitating rigorous uncertainty exploration in macro-energy system modeling. This study uses modeling techniques to generate diverse near cost-optimal net-zero CO2 pathways for the United States’ energy system. Our findings reveal consistent trends across these pathways, including rapid expansion of solar and wind power generation, substantial petroleum use reductions, near elimination of coal combustion, and increased end-use electrification. We also observe varying deployment levels for natural gas, hydrogen, direct air capture of CO2, and synthetic fuels. Notably, carbon-captured coal and synthetic fuels exhibit high adoption rates but only in select decarbonization pathways. By analyzing technology adoption correlations, we uncover interconnected technologies. These results demonstrate that diverse pathways for decarbonization exist at comparable system-level costs and provide insights into technology portfolios that enable near cost-optimal net-zero CO2 futures.

Comprehensive performance evaluation of HVAC systems integrated with direct air capture of CO2 in various climate zones

Direct Air Capture (DAC) is a rapidly evolving technology that extracts CO2 directly from ambient air. This study presents a comprehensive performance evaluation of integrating DAC in HVAC systems, which can reduce indoor CO2 concentration and improve energy efficiency of HVAC systems. The DAC equipment is modeled in Modelica based on isotherm and thermodynamic equations, and pressure drop curves of the CO2 sorbent described in literature. The model is validated with data from the literature, and then integrated into a typical HVAC system available in Modelica Buildings library. The HVAC system is a Variable Air Volume (VAV) with reheater system for a one-floor office building with standard ASHRAE 2006 control sequences. Demand control ventilation strategies are designed to reduce the outdoor air flowrates when indoor CO2 concentrations are lower than the threshold, which is to maximize the benefits of integrating DAC. Four cases are proposed to assess the impacts of integrating DAC and DCV in HVAC systems in 8 different ASHRAE climate zones in the USA. The results show that by integrating DAC unit into the HVAC system, the average indoor CO2 concentration can be significantly reduced by over 45 % against the baseline without a DAC unit. By integrating DCV, 0.39–21.66 % of annual energy savings and 226–9539 kg carbon emissions reduction are observed across different climate zones. The highest energy savings are found to be achieved with cold climatic conditions while the lowest energy savings occur with favorable weather.

Understanding Electrochemical and Mechanical Durability of Bipolar Membranes Used in Electrodialysis

Using renewable energy to drive direct carbon capture systems is a powerful way to contribute to net negative emissions. When using liquid alkaline sorbents for CO2 direct air capture, it is critical to reduce the energy demand for CO2 concentration and sorbent regeneration. Electrodialysis is an ideal candidate technology to integrate renewable energy into this process, however, to enable this ion-exchange membrane separators that can operate at high ion flux and low voltage are needed. Bipolar membranes (BPMs), that generate protons and hydroxide ions from the dissociation of water when operated in reverse bias, are the enabling component to generate acid and base in electrodialysis systems. Bipolar membrane electrodialysis (BPMED) uses a BPM to create acidifying and basifying chambers which are well suited to concentrate and release CO2 and concentrate the remaining alkaline effluent to cycle back to the capture process. Current BPM durability, however, sufferers at high current density (ion flux) and physical scale. BPMs have several known degradation mechanisms including chemical breakdown of ion exchange polymers, loss of junction adhesion, or physical breakdown due to shearing force and pressure swings in an electrodialysis cell.To assess the electrochemical and mechanical durability of BPMs under operational conditions, we investigated how fabrication conditions (including preconditioning, hot pressing, and catalyst loading) impact the adhesion of custom made BPMs. T-peel studies were performed ex-situ to quantify adhesive forces of BPMs made of different compositions and prepared under different conditions, and BPMED experiments were performed to assess the electrochemical performance of the corresponding BPMs. The BPMED results show that, while adhesion is necessary to physically maintain the BPM junction, mechanical adhesion alone cannot overcome poor ion and water transport management at the water dissociation junction. The results of this systematic comparison indicate that in order for BPMs to operate at high current densities, high adhesion forces made during fabrication of BPMs will need to be balanced with water dissociation kinetics and ion/water transport through the individual membrane layers.

Integrating direct air capture with algal biofuel production to reduce cost, energy, and GHG emissions

We investigate the potential to reduce costs and greenhouse gas emissions of the utilization of direct air capture of CO2 (DAC) for the production of algal biofuel. We examine four integrated designs for a DAC system comprised of solid amine monolith adsorbents delivering CO2 at the required level for algae cultivation with a photobioreactor (PBR)-based fuel production facility. We show that the integration of DAC with this biofuel production facility provides cost and greenhouse gas emissions benefits. Heat integration decreases operating expenses by reducing energy demand for heating requirements. Mass integration, utilizing flue gas CO2 as a carbon source for the PBRs, decreases the DAC system scale, resulting in both capital and operating cost savings. The most advantageous option depends on the interplay of heat and mass integration while matching the diurnal rhythm of algal growth with the inherently steady pace and energy requirements of the DAC system and fuel production. For these technologies, the DAC-PBR mass and energy integration provides an 18 % cost reduction and a 50 % reduction in greenhouse gas emissions for the current state of the technology.

Adsorption, Orientation, and Speciation of Amino Acids at Air-Aqueous Interfaces for the Direct Air Capture of CO2.

Amino acids make up a promising family of molecules capable of direct air capture (DAC) of CO2 from the atmosphere. Under alkaline conditions, CO2 reacts with the anionic form of an amino acid to produce carbamates and deactivated zwitterionic amino acids. The presence of the various species of amino acids and reactive intermediates can have a significant effect on DAC chemistry, the role of which is poorly understood. In this study, all-atom molecular dynamics (MD) based computational simulations and vibrational sum frequency generation (vSFG) spectroscopy studies were conducted to understand the role of competitive interactions at the air-aqueous interface in the context of DAC. We find that the presence of potassium bicarbonate ions, in combination with the anionic and zwitterionic forms of amino acids, induces concentration and charge gradients at the interface, generating a layered molecular arrangement that changes under pre- and post-DAC conditions. In parallel, an enhancement in the surface activity of both anionic and zwitterionic forms of amino acids is observed, which is attributed to enhanced interfacial stability and favorable intermolecular interactions between the adsorbed amino acids in their anionic and zwitterionic forms. The collective influence of these competitive interactions, along with the resulting interfacial heterogeneity, may in turn affect subsequent capture reactions and associated rates. These effects underscore the need to consider dynamic changes in interfacial chemical makeup to enhance DAC efficiency and to develop successful negative emission and storage technologies.

Physicochemical Properties, Equilibrium Adsorption Performance, Manufacturability, and Stability of TIFSIX-3-Ni for Direct Air Capture of CO2.

The use of adsorbents for direct air capture (DAC) of CO2 is regarded as a promising and essential carbon dioxide removal technology to help meet the goals outlined by the 2015 Paris Agreement. A class of adsorbents that has gained significant attention for this application is ultramicroporous metal organic frameworks (MOFs). However, the necessary data needed to facilitate process scale evaluation of these materials is not currently available. Here, we investigate TIFSIX-3-Ni, a previously reported ultramicroporous MOF for DAC, and measure several physicochemical and equilibrium adsorption properties. We report its crystal structure, textural properties, thermal stability, specific heat capacity, CO2, N2, and H2O equilibrium adsorption isotherms at multiple temperatures, and Ar and O2 isotherms at a single temperature. For CO2, N2, and H2O, we also report isotherm model fitting parameters and calculate heats of adsorption. We assess the manufacturability and process stability of TIFSIX-3-Ni by investigating the impact of batch reproducibility, binderless pelletization, humidity, and adsorption-desorption cycling (50 cycles) on its crystal structure, textural properties, and CO2 adsorption. For pelletized TIFSIX-3-Ni, we also report its skeletal, pellet, and bed density, total pore volume, and pellet porosity. Overall, our data enable initial process modeling and optimization studies to evaluate TIFSIX-3-Ni for DAC at the process scale. They also highlight the possibility to pelletize TIFSIX-3-Ni and the limited stability of the MOF under humid and oxidative conditions as well as upon multiple adsorption-desorption cycles.

Quaternized Graphene for High-Performance Moisture Swing Direct Air Capture of CO2.

Nowadays, moisture-swing adsorption technology still relies on quaternary ammonium resins with limited CO2 capacity under ambient air conditions. In this work, a groundbreaking moisture-driven sorbent is developed starting from commercial graphene flakes and using glycidyltrimethylammonium chloride for incorporation of CO2-sensitive quaternary ammonium functional groups. Boasting an outstanding CO2 capture performance under ultra-diluted conditions (namely, 3.24mmolg-1 at CO2 400ppm and 20% RH), the functionalized sorbent (fGO) features clear competitive advantages over current technologies for direct air capture. Notably, fGO demonstrated unprecedented moisture-swing capacity, ease of regenerability, versatility, selectivity, and longevity. These distinctive features position the fGO as an advanced and promising solution, showcasing its potential to outperform existing methods for moisture-swing direct air capture of CO2.

Investigation of effectiveness of KOH-activated olive pomace biochar for efficient direct air capture of CO2

The capture of CO2 directly from the air is one of the most promising methods under investigation in recent years to reduce the environmental concentration of this pollutant in order to mitigate its effects on climate change. In this work, the activation of olive pomace biochar with potassium hydroxide, KOH, has been studied for its use as a CO2 adsorbent. The effectiveness of biochar activated with KOH at 750 °C in an inert N2 atmosphere was evaluated, using different mass ratios of biochar/KOH, 1:0.5, 1:1, and 1:2. Various characterisation analyses of the biochar were performed to determine its chemical composition, specific surface area, pore size and volume, structure, morphology, and functional groups. The adsorption isotherm was determined at atmospheric pressure and a temperature of 10 °C. The experimental equilibrium results were fitted to the Langmuir, Freundlich, and Temkin models. Additionally, the kinetic behavior of biochar/KOH as an adsorbent was studied, and dynamic experiments were conducted at atmospheric pressure and 10 °C. The experimental data were fitted to various kinetic models (pseudo-first order, pseudo-second order, Avrami, and Elovich). Furthermore, the mass transfer mechanism during the adsorption process was evaluated using the intra-particle diffusion model. Finally, biochar regeneration was investigated for its subsequent reuse as an adsorbent. For this purpose, complete desorption of the captured CO2 in the biochar was easily carried out by modifying the temperature.

Ionic Liquid-Glycol Mixtures for Direct Air Capture of CO2: Decreased Viscosity and Mitigation of Evaporation Via Encapsulation.

Herein we address the efficiency of the CO2 sorption of ionic liquids (IL) with hydrogen bond donors (e.g., glycols) added as viscosity modifiers and the impact of encapsulating them to limit sorbent evaporation under conditions for the direct air capture of CO2. Ethylene glycol, propylene glycol, 1,3-propanediol, and diethylene glycol were added to three different ILs: 1-ethyl-3-methylimidazolium 2-cyanopyrrolide ([EMIM][2-CNpyr]), 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]), and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF4]). Incorporation of the glycols decreased viscosity by an average of 51% compared to bulk IL. After encapsulation of the liquid mixtures using a soft template approach, thermogravimetric analysis revealed average reductions in volatility of 36 and 40% compared to the unencapsulated liquid mixtures, based on 1 h isothermal experiments at 25 and 55 °C, respectively. The encapsulated mixtures of [EMIM][2-CNpyr]/1,3-propanediol and [EMIM][2-CNpyr]/diethylene glycol exhibited the lowest volatility (0.0019 and 0.0002 mmol/h at 25 °C, respectively) and were further evaluated as CO2 absorption/desorption materials. Based on the capacity determined from breakthrough measurements, [EMIM][2-CNpyr]/1,3-propanediol had a lower transport limited absorption rate for CO2 sorption compared to [EMIM][2-CNpyr]/diethylene glycol with 0.08 and 0.03 mol CO2/kg sorbent, respectively; however, [EMIM][2-CNpyr]/diethylene glycol capsules exhibited higher absorptions capacity at ∼500 ppm of CO2 (0.66 compared to 0.47 mol of CO2/kg sorbent for [EMIM][2-CNpyr]/1,3-propanediol). These results show that glycols can be used to not only reduce IL viscosity while increasing physisorption sites for CO2 sorption, but also that encapsulation can be utilized to mitigate evaporation of volatile viscosity modifiers.

Oxidation of Supported Amines for CO2 Direct Air Capture: Assessing Impact on Physical Properties and Mobility via NMR Relaxometry

AbstractAminopolymer‐based adsorbents are commonly investigated for CO2 direct air capture (DAC). In the presence of high temperature and oxygen, which can occur during adsorption‐regeneration cycles, oxidative degradation can significantly reduce adsorbent lifetime. Degradation is typically measured using adsorption performance metrics or chemical characterization. This work demonstrates that the polymer's physical properties, as measured via nuclear magnetic resonance (NMR) relaxometry and differential scanning calorimetry, can be used to quantitatively track degradation. The extent of oxidation of an alumina‐poly(ethylenimine) sample, measured by reductions in amine efficiency (A.E.), is correlated with proton T2 relaxation times. This work hypothesizes that T2 relaxation accurately tracks oxidative degradation in aminopolymers due to the reduction in polymer mobility occurring during the oxidation process. The ability to use NMR relaxometry as a noninvasive technique to probe degradation is demonstrated on a 1‐inch square‐channel monolith adsorbent exposed to actual DAC service conditions. This highlights the potential for relaxometry to evaluate the state of the adsorbent accurately and rapidly compared to typical analytical methods.

Ionic Pairs-Engineered Fluorinated Covalent Organic Frameworks Toward Direct Air Capture of CO2.

The covalent organic frameworks (COFs) possessing high crystallinity and capability to capture low-concentration CO2 (400ppm) from air are still underdeveloped. The challenge lies in simultaneously incorporating high-density active sites for CO2 insertion and maintaining the ordered structure. Herein, a structure engineering approach is developed to afford an ionic pair-functionalized crystalline and stable fluorinated COF (F-COF) skeleton. The ordered structure of the F-COF is well maintained after the integration of abundant basic fluorinated alcoholate anions, as revealed by synchrotron X-ray scattering experiments. The breakthrough test demonstrates its attractive performance in capturing (400ppm) CO2 from gas mixtures via O─C bond formation, as indicated by the in situ spectroscopy and operando nuclear magnetic resonance spectroscopy using 13C-labeled CO2 sources. Both theoretical and experimental thermodynamic studies reveal the reaction enthalpy of ≈-40kJmol-1 between CO2 and the COF scaffolds. This implies weaker interaction strength compared with state-of-the-art amine-derived sorbents, thus allowing complete CO2 release with less energy input. The structure evolution study from synchrotron X-ray scattering and small-angle neutron scattering confirms the well-maintained crystalline patterns after CO2 insertion. The as-developed proof-of-concept approach provides guidance on anchoring binding sites for direct air capture (DAC) of CO2 in crystalline scaffolds.

Understanding the effect of density functional choice and van der Waals treatment on predicting the binding configuration, loading, and stability of amine-grafted metal organic frameworks.

Metal organic frameworks (MOFs) are crystalline, three-dimensional structures with high surface areas and tunable porosities. Made from metal nodes connected by organic linkers, the exact properties of a given MOF are determined by node and linker choice. MOFs hold promise for numerous applications, including gas capture and storage. M2(4,4'-dioxidobiphenyl-3,3'-dicarboxylate)-henceforth simply M2(dobpdc), with M = Mg, Mn, Fe, Co, Ni, Cu, or Zn-is regarded as one of the most promising structures for CO2 capture applications. Further modification of the MOF with diamines or tetramines can significantly boost gas species selectivity, a necessity for the ultra-dilute CO2 concentrations in the direct-air capture of CO2. There are countless potential diamines and tetramines, paving the way for a vast number of potential sorbents to be probed for CO2 adsorption properties. The number of amines and their configuration in the MOF pore are key drivers of CO2 adsorption capacity and kinetics, and so a validation of computational prediction of these quantities is required to suitably use computational methods in the discovery and screening of amine-functionalized sorbents. In this work, we study the predictive accuracy of density functional theory and related calculations on amine loading and configuration for one diamine and two tetramines. In particular, we explore the Perdew-Burke-Ernzerhof (PBE) functional and its formulation for solids (PBEsol) with and without the Grimme-D2 and Grimme-D3 pairwise corrections (PBE+D2/3 and PBEsol+D2/3), two revised PBE functionals with the Grimme-D2 and Grimme-D3 pairwise corrections (RPBE+D2/3 and revPBE+D2/3), and the nonlocal van der Waals correlation (vdW-DF2) functional. We also investigate a universal graph deep learning interatomic potential's (M3GNet) predictive accuracy for loading and configuration. These results allow us to identify a useful screening procedure for configuration prediction that has a coarse component for quick evaluation and a higher accuracy component for detailed analysis. Our general observation is that the neural network-based potential can be used as a high-level and rapid screening tool, whereas PBEsol+D3 gives a completely qualitatively predictive picture across all systems studied, and can thus be used for high accuracy motif predictions. We close by briefly exploring the predictions of relative thermal stability for the different functionals and dispersion corrections.

Scalable and Highly Porous Membrane Adsorbents for Direct Air Capture of CO2.

Direct air capture (DAC) of CO2 is a carbon-negative technology to mitigate carbon emissions, and it requires low-cost sorbents with high CO2 sorption capacity that can be easily manufactured on a large scale. In this work, we develop highly porous membrane adsorbents comprising branched polyethylenimine (PEI) impregnated in low-cost, porous Solupor supports. The effect of the PEI molecular mass and loading on the physical properties of the adsorbents is evaluated, including porosity, degradation temperature, glass transition temperature, and CO2 permeance. CO2 capture from simulated air containing 400 ppm of CO2 in these sorbents is thoroughly investigated as a function of temperature and relative humidity (RH). Polymer dynamics was examined using differential scanning calorimetry (DSC) and broadband dielectric spectroscopy (BDS), showing that CO2 sorption is limited by its diffusion in these PEI-based sorbents. A membrane adsorbent containing 48 mass% PEI (800 Da) with a porosity of 72% exhibits a CO2 sorption capacity of 1.2 mmol/g at 25 °C and RH of 30%, comparable to the state-of-the-art adsorbents. Multicycles of sorption and desorption were performed to determine their regenerability, stability, and potential for practical applications.

The Role of Alkalis in Orchestrating Uranyl-Peroxide Reactivity Leading to Direct Air Capture of Carbon Dioxide.

Spectator ions have known and emerging roles in aqueous metal-cation chemistry, respectively directing solubility, speciation, and reactivity. Here, we isolate and structurally characterize the last two metastable members of the alkali uranyl triperoxide series, the Rb+ and Cs+ salts (Cs-U1 and Rb-U1). We document their rapid solution polymerization via small-angle X-ray scattering, which is compared to the more stable Li+, Na+ and K+ analogues. To understand the role of the alkalis, we also quantify alkali-hydroxide promoted peroxide deprotonation and decomposition, which generally exhibits increasing reactivity with increasing alkali size. Cs-U1, the most unstable of the uranyl triperoxide monomers, undergoes ambient direct air capture of CO2 in the solid-state, converting to Cs4[UVIO2(CO3)3], evidenced by single-crystal X-ray diffraction, transmission electron microscopy, and Raman spectroscopy. We have attempted to benchmark the evolution of Cs-U1 to uranyl tricarbonate, which involves a transient, unstable hygroscopic solid that contains predominantly pentavalent uranium, quantified by X-ray photoelectron spectroscopy. Powder X-ray diffraction suggests this intermediate state contains a hydrous derivative of CsUVO3, where the parent phase has been computationally predicted, but not yet synthesized.

Lignin-Based Platform as a Potential Low-Cost Sorbent for the Direct Air Capture of CO2.

The urgent need to address the current climate crisis has led to concerted efforts to develop low-cost and sustainable methods to remove carbon dioxide from the atmosphere. Carbon capture and storage (CCS) and negative emissions technologies (NET's) offer the most promising paths forward to offsetting global emissions. In this study, we explore the potential of kraft lignin, a readily available biomaterial, as a low-cost alternative for the development of a CO2 sorbent. The approach leverages the known ability of amines to reacting with carbon dioxide and forming a stable compound. Commercially available kraft lignin was modified with diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) using a one-pot synthesis approach via the Mannich reaction. The sorbent was evaluated for porosity, accessible amine density, and nitrogen content. The CO2 capture experiments revealed that the resulting sorbent can capture 0.80 (±0.03) mmol of CO2 per gram of sorbent.