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Large-scale deployment of negative emissions technologies (NETs) that permanently remove CO2 from the atmosphere is now considered essential for limiting the global temperature increase to less than 2°C by the end of this century. One promising NET is direct air capture (DAC), a technology that employs engineered chemical processes to remove atmospheric carbon dioxide, potentially at the scale of billions of metric tons per year. This review highlights one of the two main approaches to DAC based on aqueous solvents. The discussion focuses on different aspects of DAC with solvents, starting with the fundamental chemistry that includes the chemical species and reactions involved and the thermodynamics and kinetics of CO2 binding and release. Chemical engineering aspects are also discussed, including air–liquid contactor design, process development, and technoeconomic assessments to estimate the cost of the DAC technologies. Various solvents employed in DAC are reviewed, from aqueous alkaline solutions (NaOH, KOH) to aqueous amines, amino acids, and peptides, along with different solvent regeneration methods, from the traditional thermal swinging to the more exploratory carbonate crystallization with guanidines or electrochemical methods.

Research on direct air capture (DAC) of CO2 at Oak Ridge National Laboratory (ORNL) over the past five years is highlighted, starting with the initial discovery, continuing with fundamental and applied research, and concluding with commercialization by teaming up with industry.

This article presents a perspective view of the topic of direct air capture (DAC) of carbon dioxide and its role in mitigating climate change, focusing on a promising approach to DAC involving crystal engineering of metal–organic and hydrogen-bonded frameworks. The structures of these crystalline materials can be easily elucidated using X-ray and neutron diffraction methods, thereby allowing for systematic structure–property relationships studies, and precise tuning of their DAC performance.

Efforts to limit rising concentrations of CO2 have motivated the development of negative emission technologies. Direct air capture (DAC) of CO2 is one of the negative emissions technologies that ha...

We report a bench-scale direct air capture (DAC) process comprising CO2 absorption with aqueous amino acid salts (i.e., potassium glycinate, potassium sarcosinate), followed by room-temperature reg...

We report a hybrid solvent/solid-state approach to CO2 separation from flue gas, consisting of absorption with aqueous glycine or sarcosine amino acids, followed by crystallization of the bicarbona...

Carbon dioxide (CO2) absorption from power plant generated flue gas is investigated for CO2 emissions reduction. Amino acid alkaline solvents have the potential to reduce the energy required for so...

Summary Limiting global temperature rises is increasingly dependent on the development of energy-efficient carbon-capture methods. Here, we report a simple CO2-separation cycle using an aqueous bis(iminoguanidine) (BIG) sorbent that reacts with CO2 and crystallizes into an insoluble bicarbonate salt. X-ray diffraction analysis of the bicarbonate crystals revealed “anti-electrostatic” hydrogen-bonded (HCO3−)2 dimers, stabilized by guanidinium cations and water. Mild heating of the crystals releases the CO2 and regenerates the BIG sorbent quantitatively, thereby closing the CO2-separation cycle. Experimental and computational investigations support a CO2-release mechanism consisting of surface-initiated low-barrier proton transfer from guanidinium groups to bicarbonate anions with the formation of carbonic acid dimers, followed by CO2 and H2O release in the rate-limiting step, with a measured activation energy of 102 ± 12 kJ/mol. The minimum energy required for sorbent regeneration is 151.5 kJ/mol CO2, which is 24% lower than the regeneration energy of monoethanolamine, a benchmark industrial sorbent.

Low-temperature X-ray and neutron diffraction experiments are used to characterize the electron-density distribution and intermolecular interactions in the insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), a potential CO2 sequestering agent. The importance of the hydrogen-bonding ability of the cation to the anion–water structure is discussed., Chemical bonding and all intermolecular interactions in the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH2)(CO3)(H2O)4, recently employed in the direct air capture of CO2 via crystallization, have been analyzed within the framework of the quantum theory of atoms in molecules (QTAIM) based on the experimental electron density derived from X-ray diffraction data obtained at 20 K. Accurate hydrogen positions were included based on an analogous neutron diffraction study at 100 K. Topological features of the covalent bonds demonstrate the presence of multiple bonds of various orders within the PyBIGH2 2+ cation. Strong hydrogen bonds define ribbons comprising carbonate anions and water molecules. These ribbons are linked to stacks of essentially planar dications via hydrogen bonds from the guanidinium moieties and an additional one to the pyridine nitro­gen. The linking hydrogen bonds are approximately perpendicular to the anion–water ribbons. The observation of these putative interactions provided motivation to characterize them by topological analysis of the total electron density. Thus, all hydrogen bonds have been characterized by the properties of their (3,−1) bond critical points. Weaker interactions between the PyBIGH2 2+ cations have similarly been characterized. Integrated atomic charges are also reported. A small amount of cocrystallized hydroxide ion (∼2%) was also detected in both the X-ray and neutron data, and included in the multipole model for the electron-density refinement. The small amount of additional H+ required for charge balance was not detected in either the X-ray or the neutron data. The results are discussed in the context of the unusually low aqueous solubility of (PyBIGH2)(CO3)(H2O)4 and its ability to sequester atmospheric CO2.

Recognition of (thio)sulfate and phosphate in aqueous solutions has been demonstrated by using oligo-urea-based receptors functionalized with quaternary ammonium groups. The ammonium groups allow for increased aqueous solubility while simultaneously providing positive coulombic interactions and stronger hydrogen bonding through an inductive effect. This simple and generally applicable modification provides an effective way to bolster the anion binding and water solubility of oligo-urea-based receptors. With a water soluble receptor 2, selective binding of adenosine phosphates was achieved at physiological pH.

Recently $\mathrm{Eu}{\mathrm{Cd}}_{2}{\mathrm{As}}_{2}$ was predicted to be a magnetic Weyl semimetal with a lone pair of Weyl nodes generated by $A$-type antiferromagnetism and protected by a rotational symmetry. However, it was soon discovered that the actual magnetic structure broke the rotational symmetry and internal pressure was later suggested as a route to stabilize the desired magnetic state. In this work we test this prediction by synthesizing a series of ${\mathrm{Eu}}_{1\ensuremath{-}x}{\mathrm{Ba}}_{x}{\mathrm{Cd}}_{2}{\mathrm{As}}_{2}$ single crystals and studying their structural, magnetic, and transport properties via both experimental techniques and first-principles calculations. We find that small concentrations of Ba ($\ensuremath{\sim}3%--10%$) lead to a small out-of-plane canting of the Eu moment. However, for higher concentrations this effect is suppressed and a nearly in-plane model is recovered. Studying the transport properties we find that all compositions show evidence of an anomalous Hall effect dominated by the intrinsic mechanism as well as large negative magnetoresistances in the longitudinal channel. A nonmonotonic evolution of the transport properties is seen across the series which correlates to the proposed canting suggesting canting may enhance the topological effects. Careful density functional theory calculations using an all-electron approach revise prior predictions finding a purely ferromagnetic ground state with in-plane moments for both the $\mathrm{Eu}{\mathrm{Cd}}_{2}{\mathrm{As}}_{2}$ and ${\mathrm{Eu}}_{0.5}{\mathrm{Ba}}_{0.5}{\mathrm{Cd}}_{2}{\mathrm{As}}_{2}$ compounds, corroborating our experimental findings. This work suggests that Ba substitution can tune the magnetic properties in unexpected ways which correlate to changes in measures of topological properties, encouraging future work to locate the ideal Ba concentration for Eu moment canting.

Direct air capture (DAC) technologies that extract carbon dioxide from the atmosphere via chemical processes have the potential to restore the atmospheric CO2 concentration to an optimal level. This study elucidates structure-property relationships in DAC by crystallization of bis(iminoguanidine) (BIG) carbonate salts. Their crystal structures are analyzed by X-ray and neutron diffraction to accurately measure key structural parameters including molecular conformations, hydrogen bonding, and π-stacking. Experimental measurements of key properties, such as aqueous solubilities and regeneration energies and temperatures, are complemented by first-principles calculations of lattice and hydration free energies, as well as free energies of reactions with CO2, and BIG regenerations. Minor structural modifications in the molecular structure of the BIGs are found to result in major changes in the crystal structures and the aqueous solubilities within the series, leading to enhanced DAC.

Iminoguanidines, first reported in 1898, have received renewed attention in the last 5 years due to their ability to recognize and separate anions from competitive aqueous environments. Iminoguanidines display high recognition abilities towards hydrophilic oxyanions (e.g., sulfate, chromate, carbonate) through strong and complementary hydrogen bonding from the guanidinium groups. This feature article reviews the fundamental anion recognition chemistry of iminoguanidines, as well as real-world applications including sulfate removal from seawater and CO2 capture for climate change mitigations.

Cooperativity effects among the interconnected anion and cation binding sites can profoundly alter the performance of heteroditopic receptors in selective ion pair recognition, processes that are oftentimes pertinent to biological systems and chemical separations. This work reports the effect of the linker that connects both binding sites on self-assembly of heteroditopic receptors in the presence of divalent first-row transition metal salts in solution and solid phase. Introduction of backbone flexibility in the receptor results in the formation of triple-stranded ion-pair helicates with an extraordinary selectivity towards CuSO4 through an anion-induced fit.

We report a structure-properties relationship study of DAC by crystallization of bis-iminoguanidine (BIG) carbonate salts. The study focuses on a series of basic BIG structures including the glyoxal-bis(iminoguanidine) prototype (GBIG) and its simple analogs methylglyoxal-bis(iminoguanidine) (MGBIG) and diacetyl-bis(iminoguanidine) (DABIG). We find that minor structural modifications in the molecular structure of GBIG, such as substituting one or two hydrogen atoms with methyl groups, result in major changes in the crystal structures, induced by the increased conformational flexibility and steric hindrance. As a result, the corresponding aqueous solubilities within the series increase significantly, leading in turn to enhanced DAC performances.

Crystal truncation rod (CTR) measurements and density functional theory (DFT) calculations were performed to determine the atomic structure of the mineral–water interface of the {100} surface of xenotime (nominally YPO4). This mineral is important, because it incorporates a variety of rare earth elements (REEs) in its crystal structure. REEs are critical materials necessary for a variety of renewable and energy efficient technologies. Current beneficiation techniques are not highly selective for REE ore minerals, and large amounts go to waste; this is a first step toward designing more efficient beneficiation. Evidence is found for minor relaxation of the surface within the topmost monolayer with little or no relaxation in subsurface layers. Justification for ordered water at the interface is found, where water binds to surface cations and donates hydrogen bonds to surface phosphates. The average bond lengths between cations and oxygens on water are 228 pm in the best fit to the CTR data, versus 243 and 2...

Using negative emissions technologies for the net removal of greenhouse gases from the atmosphere could provide a pathway to limit global temperature rises. Direct air capture of carbon dioxide offers the prospect of permanently lowering the atmospheric CO2 concentration, providing that economical and energy-efficient technologies can be developed and deployed on a large scale. Here, we report an approach to direct air capture, at the laboratory scale, using mostly off-the-shelf materials and equipment. First, CO2 absorption is achieved with readily available and environmentally friendly aqueous amino acid solutions (glycine and sarcosine) using a household humidifier. The CO2-loaded solutions are then reacted with a simple guanidine compound, which crystallizes as a very insoluble carbonate salt and regenerates the amino acid sorbent. Finally, effective CO2 release and near-quantitative regeneration of the guanidine compound are achieved by relatively mild heating of the carbonate crystals using concentrated solar power.

We report a novel di(imino)guanidinium anion extractant with unparalleled selectivity for sulfate in a liquid-liquid separation system. In addition to a 4.4 order-of-magnitude enhancement in affinity compared to a standard benchmark, our alkylated di(imino)guanidinium receptor is economically synthesized and features good compatibility with application-relevant aliphatic solvents. Small-angle X-ray scattering results reveal the formation of reverse-micelles, which together with the significant organic-phase water content challenge traditional notions of selectivity in extraction of superhydrophilic anions.

Environmentally friendly amino-acid salt solutions are used for the absorption of carbon dioxide from concentrated flue-gas streams via chemical absorption. Process intensification reduces operating and capital costs by combining chemical reactions and separation operations. Here, we present a new process-intensification approach that combines the CO2 capture and the amino-acid regeneration steps into a single process carried out in a slurry three-phase reactor. The absorbed CO2 precipitates as a solid carbonated guanidine compound. The cycle is completed by separation of the solid precipitate to strip the CO2 and regenerate the guanidine compound, while the liquid solution is recycled to the slurry reactor. The process was studied by modifying a model developed by the authors for a gas-liquid bubble column without the presence of the guanidine compound. The guanidine precipitation reaction was accounted for using kinetic parameters calculated by the authors in another study. The proposed model was implemented by modifying an existing computer code used for the simulation of gas-liquid bubble columns. The calculated results showed that the proposed cycle can significantly reduce energy, equipment, and operating costs and can make an important contribution to developing a competitive cost-effective large-scale process for CO2 capture.

CO2 capture from powerplant-generated flue gas via a phase-changing process involving absorption with aqueous amino acids (e.g., glycine or sarcosine) and bicarbonate crystallization with bis-iminoguanidines (e.g., glyoxal-bis-iminoguanidine or GBIG) is investigated in this paper. This process is of high interest due to its potential to decrease the energy penalty for CO2 capture by significantly reducing the solvent regeneration energy typically associated with aqueous amine solvents. A critical step in the proposed CO2 capture mechanism is the regeneration of the amino acid by removal of protons and bicarbonate ions from solution through crystallization of GBIGH22+ bicarbonate salt. Here, we investigated the thermodynamics and kinetics of glycine regeneration by crystallization of GBIGH22+(HCO3–)2(H2O)2. A theoretical model was developed and compared to experimental data to simulate and predict the glycine regeneration and determine its reaction mechanism. This combined experimental and theoretical study led to the conclusion that, while the GBIGH22+ bicarbonate crystallization step provides most of the thermodynamic driving force for the glycine regeneration, the rate-limiting step is the protonation of GBIG prior to crystallization. The CO2 loading and amino acid regeneration steps were combined into a single, intensified process using a bubble column reactor. The CO2 loading capacity of GBIG was experimentally determined to be roughly 1.36 mol CO2 per mol GBIG. These results provide the fundamental basis for developing an effective carbon capture technology with phase-changing amino acid/guanidine absorbents.

In nature, proteins have evolved sophisticated cavities tailored for capturing target guests selectively among competitors of similar size, shape, and charge. The fundamental principles guiding the molecular recognition, such as self-assembly and complementarity, have inspired the development of biomimetic receptors. In the current work, we report a self-assembled triple anion helicate (host 2) featuring a cavity resembling that of the choline-binding protein ChoX, as revealed by crystal and density functional theory (DFT)-optimized structures, which binds choline in a unique dual-site-binding mode. This similarity in structure leads to a similarly high selectivity of host 2 for choline over its derivatives, as demonstrated by the NMR and fluorescence competition experiments. Furthermore, host 2 is able to act as a fluorescence displacement sensor for discriminating choline, acetylcholine, l-carnitine, and glycine betaine effectively., The choline-binding protein ChoX exhibits a synergistic dual-site binding mode that allows it to discriminate choline over structural analogues. Here, the authors design a biomimetic triple anion helicate receptor whose selectivity for choline arises from a similar binding mechanism.

In this paper we report the synthesis, magnetization, and heat capacity of the frustrated magnets $A{\mathrm{ErSe}}_{2}$($A=\mathrm{Na},\mathrm{K}$) which contain perfect triangular lattices of ${\mathrm{Er}}^{3+}$. The magnetization data suggests no long-range magnetic order exists in $A{\mathrm{ErSe}}_{2}$($A=\mathrm{Na},\mathrm{K}$), which is consistent with the heat capacity measurements. Large anisotropy is observed between the magnetization within the $ab$ plane and along the $c$ axis of both compounds. When the magnetic field is applied along the $ab$ plane, anomalies are observed at 1.8 ${\ensuremath{\mu}}_{B}$ in ${\mathrm{NaErSe}}_{2}$ at 0.2 T and 2.1 ${\ensuremath{\mu}}_{B}$ in ${\mathrm{KErSe}}_{2}$ at 0.18 T. Unlike ${\mathrm{NaErSe}}_{2}$, a plateaulike field-induced metamagnetic transition is observed for $\mathrm{H}\ensuremath{\parallel}c$ below 1 K in ${\mathrm{KErSe}}_{2}$. Two broad peaks are observed in the heat capacity below 10 K indicating possible crystal electric field (CEF) effects and magnetic entropy released under different magnetic fields. All results indicate that $A{\mathrm{ErSe}}_{2}$ are strongly anisotropic, frustrated magnets with field-induced transition at low temperature. The lack of signatures for long-range magnetic order implies that these materials are candidates for hosting a quantum spin liquid ground state.

A bench-scale direct air capture process is reported, based on CO2 absorption with aqueous amino acids and carbonate crystallization with a guanidine compound.

We introduce a new supramolecular strategy where an anion receptor modifies the selectivity ligands for cations. This is demonstrated by combining the classic anion receptor calix[4]pyrrole (C4P) and a phenolic ligand, which leads to remarkable enhancement in selectivity for Cs+ over Na+. Crystal structures and molecular simulations confirmed the persistent formation of ion-pair C4P-Cs+-phenolate complexes, while the smaller Na+ ion cannot efficiently interact.

A hybrid solvent/solid-state approach to carbon capture is demonstrated based on absorption with glycine or sarcosine, followed by crystallization of a guanidinium bicarbonate salt.

Summary Negative emission technologies, including direct air capture (DAC) of carbon dioxide, are now considered essential for mitigating climate change, but existing DAC processes tend to have excessively high energy requirements, mostly associated with sorbent regeneration. Here, we demonstrate a promising approach to DAC that combines atmospheric CO2 absorption by an aqueous oligopeptide (e.g., glycylglycine) with bicarbonate crystallization by a simple guanidine compound (e.g., glyoxal-bis-iminoguanidine). In this phase-changing system, the peptide and the guanidine compounds work in synergy, and the cyclic CO2 capacity can be maximized by matching the pKa values of the two components. Compared with glycine, the simpler amino acid congener, the cyclic CO2 capacity of the glycylglycine peptide combined with glyoxal-bis-iminoguanidine is twice as high (0.16 mol/mol). The resulting DAC process has a significantly lower regeneration energy compared with state-of-the-art solvent-based DAC technologies.

Selective crystallization of sulfate with a simple bis-guanidinium ligand, self-assembled in situ from terephthalaldehyde and aminoguanidinium chloride, was employed as an effective way to separate the highly hydrophilic sulfate anion from aqueous solutions. The resulting bis-iminoguanidinium sulfate salt has exceptionally low aqueous solubility (Ksp =2.4×10-10 ), comparable to that of BaSO4 . Single-crystal X-ray diffraction analysis showed the sulfate anions are sequestered as [(SO4 )2 (H2 O)4 ]4- clusters within the crystals. Variable-temperature solubility measurements indicated the sulfate crystallization is slightly endothermic (ΔHcryst =3.7 kJ mol-1 ), thus entropy driven. The real-world utility of this crystallization-based approach for sulfate separation was demonstrated by removing up to 99 % of sulfate from seawater in a single step.

Here we used single-crystal X-ray diffraction data to determine crystal structure of CsCe2Cl7. It crystallizes in a P1121/b space group with a = 19.352(1) Å, b = 19.352(1) Å, c = 14.838(1) Å, γ = 119.87(2) ° , and V = 4818.6(5) Å3. Differential scanning calorimetry measurements combined with the structural evolution of CsCe2Cl7 via X-ray diffractometry over a temperature range from room temperature to the melting point indicates no obvious intermediate solid-solid phase transitions. The anisotropy in the average linear coefficient of thermal expansion of the a axis (21.3 10-6/ °C) with respect to the b and c axes (27.0 10-6/ °C) was determined through lattice parameter refinement of the temperature dependent diffraction patterns. Lastly, these findings suggest that the reported cracking behavior during melt growth of CsCe2Cl7 bulk crystals using conventional Bridgman and Czochralski techniques may be largely attributed to the anisotropy in thermal expansion.

The thermodynamics and kinetics of crystallization of sodium sulfate with a tripodal tris-urea receptor (L1) from aqueous alkaline solutions have been measured in the 15–55 °C temperature range for a fundamental understanding of the elementary steps involved in this sulfate separation method. The use of radiolabeled Na235SO4 provided a practical way to monitor the sulfate concentration in solution by β liquid scintillation counting. Our results are consistent with a two-step crystallization mechanism, involving relatively quick dissolution of crystalline L1 followed by the rate-limiting crystallization of the Na2SO4(L1)2(H2O)4 capsules. We found that temperature exerted relatively little influence over the equilibrium sulfate concentration, which ranged between 0.004 and 0.011 M. This corresponds to 77–91% removal of sulfate from a solution containing 0.0475 M initial sulfate concentration, as found in a typical Hanford waste tank. The apparent pseudo-first-order rate constant for sulfate removal increase...

We report a new family of preorganized bis-lactam-1,10-phenanthroline (BLPhen) complexants that possess both hard and soft donor atoms within a convergent cavity and show unprecedented extraction strength for the trivalent f-block metal ions. BLPhen ligands with saturated and unsaturated δ-lactam rings have notable differences in their affinity and selectivity for Am(III) over Eu(III), with the latter being the most selective mixed N,O-donor extractant of Am(III) reported to date. Saturated BLPhen was crystallized with five Ln(III) nitrates to form charge-neutral 1:1 complexes in the solid state. DFT calculations further elaborate on the variety of effects that dictate the performance of these preorganized compounds.

Alkali metal cation extraction behaviour for two series of 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionisable group (PIG) is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the PIG is attached to one para position in the calixarene framework, thereby positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same PIG are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the position of the PIG relative to the crown ether cavity. Solid-state structures of two unionised ligands from Series 2 are presented. Also described is a crystal containing two different ionised ligand–Cs+ complexes.

We present a generalized approach toward the design of ion-pair ML3A helicates assembled by coordination of metal cations (M) and anions (A) by ditopic chelating ligands (L). This computational approach, based on de novo structure-based design principles implemented in the HostDesigner software, led to identification of synthetically accessible ditopic ligands that are structurally encoded to form charge-neutral ion-pair helicates with FeSO4 or LnPO4.

A unique class of air-stable and non-pyrophoric magnesium electrolytes has been developed based on alkoxide magnesium compounds. The crystals obtained from this class of electrolytes exhibit a unique structure of tri-magnesium cluster, [Mg3Cl3(OR)2(THF)6]+ [(THF)MgCl3]−. High reversible capacities and good rate capabilities have been obtained in Mg–Mo6S8 batteries using these new electrolytes at both 20 and 50 °C.

The development of cationic polymers for anion-exchange membranes (AEMs) with high alkaline stability and conductivity is a considerable challenge in materials chemistry. However, the commonly employed organic cations have limited alkaline stability, especially at high temperatures, which restricts the commercialization of AEM alkaline fuel cell technology. To address this problem, we have designed and synthesized a series of novel imidazolium-based AEMs for alkaline fuel cell applications. Degradation rates and mechanisms of small organic cations were analyzed by NMR spectroscopy and rationalized using density functional theory (DFT) calculations. The substituent selection at each position of the imidazolium ring has a dramatic effect on the overall cation stability, correlating to the stability profiles of corresponding AEMs. The most stable imidazoliums were chosen to polymerize robust AEMs, while their stability was examined by dynamic vapor sorption (DVS) technique, and conductivity was measured with the four-probe method. The results have shown the superior alkaline stability and conductivity of our imidazolium-based AEMs even at high temperature (80 °C), confirming they are promising AEM candidates for practical application in alkaline fuel cell.