Supramolecular Complexation-enhanced CO2 Chemisorption in Amine-derived Sorbents.

A supramolecular complexation approach is developed to improve the CO2 chemisorption performance of solvent-lean amine sorbents. Operando spectroscopy techniques reveal the formation of carbamic acid in the presence of a crown ether. The reaction pathway is confirmed by theoretical simulation, in which the crown ether acts as proton acceptor and shuttle to drive the formation and stabilization of carbamic acid. Improved CO2 capacity and diminished energy consumption in sorbent regeneration was achieved.

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 (400 ppm) 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 (400 ppm) 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 ≈-40 kJ mol-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.

Low-Temperature Molten Salt Electrochemical CO2 Upcycling for Advanced Energy Materials.

One strategy for addressing the climate crisis caused by CO2 emissions is to efficiently convert CO2 to advanced materials suited for green and clean energy technology applications. Porous carbon is widely used as an advanced energy storage material because of its enhanced energy storage capabilities as an anode. Herein, we report electrochemical CO2 upcycling to solid carbon with a controlled microstructure and porosity in a ternary molten carbonate melt at 450 °C. Controlling the electrochemical parameters (voltage, temperature, cathode material) enabled the conversion of CO2 to porous carbon with a tunable morphology and porosity for the first time at such a low temperature. Additionally, a well-controlled morphology and porosity are beneficial for reversible energy storage. In fact, these carbon materials delivered high specific capacity, stable cycling performances, and exceptional rate capability even under extremely fast charging conditions when integrated as an anode in lithium-ion batteries (LIBs). The present approach not only demonstrated efficient upcycling of CO2 into porous carbon suitable for enhanced energy storage but can also contribute to a clean and green energy technology that can reduce carbon emissions to achieve sustainable energy goals.

Surpassing the Performance of Phenolate-derived Ionic Liquids in CO2 Chemisorption by Harnessing the Robust Nature of Pyrazolonates.

Superbase-derived ionic liquids (SILs) are promising sorbents to tackle the carbon challenge featured by tunable interaction strength with CO2 via structural engineering, particularly the oxygenate-derived counterparts (e. g., phenolate). However, for the widely deployed phenolate-derived SILs, unsolved stability issues severely limited their applications leading to unfavorable and diminished CO2 chemisorption performance caused by ylide formation-involved side reactions and the phenolate-quinone transformation via auto-oxidation. In this work, robust pyrazolonate-derived SILs possessing anti-oxidation nature were developed by introducing aza-fused rings in the oxygenate-derived anions, which delivered promising and tunable CO2 uptake capacity surpassing the phenolate-based SIL via a carbonate formation pathway (O-C bond formation), as illustrated by detailed spectroscopy studies. Further theoretical calculations and experimental comparisons demonstrated the more favorable reaction enthalpy and improved anti-oxidation properties of the pyrazolonate-derived SILs compared with phenolate anions. The achievements being made in this work provides a promising approach to achieve efficient carbon capture by combining the benefits of strong interaction strength of oxygenate species with CO2 and the stability improvement enabled by aza-fused rings introduction.

Facile Strategy to Prepare Poly(ionic liquid)-Coated Solid Polymer Electrolytes through Layer-by-Layer Assembly.

The inability of solid polymer electrolytes to preserve strong mechanical strength with high ionic conductivity hinders the commercialization of lithium metal batteries (LMBs). The success of fabricating layer-by-layer (LbL)-assembled electrolytes has realized the application of flexible solid polymer electrolytes in electrochemical devices. Here, we demonstrate a rational strategy to construct solid electrolytes coated with multiple ultrathin layers of polyanions (poly(sodium 4-styrenesulfonate)) and polycations (linear poly(1-butyl-3-(4-vinylbenzyl)-1H-imidazolium chloride) (BVIC)/linear poly(PEG4-VIC)/SiO2-g-poly(PEG4-VIC)) using an LbL assembly method. Poly(ionic liquid) backbones and PEG side groups are employed to facilitate the transport of lithium ions via the segmental motion of the macromolecular matrix. The fabricated free-standing membranes exhibited good ionic conductivities of 9.03-10 × 10-4 S cm-1. Furthermore, a Li/LiFePO4 cell assembled with the LbL-membrane electrolytes exhibits an initial high discharge capacity of 143-158 mAhg-1 at 60 °C with high columbic efficiency. This approach, which combines polymer synthesis and LbL self-assembly, is an effective and facile route to fabricate solid polymer electrolyte membranes with superior ionic conductivity and mechanical robustness, which are useful for electrochemical devices and high-voltage battery applications.

Effects of Methylating Imidazolium-Based Ionic Liquids on Viscosity: New Insights from the Compensated Arrhenius Formalism.

Methylation of the C(2) carbon on imidazolium-based room temperature ionic liquids (RTILs) causes an unexpected increase in viscosity when paired with the anion bis(trifluoromethylsulfonamide) [Tf2N]-, but the viscosity decreases when the methylated imidazolium is paired with a tetracyanoborate [B(CN)4]- anion. This paper investigates these different observations in viscosity using the compensated Arrhenius formalism (CAF) for fluidity (inverse viscosity), which assumes fluidity to be a thermally activated process. CAF activation energies are determined for imidazolium [Tf2N]- and methylated imidazolium [Tf2N]- and compared to imidazolium [B(CN)4]- and methylated imidazolium [B(CN)4]-. The results show that the activation energy increases with methylation for [Tf2N]-, but it decreases with methylation for [B(CN)4]-. The CAF results also yield information concerning the entropy of activation, which are compared for the two systems.

Revolutionizing Porous Liquids: Stabilization and Structural Engineering Achieved by a Surface Deposition Strategy.

Facile approaches capable of constructing stable and structurally diverse porous liquids (PLs) that can deliver high-performance applications are a long-standing, captivating, and challenging research area that requires significant attention. Herein, a facile surface deposition strategy is demonstrated to afford diverse type III-PLs possessing ultra-stable dispersion, external structure modification, and enhanced performance in gas storage and transformation by leveraging the expeditious and uniform precipitation of selected metal salts. The Ag(I) species-modified zeolite nanosheets are deployed as the porous host to construct type III-PLs with ionic liquids (ILs) containing bromide anion , leading to stable dispersion driven by the formation of AgBr nanoparticles. The as-afforded type-III PLs display promising performance in CO2 capture/conversion and ethylene/ethane separation. Property and performance of the as-produced PLs can be tuned by the cation structure of the ILs, which can be harnessed to achieve polarity reversal of the porous host via ionic exchange. The surface deposition procedure can be further extended to produce PLs from Ba(II)-functionalized zeolite and ILs containing [SO4 ]2- anion driven by the formation of BaSO4 salts. The as-produced PLs are featured by well-maintained crystallinity of the porous host, good fluidity and stability, enhanced gas uptake capacity, and attractive performance in small gas molecule utilization.

CO2 Chemisorption Behavior in Conjugated Carbanion-Derived Ionic Liquids via Carboxylic Acid Formation.

Superbase-derived task-specific ionic liquids (STSILs) represent one of the most attractive and extensively studied systems in carbon capture via chemisorption, in which the obtained CO2 uptake capacity has a strong relationship with the basicity of the anions. High energy input in desorption and side reactions caused by the strong basicity of the anions are still unsolved issues. The development of other customized STSILs leveraging an alternative driving force to achieve efficient CO2 chemisorption/desorption is highly desirable yet challenging. In this work, carbanion-derived STSILs were developed for efficient CO2 chemisorption via a carboxylic acid formation pathway. The STSIL with the deprotonated malononitrile molecule ([MN]) as the anion exhibited much higher CO2 uptake capacity than the one derived from 2-methylmalononitrile ([MMN]). Notably, this trend was opposite to their basicity ([MN] < [MMN]). Detailed characterization of the products, supported by density functional theory simulations of spectra and calculations of the reaction energetics, demonstrated that carboxylic acid was formed upon reacting with CO2 via proton transfer in [MN]-derived STSILs but not in the case of [MMN] due to lack of an α-H. The preference of the carboxylic acid product over carboxylate formation was driven by the extended conjugation among the central sp2 carbon, the as-formed carboxylic acid, and the two nitrile groups. The achievements made in this work provide an alternative design principle of STSILs by leveraging the extended conjugation in the CO2-integrated product.

New-Generation Carbon-Capture Ionic Liquids Regulated by Metal-Ion Coordination.

Development of efficient carbon capture-and-release technologies with minimal energy input is a long-term challenge in mitigating CO2 emissions, especially via CO2 chemisorption driven by engineered chemical bond construction. Herein, taking advantage of the structural diversity of ionic liquids (ILs) in tuning their physical and chemical properties, precise reaction energy regulation of CO2 chemisorption was demonstrated deploying metal-ion-amino-based ionic liquids (MAILs) as absorbents. The coordination ability of different metal sites (Cu, Zn, Co, Ni, and Mg) to amines was harnessed to achieve fine-tuning on stability constants of the metal ion-amine complexes, acting as the corresponding cations in the construction of diverse ILs coupled with CO2 -philic anions. The as-afforded MAILs exhibited efficient and controllable CO2 release behavior with great reduction in energy input and minimal sacrifice on CO2 uptake capacity. This coordination-regulated approach offers new prospects for the development of ILs-based systems and beyond towards energy-efficient carbon capture technologies.

Bifunctional Ionic Covalent Organic Networks for Enhanced Simultaneous Removal of Chromium(VI) and Arsenic(V) Oxoanions via Synergetic Ion Exchange and Redox Process.

Chromium (VI) and arsenic (V) oxoanions are major toxic heavy metal pollutants in water threatening both human health and environmental safety. Herein, the development is reported of a bifunctional ionic covalent organic network (iCON) with integrated guanidinium and phenol units to simultaneously sequester chromate and arsenate in water via a synergistic ion-exchange-redox process. The guanidinium groups facilitate the ion-exchange-based adsorption of chromate and arsenate at neutral pH with fast kinetics and high uptake capacity, whereas the integrated phenol motifs mediate the Cr(VI)/Cr(III) redox process that immobilizes chromate and promotes the adsorption of arsenate via the formation of Cr(III)-As(V) cluster/complex. The synergistic ion-exchange-redox approach not only pushes high adsorption efficiency for both chromate and arsenate but also upholds a balanced Cr/As uptake ratio regardless of the change in concentration and the presence of interfering oxoanions.

Synthesis of Poly(ionic Liquid)s-block-poly(methyl Methacrylate) Copolymer-Grafted Silica Particle Brushes with Enhanced CO2 Permeability and Mechanical Performance.

Poly(ionic liquid) (PIL)-based block copolymers are of particular interest as they combine the specific properties of PILs with the self-assembling behaviors of block copolymers, broadening the range of potential applications for PIL-based materials. In this work, three particle brushes: SiO2-g-poly(methyl methacrylate) (PMMA), SiO2-g-PIL, and SiO2-g-PMMA-b-PIL were prepared through surface-initiated atom transfer radical polymerization. Unlike the homogeneous homopolymer particle brushes, the block copolymer particle brush SiO2-g-PMMA-b-PIL exhibited a bimodal chain architecture and unique phase-separated morphology, which were confirmed by size-exclusion chromatography and transmission electron microscopy. In addition, the influence of the introduction of the PMMA segment on the gas separation and mechanical performance of the PIL-containing block copolymer particle brushes were investigated. A significant improvement of Young's modulus was observed in the SiO2-g-PMMA-b-PIL compared to the SiO2-g-PIL bulk films; meanwhile, their gas separation performances (CO2 permeability and CO2/N2 selectivity) were the same, which demonstrates the possibility of improving the mechanical properties of PIL-based particle brushes without compromising their gas separation performance.

CO2 Chemisorption Behavior of Coordination-Derived Phenolate Sorbents.

Invited for this month's cover is the group of Sheng Dai at the Oak Ridge National Laboratory. The image shows the CO2 chemisorption behavior of coordination-derived phenolate sorbents. The Communication itself is available at 10.1002/cssc.202100666.

X-ray scattering reveals ion clustering of dilute chromium species in molten chloride medium.

Enhancing the solar energy storage and power delivery afforded by emerging molten salt-based technologies requires a fundamental understanding of the complex interplay between structure and dynamics of the ions in the high-temperature media. Here we report results from a comprehensive study integrating synchrotron X-ray scattering experiments, ab initio molecular dynamics simulations and rate theory concepts to investigate the behavior of dilute Cr3+ metal ions in a molten KCl-MgCl2 salt. Our analysis of experimental results assisted by a hybrid transition state-Marcus theory model reveals unexpected clustering of chromium species leading to the formation of persistent octahedral Cr-Cr dimers in the high-temperature low Cr3+ concentration melt. Furthermore, our integrated approach shows that dynamical processes in the molten salt system are primarily governed by the charge density of the constituent ions, with Cr3+ exhibiting the slowest short-time dynamics. These findings challenge several assumptions regarding specific ionic interactions and transport in molten salts, where aggregation of dilute species is not statistically expected, particularly at high temperature.

Polymer-Grafted Porous Silica Nanoparticles with Enhanced CO2 Permeability and Mechanical Performance.

Three different types of polymer ligands, poly(methyl methacrylate) (PMMA), poly(methyl methacrylate-random-poly(ethylene glycol)methyl ether methacrylate) (PMMA-r-PEGMEMA), and poly(ionic liquid)s (PIL), were grafted onto the surface of 15 nm solid and large hollow porous silica nanoparticles (average particle size ∼60 nm) by surface-initiated atom transfer radical polymerization (SI-ATRP) to demonstrate the enhanced carbon dioxide (CO2) permeability as well as mechanical properties. After characterizing the purified products, free-standing bulk films were fabricated by the solvent-casting method. The poly(ionic liquid) nanocomposite films exhibited a much higher carbon dioxide permeance than PMMA and PMMA-r-PEGMEMA systems with a similar silica content. Also, the hollow silica-mixed matrix membranes showed a significant enhancement in CO2 permeability compared to the 15 nm solid silica films because of the pore structure. Despite the transparency loss due to the scattering of larger particle sizes, the hollow silica particle brush films exhibited the same mechanical properties as the 15 nm solid silica-derived ones.

Formation of three-dimensional bicontinuous structures via molten salt dealloying studied in real-time by in situ synchrotron X-ray nano-tomography.

Three-dimensional bicontinuous porous materials formed by dealloying contribute significantly to various applications including catalysis, sensor development and energy storage. This work studies a method of molten salt dealloying via real-time in situ synchrotron three-dimensional X-ray nano-tomography. Quantification of morphological parameters determined that long-range diffusion is the rate-determining step for the dealloying process. The subsequent coarsening rate was primarily surface diffusion controlled, with Rayleigh instability leading to ligament pinch-off and creating isolated bubbles in ligaments, while bulk diffusion leads to a slight densification. Chemical environments characterized by X-ray absorption near edge structure spectroscopic imaging show that molten salt dealloying prevents surface oxidation of the metal. In this work, gaining a fundamental mechanistic understanding of the molten salt dealloying process in forming porous structures provides a nontoxic, tunable dealloying technique and has important implications for molten salt corrosion processes, which is one of the major challenges in molten salt reactors and concentrated solar power plants.

Unraveling Local Structure of Molten Salts via X-ray Scattering, Raman Spectroscopy, and Ab Initio Molecular Dynamics.

In this work, we resolve a long-standing issue concerning the local structure of molten MgCl2 by employing a multimodal approach, including X-ray scattering and Raman spectroscopy, along with the theoretical modeling of the experimental spectra based on ab initio molecular dynamics (AIMD) simulations utilizing several density functional theory (DFT) methods. We demonstrate the reliability of AIMD simulations in achieving excellent agreement between the experimental and simulated spectra for MgCl2 and 50 mol % MgCl2 + 50 mol % KCl, and ZnCl2, thus allowing structural insights not directly available from experiment alone. A thorough computational analysis using five DFT methods provides a convergent view that octahedrally coordinated magnesium in pure MgCl2 upon melting preferentially coordinates with five chloride anions to form distorted square pyramidal polyhedra that are connected via corners and to a lesser degree via edges. This is contrasted with the results for ZnCl2, which does not change its tetrahedral coordination on melting. Although the five-coordinate MgCl53- complex was not considered in the early literature, together with an increasing tendency to form a tetrahedrally coordinated complex with decreasing the MgCl2 content in the mixture with alkali metal chloride systems, current work reconciles the results of most previous seemingly contradictory experimental studies.

CO2 Chemisorption Behavior of Coordination-Derived Phenolate Sorbents.

CO2 chemisorption via C-O bond formation is an efficient methodology in carbon capture especially using phenolate-based ionic liquids (ILs) as the sorbents to afford carbonate products. However, most of the current IL systems involve alkylphosphonium cations, leading to side reactions via the ylide intermediate pathway. It is important to figure out the CO2 chemisorption behavior of phenolate-derived sorbents using inactive and easily accessible cation counterparts without active protons. Herein, phenolate-based systems were constructed via coordination between alkali metal cations with crown ethers to avoid the participation of active protons in CO2 chemisorption. Reaction pathway study revealed that CO2 uptake could be achieved by O-C bond formation to afford carbonate. CO2 uptake capacity and reaction enthalpy were significantly influenced by the coordination effect, alkali metal types, and alkyl groups on the benzene ring.

Design of Graphene/Ionic Liquid Composites for Carbon Capture.

Pore size is a crucial factor impacting gas separation in porous separation materials, but how to control the pore size to optimize the separation performance remains a challenge. Here, we propose a design of graphene/ionic liquid composites with tunable slit pore sizes, where cations and anions of ionic liquids are intercalated between graphene layers. By varying the sizes of the ions, we show from first-principles density functional theory calculations that the accessible pore size can be tuned from 3.4 to 6.0 Å. Grand canonical Monte Carlo simulations of gas sorption find that the composite materials possess high CO2 uptake at room temperature and 1 bar (up to ∼8.5 mmol/g). Further simulations of the sorption of gas mixtures reveal that high CO2/N2 and CO2/CH4 adsorption selectivities can be obtained when the accessible pore size is <5 Å. This work suggests a new strategy to achieve tunable pore sizes via the graphene/IL composites for highly selective CO2/N2 and CO2/CH4 adsorption.