Cascade CO2 Insertion in Carbanion Ionic Liquids Driven by Structure Rearrangement.

The CO2 chemisorption in state-of-the-art sorbents based on oxide/hydroxide/amine moieties is driven by strong chemical bonding formation in the carbonate/bicarbonate/carbamate products, which in turn leads to high energy input in sorbent regeneration. In addition, the CO2 uptake capacity was limited by the active sites' utilization efficiency, with each active site incorporating one CO2 molecule or less. In this work, a new concept and generation of sorbent was developed to achieve cascade insertion of multiple CO2 molecules by leveraging structure rearrangement as the driving force, leading to in situ generation of extra CO2-binding sites and significantly reduced energy input for CO2 release. The designed ionic liquids (ILs) containing carbanions with conjugated and asymmetric structure, deprotonated (methylsulfonyl)acetonitrile ([MSA]) anion, allowed the cascade insertion of two CO2 molecules via consecutive C-C and O-C bond formations. The proton transfer and structure rearrangement of the carboxylic acid intermediates played critical roles in stabilizing the first integrated CO2 and generating extra electron-rich oxygen sites for the insertion of the second CO2. The structure variation and reaction pathway were confirmed by operando spectroscopy, magnetic resonance spectroscopy (NMR), mass spectroscopy, and computational chemistry. The energy input in sorbent regeneration could be further reduced by harnessing the phase-changing behavior of the carbanion salts in ether solutions upon reacting with CO2, avoiding the energy consumption in heating the solvent. The fundamental insights obtained herein provide a promising approach to greatly improve the CO2 sorption performance via sophisticated molecular-scale structural engineering of the sorbents.

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.

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 a proton acceptor and shuttle to drive the formation and stabilization of carbamic acid. Improved CO2 capacity and diminished energy consumption in sorbent regeneration are achieved.

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.

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.

Broadening the Gas Separation Utility of Monolayer Nanoporous Graphene Membranes by an Ionic Liquid Gating.

Ultrathin two-dimensional (2D) monolayer atomic crystal materials offer great potential for extending the field of novel separation technology due to their infinitesimal thickness and mechanical strength. One difficult and ongoing challenge is to perforate the 2D monolayer material with subnanometer pores with atomic precision for sieving similarly sized molecules. Here, we demonstrate the exceptional separation performance of ionic liquid (IL)/graphene hybrid membranes for challenging separation of CO2 and N2. Notably, the ultrathin ILs afford dynamic tuning of the size and chemical affinity of nanopores while preserving the high permeance of the monolayer nanoporous graphene membranes. The hybrid membrane yields a high CO2 permeance of 4000 GPU and an outstanding CO2/N2 selectivity up to 32. This rational hybrid design provides a universal direction for broadening gas separation capability of atomically thin nanoporous membranes.

Structure and dynamics of the molten alkali-chloride salts from an X-ray, simulation, and rate theory perspective.

Molten salts are of great interest as alternative solvents, electrolytes, and heat transfer fluids in many emerging technologies. The macroscopic properties of molten salts are ultimately controlled by their structure and ion dynamics at the microscopic level and it is therefore vital to develop an understanding of these at the atomistic scale. Herein, we present high-energy X-ray scattering experiments combined with classical and ab initio molecular dynamics simulations to elucidate structural and dynamical correlations across the family of alkali-chlorides. Computed structure functions and transport properties are in reasonably good agreement with experiments providing confidence in our analysis of microscopic properties based on simulations. For these systems, we also survey different rate theory models of anion exchange dynamics in order to gain a more sophisticated understanding of the short-time correlations that are likely to influence transport properties such as conductivity. The anion exchange process occurs on the picoseconds time scale at 1100 K and the rate increases in the order KCl < NaCl < LiCl, which is in stark contrast to the ion pair dissociation trend in aqueous solutions. Consistent with the trend we observe for conductivity, the cationic size/mass, as well as other factors specific to each type of rate theory, appear to play important roles in the anion exchange rate trend.

Ambient Temperature Graphitization Based on Mechanochemical Synthesis.

Graphite has become a critical material because of its high supply risk and essential applications in energy industries. Its present synthesis still relies on an energy-intensive thermal treatment pathway (Acheson process) at about 3000 °C. Herein, a mechanochemical approach is demonstrated to afford highly crystalline graphite nanosheets at ambient temperature. The key to the success of our methodology lies in the successive decomposition and rearrangement of a carbon nitride framework driven by a denitriding reaction in the presence of magnesium. The afforded graphite features high crystallinity, a high degree of graphitization, a thin nanosheet architecture, and a small flake size, which endow it with superior efficiency in lithium-ion batteries as an anode material in terms of rate capacity and cycle stability. The mild and cost-effective pathway used in this study could be a promising alternative for graphite production.

Guanidinium-Based Ionic Covalent Organic Framework for Rapid and Selective Removal of Toxic Cr(VI) Oxoanions from Water.

Ionic covalent organic frameworks make up an emerging class of functional materials in which the included ionic interfaces induce strong and attractive interactions with ionic species of the opposite charge. In this work, the strong and selective binding forces between the confined diiminoguanidinium groups in the framework and tetrahedral oxoanions have led to unparalleled effectiveness in the removal of the toxic chromium(VI) pollutant from aqueous solutions. The new functional framework can take up from 90 to 200 mg/g of chromium(VI), depending on the solution pH, and is capable of decreasing the chromium(VI) concentration in water from 1 ppm to 10 ppb within minutes (an order of magnitude below the current U.S. Environmental Protection Agency maximum contaminant level of 100 ppb), demonstrating superior properties among known ion exchange materials and natural sorbents.

Fibers with Hyper-Crosslinked Functional Porous Frameworks.

The incorporation of robust porous frameworks into polymer fibers with handleable morphologies and flexible chemical compositions exhibits significant advantages for device fabrication in a wide range of applications. However, the soft linear polymeric chains of the fibers make the generation of nanopores extremely challenging. Herein, a facile synthetic strategy based on a combination of functional monomer grafting and hyper-crosslinking technology is developed for the porous engineering of polymeric fibers. In this methodology, the nanoporous framework originating from the hyper-crosslinking of aromatic monomers is covalently grafted onto fibers, which is beneficial to retaining their unique fiber morphology and to preserving their excellent mechanical properties. Moreover, this promising protocol can be further extended to the porous functionalization of polymeric matrices with diverse morphologies for target-specific applications.

Ion-Gated Gas Separation through Porous Graphene.

Porous graphene holds great promise as a one-atom-thin, high-permeance membrane for gas separation, but to precisely control the pore size down to 3-5 Å proves challenging. Here we propose an ion-gated graphene membrane comprising a monolayer of ionic liquid-coated porous graphene to dynamically modulate the pore size to achieve selective gas separation. This approach enables the otherwise nonselective large pores on the order of 1 nm in size to be selective for gases whose diameters range from 3 to 4 Å. We show from molecular dynamics simulations that CO2, N2, and CH4 all can permeate through a 6 Å nanopore in graphene without any selectivity. But when a monolayer of [emim][BF4] ionic liquid (IL) is deposited on the porous graphene, CO2 has much higher permeance than the other two gases. We find that the anion dynamically modulates the pore size by hovering above the pore and provides affinity for CO2, while the larger cation (which cannot go through the pore) holds the anion in place via electrostatic attraction. This composite membrane is especially promising for CO2/CH4 separation, yielding a CO2/CH4 selectivity of about 42 and CO2 permeance of ∼105 GPU (gas permeation unit). We further demonstrate that selectivity and permeance can be tuned by the anion size, pore size, and IL thickness. The present work points toward a promising direction of using the atom-thin ionic liquid/porous graphene hybrid membrane for high-permeance, selective gas separation that allows a greater flexibility in substrate pore size control.

Neutron vibrational spectroscopic studies of novel tire-derived carbon materials.

Sulfonated tire-derived carbons have been demonstrated to be high value-added carbon products of tire recycling in several energy storage system applications including lithium, sodium, potassium ion batteries and supercapacitors. In this communication, we compared different temperature pyrolyzed sulfonated tire-derived carbons with commercial graphite and unmodified/non-functionalized tire-derived carbon by studying the surface chemistry and properties, vibrational spectroscopy of the molecular structure, chemical bonding such as C-H bonding, and intermolecular interactions of the carbon materials. The nitrogen adsorption-desorption studies revealed the tailored micro and meso pore size distribution of the carbon during the sulfonation process. XPS and neutron vibrational spectra showed that the sulfonation of the initial raw tire powders could remove the aliphatic hydrogen containing groups ([double bond splayed left]CH2 and -CH3 groups) and reduce the number of heteroatoms that connect to carbon. The absence of these functional groups could effectively improve the first cycle efficiency of the material in rechargeable batteries. Meanwhile, the introduced -SO3H functional group helped in producing terminal H at the edge of the sp2 bonded graphite-like layers. This study reveals the influence of the sulfonation process on the recovered hard carbon from used tires and provides a pathway to develop and improve advanced energy storage materials.

Highly Efficient Carbon Monoxide Capture by Carbanion-Functionalized Ionic Liquids through C-Site Interactions.

A novel method for the highly efficient and reversible capture of CO in carbanion-functionalized ionic liquids (ILs) by a C-site interaction is reported. Because of its supernucleophilicity, the carbanion in ILs could absorb CO efficiently. As a result, a relatively high absorption capacity for CO (up to 0.046 mol mol-1 ) was achieved under ambient conditions, compared with CO solubility in a commonly used IL [Bmim][Tf2 N] (2×10-3  mol mol-1 ). The results of quantum mechanical calculations and spectroscopic investigation confirmed that the chemical interaction between the C-site in the carbanion and CO resulted in the superior CO absorption capacities. Furthermore, the subsequent conversion of captured CO into valuable chemicals with good reactivity was also realized through the alkoxycarbonylation reaction under mild conditions. Highly efficient CO absorption by carbanion-functionalized ILs provides a new way of separating and converting CO.

Electrostatic-Assisted Liquefaction of Porous Carbons.

Porous liquids are a newly developed porous material that combine unique fluidity with permanent porosity, which exhibit promising functionalities for a variety of applications. However, the apparent incompatibility between fluidity and permanent porosity makes the stabilization of porous nanoparticle with still empty pores in the dense liquid phase a significant challenging. Herein, by exploiting the electrostatic interaction between carbon networks and polymerized ionic liquids, we demonstrate that carbon-based porous nanoarchitectures can be well stabilized in liquids to afford permanent porosity, and thus opens up a new approach to prepare porous carbon liquids. Furthermore, we hope this facile synthesis strategy can be widely applicated to fabricate other types of porous liquids, such as those (e.g., carbon nitride, boron nitride, metal-organic frameworks, covalent organic frameworks etc.) also having the electrostatic interaction with polymerized ionic liquids, evidently advancing the development and understanding of porous liquids.

Controlled Gas Exfoliation of Boron Nitride into Few-Layered Nanosheets.

The controlled exfoliation of hexagonal boron nitride (h-BN) into single- or few-layered nanosheets remains a grand challenge and becomes the bottleneck to essential studies and applications of h-BN. Here, we present an efficient strategy for the scalable synthesis of few-layered h-BN nanosheets (BNNS) using a novel gas exfoliation of bulk h-BN in liquid N2 (L-N2 ). The essence of this strategy lies in the combination of a high temperature triggered expansion of bulk h-BN and the cryogenic L-N2 gasification to exfoliate the h-BN. The produced BNNS after ten cycles (BNNS-10) consisted primarily of fewer than five atomic layers with a high mass yield of 16-20 %. N2 sorption and desorption isotherms show that the BNNS-10 exhibited a much higher specific surface area of 278 m(2) g(-1) than that of bulk BN (10 m(2) g(-1) ). Through the investigation of the exfoliated intermediates combined with a theoretical calculation, we found that the huge temperature variation initiates the expansion and curling of the bulk h-BN. Subseqently, the L-N2 penetrates into the interlayers of h-BN along the curling edge, followed by an immediate drastic gasification of L-N2 , further peeling off h-BN. This novel gas exfoliation of high surface area BNNS not only opens up potential opportunities for wide applications, but also can be extended to produce other layered materials in high yields.

Porous liquids: a promising class of media for gas separation.

A porous liquid containing empty cavities has been successfully fabricated by surface engineering of hollow structures with suitable corona and canopy species. By taking advantage of the liquid-like polymeric matrices as a separation medium and the empty cavities as gas transport pathway, this unique porous liquid can function as a promising candidate for gas separation. Moreover, such a facile synthetic strategy can be further extended to the fabrication of other types of nanostructure-based porous liquid, opening up new opportunities for preparation of porous liquids with attractive properties for specific tasks.

Hypercrosslinked phenolic polymers with well-developed mesoporous frameworks.

A soft chemistry synthetic strategy based on a Friedel-Crafts alkylation reaction is developed for the textural engineering of phenolic resin (PR) with a robust mesoporous framework to avoid serious framework shrinkage and maximize retention of organic functional moieties. By taking advantage of the structural benefits of molecular bridges, the resultant sample maintains a bimodal micro-mesoporous architecture with well-preserved organic functional groups, which is effective for carbon capture. Moreover, this soft chemistry synthetic protocol can be further extended to nanotexture other arene-based polymers with robust frameworks.

Electrochemical control of ion transport through a mesoporous carbon membrane.

We report a carbon-based, three-dimensional nanofluidic transport membrane that enables gated, or on/off, control of the transport of organic molecular species and metal ions using an applied electrical potential. In the absence of an applied potential, both cationic and anionic molecules freely diffuse across the membrane via a concentration gradient. However, when an electrochemical potential is applied, the transport of ions through the membrane is inhibited.

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.