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At least 109 records · Page 6

Electrostatic limits on charge selectivity in ultrahigh charge density polymer membranes

Ion-exchange membranes (IEMs) with ultrahigh charge densities offer the promise of enhanced ion transport for electrochemical technologies, yet the fundamental limits of this membrane design strategy are not yet understood. In this work, we present a systematic study of bis(1-vinyl-3-imidazolium) cross-linked polymer membranes with fixed charge contents ranging from 6 to 9 mol/L[dry polymer], synthesized to isolate the effects of charge density at constant membrane water content. While ionic conductivity increases monotonically with increasing charge density, a sharp decline in charge selectivity is observed for the most densely charged membranes, defying conventional expectations. Structural, thermal, and mechanical analyses reveal a critical onset of network disruption and anomalous ion partitioning behavior in these densely charged membranes. With proper consideration of cross-linker geometry, these results are interpreted using Manning's counter-ion condensation theory, which suggests that closely packed charged cross-linkers amplify inter-chain electrostatic interactions and trigger excess counter-ion condensation. Our findings suggest that, beyond a threshold spacing between fixed charges, increased functionalization may harm rather than help charge selectivity of IEMs.

36 MATERIALS SCIENCE↗

DFT-based investigation of solvation of Nd(III)/Yb(III) cations in room-temperature ionic-liquid

We report a DFT study on the solvation of bare rare-earth (RE) cations [Nd(III) and Yb(III)] in the room-temperature ionic-liquid (RTIL) based on 1,3-dimethyl-imidazolium + , PF 6 - , [MMI][PF 6 ]. In the present article, we aim to investigate whether the chosen RTIL can preferentially solvate any of the RE cations under study. First, the RTIL binding to the RE cation is studied in the gas phase, and then explored with continuum solvation model employing RTIL parameters. First, we considered the formation of the first solvation shell, where the PF 6 - anions directly bond with the Ln(III) cation. We then further surrounded the first solvation shell with [MMI]+ cations to form the second solvation shell. The stability of PF 6 - coordinated complexes is studied by calculating the binding energy values. The number of PF 6 - anions for both Ln(III) cations starts with three ligands and goes until the maximum binding energy in the RTIL medium is reached. The coordination number and binding modes of PF 6 - depend on the size of the RE cation. Comparing the binding energy values between the RE cations for the first solvation shell complexes, it is noticed that Yb-complexes have relatively greater binding energy than Nd-complexes. We have further performed a Boltzmann population analysis to find out the most dominant conformer among each category of PF 6 - coordinated complexes. A study using Natural Population Analysis shows that after complexation with PF 6 - the charge on the Yb-centers lower to a greater extent than Nd-centers, implying stronger bonding between Yb and PF 6 - , which is in harmony with the binding energy analysis. Overall, the computational investigation provides an in-depth understanding of the complexation phenomena of RE cations in RTIL, which can be useful for the practical separation of RE cations using RTIL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The power of lanthanides: same composition, but different lanthanides leading to different interesting materials properties, from magnetocalorics to molecular magnets and phosphors

Commonly accepted design concepts for ionic liquids (ILs) state that the constituting ions must be large and carry low, well-dispersed charges. A series of ILs based of pentadeca charged ILs with pentanuclear linear {Ln 5 } units ([Ln 5 (C 2 H 5 -C 3 H 3 N 2 -CH 2 COO) 16 (H 2 O) 8 ](Tf 2 N) 15 (C 3 H 3 N 2 = imidazolium moiety, Tf 2 N = bis(trifluoromethanesulfonyl)amide) with Ln = Er, Ho, Tm) demonstrates that these criteria are not absolute. Highly charged ions can also support IL formation, provided they are sufficiently large. Expanding the series of these unconventional, record pentadeca charged with new lanthanide representatives, led to the discovery of additional unprecedented properties for ILs: The Gd compound exhibits a strong magnetocaloric effect (MCE) in the liquid state with a maximum magnetic entropy change of −ΔS M = −11 J⋅kg −1 ⋅K −1 at 2 K for Δμ 0 H = 7 T. Albeit the Dy representative shows slow magnetic relaxation, the relaxation times are not favorable for practical application as a molecular magnet. Lastly, for both the Gd and the Y compound, phosphorescence in the seconds time scale is observed, which is, to the best of our knowledge, the longest ever reported for an IL.

Ionic Liquids↗

Understanding the reversible electrodeposition of aluminum in low-cost room-temperature molten salts

Aluminum is the most earth-abundant metal, trivalent, and inert in ambient air; it also has a density approximately five times that of lithium at room temperature, making it attractive for cost-effective, long-duration storage in batteries. Here, we investigate structural requirements and physicochemical and transport properties of ionic liquid (IL) electrolytes thought to enable high reversibility of Al battery anodes. We find that intentionally designed, low-cost IL analogs, including ammonium-based molten salts, offer comparable Al anode reversibility to state-of-the-art imidazolium-based IL melts. A critical ratio of solvated Al-ion species is required to balance the effects of Lewis acidity needed to continuously etch native Al 2 O 3 and form a stable solid electrolyte interphase on Al. Our findings open new opportunities for developing simple, cost-effective, room-temperature Al batteries that enable long-duration electrical energy storage.

25 ENERGY STORAGE↗

Batch Scale Production of 3D Printed Extraction Sorbents Using a Low-Cost Modification to a Desktop Printer

This study reports a simple modification to a commercial resin 3D printer that significantly reduces the amount of prepolymer material needed for the production of extraction sorbents. Here, the modified printing platform is demonstrated in the printing of two imidazolium-based ionic liquid (IL) monomers. Two geometries resembling a blade-type polymeric ionic liquid (PIL) sorbent used in thin-film microextraction and a fiber-type sorbent used in solid-phase microextraction (SPME) were printed. The SPME PIL sorbents were used to extract 10 organic contaminants, including plasticizers, antimicrobial agents, UV filters, and pesticides, from water followed by high-performance liquid chromatographic (HPLC) analysis. To compare the extraction performance of the SPME sorbents, seven fibers printed with the same prepolymer composition from the same printing batch as well as different batches were evaluated. The results revealed highly reproducible extraction efficiencies for all tested sorbents with no statistical difference in their extraction performance. Method validation showed acceptable linearity ($R$ 2 > 0.92) for all analytes with limits of detection and limits of quantification ranging from 0.13 to 45 μg L –1 and 0.43 to 150 μg L –1 , respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Identifying Order and Disorder in Double Four-Membered Rings via Raman Spectroscopy during Crystallization of LTA Zeolite

Fluoride (F – ) has been essential for the synthesis of low-defect siliceous zeolites. It has been hypothesized that F – balances the positive charges from organic structure-directing agents (OSDAs) and stabilizes key building units during zeolite crystallization such as the double four-membered ring (D4R). However, due to the lack of characterization techniques for investigating medium-range structures, including rings and cages formed during zeolite crystallization, the roles of F – in stabilizing building units and maintaining local charge balance during zeolite assembly are not yet fully understood. Here, the crystallization of siliceous Linde type A (LTA) zeolite in the presence of F – was investigated using Raman spectroscopy and periodic density functional theory (DFT) calculations. We have discovered that the F – -filled double four-membered ring (F – /D4R) and the empty D4R exhibit rather distinct Raman features. Both the F – /D4R and empty D4R are formed in the LTA zeolite synthesized in the presence of F – using 1,2-dimethyl-3-(4-methylbenzyl) imidazolium as the OSDA. Observed Raman bands of the F – /D4R and empty D4R, along with predictive DFT calculations on LTA supercells, reveal an ordered distribution of these two D4R units in the final as-made LTA zeolite. The discovery of these distinct Raman signatures of F – /D4R and empty D4R units opens an interesting new window for studying defects in the D4R during zeolite formation. In particular, we have observed variation in Raman intensities of F – /D4R and empty D4R bands during LTA crystallization; periodic DFT calculations indicate that the observed Raman behavior is consistent with empty D4R units containing one or two Si vacancies surrounded by Q 3 Si—consistent also with solid-state nuclear magnetic resonance measurement. These defects appear to heal during further crystallization, leading to the formation of defect-free LTA zeolite crystals. Altogether, our results provide deeper understanding on the roles of F – in charge balancing and stabilizing intact D4R units during zeolite formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Titrating Controlled Defects into Si-LTA Zeolite Crystals Using Multiple Organic Structure-Directing Agents

Controlling defects in zeolites is crucial for tuning their adsorption and catalytic properties. In this work, we have performed an integrated zeolite synthesis, spectroscopy, and density functional theory study to test the limit of F– as a charge-balancing agent that mitigates defects in siliceous zeolites. We focused on the synthesis of siliceous zeolite LTA at 150 °C with 1,2-dimethyl-3-(4-methylbenzyl) imidazolium as the primary organic structure-directing agent (OSDA) and tetramethyl ammonium (TMA) as the secondary OSDA. By varying the amount of TMA in the synthesis gel, positive charges were titrated into the resulting as-made Si-LTA. Surprisingly, we found that greater TMA concentration does not induce more F– to enter into the zeolite. 29Si solid-state MAS NMR, Raman spectroscopy, and density functional theory suggest that this system has surpassed its capacity for F– to balance OSDA charge, and additional positive charge is balanced by Si–O– framework defects. The number of defects in the as-made Si-LTA can be precisely titrated by the amount of TMA in the zeolite structures. For the Si-LTA synthesized without TMA, framework defects formed in the early stage of crystal growth were found to heal during later crystallization, leading to defect-free Si-LTA. However, for the Si-LTA synthesized with TMA, the defects formed in early stages do not heal. A DFT thermodynamic analysis explains that crowding of Si-LTA pores by TMA impedes defect healing; this prediction is corroborated by synthesis experiments at an elevated temperature (170 °C). These results indicate that F– can have a limited capacity to balance OSDA charge in zeolite synthesis, opening up a third route to zeolite synthesis intermediate between the fluoride and hydroxide routes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Side Chain Chemistry on Lithium Transport in Mixed Ion–Electron-Conducting Polymers

We discuss how typical design strategies for mixed ion-electron conduction in polymers have focused on overall ionic conductivity, without specificity for anion vs. cation conduction. Here, we demonstrate that side chain chemistry can be used to control Li+ conductivity in semiconducting polymers. This design principle is significant for applications which require Li+ specific transport, such as Li-ion batteries. We show that a polythiophene functionalized with an ionic liquid side chain demonstrates higher conductivity and lithium transference than a more commonly studied ether-functionalized P3AT derivative. Poly(3-(6’-(N-methylimidazolium) hexyl)thiophene TFSI–) (P3HT-Im+TFSI–) can solvate and conduct ions up to salt concentrations of r=1.0 (where r = [moles of salt]/[moles of monomer]) while achieving ionic conductivity of ≈10–3 S/cm at 80°C, and a lithium transference number of 0.36. On the other hand, poly(3¬-(methoxyethoxyethoxymethyl) thiophene) (P3MEEMT) shows a peak conductivity of ≈10–5 S/cm at r=0.05 and 80°C, with near zero lithium transport. This work shows that multiple high dielectric moieties can be used to drive ion conduction in semiconducting polymers, but diffuse, cationic side chains such as imidazolium are preferred for Li-ion conduction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Removing Fluoride from Double Four-Membered Rings Yielding Defect-Free Zeolites under Mild Conditions Using Ozone

We have investigated ozone treatment of as-made LTA zeolites under mild temperature conditions (175 °C) using experiments and periodic DFT as a method of energy savings and engineering defects such as silanol nests in comparison with conventional calcination at 550 °C. We have studied ozone treatment on LTA samples synthesized with 1,2-dimethyl-3-(4-methylbenzyl) imidazolium (denoted as “BULKY”) as the primary organic structure-directing agent (OSDA) and with various amounts of tetramethylammonium (TMA) as a secondary OSDA. Ozone treatment of LTA-BULKY at 175 °C was found to give defect-free, pristine LTA materials as determined by 29 Si NMR, 13 C NMR, Raman spectra, and DFT to assign the spectra. This represents a significant and unexpected finding: that fluoride ions can be completely removed from double four-membered rings (D4Rs) under such mild conditions. Furthermore, ozone treatment of LTA-BULKY-TMA samples removed BULKY but left behind TMA/F, giving a new and more diverse structural landscape of Si environments in LTA. Ab initio MetaDynamics calculations provide pathways with relatively low barriers, explaining how fluoride ions can be removed from D4Rs, leaving behind defect-free LTA materials under mild conditions.

36 MATERIALS SCIENCE↗

Synthesis and Characterization of Macrocyclic Ionic Liquids for CO 2 Separation

In this work, a series of ionic liquids with symmetric, macrocyclic cations composed of N-heterocycles connected by alkyl or ether linkages coupled with bis(trifluoromethylsulfonyl)imide or bis(pentafluoroethanesulfonyl)amide anions were synthesized to explore their application in CO 2 separation. These novel ionic liquids showed selective physical absorption of CO 2 compared to N 2 making them potential candidates for carbon capture. We examined the effect of cation structure on the physicochemical and separations properties of the ionic liquid and showed that these ionic liquids exhibit an inverse relationship between molar volume and CO 2 sorption capacity following the trend predicted by models based on regular solution theory. The fractional free volumes of the ionic liquids were lower than typical alkyl-imidazolium ionic liquids despite the cyclic structure of the cations which could be related to the flexibility of the alkyl and ether linkages. These results provide added insight into our understanding of structure–property relationships in CO 2 solubility in ionic liquids and afford a path toward enhancing the separations properties based on structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Separating Miscible Liquid–Liquid Mixtures Using Supported Ionic Liquid Membranes

Supported liquid membranes (SLMs) are promising in separating miscible liquid–liquid mixtures, which has been a key challenge in wastewater treatment and other applications. However, SLMs suffer from poor durability due to the loss of the liquid phase. In current work, ionic liquids (ILs) with high stability have been impregnated into polyvinylidene fluoride membranes to separate miscible benzene–heptane mixtures. The two imidazolium-based ILs, that is, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF 6 ]) and 1-butyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate ([BMIM][FAP]), were tested in supported ionic liquid membranes (SILMs) for the benzene–heptane separation. Both ILs show successful separation within 48 h as indicated by nuclear magnetic resonance results. Compared to the SILM with [BMIM][FAP], the SILM with [BMIM][PF 6 ] has lower throughput and higher selectivity. The higher selectivity can be attributed to the higher hydrophilicity of [BMIM][PF 6 ], which results in strong repulsion against heptane. The lower throughput can be attributed to the higher hydrophilicity as well since it lowers the solubility of benzene in [BMIM][PF 6 ]. The stability of IL in SILMs has also been investigated via multiple separation cycles. The scanning electron microscopy, weight change of SILMs, and separation results indicate that the separation efficiency of the [BMIM][PF 6 ] SILM does not degrade for up to 144 h. The SILM has been further optimized with curvature design (i.e., curved SILM) to increase the interfacial area and thus increase the separation throughput, where the curved SILM separation device was 3D-printed. Here, the findings here have important implications on design and application of SILMs in separating miscible liquid–liquid mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cooperative Lanthanide Solvation in an Ionic Liquid for Critical Materials Separations

Effectively separating critical materials, including intra-lanthanide separations, is crucial for meeting growing application demands. Liquid–liquid extraction (LLE) is the industry standard for lanthanide separations, where the selectivity can depend on small changes in metal coordination. In this work, we investigate representative lanthanide Eu coordination with a neutral malonamide extractant in an imidazolium bistriflimide ionic liquid (IL) solvent. Through systematic titrations of the water and extractant and under extraction conditions, we observe surprising cooperative Eu solvation with the IL anion and extractant. Time-resolved fluorescence spectroscopy measurements show strong extractant coordination in water-saturated IL. Lifetime measurements show no water coordination, and extended X-ray fine structure spectroscopy data provide a coordination number of 10. Molecular dynamics simulations confirm this coordination number and reveal IL anion coordination in the final Eu complex, even though it is ordinarily a significantly weaker ligand compared to water. The lack of water in the final extracted complex and IL anion coordination potentially explain the increased extraction in LLE systems using ILs, as evidenced by higher distribution ratios for cation exchange extraction, despite the energetic cost of cation transfer to the aqueous phase. These results highlight the opportunities for tuning metal coordination to drive extraction in unique solvent systems.

Carr, Amanda J.↗

NMR and Theoretical Study of In-Pore Diffusivity of Ionic Liquid–Solvent Mixtures

We report despite having a lower energy density than common batteries, electric double-layer capacitors (EDLCs) offer several advantages for high-power applications, including high power density, quick charge and discharge time, and long cycle life. Room-temperature ionic liquids (RTILs) have been intensely studied as promising electrolytes for applications in ELDCs because of their wide potential window, low volatility, as well as thermal and chemical stability. The main deficiency of neat RTILs in such applications is the sluggish diffusivity, which restricts the EDLCs’ power density. To alleviate the slow diffusivity, RTILs can be used in a mixture with organic solvents. In this study, we applied two-dimensional exchange nuclear magnetic resonance spectroscopy (2D EXSY NMR) and molecular dynamics (MD) simulations to investigate the diffusivity of anions of an RTIL, namely, 1-butyl-3-methyl-imidazolium bis(trifluoromethylsulfonyl)imide (BMIM + –TFSI – ), dissolved in five different organic solvents, in the micropores of activated carbon. We determined that the relative concentrations of ions in solutions in the micropores were higher than those in the bulk solutions and were also solvent-dependent. The ion diffusivities in the pores were found to be almost 2 orders of magnitude slower than in the bulk solutions, with methanol showing the largest relative disparity. These results suggested that the interactions of solvents with the activated carbon are critical not only to the power density of EDLCs but also to the energy density. The comparisons of ion diffusivities between the experiments and the MD simulations suggest the need to consider also the surface functionalities of activated carbon for the simulation of ion diffusion in the micropores of activated carbon.

electric double layer capacitors↗

Self-Assembled Oligomers Facilitate Amino Acid-Driven CO 2 Capture at the Air–Aqueous Interface

Direct air capture of CO 2 using amino acid absorbents, such as glycine or sarcosine, is constrained by the relatively slow mass transfer of CO 2 through the air–aqueous interface. Our recent study showed a marked improvement in CO 2 capture by introducing CO 2 -permeable oligo-dimethylsiloxane (ODMS-MIM + ) oligomers with cationic (imidazolium, MIM + ) headgroups. Here, in this work, we have employed all-atom molecular dynamics simulations in combination with subensemble analysis using network theory to provide a detailed molecular picture of the behavior of CO 2 and the glycinate anions (Gly – ) at the ODMS-MIM + decorated air–aqueous interfaces. We show that the cationic head groups of the surfactants enhance the concentration and lifetime of Gly – in the interfacial region, while ODMS tails promote the physisorption of CO 2 in the interfacial region. Together, these two factors increase the effective region of contact and the probability of interactions between CO 2 and Gly – compared to that of the pure air–aqueous interface. The fundamental insights gained in this work establish essential foundations for developing hybrid systems with oligomer-decorated interfaces to maximize the overall CO 2 capture rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge Tethering Drives Intermediate-Range Order and Slow Dynamics in Zwitterionic Liquids

We have synthesized and characterized a family of zwitterionic liquids (ZwLs) based on the poly(ethylene oxide) imidazolium cation and the alkyl sulfonate anion. To better rationalize ZwLs′ structural behavior and networkforming properties, we have computationally studied them in contrast to isostructural but chemically untethered ionic liquid (IL) analogues. Perhaps surprisingly, it is the molecular liquids and not the ILs that show the most selfassembly and intermediate-range order associated with scattering prepeaks; the ZwLs display also the slowest dynamics. This is consistent with prior work showing the importance of networks in considering the viscoelastic relaxation of liquids. We find that, because of their significantly large molecular dipoles, these zwitterions are versatile network-building blocks that result in highly viscous liquids. From a structural perspective, networks in these ZwLs sit somewhere in between what would be true chemical connectivity and the Coulombic networks observed in ionic liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Squeezing Out Interfacial Solvation: The Role of Hydrogen-Bonding in the Structural and Orientational Freedom of Molecular Self-Assembly

We report bioinspired membrane molecules with improved physical properties and enhanced stability can serve as functional models for conventional lipid or amphiphilic species. Importantly, these molecules can also provide new insights into emergent phenomena that manifest during self-assembly at interfaces. Here, we elucidate the structural response and mechanistic steps underlying the self-assembly of the amphiphilic, charged oligodimethylsiloxane imidazolium cation (ODMS-MIM+) at the air–aqueous interface using Langmuir trough methods with coincident surface-specific vibrational sum-frequency generation (SFG) spectroscopy. We find evidence for a new compression-induced desolvation step that precedes commonly known disordered-to-ordered phase transitions to form nanoscopic assemblies. The experimental data was supported by atomistic molecular dynamics (MD) simulations to provide a detailed mechanistic picture underlying the assembly and the role of water in these phase transitions. The sensitivity of the hydrophobic ODMS tail conformations to compression-owing to distinct water–ODMS interactions and tail–tail solvation properties-offers new strategies for the design of interfaces that can be further used to develop soft-matter electronics and low-dimensional materials using physical and chemical controls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Unexpected Role of Cations in the Self-Assembly of Positively Charged Amphiphiles at Liquid/Liquid Interfaces

Conventional wisdom suggests that cations play a minimal role in the assembly of cationic amphiphiles. Here, we show that at liquid/liquid (L/L) interfaces, specific cation effects can modulate the assemblies of hydrophobic tails in an oil phase despite being attached to cationic headgroups in the aqueous phase. In this work, we used oligo-dimethylsiloxane (ODMS) methyl imidazolium amphiphiles to identify these specific interactions at hexadecane/aqueous interfaces. Small cations, such as Li + , bind to the O atoms in the ODMS tail and pin it to the interface, thereby imposing a kinked conformation-as evidenced by vibrational sum frequency generation spectroscopy and molecular dynamics simulations. While larger Cs + ions more readily partition to the interface, they do not form analogous complexes. Our data not only point to ways for controlling amphiphile structure at L/L interfaces but also suggest a means for the separation of Li + , or related applications, in soft-matter electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Key Experimental Considerations When Evaluating Functional Ionic Liquids for Combined Capture and Electrochemical Conversion of CO 2

Ionic liquids (ILs) are considered functional electrolytes for the electrocatalytic reduction of CO 2 (ECO 2 R) due to their role in the double-layer structure formation and increased CO 2 availability at the electrode surface, which reduces the voltage requirement. However, not all ILs are the same, considering the purity and degree of the functionality of the IL. Further, there are critical experimental factors that impact the evaluation of ILs for ECO 2 R including the reference electrode, working electrode construction, cosolvent selection, cell geometry, and whether the electrochemical cell is a single compartment or a divided cell. Here, we describe improved synthesis methods of imidazolium cyanopyrrolide IL for electrochemical studies in consideration of precursor composition and reaction time. We explored how IL with cosolvents (i.e. acetonitrile, dimethylformamide, dimethyl sulfoxide, propylene carbonate, and n-methyl-2-pyrrolidone) affects conductivity, CO 2 mass transport, and ECO 2 R activation overpotential together with the effects of electrode materials (Sn, Ag, Au, and glassy carbon). Acetonitrile was found to be the best solvent for lowering the onset potential and increasing the catalytic current density for the production of CO owing to the enhanced ion mobility in combination with the silver electrode. Further, the ECO 2 R activity of molecular catalysts Ni(cyclam)Cl 2 and iron tetraphenylsulfonato porphyrin (FeTPPS) on the carbon cloth electrode maintained high Faradaic efficiencies for CO in the presence of the IL. This study presents best practices for examining nontraditional multifunctional electrolytes amenable to integrated CO 2 capture and conversion technologies for homogeneous and heterogeneous ECO 2 R.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗