Showing papers on "Ether published in 2020"

K-Ion Storage Enhancement in Sb2O3/Reduced Graphene Oxide Using Ether-Based Electrolyte

Abstract: In this work, an ether-based electrolyte is adopted instead of conventional ester-based electrolyte for an Sb2O3-based anode and its enhancement mechanism is unveiled for K-ion storage. The anode is fabricated by anchoring Sb2O3 onto reduced graphene oxide (Sb2O3-RGO) and it exhibits better electrochemical performance using an ether-based electrolyte than that using a conventional ester-based electrolyte. By optimizing the concentration of the electrolyte, the Sb2O3-RGO composite delivers a reversible specific capacity of 309 mAh g(-1) after 100 cycles at 100 mA g(-1). A high specific capacity of 201 mAh g(-1) still remains after 3300 cycles (111 days) at 500 mA g(-1) with almost no decay, exhibiting a longer cycle life compared with other metallic oxides. In order to further reveal the intrinsic mechanism, the energy changes for K atom migrating from surface into the sublayer of Sb2O3 are explored by density functional theory calculations. According to the result, the battery using the ether-based electrolyte exhibits a lower energy change and migration barrier than those using other electrolytes for K-ion, which is helpful to improve the K-ion storage performance. It is believed that the work can provide deep understanding and new insight to enhance electrochemical performance using ether-based electrolytes for KIBs.

Degradation of Perfluoroalkyl Ether Carboxylic Acids with Hydrated Electrons: Structure–Reactivity Relationships and Environmental Implications

Abstract: This study explores structure-reactivity relationships for the degradation of emerging perfluoroalkyl ether carboxylic acid (PFECA) pollutants with ultraviolet-generated hydrated electrons (eaq-). The rate and extent of PFECA degradation depend on both the branching extent and the chain length of oxygen-segregated fluoroalkyl moieties. Kinetic measurements, theoretical calculations, and transformation product analyses provide a comprehensive understanding of the PFECA degradation mechanisms and pathways. In comparison to traditional full-carbon-chain perfluorocarboxylic acids, the distinct degradation behavior of PFECAs is attributed to their ether structures. The ether oxygen atoms increase the bond dissociation energy of the C-F bonds on the adjacent -CF2- moieties. This impact reduces the formation of H/F-exchanged polyfluorinated products that are recalcitrant to reductive defluorination. Instead, the cleavage of ether C-O bonds generates unstable perfluoroalcohols and thus promotes deep defluorination of short fluoroalkyl moieties. In comparison to linear PFECAs, branched PFECAs have a higher tendency of H/F exchange on the tertiary carbon and thus lower percentages of defluorination. These findings provide mechanistic insights for an improved design and efficient degradation of fluorochemicals.

Hydrophilic Flexible Ether Containing, Cross-Linked Anion-Exchange Membrane Quaternized with DABCO

Abstract: Anion-exchange membranes (AEM) with high ion content usually suffer from excessive water absorption and dilution effects that impair conductivity and mechanical properties. We herein report a novel ether containing a cross-linking strategy without adopting high ion-exchange capacity (IEC). The ether-containing cross-links and the quaternized structure are created simultaneously by introducing an ether-containing flexible hydrophilic spacer between two 1,4-diazabicyclo[2,2,2,2]octane or DABCO molecules; the resultant bi-DABCO structure was further employed to react with chloromethylated polysulfone. The long spacer with the ether moiety may benefit the hydroxide ion transport, and the cross-links will control the swelling and water absorption of the AEM. The two ether groups in the long spacer of the cross-links will also shield the DABCO cation from OH- attack due to an electron-donating effect. The prepared membranes exhibited an improved conductivity of 31 mS/cm (at 25 °C) at a comparatively low IEC (1.08 mmol/g) with a rational water absorption and low swelling ratio (95.0 and 27.1%, respectively); they also displayed an enhanced alkaline stability in 1 M NaOH aqueous solution at 80 °C for 150 h. The density functional theory study and physical characterization after the alkaline treatment further confirm the better chemical stability of the cross-linked membrane over its counterpart. Our work presents an effective strategy to balance AEM conductivity and robustness.

Ether-Free Polybenzimidazole Bearing Pendant Imidazolium Groups for Alkaline Anion Exchange Membrane Fuel Cells Application

Abstract: A series of ether-bond free polybenzimidazole (PBI) bearing pendant imidazolium groups (HIm-PBI and PIm-PBI) are synthesized via a low cost preparation process under mild reaction conditions. HIm-P...

Unlocking Structure–Reactivity Relationships for Catalytic Hydrogenolysis of Lignin into Phenolic Monomers

Abstract: Lignin depolymerization into aromatic monomers with high yields and selectivity is essential for the economic feasibility of biorefinery. However, the relationship between lignin structure and its reactivity for upgradeability is still poorly understood, in large part owing to the difficulty in quantitative characterization of lignin structural properties. To overcome these shortcomings, advanced NMR technologies [2D HSQC (heteronuclear single quantum coherence) and 31 P] were used to accurately quantify lignin functionalities. Diverse lignin samples prepared from Eucalyptus grandis with varying β-O-4 linkages were subjected to Pd/C-catalyzed hydrogenolysis for efficient C-O bond cleavage to achieve theoretical monomer yields. Strong correlations were observed between the yield of monomeric aromatic compounds and the structural features of lignin, including the contents of β-O-4 linkages and phenolic hydroxyl groups. Notably, a combined yield of up to 44.1 wt % was obtained from β-aryl ether rich in native lignin, whereas much lower yields were obtained from technical lignins low in β-aryl ether content. This work quantitatively demonstrates that the lignin reactivity for acquiring aromatic monomer yields varies depending on the lignin fractionation processes.

Catalytic Fast Pyrolysis of Poly (Ethylene Terephthalate) (PET) with Zeolite and Nickel Chloride.

Abstract: The pyrolysis of poly (ethylene terephthalate) (PET) in the presence of ZSM-5 zeolite and NiCl2 as a catalyst was studied at different temperatures under N2 atmosphere. Quantitative 13C nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FT-IR) were applied to characterize the waxy and solid residue. The carboxyl and aliphatic hydroxyl groups in the waxy residue have been greatly depleted after the use of zeolite during pyrolysis on the basis of the results of 13C NMR and FT-IR analysis. The proportion of aromatic hydroxyl groups increased by 21.82% when the mass ratio of zeolite to PET was set to 2.0/1.0. The results indicate that ZSM-5 is able to facilitate the decomposition of carboxyl, aliphatic groups, and ether bonds in the primary products produced from the pyrolysis of PET. In addition, the deoxygenation effects on the waxy products have been significantly enhanced with the addition of zeolite based on the results of NMR.

Solvent Suitability for HFPO-DA (“GenX” Parent Acid) in Toxicological Studies

Abstract: Per- and polyfluorinated alkyl substances (PFAS) are of significant interest because of their prevalence and environmental persistence. Further, for many PFAS, including fluorinated ethers, such as hexafluoropropylene oxide dimer acid (HFPO-DA, or the parent acid of "GenX"), toxicological data are sparse. In general, in vitro testing frequently uses dimethyl sulfoxide (DMSO) as a carrier solvent due to its low toxicity, solubility across vast chemical space, and permeation across biological barriers. For PFAS, laboratory practice has assumed that the materials are stable across a wide range of solvents, pHs, and temperatures. In this study, HFPO-DA stability was evaluated with DMSO and other commonly used solvents to determine each solvent's suitability for use in toxicity assays. The formation of HFPO-DA's degradation product, heptafluoropropyl 1,2,2,2-tetrafluoroethyl ether (Fluoroether E-1), was monitored by headspace gas chromatography-mass spectrometry (GC-MS) over time. These experiments revealed degradation of HFPO-DA to Fluoroether E-1 in DMSO and other aprotic, polar solvents, with half-lives on the order of hours (1 h, 1.25 h, and 5.2 h for DMSO, acetone, and acetonitrile, respectively). This rapid degradation suggests the need for caution when performing or using data from toxicity assessments on HFPO-DA and closely related PFAS compounds.

Chalcogen Bond Mediated Enhancement of Cooperative Ion-Pair Recognition.

Abstract: A series of heteroditopic receptors containing halogen bond (XB) and unprecedented chalcogen bond (ChB) donors integrated into a 3,5-bis-triazole pyridine structure covalently linked to benzo-15-crown-5 ether motifs exhibit remarkable cooperative recognition of halide anions. Multi-nuclear 1 H, 13 C, 125 Te and 19 F NMR, ion pair binding investigations reveal sodium cation-benzo-crown ether binding dramatically enhances the recognition of bromide and iodide halide anions, with the chalcogen bonding heteroditopic receptor notably displaying the largest enhancement of halide binding strength of over two hundred-fold, in comparison to the halogen bonding and hydrogen bonding heteroditopic receptor analogues. DFT calculations suggest crown ether sodium cation complexation induces a polarisation of the sigma hole of ChB and XB heteroditopic receptor donors as a significant contribution to the origin of the unique cooperativity exhibited by these systems.

Complete debromination of 2,2′,4,4′-tetrabromodiphenyl ether by visible-light photocatalysis on g-C3N4 supported Pd

Abstract: Deep debromination of polybrominated diphenyl ethers (PBDEs) by visible light photocatalysis is still a challenge in the field of halogenated pollutants control. Here, an efficient photocatalyst (Pd/g-C3N4) was prepared by a simple impregnation-chemical reduction method with bulk g-C3N4 and PdCl2 as precursors. Under preferred reaction conditions (visible light irradiation for 120 min), the use of the 0.5% Pd/g-C3N4 composites (0.4 g L−1) yielded an almost complete debromination of BDE47 (10 μmol L−1) in methanol-water mixture, while the debromination of BDE47 did not occur on pure g-C3N4. A “Pd-promoted active H atom species attack and C-Br bond cleavage” route was proposed according to the identified degradation intermediates. A catalytic mechanism was further clarified: Pd nanoparticles exerted affinity interaction with bromine atoms, and the storing of electrons on Pd would increase the binding interaction. In the debromination process, methanol acts as both a hole scavenger and a hydrogen donor to provide active H atom species through the reaction of H+ and photogenerated electrons on Pd nanoparticles. The initiation of BDE47 debromination on Pd nanoparticles required an induction period to enrich a critical amount of electrons for stretching the C-Br bond and its subsequent being attacked by active H atoms. The generated 2,2′-dibromodiphenyl ether (BDE4) would be further reduced to bromine-free products by hydro-debromination process or coupling reaction.

Acid-catalysed α-O-4 aryl-ether bond cleavage in methanol/(aqueous) ethanol: understanding depolymerisation of a lignin model compound during organosolv pretreatment

Abstract: The selective lignin conversion into bio-based organic mono-aromatics is a major general challenge due to complex structure itself/additional macromolecule modifications, caused by the cleavage of the ether chemical bonds during the lignocellulosic biomass organosolv pulping in acidified aqueous ethanol. Herein, the acido-lysis of connected benzyl phenyl (BPE), being a representative model compound with α-O-4 linkage, was investigated in methanol, EtOH and 75 vol% EtOH/water mixture solutions, progressing each time with protonating sulfuric acid. The effect of the physical solvent properties, acidity of the reaction process media and temperature on rate was determined. Experiments suggested BPE following SN1 mechanism due to the formation of a stable primary carbocation/polarity. The product species distribution in non-aqueous functional alcohols was strongly affected. The addition of H2O was advantageous, especially for alkoxylation. Yield was reduced by a factor of 3, consequently preserving reactive hydroxyl group. Quantitative experimental results indicated key performance parameters to achieve optimum. Organosolv lignins were further isolated under significantly moderate conditions. Consecutive structural differences observed supported findings, obtained when using BPE. H2O presence was again found to grant a higher measured -OH content. Mechanistic pathway analysis thus represents the first step when continuing to kinetics, structure-activity relationships or bio-refining industrial resources.

Multiple Enhancement Effects of Crown Ether in Tröger's Base Polymers on the Performance of Anion Exchange Membranes.

Abstract: The development of anion exchange membranes (AEMs) is hindered by the trade-off of ionic conductivity, alkaline stability, and mechanical properties. Troger's base polymers (Tb-polymers) are recognized as promising membrane materials to overcome these obstacles. Herein, the AEMs made from Tb-poly(crown ether)s (Tb-PCEs) show good comprehensive performance. The influence of crown ether on the conductivity and alkaline stability of AEMs has been investigated in detail. The formation of hydronium ion-crown ether complexes and an obvious microphase-separated structure formed by the existence of crown ether can enhance the conductivity of the AEMs. The maximum OH- conductivity of 141.5 mS cm-1 is achieved from the Tb-PCEs based AEM (Tb-PCE-1) at 80 °C in ultrapure water. The ion-dipole interaction of the Na+ with crown ether can protect the quaternary ammonium from the attack of OH- to improve the alkaline stability of AEMs. After 675 h of alkaline treatment, the OH- conductivity of Tb-PCE-1 decreases by only 6%. The Tb-PCE-1-based single cell shows a peak power density of 0.202 W cm-2 at 80 °C. The prominent physicochemical properties are attributed to the well-developed microstructure of the Tb-PCEs, as revealed by TEM, AFM, and SAXS observations.

Ether functionalisation, ion conformation and the optimisation of macroscopic properties in ionic liquids

Abstract: Ionic liquids are an attractive material class due to their wide liquid range, intrinsic ionic conductivity, and high chemical as well as electrochemical stability. However, the widespread use of ionic liquids is hindered by significantly higher viscosities compared to conventional molecular solvents. In this work, we show how the transport properties of ionic liquids can be altered significantly, even for isostructural ions that have the same backbone. To this end, structure–property relationships have been determined for a set of 16 systematically varied representative ionic liquids. Variations in molecular structure include ammonium vs. phosphonium, ether vs. alkyl side chains, and rigid vs. flexible anions. Ab initio calculations are used to relate molecular structures to the thermal, structural and transport properties of the ionic liquids. We find that the differences in properties of ether and alkyl functionalised ionic liquids are primarily dependent on minimum energy geometries, with the conformational flexibility of ether side chains appearing to be of secondary importance. We also show unprecedented correlations between anion conformational flexibility and transport properties. Critically, increasing fluidity upon consecutive introduction of ether side chains and phosphonium centres into the cation is found to be dependent on whether the anion is flexible or rigid. We demonstrate that targeted design of functional groups based on structure–property relationships can yield ionic liquids of exceptionally high fluidity.

Sulfonated Poly(ether ether ketone) Hybrid Membranes with Amphoteric Graphene Oxide Nanosheets as Interfacial Reinforcement for Vanadium Redox Flow Battery

Abstract: Sulfonated poly(ether ether ketone) (SPEEK) hybrid membranes are prepared by incorporating 2,2′-benzidinedisulfonic acid-functionalized amphoteric graphene oxide (GO-BDSA) nanosheets. The optimized...

The Critical Role of Reductive Steps in the Nickel‐Catalyzed Hydrogenolysis and Hydrolysis of Aryl Ether C‐O Bonds

Abstract: The hydrogenolysis of the aromatic C-O bond in aryl ethers catalyzed by Ni was studied in decalin and water. Observations of a significant kinetic isotope effect (kH /kD =5.7) for the reactions of diphenyl ether under H2 and D2 atmosphere and a positive dependence of the rate on H2 chemical potential in decalin indicate that addition of H to the aromatic ring is involved in the rate-limiting step. All kinetic evidence points to the fact that H addition occurs concerted with C-O bond scission. DFT calculations also suggest a route consistent with these observations involving hydrogen atom addition to the ipso position of the phenyl ring concerted with C-O scission. Hydrogenolysis initiated by H addition in water is more selective (ca. 75 %) than reactions in decalin (ca. 30 %).

Multiple Mechanisms Mapped in Aryl Alkyl Ether Cleavage via Aqueous Electrocatalytic Hydrogenation over Skeletal Nickel.

Abstract: We present here detailed mechanistic studies of electrocatalytic hydrogenation (ECH) in aqueous solution over skeletal nickel cathodes to probe the various paths of reductive catalytic C–O bond cleavage among functionalized aryl ethers relevant to energy science. Heterogeneous catalytic hydrogenolysis of aryl ethers is important both in hydrodeoxygenation of fossil fuels and in upgrading of lignin from biomass. The presence or absence of simple functionalities such as carbonyl, hydroxyl, methyl, or methoxyl groups is known to cause dramatic shifts in reactivity and cleavage selectivity between sp3 C–O and sp2 C–O bonds. Specifically, reported hydrogenolysis studies with Ni and other catalysts have hinted at different cleavage mechanisms for the C–O ether bonds in α-keto and α-hydroxy β-O-4 type aryl ether linkages of lignin. Our new rate, selectivity, and isotopic labeling results from ECH reactions confirm that these aryl ethers undergo C–O cleavage via distinct paths. For the simple 2-phenoxy-1-phenylet...

Hydrodeoxygenation of lignin model compounds to alkanes over Pd–Ni/HZSM-5 catalysts

Abstract: In this work, a bimetallic catalyst of Pd and Ni supported on HZSM-5 was designed and evaluated in the hydrodeoxygenation of model compounds representing various C–O bonds in lignin. The effects of temperature, holding time, and initial H2 pressure on the catalytic performance of the Pd–Ni/HZSM-5 catalyst were investigated. The results indicated that the Pd–Ni/HZSM-5 catalyst exhibited superior catalytic activity towards the conversion of the model compounds to alkanes compared to its monometallic counterparts. Direct cleavage of the C–O bond in DPE was achieved under low H2 pressure, mainly producing benzene and minor amounts of phenol and cyclohexane, while at high H2 pressure, the reaction pathway was altered towards hydrogenation of the benzene ring, followed by then cleavage of the C–O bond to afford only cyclohexane. Moreover, the Pd–Ni/HZSM-5 catalyst showed high activities when applying other substrates including anisole, veratrole, guaiacol, benzyloxybenzene, phenethyl phenyl ether, and dibenzyl ether.

Electrocatalytic cleavage of lignin model dimers using ruthenium supported on activated carbon cloth

Abstract: Biomass lignin is the largest natural source of renewable aromatic compounds, creating an opportunity for its use as a feedstock provided that deconstruction and upgrading methods become available. Valorization of lignin is challenging because its complex structure is naturally recalcitrant to biological degradation. Deconstruction of this amorphous cross-linked polymer requires cleavage of aryl ether bonds, which account for more than half of the linkages between lignin's phenylpropanoid building blocks. High temperature cracking of lignin is possible via pyrolysis, but linkages such as 4-O-5 bonds are resistant to thermal degradation. Electrocatalytic hydrogenation offers a mild alternative; operated at low temperature and atmospheric pressure, it cleaves ether bonds while saturating aromatic rings with in situ generated hydrogen. To investigate the use of catalytic ruthenium supported on activated carbon cloth to cleave 4-O-5 bonds, model compounds that exhibit this linkage were selected, including 3-phenoxyphenol, 4-phenoxyphenol, 3-phenoxyanisole, and 3-phenoxytoluene. The two phenols, 3-phenoxyphenol and 4-phenoxyphenol, were cleaved and hydrogenated to form cyclohexanol. 3-Phenoxyanisole and 3-phenoxytoluene were also cleaved but with lower conversion rates and cyclohexanol yields. Alkaline electrolyte solutions showed the highest cyclohexanol yields for both substrates. Increasing substrate concentrations from 10 mM to 40 mM increased faradaic efficiency to 25%, while decreasing current density from 100 mA (33.33 mA cm−2) to 20 mA (6.67 mA cm−2) greatly improved the faradaic efficiency to 96%.