Carbanion-based ionic liquids are proposed and utilized as the key components for the construction of five super-nucleophilic deep eutectic solvents (SNDESs) in the paper. The super-nucleophilic nature of carbanion-based ILs is found to enable the capture of CO with large absorption capacity. However, the absorption is very slow in the IL due to high viscosity. The synergy of carbanion siting and hydrogen bonding is found to enable high and fast absorption of CO in [N][CH(CN)]-ethylimidazole (Eim), and a synergistic absorption mechanism is proposed and validated from spectroscopic analyses and quantum calculations. The enthalpy change of CO absorption in [N][CH(CN)]-Eim is calculated to be -39.6 kJ/mol according to the thermodynamic model, and the moderate value implies that both absorption and desorption of CO in the DES are favored and well balanced. The synergism of carbanion and hydrogen bond mediated by SNDESs provides a novel insight into the efficient CO capture.
The deep-processing utility of pure hydrogen sulfide (H2S) is a significant direction in natural gas chemical industry. Herein, a brand-new strategy of H2S conversion by α,β-unsaturated carboxylate esters into thiols or thioethers using task-specific carboxylate ionic liquids (ILs) as catalyst has been developed, firstly accomplishing the phase separation of product and catalyst without introducing the third component. It can be considered as a cascade reaction in which the product selectivity can be controlled by adjusting the molar ratio of H2S to α,β-unsaturated carboxylate esters. Also, the effects of ILs with different anions and cations, intermittent feeding operations, as well as pressure−time kinetic behaviors on cascade reaction were investigated. Furthermore, the proposed interaction mechanism of H2S conversion using butyl acrylate catalyzed by [Emim][Ac] was revealed by DFT-based theoretical calculation. The approach enables the self−phase separation promotion of catalyst and product and achieves 99% quantitative conversion under mild conditions in the absence of solvent, making the entire process ecologically benign. High-efficiency reaction activity can still be maintained after ten cycles of the catalyst. Therefore, the good results, combined with its simplicity of operation and the high recyclability of the catalyst, make this green method environmentally friendly and cost−effective. It is anticipated that this self-separation method mediated by task-specific ILs will provide a feasible strategy for H2S utilization, which will guide its application on an industrial scale.
Abstract Organogels are less explored toward on‐sink flexible and stretchable electronics compared to hydrogels, due to the challenges in simultaneously achieving biocompability, satisfactory mechanical properties, environmental‐adaptive adhesion capability, and fast stimuli‐response. Herein, it is shown that a boronate ester polymer organogel with dynamic covalent and hydrogen bonds formed between the polymer networks and organic solvents meets all the above requirements. This is achieved through the gelation of a polymer bearing with boronic acid, imidazolium salt, and amide groups (named QBAM) in ethylene glycol (EG). The strong interactions between the polymer chains and the EG not only improve the toughness of QBAMs, but also inhibit the volatilization of EG, leading to a wide temperature (−10 to 190 °C) adaptability. Due to the abundant hydrogen bonds and electrostatic interaction, QBAM organogels are highly adhesive to a variety of substrates. The presence of imidazolium salt endows QBAM organogels with promising ionic conductivity. Strain sensors fabricated with QBAM organogels fit well on human skin and exhibit the advantages of high strain sensitivity (GF = 9.049), fast response (≈60.4 ms), good cyclic stability, and broaden temperature adaptability. This work opens up a new avenue for the design of multifunctional and biocompatible organogels for on‐skin devices.
Polyacrylate elastomers have enormous application potential in various fields. However, facile and universal synthetic strategies remain rare for ultrastretchable polyacrylates (especially those with extension ratios ≥50) that are adaptable to various building blocks. Here, we develop a novel chain lubrication strategy to reduce the interchain friction and improve the slip of polymer chains during deformation. By constructing polyacrylates with soft, hard, and quaternary ammonium segments, we fabricate ultrastretchable elastomers (extension ratios up to 323) through emulsion polymerization and film casting, using quaternary ammonium surfactants (QASs) as emulsifiers. The lubricating mechanism of QASs is explored by varying the chemical structures of QASs, and it is demonstrated that QASs enhance the fluidity of polymer chains while forming eutectics with quaternary ammonium segments to construct physical cross-linking sites in the polymer networks. We also demonstrate the successful synthesis of a variety of ultrastretchable elastomers by replacing soft and hard segment monomers or surfactants, confirming the effectiveness and generalizability of the chain lubrication strategy. The chain lubrication strategy promises to pioneer new methods for fabricating highly ductile elastomers and advancing industrial rubbers.
Sodium batteries are attractive alternatives to the rapidly emerging large-scale intermittent renewable energy storage devices due to their low production cost and abundant sodium resources. The electrochemical performances of sodium batteries are highly dependent on the compatibility and interface resistances between electrode materials and electrolytes. Herein, we develop a simple method to modify a glass fiber (GF) separator by interfacial ionization and in situ introduction of a sodium source into the separator for a sodium metal battery. Polyionic liquid/ionic liquid gels were synthesized to incorporate into modified GF separators to prepare supported ionic liquid gel membranes (SILGMs) as dual separators and electrolytes for sodium batteries. The sodium-ion transference number of ionogel electrolytes incorporated on the support with and without modification was measured. The electrochemical performance characteristics of the battery with and without GF modification were evaluated by cyclic voltammetry, galvanostatic charge–discharge tests, and cycling stability as well as the galvanostatic intermittent titration technique (GITT). It was found that the specific capacity of the sodium metal battery increased by more than 20% after modification at a relatively high current density. Surprisingly, the specific discharge capacity of the assembled sodium metal battery can reach 112 mAh·g–1 at 0.1 C, fairly close to the theoretical capacity of cathode materials. The specific capacity retention of the battery with the modified GF separator was up to 99% after 100 cycles at 1.0 C. This work presents a novel method for separator modification to alter the interface compatibility between electrode materials and electrolytes for sodium metal batteries and provides a new insight to improve battery performance.
Abstract Heterogeneous single‐metal‐site catalysts (SMSCs) have received increasing attention due to their outstanding stability and recyclability. In this work, a novel Ir‐based SMSC was successfully constructed through the coordination polymerization between zirconium and triphenylphosphine derivatives with carboxyl functional groups for efficient propylene hydroformylation with CO. The Ir‐based SMSC reported here can achieve a turnover number of over 20,000 (being 7.3 times higher than the most effective Ir‐base catalyst to date) with 99% selectivity and 56% yield for aldehyde. Besides, it represents the first example with a higher selectivity of isobutyraldehyde than n‐butyraldehyde (i.e., n/i = 0.62) among the reported Ir‐based catalysts. The Ir‐based SMSC can be easily reused for at least 10 cycles without losing its reactivity, whereas the homogeneous monomer catalyst quickly loses its reactivity after the second cycle. Furthermore, the catalytic mechanism of Ir‐based SMSC is proposed based on reaction explorations and in situ co‐adsorption tests by the method of diffuse reflectance infrared Fourier transform spectroscopy, which has also been revealed by theoretical calculations. This work provides a novel insight into the design of SMSCs with great potential for application in the hydroformylation field.
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