Showing papers on "Solvent published in 2021"

High Concentration of Ti3C2Tx MXene in Organic Solvent.

Abstract: MXenes are currently one of the most widely studied two-dimensional materials due to their properties. However, obtaining highly dispersed MXene materials in organic solvent remains a significant challenge for current research. Here, we have developed a method called the tuned microenvironment method (TMM) to prepare a highly concentrated Ti3C2Tx organic solvent dispersion by tuning the microenvironment of Ti3C2Tx. The as-proposed TMM is a simple and efficient approach, as Ti3C2Tx can be dispersed in N,N-dimethylformamide and other solvents by stirring and shaking for a short time, without the need for a sonication step. The delaminated single-layer MXene yield can reach 90% or greater, and a large-scale synthesis has also been demonstrated with TMM by delaminating 30 g of multilayer Ti3C2Tx raw powder in a one-pot synthesis. The synthesized Ti3C2Tx nanosheets dispersed in an organic solvent possess a clean surface, uniform thickness, and large size. The Ti3C2Tx dispersed in an organic solvent exhibits excellent oxidation resistance even under aerobic conditions at room temperature. Through the experimental investigation, the successful preparation of a highly concentrated Ti3C2Tx organic solvent dispersion via TMM can be attributed to the following factors: (1) the intercalation of the cation can lead to the change in the hydrophobicity and surface functionalization of the material; (2) proper solvent properties are required in order to disperse MXene nanosheets well. To demonstrate the applicability of the highly concentrated Ti3C2Tx organic solvent dispersion, a composite fiber with excellent electrical conductivity is prepared via the wet-spinning of a Ti3C2Tx (dispersed in DMF) and polyacrylonitrile mixture. Finally, various types of MXenes, such as Nb2CTx, Nb4C3Tx, and Mo2Ti2C3Tx, can also be prepared as highly concentrated MXene organic solvent dispersions via TMM, which proves the universality of this method. Thus, it is expected that this work demonstrates promising potential in the research of the MXene material family.

Solvent molecules form surface redox mediators in situ and cocatalyze O2 reduction on Pd

Abstract: Solvent molecules influence the reactions of molecular hydrogen and oxygen on palladium nanoparticles Organic solvents activate to form reactive surface intermediates that mediate oxygen reduction through pathways distinct from reactions in pure water Kinetic measurements and ab initio quantum chemical calculations indicate that methanol and water cocatalyze oxygen reduction by facilitating proton-electron transfer reactions Methanol generates hydroxymethyl intermediates on palladium surfaces that efficiently transfer protons and electrons to oxygen to form hydrogen peroxide and formaldehyde Formaldehyde subsequently oxidizes hydrogen to regenerate hydroxymethyl Water, on the other hand, heterolytically oxidizes hydrogen to produce hydronium ions and electrons that reduce oxygen These findings suggest that reactions of solvent molecules at solid-liquid interfaces can generate redox mediators in situ and provide opportunities to substantially increase rates and selectivities for catalytic reactions

Solvent-Resistant Lignin-Epoxy Hybrid Nanoparticles for Covalent Surface Modification and High-Strength Particulate Adhesives.

Abstract: Fabrication of spherical lignin nanoparticles (LNPs) is opening more application opportunities for lignin. However, dissolution of LNPs at a strongly alkaline pH or in common organic solvent systems has prevented their surface functionalization in a dispersion state as well as processing and applications that require maintaining the particle morphology under harsh conditions. Here, we report a simple method to stabilize LNPs through intraparticle cross-linking. Bisphenol A diglycidyl ether (BADGE), a cross-linker that, like lignin, contains substituted benzene rings, is coprecipitated with softwood Kraft lignin to form hybrid LNPs (hy-LNPs). The hy-LNPs with a BADGE content ≤20 wt % could be intraparticle cross-linked in the dispersion state without altering their colloidal stability. Atomic force microscopy and quartz crystal microbalance with dissipation monitoring were used to show that the internally cross-linked particles were resistant to dissolution under strongly alkaline conditions and in acetone-water binary solvent that dissolved unmodified LNPs entirely. We further demonstrated covalent surface functionalization of the internally cross-linked particles at pH 12 through an epoxy ring-opening reaction to obtain particles with pH-switchable surface charge. Moreover, the hy-LNPs with BADGE content ≥30% allowed both inter- and intraparticle cross-linking at >150 °C, which enabled their application as waterborne wood adhesives with competitive dry/wet adhesive strength (5.4/3.5 MPa).

Structure and properties of chitosan films: Effect of the type of solvent acid

Abstract: The properties of chitosan films can be modified by changing the solvent type, attributing to the different interaction patterns between chitosan and acids. However, little is known about how these interactions affect the structure and properties of chitosan films. In this work, the influence of acid type on the structure and properties of chitosan films was studied by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). FTIR spectra showed that the ionic interactions and hydrogen bonding could occur between chitosan and acid ions. Structural analysis revealed that chitosan was partially crystalline in hydrochloric and acetic acid films, whereas it was amorphous in lactic and citric acid films. DSC result indicated that the glass transition temperature of chitosan was much lower in citric acid film with low water content than in all the other films, suggesting that the citrate ions interacted more strongly with chitosan. A melting transition appeared in hydrochloric and acetic acid films. In addition, the tensile strength of these films decreased with an increase in the volume of acid. These observations indicate that the choice of a proper solvent for chitosan may be desirable for certain special applications.

Recognition of Water-Induced Effects toward Enhanced Interaction between Catalyst and Reactant in Alcohol Oxidation.

Abstract: Pickering emulsion stabilized by solid nanoparticles provides a diverse solvent microenvironment and enables to promote the phase transfer of reaction substrates/products in catalytic reactions, but the intrinsic role of solvent is still not clear. Herein, using benzyl alcohol (BA) as a model reactant, we demonstrate the nature of the water-promoted activity for alcohol oxidation over the Pd/MgAl-LDO catalyst. Depending on the water in the solvent, we observe different reactivities regarding the proportion of the water in the system. Kinetic isotope effects confirm the participation and positive effects of water for oxidation of BA. The water promotion effects are recognized and identified by the water vapor pulse adsorption coupled with temperature program desorption. Moreover, the adsorption behavior of BA or benzaldehyde at the interface of water and Pd/MgAl-LDO is also investigated by quasi-in-situ Raman spectroscopy. In addition, the mechanism of water-promoted alcohol oxidation is rationally proposed based on the Langmuir-Hinshelwood mechanism. The general applicability of the water promotion effects is further demonstrated over different supports and substrates, which well achieves excellent catalytic activity and selectivity in Pickering emulsion compared to that in the pure toluene system.

A Novel Dual-Stage Phase Separation Process for CO2 Absorption into a Biphasic Solvent with Low Energy Penalty.

Abstract: An amine-based biphasic solvent is promising to cut down the energy penalty of CO2 capture. However, the high viscosity of the CO2-enriched solvent retards its industrial application. This work proposed a novel dual-stage phase separation process using a triethylenetetramine and 2-(diethylamino)ethanol blend as a biphasic solvent, which separates a certain proportion of CO2-enriched phase during CO2 absorption to reduce its viscosity. Experimental results showed that the proposed dual-stage phase separation process improved the phase separation behavior and effectively enhanced the absorption rate by 49% at 50 °C, when 50 vol % CO2-enriched phase was separated at 0.3 mol mol-1. Kinetic analysis showed that the absorption rate was mainly controlled by liquid-side mass transfer. The regeneration heat of the dual-stage phase separation process cut down the energy penalty by 33% compared with the monoethanolamine-based process. Compared with the conventional biphasic solvent-based process, the heat duty was further declined by 8%. The 1H nuclear magnetic resonance analysis showed that the dual-stage phase separation process could effectively control the generation of absorption products and intensify the interphase migration of tertiary amines.

Protic Ionic Liquid as Reagent, Catalyst, and Solvent: 1-Methylimidazolium Thiocyanate

Abstract: We propose a new concept of the triple role of protic ionic liquids with nucleophilic anions: a) a regenerable solvent, b) a Bronsted acid inducing diverse transformations via general acid catalysis, and c) a source of a nucleophile. The efficiency of this strategy was demonstrated using thiocyanate-based protic ionic liquids for the ring-opening of donor-acceptor cyclopropanes. A wide variety of activated cyclopropanes were found to react with 1-methylimidazolium thiocyanate under mild metal-free conditions via unusual nitrogen attack of the ambident thiocyanate ion on the electrophilic center of the three-membered ring affording pyrrolidine-2-thiones bearing donor and acceptor substituents at the C(5) and C(3) atoms, respectively, in a single time-efficient step. The ability of 1-methylimidazolium thiocyanate to serve as a triplex reagent was exemplarily illustrated by (4+2)-annulation with 1-acyl-2-(2-hydroxyphenyl)cyclopropane, epoxide ring-opening and other organic transformations.

A Carboxyl-Functionalized Covalent Organic Framework Synthesized in a Deep Eutectic Solvent for Dye Adsorption.

Abstract: Instead of using organic solvents, a deep eutectic solvent (DES) composed of tetrabutylammonium bromide and imidazole (Bu4 NBr/Im) was employed as a solvent for the first time to synthesize covalent organic frameworks (COFs). Due to the low vapor pressure of the Bu4 NBr/Im-based DES, a new carboxyl-functionalized COF (TpPa-COOH) was synthesized under environmental pressure. The as-synthesized TpPa-COOH has open channels, and the DES can be removed completely from the pores. The dye adsorption performance of TpPa-COOH was examined for three organic dyes with similar molecular sizes: one anionic dye (eosin B, EB) and two cationic dyes (methylene blue, MB and safranine T, ST). TpPa-COOH showed an excellent selective adsorption effect on MB and ST. The electronegative keto form in TpPa-COOH might help to form electrostatic and π-π interactions between the π-stacking frameworks of TpPa-COOH and the positive plane MB and ST molecules. The adsorption isotherms of MB and ST on TpPa-COOH were further investigated in detail, and the equilibrium adsorption was well modeled by using a Langmuir isotherm model. Together with hydrogen bonding, TpPa-COOH showed higher adsorption capacity for ST than for MB (1135 vs. 410 mg g-1 ). These results could provide a guidance for the green synthesis of adsorbents in removing organic dyes from wastewater.