Effective biomass conversion to 5-HMF(5-hydroxymethylfurfural) is still a challenge and needs to be improved because of the 5-HMF importance as building blocks for valuable monomers and fuel ...precursors. We suggest for the first time utilization of low-cost metal-free Brønsted acidic Ionic liquid (IL) N,N-Diethyl-1,4-phenylenediamine hydrogen sulfate, DPhDAHSO4 as a catalyst for the α-glucose dehydration to 5-HMF. Quantitative α-glucose conversion is achieved via optimizing the reaction condition: 91.4% 5-HMF yield with 30 mol% DPhDAHSO4 in the presence of DMSO as a solvent at 160 °C in 30 min (TOF 6.1 h−1). 3-fold increase in reaction time leads to higher (94%) 5-HMF yield at 160 °C with lower TOF 1.6 h−1. The IL surprising catalytic performance is scrutinized with its amphiprotic nature (availability of basic and acidic spots in its structure (Fig. 1)). Further computational mechanistic studies revealed the function of the catalytic sites in the α-glucose dehydration. We calculated five-membered ring formation and water extrusion in one concerted transition state (TS2A, ΔG‡ = 38.8 kcal/mol) following the α-glucose ring-opening (TS1, ΔG‡ = 20.4 kcal/mol). Further four steps (sp3-s, C–H bond cleavages (TS3, TS6) and dehydroxylation (TS4A, TS5)) are quite straightforward to reach the product (5-HMF).
Display omitted
•Brønsted acidic ionic liquid efficiently catalyzes glucose dehydration to 5-HMF.•A high 5-HMF yield (91.4%) is achieved with 30 mol% of ionic liquid in 30 min.•Turnover frequency (6.1 h−1) shows industrial applicability of ionic liquid.•DFT studies unveil the superior catalytic performance of ionic liquid.
•A flexible ionic liquid-Polyurethane sponge super-capacitive sensor for measuring tactile pressure has been developed.•This innovative flexible sensor provides a high sensitivity (up to 5.28 nF/Kpa) ...and rapid dynamic responses (milliseconds).•The developed sensor is not sensitive to arbitrary humidity or temperature range below 50 ℃.•The fabrication process of this sensor is very simple with low cost.
A flexible microfluidic polyurethane sponge super-capacitive pressure sensor is developed to measure the pressure. The innovative sensor contains a polyurethane sponge filled with ionic liquid dielectric layer, and coated with two indium tin oxide polyethylene terephthalate (ITO-PET) films on the top and bottom, respectively. When external pressure is applied on the sensor, the contact area between ITO-PET electrode and ionic liquid polyurethane sponge (ILPU) dielectric layer increases and the distance between two ITO-PET electrodes decreases due to the structural deformation, resulting in the capacitance of the sensor increasing rapidly. The external pressure will be determined based on the change of capacitance. Comparing to traditional pressure sensor, the developed sensor provides a high sensitivity up to 5.28 nF/KPa and rapid dynamic responses for pressure measurement. Experiments are also conducted to investigate the influence of the temperature and humidity.
High tunability of both ionic liquids (ILs) and metal organic frameworks (MOFs) enables great opportunity in the rational designation of IL/MOF composites for physical adsorption and separation. ...Traditionally, cations and anions of ILs as an entirety are combined with MOFs either inside or outside the microchannels. Herein, organic cations of ILs were confined into Cu‐BTC and the champion adsorbent is obtained by using 1‐propionic acid‐3‐vinylimidazole bromide as the precursor with a moderate loading amount, exhibiting higher CO2 uptakes of 8/5 mmol g−1 than Cu‐BTC (6.0/3.5 mmol g−1) at 273/298 K and 100 kPa, associating with significantly improved CO2/N2(CH4) selectivities. The organic cations are interacted with two adjacent CuII2(CRO2)2 paddle wheel units of Cu‐BTC, expanding the CuO bond to strengthen the CO2 affinity of open Cu sites and also serving as an additive CO2 adsorptive site. The promotion of CO2 capture ability is further reflected in the dynamic column breakthrough experiment.
The capability of peptide and amino acid‐based molecules to act as ionogelators and eutectogelators entrapping ionic liquids (ILs) and deep eutectic solvents (DESs) forming ionogels and eutectogels ...has gathered attention in recent decades. The self‐assembly process, primarily driven by non‐covalent interactions as hydrogen bonding, remains serendipitous in nature. This review provides a comprehensive and detailed report on self‐assembly of unmodified and modified amino acids and peptides in the non‐conventional solvents, ILs and DESs. Understanding these processes holds great promise for the development of innovative soft‐materials, and to the progress of supramolecular systems in non‐conventional solvent environments.
Ionic liquids and deep eutectic solvents are considered ideal choices for soft materials under environmental conditions. Understanding the self‐assembly mechanisms of biological molecules, and specifically unmodified and modified peptide and amino acids, in these solvents is crucial for accelerating future research, fostering the development of innovative, bio‐based soft materials.
Metallic Zn is one of the most promising anodes, but its practical application has been hindered by dendritic growth and serious interfacial reactions in conventional electrolytes. Herein, ionic ...liquids are adopted to prepare intrinsically safe electrolytes via combining with TEP or TMP solvents. With this synergy effect, the blends of TEP/TMP with an IL fraction of ≈25 wt% are found to be promising electrolytes, with ionic conductivities comparable to those of standard phosphate‐based electrolytes while electrochemical stabilities are considerably improved; over 1000 h at 2.0 mA cm−2 and ≈350 h at 5.0 mA cm−2 with a large areal capacity of 10 mAh cm−2. The use of functionalized IL turns out to be a key factor in enhancing the Zn2+ transport due to the interaction of Zn2+ ions with IL‐zincophilic sites resulting in reduced interfacial resistance between the electrodes and electrolyte upon cycling leading to spongy‐like highly porous, homogeneous, and dendrite‐free zinc as an anode material.
The electrochemical performances of Zn metal anodes are adjusted using functionalized ionic liquid and phosphate‐based safe organic solvents, resulting in high Columbic efficiency (CE) of over 99 %, long cycle life up to 5.0 mA cm−2, and large areal capacity of 10 mAh cm−2. The interface derived from ionic liquid effectively accelerates the Zn nucleation, ensures smooth deposition, and reduces side reactions.
Biobutanol is a promising candidate as the biofuel of the future. Four isomers exist, of which 1-butanol, isobutanol, and 2-butanol are the most promising candidates for biobutanol production. ...However, sensing isomers are slightly challenging due to the same molecular formula and molar mass. In this study, a sensor array system was built, which consists of three microgravimetric and three amperometric sensors coated with three room temperature ionic liquids with different pairs of cation and anion combinations, i.e., 1-ethyl-3-methylimidazolium acetate, 1-butyl-3-methylimidazolium bromide, and 1-hexyl-3-methylimidazolium chloride. In the microgravimetric sensor, quartz crystal microbalance coated with different sensing films was used to gain selectivity. In addition, the interdigitated electrode was selected where a microdroplet of room temperature ionic liquid was used for the electrolytes to substitute for the conventional bulky amperometric sensor. The different mechanisms of the two sensor types are expected to enhance the separation power among butanol isomers. The reproducibility and the concentration dependency were also studied to explore the sensor characteristics. A typical statistic parameter, the Wilks' lambda, was used to calculate the discrimination power numerically from different sensor combinations. According to the numerical result, the lowest Wilks' lambda with the numerical value of 4.82×10 -8 , where the separation among butanol isomers was enhanced, was achieved from two type sensor combinations, i.e., quartz crystal microbalance with three sensing films and amperometric sensor with the electrolyte of 1-ethyl-3-methylimidazolium acetate.
•A superhydrophobic coating was fabricated by electrodeposition from the ionic liquid.•A one-step electrodeposition approach was used to fabricate the micro-nano superhydrophobic structure.•The ...superhydrophobic coating provided a good corrosion protection for the copper.
A one-step electrodeposition approach to make a micro-nano superhydrophobic structure on the surface of copper was developed by using Choline chloride (ChCl)-based ionic liquid as the electrolyte. As compared with bare Cu, the contact angle of electrodeposited superhydrophobic coating reaches 157.8°. The corrosion behavior of superhydrophobic copper coating in 3.5 wt% NaCl solution was studied, and the results demonstrate that it exhibited an extraordinary corrosion resistance and had a good protective effect to the Cu substrate.
Utilizing covalent organic framework (COF) as a hypotoxic and porous scaffold to encapsulate enzyme (enzyme@COF) has inspired numerous interests at the intersection of chemistry, materials, and ...biological science. In this study, we report a convenient scheme for one‐step, aqueous‐phase synthesis of highly crystalline enzyme@COF biocatalysts. This facile approach relies on an ionic liquid (2 μL of imidazolium ionic liquid)‐mediated dynamic polymerization mechanism, which can facilitate the in situ assembly of enzyme@COF under mild conditions. This green strategy is adaptive to synthesize different biocatalysts with highly crystalline COF “exoskeleton”, as well evidenced by the low‐dose cryo‐EM and other characterizations. Attributing to the rigorous sieving effect of crystalline COF pore, the hosted lipase shows non‐native selectivity for aliphatic acid hydrolysis. In addition, the highly crystalline linkage affords COF “exoskeleton” with higher photocatalytic activity for in situ production of H2O2, enabling us to construct a self‐cascading photo‐enzyme coupled reactor for pollutants degradation, with a 2.63‐fold degradation rate as the poorly crystalline photo‐enzyme reactor. This work showcases the great potentials of employing green and trace amounts of ionic liquid for one‐step synthesis of crystalline enzyme@COF biocatalysts, and emphasizes the feasibility of diversifying enzyme functions by integrating the reticular chemistry of a COF.
We herein report an ionic liquid‐mediated dynamic polymerization for designing highly crystalline enzyme‐covalent organic framework (COF) biocatalysts. The highly crystalline COF “exoskeleton” affords the hosted lipase with non‐native catalytic selectivity for aliphatic acid hydrolysis. Meanwhile the high photocatalytic activity of crystalline COF enables us to construct a self‐cascading photo‐enzyme coupled nanoreactor for pollutants degradation.
Display omitted
•A novel magnetic-cellulose base polymeric ionic liquid was synthesized.•Polymeric ionic liquid was used as a biosorbent for anionic dye adsorption.•Response surface methodology was ...used for optimizing effective parameters.
Ionic liquids are considered to be a class of environmentally friendly compounds as combination of them with bioresource polymeric substances such as; cellulose, constitute emerging coating materials. Biosorption by polymeric ionic liquids exhibits an attractive green way that involves low cost and irrespective of toxicity. As a result, a novel polymeric ionic liquid has been developed by the reaction of one step synthesized Fe3O4-cellulose nanohybrid, epichlorohydrin and 1-methylimidazole and employed as a green sorbent for efficient biosorption of Congo red dye. Effective parameters on dye removing as well as their interactions were determined with response surface methodology (RSM). Congo red adsorption showed fast equilibrium time (11min) with maximum uptake of 131mgg−1. Isotherm study revealed that Langmuir adsorption model can better describe dye adsorption behavior. Regeneration of the sorbent was performed with a mixture of methanol–acetone–NaOH (3.0molL−1) solution.
