Ionic liquids and deep eutectic solvents are of growing interest as solvents for the resource‐efficient synthesis of inorganic materials. This Review covers chemical reactions of various deep ...eutectic solvents and types of ionic liquids, including metal‐containing ionic liquids, BF4−‐ or PF6−‐based ionic liquids, basic ionic liquids, and chalcogen‐containing ionic liquids. Cases in which cations, anions, or both are incorporated into the final products are also included. The purpose of this Review is to raise caution about the chemical reactivity of ionic liquids and deep eutectic solvents and to establish a guide for their proper use.
The chemical reactivity of ionic liquids and deep eutectic solvents can intentionally be exploited as a synthetic tool to prepare inorganic materials that are difficult or even impossible to obtain by traditional synthetic routes. This Review summarizes recent developments in inorganic syntheses that take advantage of reactions with ionic liquids or deep eutectic solvents.
Abstract
Developing effective catalysts based on earth abundant elements is critical for CO
2
electroreduction. However, simultaneously achieving a high Faradaic efficiency (FE) and high current ...density of CO (
j
CO
) remains a challenge. Herein, we prepare a Mn single-atom catalyst (SAC) with a Mn-N
3
site embedded in graphitic carbon nitride. The prepared catalyst exhibits a 98.8% CO FE with a
j
CO
of 14.0 mA cm
−2
at a low overpotential of 0.44 V in aqueous electrolyte, outperforming all reported Mn SACs. Moreover, a higher
j
CO
of 29.7 mA cm
−2
is obtained in an ionic liquid electrolyte at 0.62 V overpotential. In situ X-ray absorption spectra and density functional theory calculations demonstrate that the remarkable performance of the catalyst is attributed to the Mn-N
3
site, which facilitates the formation of the key intermediate COOH
*
through a lowered free energy barrier.
In this paper, we propose “The Infinite Separation Principle”. This principle contains two implications: firstly, even exhausting all separation approaches, including chemical techniques, it is ...impossible to achieve 100% purity for separating a mixture; secondly, separation can continue infinitely without an endpoint.
Display omitted
•“The Infinite Separation Principle” is proposed for the first time.•The principle is systematically elaborated from a thermodynamic perspective.•The principle provides an important guidance for practical separation process.
This comprehensive database on physical properties of pure ionic liquids (ILs) contains data collected from 269 peer-reviewed papers in the period from 1982 to June 2008. There are more than 9,400 ...data points on the 29 kinds of physicochemical properties for 1886 available ionic liquids, from which 807 kinds of cations and 185 kinds of anions were extracted. This book includes nearly all known pure ILs and their known physicochemical properties through June 2008. In addition, the authors incorporate the main applications of individual ILs and a large number of references.
-Nearly 50 tables include typical data, experimental and modelling or simulation comparison, and model parameters, enhancing the application of ILs.-100 figures--from QSPR, EOS and gE models to quantum and molecular simulations--help readers understand ILs at molecular level.-Applications illustrate the role of IL properties in industry, in particular the development of novel clean processes and products.
Cellulose is one of the most abundant bio-renewable materials on the earth and its conversion to biofuels provides an appealing way to satisfy the increasing global energy demand. However, before ...carrying out the process of enzymolysis to glucose or polysaccharides, cellulose needs to be pretreated to overcome its recalcitrance. In recent years, a variety of ionic liquids (ILs) have been found to be effective solvents for cellulose, providing a new, feasible pretreatment strategy. A lot of experimental and computational studies have been carried out to investigate the dissolution mechanism. However, many details are not fully understood, which highlights the necessity to overview the current knowledge of cellulose dissolution and identify the research trend in the future. This perspective summarizes the mechanistic studies and microscopic insights of cellulose dissolution in ILs. Recent investigations of the synergistic effect of cations/anions and the distinctive structural changes of cellulose microfibril in ILs are also reviewed. Besides, understanding the factors controlling the dissolution process, such as the structure of anions/cations, viscosity of ILs, pretreatment temperature, heating rate,
etc.
, has been discussed from a structural and physicochemical viewpoint. At the end, the existing problems are discussed and future prospects are given. We hope this article would be helpful for deeper understanding of the cellulose dissolution process in ILs and the rational design of more efficient and recyclable ILs.
This perspective summarizes mechanistic studies on cellulose dissolution in ionic liquids, highlighting the synergistic mechanism, physicochemical aspects and future research trends.
The global demand for energy is constantly on the rise because of population explosion, rapid urbanization, and industrial growth. Existing energy resources are struggling to cope with the current ...energy requirements. Aside from exploring renewable energy alternatives, available energy resources must be utilized to their maximum potential. Coke oven gas (COG) is highly rated as a valuable by-product of coal carbonization to produce coke in the steel industry. Typically, a single ton of coke generates approximately 360m3 COG. China annually produces 70billion Nm3 COG; however, only 20% of the gas produced is utilized as fuel. Disposing COG without an effective recovery and efficient utilization is a serious waste of an energy resource and results in environmental pollution. COG is regarded as a potential feedstock for hydrogen separation, methane enrichment, and syn-gas and methanol production. It can also be effectively utilized to produce electricity and liquefied natural gas. The availability, properties, purification, and utilization of COG are reviewed in the current study. COG utilization routes are summarized in detail, with focus on some major industrial projects in China and other countries that are based on COG utilization technology.
Covalent organic frameworks (COFs) are generally obtained as insoluble, cross-linked powders or films, hindering their superior processable properties especially for device implementation. Here, a ...soluble COF is created with atomically well-organized positive charged centers constrained in the planar direction, exhibiting exceptional solubility through an in situ charge exfoliation pathway. Once dissolved, the obtained true solution retains homogeneity even after standing over a year. Moreover, the as-designed soluble COF contains ordered N-coordinated Fe single atom centers and conjugated structures, providing a small work function (4.84 eV) and superior catalytic performance for oxygen reduction (high half-wave potential of ∼900 mV). The obtained COF true solution can be directly used as a highly efficient Pt-replaced catalyst for zinc–air flow batteries, generating prominent performance and outstanding stability.
Recently, it has been reported that addition of a cosolvent significantly influences solubility of cellulose in ionic liquids (ILs), but little is known about the influence mechanism of the cosolvent ...on the molecular level. In this work, four kinds of typical molecular solvents (dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), CH3OH, and H2O) were used to investigate the effect of cosolvents on cellulose dissolution in C4mimCH3COO by molecular dynamics simulations and quantum chemistry calculations. It was found that dissolution of cellulose in IL/cosolvent systems is mainly determined by the hydrogen bond interactions between CH3COO− anions and the hydroxyl protons of cellulose. The effect of cosolvents on the solubility of cellulose is indirectly achieved by influencing such hydrogen bond interactions. The strong preferential solvation of CH3COO− by the protic solvents (CH3OH and H2O) can compete with the cellulose–CH3COO− interaction in the dissolution process, resulting in decreased cellulose solubility. On the other hand, the aprotic solvents (DMSO and DMF) can partially break down the ionic association of C4mimCH3COO by solvation of the cation and anion, but no preferential solvation was observed. The dissociated CH3COO− would readily interact with cellulose to improve the dissolution of cellulose. Furthermore, the effect of the aprotic solvent-to-IL molar ratio on the dissolution of cellulose in C4mimCH3COO/DMSO systems was investigated, and a possible mechanism is proposed. These simulation results provide insight into how a cosolvent affects the dissolution of cellulose in ILs and may motivate further experimental studies in related fields.
Display omitted
•Ternary nanohybrid based on rGO, NiMn2O4, and polyaniline (GNMOP) was fabricated by a three-step green process for supercapacitor applications.•GNMOP exhibited high specific ...capacitance of 757Fg−1 at 1Ag−1 of current density.•GNMOP showed 93% of specific capacitance retention after 2000 cycles.•GNMOP also exhibited high energy density of up to 70Whkg−1 and high power density of up to 12000Wkg−1.
This paper reports a novel porous ternary nanohybrid based on NiMn2O4, reduced graphene oxide, and polyaniline (GNMOP) as a superior supercapacitor electrode material. GNMOP was fabricated using a hydrothermal-assisted thermal annealing method, followed by the conductive wrapping of polyaniline through in-situ polymerization. The structure and morphology of the ternary nanohybrid were characterized by field emission scanning electron microscopy (FESEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Fourier transform infrared spectroscopy (FTIR). FTIR, XRD, and XPS confirmed the formation of ternary nanohybrid. SEM and Brunauer–Emmett–Teller (BET) measurement revealed the porous nature of GNMOP, whereas HRTEM analysis demonstrated the wrapping of conducting polyaniline (PANI) on binary composite. Such PANI wrapping enhanced the electrochemical performance of the binary nanocomposite. A specific capacitance of 757Fg−1 was achieved for GNMOP at a current density of 1Ag−1, which is much higher than that of the binary nanocomposite and mixed transition metal oxide. In addition, GNMOP exhibited a maximum energy density of 70Whkg−1 and high capacitance retention of ∼93% after 2000 cycles. These outstanding electrochemical performances of GNMOP can be attributed to the proper wrapping of conducting polymer and the synergistic impact of distinct components.
PDF
