The replacement of fossil resources that currently provide more than 90% of our energy needs and feedstocks of the chemical industry in combination with reduced emission of carbon dioxide is one of the most pressing challenges of mankind. Biomass as a globally available resource has been proposed as an alternative feedstock for production of basic building blocks, which could partially or even fully replace the currently utilized fossil-based ones in well-established chemical processes. The destruction of lignocellulosic feed followed by oxygen removal from its cellulose and hemicellulose content by catalytic processes results in the formation of initial platform chemicals (IPCs). However, their sustainable production strongly depends on the availability of resources, their efficient or even industrially viable conversion processes, and replenishment time of feedstocks. Herein, we overview recent advances and developments in catalytic transformations of the carbohydrate content of lignocellulosic biomass ...

Catalytic Conversion of Carbohydrates to Initial Platform Chemicals: Chemistry and Sustainability

Ionic liquid with acidic properties is an important branch in the wide ionic liquid field and the aim of this article is to cover all aspects of these acidic ionic liquids, especially focusing on the developments in the last four years. The structural diversity and synthesis of acidic ionic liquids are discussed in the introduction sections of this review. In addition, an unambiguous classification system for various types of acidic ionic liquids is presented in the introduction. The physical properties including acidity, thermo-physical properties, ionic conductivity, spectroscopy, and computational studies on acidic ionic liquids are covered in the next sections. The final section provides a comprehensive review on applications of acidic ionic liquids in a wide array of fields including catalysis, CO2 fixation, ionogel, electrolyte, fuel-cell, membrane, biomass processing, biodiesel synthesis, desulfurization of gasoline/diesel, metal processing, and metal electrodeposition.

Acidic Ionic Liquids.

Catalytic conversion of renewable biomass to “green” chemicals and fuel additives has been extensively investigated in the past few decades. Interests on two top platform intermediates for biofuel production, i.e. levulinic acid (LA) and 5-hydroxymethylfurfural (HMF), have increased significantly. These two chemicals are generally produced from biomass through acid hydrolysis. This review summarizes the discoveries of the most recent studies on acid-catalyzed hydrolysis, including (i) biomass pretreatment, (ii) glucose production from cellulose hydrolysis, (iii) fructose formation from glucose isomerization, (iv) HMF formation from glucose/fructose dehydration and (v) LA production from HMF rehydration. Humins, the main byproducts, are also discussed in the aspect of their influence on the hydrolysis process, structure, formation mechanism, and applications.

From lignocellulosic biomass to levulinic acid: A review on acid-catalyzed hydrolysis

Temperature-responsive ionic liquids (ILs), their fundanmental behaviors, and catalytic applications were introduced, especially the concepts of upper critical solution temperature (UCST) and lower critical solution temperature (LCST). It is described that, during a catalytic reaction, they form a homogeneous mixture with the reactants and products at reaction temperature but separate from them afterward at ambient conditions. It is shown that this behavior offers an effective alternative approach to overcome gas/liquid–solid interface mass transfer limitations in many catalytic transformations. It should be noted that IL-based thermomorphic systems are rarely elaborated until now, especially in the field of catalytic applications. The aim of this article is to provide a comprehensive review about thermomorphic mixtures of an IL with H2O and/or organic compounds. Special focus is laid on their temperature dependence concerning UCST and LCST behavior, including systems with conventional ILs, metal-containi...

Temperature-Responsive Ionic Liquids: Fundamental Behaviors and Catalytic Applications

In this research, a facile co-precipitation method was used to synthesize pure and Mg-doped ZnO nanoparticles (NPs). The structure, morphology, chemical composition, and optical and antibacterial activity of the synthesized nanoparticles (NPs) were studied with respect to pure and Mg-doped ZnO concentrations (0–7.5 molar (M) %). X-ray diffraction pattern confirmed the presence of crystalline, hexagonal wurtzite phase of ZnO. Scanning electron microscope (SEM) images revealed that pure and Mg-doped ZnO NPs were in the nanoscale regime with hexagonal crystalline morphology around 30–110 nm. Optical characterization of the sample revealed that the band gap energy (Eg) decreased from 3.36 to 3.04 eV with an increase in Mg2+ doping concentration. Optical absorption spectrum of ZnO redshifted as the Mg concentration varied from 2.5 to 7.5 M. Photoluminescence (PL) spectra showed UV emission peak around 400 nm. Enhanced visible emission between 430 and 600 nm with Mg2+ doping indicated the defect density in ZnO by occupying Zn2+ vacancies with Mg2+ ions. Photocatalytic studies revealed that 7.5% Mg-doped ZnO NPs exhibited maximum degradation (78%) for Rhodamine B (RhB) dye under UV-Vis irradiation. Antibacterial studies were conducted using Gram-positive and Gram-negative bacteria. The results demonstrated that doping with Mg ions inside the ZnO matrix had enhanced the antibacterial activity against all types of bacteria and its performance was improved with successive increment in Mg ion concentration inside ZnO NPs.

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Influence of Mg Doping on ZnO Nanoparticles for Enhanced Photocatalytic Evaluation and Antibacterial Analysis

A series of Lewis acidic metal salts were used for glucose dehydration to 5-hydroymethylfurfural (HMF) in water. Effect of valence state, ionic radii of Lewis acidic cation, and the type of anions on the catalytic performance have been studied systematically. The experimental results showed that the valence state played an important role in determining catalytic activity and selectivity. It was found that a higher glucose conversion rate and HMF selectivity could be obtained over high valent Lewis acid salts, where the ionic radii of these Lewis acidic metal salts are usually relatively small. Analysis on the effect of the anions of Lewis acid salts on the catalytic activity and the selectivity suggested that a higher glucose conversion and HMF selectivity could be readily obtained with Cl−. Furthermore, the recyclability of high valence state Lewis acid salt was also studied, however, inferior catalytic performance was observed. The deactivation mechanism was speculated to be the fact that high valence state Lewis acid salt was comparatively easier to undergo hydrolysis to yield complicated metal aqua ions with less catalytic activity. The Lewis acidic activity could be recovered by introducing a stoichiometric amount of hydrochloric acid (HCl) to the catalytic before the reaction.

Catalytic Conversion of Glucose into 5-Hydroxymethylfurfural by Hf(OTf)4 Lewis Acid in Water

A mesoporous SBA-15 supported sulfonic acid catalyst (SBA-15-SO3H) was successfully prepared and used for the selective conversion of fructose to 5-hydroxymethylfurfural (HMF). Up to 96% of HMF selectivity with 100% fructose conversion was obtained under mild conditions (120 °C, 60 min, DMSO as solvent). Solvent effect, reaction time, reaction temperature and fructose-to-catalysts mass ratio have been investigated. The SBA-15-SO3H solid acid catalyst can be separated from the reaction mixture after reaction and reused by simple centrifugalization, and 100% fructose conversion with 95% HMF yield could be retained. Further, reaction activation energy of 56.4 kJ/mol has been fitted with kinetic analysis, which means that the dehydration of fructose into HMF is relative easier over SBA-15-SO3H catalyst in this work. Besides, X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR) and scanning electron microscopy (SEM) measurements reveal that the –SO3H grafting on the SBA-15 surface have no obvious influence on its mesoporous structure even after five catalytic cycles, and acid site measurements demonstrate that there was no significant loss of acid site concentration, indicating high catalytic stability. This fruit give a useful reference to chemical engineering and materials, besides future energy and smart city.

High selective production of 5-hydroxymethylfurfural from fructose by sulfonic acid functionalized SBA-15 catalyst

In this work, a thermo-regulated recyclable catalytic system using ionic liquid [HO2CMMIm]Cl as the catalyst and isopropanol as the solvent has been demonstrated to be effective for the dehydration of fructose to synthesize 5-hydroxymethylfurfural (HMF). The solubility of [HO2CMMIm]Cl ionic liquid in isopropanol is temperature-dependent, being miscible with isopropanol at a temperature range suitable for fructose dehydration (e.g., above 80 °C) while not soluble at lower temperatures such as room temperature. Temperature-responsive solubilization/precipitation of [HO2CMMIm]Cl in isopropanol renders the acidic ionic liquid an appealing thermo-regulated phase-switchable catalyst. Furthermore, the effects of various parameters including catalyst loading, fructose concentration, reaction time and temperature on the catalytic performance of fructose dehydration have been studied systematically. Under optimized reaction conditions, up to 91.2 mol% HMF yield could be obtained. Additionally, when the ionic liquid catalyst precipitated out after the reaction, the solvent can be simply decanted and [HO2CMMIm]Cl could be directly reused for the next run with freshly added solvent and substrate. It was found that [HO2CMMIm]Cl could be reused at least five times without considerable loss of activity. Furthermore, a kinetic analysis was carried out, indicating the activation energy for the reaction to be 62.1 kJ mol−1. This catalytic system can be envisioned to find applications in a wide range of acid-catalyzed reactions with facile, thermo-regulated catalyst recovery features.

Hongyi Li

Papers

Catalytic Conversion of Glucose into 5-Hydroxymethylfurfural by Hf(OTf)4 Lewis Acid in Water

High selective production of 5-hydroxymethylfurfural from fructose by sulfonic acid functionalized SBA-15 catalyst

Production of 5-hydroxymethylfurfural from fructose by a thermo-regulated and recyclable Brønsted acidic ionic liquid catalyst

Tandem hydroformylation and hydrogenation of dicyclopentadiene by Co3O4 supported gold nanoparticles

Environment-friendly synthesis of diethyl carbonate via ethyl carbamate alcoholysis over cerium oxide catalyst.