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Levulinic acid (LA) is considered as an important intermediate for production of chemicals, resins, polymers, and fuel additives. Herein, five Bronsted–Lewis acidic ionic liquids (ILs) were synthesized and their acidities of ILs were characterized using FT-IR spectroscopy. The order of their acidic strength was similar to that of the used metal chlorides (ZnCl2 > FeCl3 > CuCl > CrCl3). Cellulose was effectively converted to LA in pure water at 180 °C in 10 h without additives, and the maximum yield of LA was more than 49% over the Bronsted–Lewis IL [HO3S-(CH2)3-py]Cl-FeCl3. The synergistic catalytic effect of the Lewis and Bronsted acidic centers of the catalyst played a significant role for the conversion of cellulose to LA. Some solid residues were formed along with the synthesis of LA, and the result of its characterization suggested that they had good thermal stability and their structures were benzene or amorphous (partially hydrogenated) fused benzene ring. Otherwise, the IL reusability was good, and when it was reused for five times, its catalytic performance was not changed. Therefore, the conversion route for cellulose to LA in pure water with the Bronsted–Lewis acidic ILs provides an environmentally friendly method for biobased-platform from biomass.

Background Propionic acid as a very valuable chemical is in high demand, and it is industrially produced via the oxo-synthesis of ethylene or ethyl alcohol and via the oxidation of propionaldehyde with oxygen. It is urgent to discover a new preparation method for propionic acid via a green route. Recyclable amino-acid-based organic–inorganic heteropolyoxometalates were first used to high-efficiently catalyse the selective oxidation of 1-propanol to propionic acid with H2O2 as an oxidant. Result A series of amino-acid-based heteropoly catalysts using different types of amino acids and heteropoly acids were synthesized, and the experimental results showed proline-based heteropolyphosphatotungstate (ProH)3[PW12O40] exhibited excellent catalytic activity for the selective catalytic oxidation of 1-propanol to propionic acid owing to its high capacity as an oxygen transfer agent and suitable acidity. Under optimized reaction conditions, the conversion of 1-propanol and the selectivity of propionic acid reached 88% and 75%, respectively. Over four cycles, the conversion remained at >80%, and the selectivity was >60%. (ProH)3[PW12O40] was also used to catalyse the oxidations of 1-butanol, 1-pentanol, 1-hexanol, and benzyl alcohol. All the reactions had high conversions, with the corresponding acids being the primary oxidation product. Conclusions Proline-based heteropolyoxometalate (ProH)3[PW12O40] has been successfully used to catalyse the selective oxidation of primary alcohols to the corresponding carboxylic acids with H2O2 as the oxidant. The new developed catalytic oxidation system is mild, high-efficient, and reliable. This study provides a potential green route for the preparation propionic acid.

The preparation of small molecule compounds with a high value from biomass has always been the focus of research, and catalysts with high activity and stability are an essential part of biomass con...

A green and facile synthesis of anisotropic 3D architecture high-performance carbon catalyst has been a hot research topic. Herein, a facile and scalable strategy was developed to fabricate an N, S co-doped microcellular carbon from natural polymers of chitosan (N-source) and lignosulfonate (S-source), with the properties enhanced as a result of pre-cryocrushing of natural polymer-based carbon precursors. The as-prepared 3D architecture carbon is mechanically strong and contains cross-linked hierarchical porous micro-sheets and micro-channels. This N and S co-doped carbon, prepared from pre-cryocrushing of chitosan (60%) and lignosulfonate (40%) precursor (NSC/CC-C/L (60/40)), annealed at 900 °C shows unique structures, with significant defects, rough edges, rich micro/meso-pores, large surface area, N and S doping, and high pyridinic-N and thiophene-S contents. The NSC/CC-C/L (60/40)-900 sample exhibits superior performance with favorable kinetics, methanol resistance, and excellent durability as an ORR catalyst, all of which are much better than a commercial Pt/C and most reported metal-free catalysts. Impressively, the onset potential of the NSC/CC-C/L-900 sample reaches 1.08 V (vs. reversible hydrogen electrode) and the half-wave potential is 0.98 V, which are compared to 1.02 and 0.92 V for Pt/C.

The new catalyst Pd@mSiO2 was synthesized by a simple and gentle one-step process, mesoporous silica as the shell and metal particles as the core. The characterization showed that the catalyst structure was regular, the core–shell structure was clear, and each microsphere guarantees the existence of a single nucleus. The pore size and the thickness of mesoporous silica layer can be effectively adjusted by adjusting the molecular weight of template and the amount of silicon source. The Pd@mSiO2 was applied in the hydrogenation of levulinic acid to prepare γ-valerolactone, the conversion of levulinic acid was 95%, and the selectivity of γ-valerolactone was close to 96%. In addition, the catalyst had a good reuse performance compared to commercial catalysts. After repeated use for ten times, the catalytic activity did not decrease, which was mainly attributed to the fact that the core–shell structure can better protect the active metal particles and prevent the particles from agglomeration and loss at high temperature.

Conversion of rosin to its pentaerythritol ester provides a means of improving its water resistance, alkali resistance, and oxidation resistance, thereby increasing its stability. Rosin pentaerythritol ester is much more amenable to industrial applications than the parent compound. To overcome the difficulty of catalyst recovery and its associated high cost during the synthesis of rosin pentaerythritol ester, Fe3O4-supported ZnO catalysts, such as Fe3O4@ZnO and Fe3O4@SiO2–ZnO, have been designed and synthesized. The structures, morphologies, and compositions of the materials have been characterized by TEM, XRD, and XPS. The results of esterification reactions demonstrate that Fe3O4@SiO2–ZnO has excellent catalytic performance and stability. The degree of esterification in the production of rosin pentaerythritol ester reached 87.9%, far exceeding the yields attained with other catalysts. Moreover, the catalyst could be reused five times without incurring a loss of activity. The effects of zinc source, zinc loading, and reaction conditions on the esterification have been investigated in detail. This study provides a class of heterogeneous catalysts with excellent properties for the synthesis of rosin pentaerythritol ester. In our paper, the optimum process conditions for obtaining rosin pentaerythritol ester have been identified as zinc nitrate as the zinc source, a theoretical loading of zinc source of 0.45 g, a reaction temperature of 250 °C, a reaction time of 5 h, and a catalyst loading of 0.2 g, when starting from rosin (15 g) and pentaerythritol (1.7 g). The conversion rate was 87.9%, and the acid value was 25.0 mg KOH g−1. This research provides an improved protocol for the rosin esterification reaction.

Hβ zeolite is modified in the microwave acetic acid and evaluated in the one-pot synthesis of anthraquinone from benzene and phthalic anhydride. Under the optimized conditions, the Hβ zeolite modified in 0.9 mol/L acetic acid solution exhibits the best catalytic activity, in which the conversion of phthalic anhydride and its selectivity to anthraquinone are 54.71% and 62.56%, respectively. A series of catalysts are characterized using BET, XRD, XRF, NH3-TPD, FT-IR, Py-IR, SEM, and XPS. The high activity is mainly attributed to the suitable acid strength. Increasing the specific surface area and pore volume fraction also promotes the reaction. On the other hand, the deposition of carbon atoms results in the deactivation of the catalyst. However, the catalytic activity can be effectively recovered by calcination regeneration, and still shows good catalytic activity after five times.

The use of lignin to prepare fine chemicals is a hot research topic. Here, we propose a strategy for esterification of the syringyl group, which is abundant in lignin, to produce 3,4-dimethoxyphenyl acetic acid ester. Lignin reacts with alcohols over acidic pure silica catalyst, L-MCM-41, to generate 3,4-dimethoxyphenyl acetic acid esters. The esterification yield from alkali lignin (Indulin AT) reached more than 60%. Furthermore, L-MCM-41 was easily and quickly prepared using hydroxyl free radicals. The obtained L-MCM-41 exhibited enhanced Lewis acidity and stability compared to silica MCM-41 derived from a traditional hydrothermal system. The enhanced Lewis acidity of the surface silicon atoms of L-MCM-41 can be attributed to the electron-withdrawing effect of abundant geminal hydroxyl groups that they bear. Based on spectroscopic data and the concentration of hydroxyl free radicals, the mechanism underpinning the enhanced acidity and stability of the mesoporous silica molecular sieves is proposed. This work enables production of fine chemicals using lignin as feedstock and provides a reliable and simple method for the synthesis of strongly acidic mesoporous silica molecular sieves.

The use of cellulose instead of oil to produce 1,2-propylene glycol (1,2-PG) is of great significance for building a sustainable world. Herein, we synthesize Fe3O4@SiO2/Ru-WOx core–shell magnetical...

In this study, a novel silk fibroin films with robust mechanical properties was fabricated by dissolving silk under ultraviolet light (Uv-light) in ionic liquid. Uv-light irradiation can promote the transformation of the silk fibroin structure from the α-helix to the β-sheet, thereby the strength of the film was enhanced. The wavelength of the Uv-light, the irradiation time and the distance from the light source all have an effect on the strength of the silk fibroin film. Under the optimum conditions, the strength of silk fibroin film could reach 23.7Mpa, which was nearly 85% higher than that of the conventional system. In the meantime, the wettability and swellability of the film were investigated. The results showed that groups with oxygen atoms on the surface of silk fibroin film increased after irradiation, and its wettability and swellability increased significantly, which was more conducive to cell adhesion. Furthermore, the silk fibroin film exhibit excellent biocompatibility, supporting L-929 (mouse fibroblasts) adhesion and proliferation. The study provides a new direction for the preparation of high-strength silk fibroin films, as well as its application in life sciences.

A series of amino-acid-based ionic liquids was synthesized via one-step protonation of the corresponding L-amino acid by utilizing an array of proton sources. The catalytic activity of the amino-acid-based ionic liquids for the Baeyer-Villiger oxidation of cyclic ketones was investigated using cyclopentanone as a model cycloketone. The proline-based ionic liquid [ProH]CF3SO3 was shown to exhibit the best catalytic activity. The reaction condition was optimized to give the following reagent ratio of n(cyclopentanone):n(catalyst):n(H2O2)=1:0.06:4, 60 °C and 6 h. Under the optimum conditions, the conversion of cyclopentanone was 96.57% and the selectivity for δ-valerolactone was 73.01%. The catalytic activity was shown to be constant after 4 cycles. A simple treatment was allowed for the recover and the reuse of [ProH]CF3SO3. The successful utilization of [ProH]CF3SO3 to catalyze a host of cyclic ketones via Baeyer-Villiger oxidation clearly demonstrated the capacity of [ProH]CF3SO3 to tolerate variation in the substrate.

A hypercrosslinked resin, named St-DVB-Al, was prepared by optimizing the conditions of the Friedel–Crafts reaction. The nitro and amine groups were further introduced into the skeleton to prepare the composite functional resins St-DVB-nitro and St-DVB-amine. The adsorption capacity of the modified resins for phenolic compounds reached to 412.9 mg/g, which were 16.4–47.7% higher than the commercial resin H103 with similar physical structure. For the p-nitrophenol and p-hydroxybenzoic acid, the adsorption capacity trends were St-DVB-amine > St-DVB-Al > St-DVB-nitro, but for the hydroquinone was St-DVB-nitro > St-DVB-amine > St-DVB-Al. The reason St-DVB-nitro exhibited efficient adsorption for hydroquinone was that the electron-acceptor group enhanced the synergistic conjugation with the electron-donating compound. The introduction of the electron-donor group in St-DVB-amine enhanced the synergistic conjugation with electron-acceptor compounds as well as the hydrogen bonding and acid-base interaction, thus exhibiting highly efficient adsorption for p-nitrophenol and p-hydroxybenzoic acid. The DFT model was used to calculate the ΔE values of St-DVB-nitro, St-DVB-amine and St-DVB-Al with three adsorbates, and the results were consistent with the adsorption trends. Relationship between adsorption capacity and adsorption behavior was clarified by a quantitative perspective.

Ruthenium (Ru) nanoparticles synthesized using hydroxyethyl cellulose (HEC-Ru) were used to hydrogenate α-pinene in an aqueous medium. The results showed that HEC had a good dispersion effect on Ru nanoparticles and most of the particle sizes were ranged from 4 to 6 nm. The micelles formed with HEC appeared to act as “microreactors” in which the Ru nanoparticles had good stability and uniform distribution. In addition, α-pinene was loaded into the HEC micelles through hydrophobic interaction, resulting in good contact with Ru nanoparticles. Thereby, HEC-Ru nanoparticles significantly improved the hydrogenation of α-pinene, and 99.6% of α-pinene conversion and 98.6% of cis-pinane selectivity were obtained. Compared with the Pd/C, Ru/H2O, and HEC-Ru/ethanol catalyst systems, the HEC-Ru/H2O system had the maximum α-pinene conversion. In addition, considerable α-pinene conversion could be obtained after 10 times reuse with no fresh addition.

Layered porous carbon (NCSIL-900) with a graphitization-like layered structure possessing developed oxygen- and nitrogen-containing groups were prepared via hydrothermal carbonization of chitosan in the presence of an ionic liquid (IL; 1-butyl-3-methylimidazolium chloride). The IL served as a dispersant, structure-directing agent and nitrogen source during the reaction, and facilitated the formation of a layered and mesoporous structure. Thus, NCSIL-900 exhibited developed micro/mesoporous characteristics in layered structures. When evaluated as an electrode material for supercapacitors, NCSIL-900 exhibited specific capacitance of 355 F/g at 0.2 A/g in (1 M H2SO4 electrolyte) and 275 F/g at 0.2 A/g in (6 M KOH electrolyte) in a three-electrode system. The values were 157.5 F/g at 0.5 A/g in (1 M H2SO4 electrolyte) and 120.8 F/g at 0.5 A/g in (6 M KOH electrolyte) in a two-electrode system. The layered porous structure and nitrogen-containing groups of NCSIL-900 contributed to its high specific capacitance. In this work, layered carbon materials that are promising candidates for electrode materials were prepared via a “green” route using “green” solvent and raw materials.

Cyclohexanone is an important intermediate in the manufacture of polyamides in chemical industry, but direct selective hydrogenation of phenol to cyclohexanone under mild conditions is a challenge. Hydrogenation of phenol to cyclohexanone has been investigated in the presence of the composite catalytic system of Pd/C-heteropoly acid. 100% conversion of phenol and 93.6% selectivity of cyclohexanone were achieved within 3 h under 80 °C and 1.0 MPa hydrogen pressure. It has been found that a synergetic effect of Pd/C and heteropoly acid enhanced the catalytic performance of the composite catalytic system which suppressed the hydrogenation of cyclohexanone to cyclohexanol.

In aqueous medium without any other additives, palladium (Pd) nanoparticles with water-soluble polyvinyl alcohol (PVA) as stabilizer were synthesized for the catalytic hydrogenation of nitrobenzene. Under the optimum experimental conditions, the nitrobenzene conversion and the selectivity for aniline were 99.3 % and 100 %, respectively. Comprehensive characterization methods, including TEM, UV/Vis, confocal laser scanning microscopy (CLSM), XRD and XPS allowed a better understanding of the role of PVA aggregates and the properties of Pd nanoparticles. The nitrobenzene conversion exceeded 80 % even after 6 cycles without any treatment of the catalyst. A mechanism about the hydrogenation of nitrobenzene catalyzed by Pd/PVA system was proposed. The Pd/PVA catalyst also exhibited excellent activity and selectivity, particularly to ortho-fluoronitrobenzene and ortho-nitrotoluene. This research can provide a reference for the environmentally friendly catalysis for hydrogenation of nitrobenzene and other substituted nitrobenzene compounds.

Two types of carbon microspheres with abundant nitrogen-containing groups and porous structure were prepared via feasible and cost-effective methods, using chitosan (NCS-T) and glucose (NCSNH3-T) as the raw materials, chitosan and ammonia as nitrogen source respectively. The effect of nitrogen sources on structure of N-doped porous carbon and their supercapacitors/CO2 adsorption performance were discussed in details. The obtained carbon materials both exhibit a graphite-like structure with developed porous structures. For the NCS-T samples, N-5 and N-6 were the main nitrogen-containing groups, and O Ⅰ and O Ⅱ were the main oxygen-containing groups. For NCSNH3-T samples, N exists as N-5, N-6 N-Q, and N-X groups, and O exists as O Ⅰ, O Ⅱ, and O Ⅲ groups. Micro-mesoporous structures developed, and on the specific surface area, pore volumes are more developed in NCSNH3-T, mainly due to ammonia activation, which results in additional micropores especially ultramicropores (sizes＜0.9 nm). The obtained carbon materials are well suited for use as an electrode material and adsorbent. In three-electrode system, the specific capacitances were in the range of 96–161 F/g for NCS-T, and the values reached 220–244 F/g for NCSNH3-T at 0.2 A/g in 1 M H2SO4 electrolyte, it's the combination of electric double layer capacitors and faradaic pseudocapacitance. The CO2 capture capacities were 51–141 mg/g for NCS-T and 180–243 mg/g for NCSNH3-T, due to the developed micropores and ultramicropores. The results suggest that NCSNH3-T can be a candidate as both electrode material and adsorbent.

In this work, Mo-MCM-41, Zr-MCM-41, Sn-MCM-41 and Ti-MCM-41 mesoporous molecular sieves were successfully synthesized via hydrothermal synthesis. An acidic group (SO42−, PTSA etc.) was introduced into the mesoporous molecular sieves to obtain modified mesoporous molecular sieve catalysts. The XRD, N2 absorption–desorption isotherms, FT-IR and Py-IR results reveal that PTSA/ZrO2/Mo-MCM-41 had a mesoporous molecular sieve structure containing a large number of acidic centers. The PTSA/ZrO2/Mo-MCM-41 catalyst illustrated superior catalytic performance for synthesis of rosin methyl ester and the esterification rate was 88.2% under the optimized conditions. At the same time, the PTSA/ZrO2/Mo-MCM-41 catalyst has excellent stability and can be recycled and reused with negligible loss in activity over six cycles.

A new type of Pd@mSiO2 composite nanospheres with controlled pore structure, consisting of internal Pd cores and controlled mesoporous silica shells, has been prepared by a facile one-pot method. The thickness and pore size of the shell could be easily tuned by changing the amounts of TEOS and the hydrophobic block length, respectively, during synthesis. In this perspective, the effects of CTAB concentration, pH, and TEOS concentration on the monodisperse sphere morphology of Pd@mSiO2 nanoparticles (NPs) were investigated. In addition, a nucleation mechanism was proposed. Hydrogenation of nitrobenzene to aniline was used as a model reaction to discuss the effect of pore size on the transport rate of the reactants and the product selectivity in metal-catalyzed hydrogenation. The catalysts exhibited a high conversion rate and significantly enhanced stability, leading to a higher recyclability without loss of catalytic activity compared to conventional supported catalysts and commercial catalysts.

The major limitation of classic biphasic ionic liquid (IL) catalysis is the heavy use of solvent ILs, which not only violates green chemistry principles but also even worsens catalytic efficiency. So it has always been a challenge finding ways to use ILs more efficiently, economically, and greenly to construct highly effective and long term stable IL catalytic systems. In this work, we synthesized a class of room temperature phosphine-functionalized polyether guanidinium ionic liquids (RTP-PolyGILs) by a convenient ion exchange reaction of polyether guanidinium ionic liquids (PolyGILs) with phosphine-sulfonate ligands based on the concept of the integration of both the phosphine ligand and IL. The resulting RTP-PolyGILs existed as liquids at room temperature and possessed dual functions of both the phosphine ligand and solvent IL; therefore they could both form catalysts by complexing with transition metals and act as catalyst carriers, thus achieving the integration of phosphine ligands with ILs both in structure and properties. Based on the unique properties of these multi-functional integrated RTP-PolyGILs, we constructed a highly effective homogeneous catalysis-biphasic separation (HCBS) system for Rh-catalyzed hydroformylation of higher olefins using only a catalytic amount of RTP-PolyGILs (equivalent to 0.025–0.4 mol% of 1-alkenes). Our HCBS system could be flexibly regulated with regard to catalytic performance (activity and linear selectivity) by changing the structure or type of the sulfonated ligand anion on RTP-PolyGILs. Specifically, it presented a TOF value of 3000–26 000 h−1 and a linear selectivity of 68%–98% (corresponding to the l/b ratio of 2.2–37.5) with a total turnover number (TTON) of 11 000–45 000 and an extremely low Rh leaching of only 0.02–0.4 ppm. Therefore, the HCBS system can effectively combine the advantages of both homogeneous (high activity and good selectivity) and biphasic catalysis (easy catalyst separation). We additionally extended the application of the HCBS system to the hydrogenation of olefins to demonstrate the universality of the RTP-PolyGILs in catalytic reactions.

Mesoporous carbon (MC) was prepared by the nano-MgO template method and used as a support for the preparation of a Pt-based reductive alkylation catalyst. N2 physical adsorption–desorption, scanning electron microscopy, transmission electron microscopy and X-ray diffraction were used to characterize the carbon supports and supported Pt catalysts. The effects of the pore structure of the Pt/MC catalyst on its performance for reductive alkylation of p-aminodiphenylamine with methyl isobutyl ketone were investigated. The results show that the surface area and pore structure of the MgO-templated mesoporous carbons can be modulated directionally by varying the size of nano-MgO particles and the MgO/PF mass ratio. The catalytic activity and stability of the catalysts for N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine synthesis increases with an increase in the pore size of the mesoporous carbons. Complete conversion of p-ADPA and 100% selectivity to 6PPD were obtained over Pt/MC50(1/1) within 4 hours, which could maintain a high catalytic activity after being reused 10 times. The characterization results indicate that there was an obvious decrease in the BET specific surface area, pore volume and Pt specific surface area of all used catalysts compared with the fresh catalysts, and the trend was more obvious with the decrease of catalyst pore size, which should be the primary reason for the degradation of catalytic performance.

A series of post-crosslinked resins were synthesized from macroporous chloromethylated styrene-divinylbenzene copolymer by controlling post-crosslinked reaction conditions. Adsorption study towards aniline showed that the three resins, ST-DVB-WH5, ST-DVB-WH6, and ST-DVB-WH7, prepared at different temperatures, and which had nearly identical static adsorption capacity, displayed great disparity in kinetic behavior. The rate constant of ST-DVB-WH7 by the pseudo-first-order model was 1.50 and 1.19 times higher than that of ST-DVB-WH5 and ST-DVB-ST-DVB-WH6. Further analysis of the diffusion model showed that the three resins exhibited different diffusion rates due to the difference in oxygen content and pore structure of each resin. The results showed that the adsorption capacity was mainly decided by the pore volume within 1.14 and 3.42 nm and the adsorption rate was mainly decided by the oxygen content of the resin. In addition, as the best synthetic resin for aniline adsorption, the equilibrium adsorption capacity of ST-DVB-WH7 was 1.57 times and 1.44 times higher than that of H-103 and NKA-II, respectively.

In this study, a series of polystyrene-divinylbenzene resins with precise physical structure regulation and chemical modification were successfully synthesized. The regulation of Friedel–Crafts reaction conditions resulted in several physical resins with various BET surface areas and pore structures, while the adsorption of 1,3-propanediol revealed that the molecular size and other physical properties exhibited a moderate contribution to the adsorption of hydrophilic compounds. The adsorption processes between 1,3-propanediol and nitrogen, oxygen and boron functional group modified resins were further explored, and boronic acid modified resins named PS-3NB and PS-SBT exhibited higher adsorption capacities than commercial resin CHA-111. The adsorption capacity of PS-3NB and PS-SBT reached 17.54 mg g−1 and 17.23 mg g−1, respectively, which were 37% and 35% higher than that of commercial resin CHA-111. Furthermore, the adsorption mechanism demonstrated that the content of boronic acid, solution pH and adsorbate hydrophobicity were the primary adsorption driving forces. Herein, we provided a method to modify polystyrene-divinylbenzene materials with boronic acid to selectively adsorb hydrophilic polyols via the specific affinity between boronic acid and diol molecule.

In this study, a versatile cellulose conductive hydrogels with outstanding mechanical properties, rapid self-healing performance, and excellent thermal sensitivity were successfully fabricated. The tensile strength and toughness of the gels gradually increased to 249 kPa and 1.57 MJ/m3, respectively, and the healing efficiency of the hydrogels quickly reached 96.3% within 60 min. Importantly, the hydrogels exhibited a broad strain window (0–2066%) with a gauge factor ranging from 0.22 to 6.7, which could monitor of both obvious and subtle motion of the human body with high sensitivity and good repeatability. Moreover, the sensors also possessed good thermal sensitivity in the 0% and 400% state, and the response of the gel sensors increased from 8.3 to 87.9 when the temperature was increased from 35 to 85 °C. This study provides inspiration for the development of biocompatible and multifunctional cellulose-based wearable sensors with excellent mechanical, strain and temperature sensing and self-healing properties.

A new group of basic species, CaO(SrO and BaO), supported on mesocellular siliceous foam (MCF) has been prepared and used for catalyzing glycolysis of poly(ethylene terephthalate), or PET. The physicochemical properties, structural features and catalytic activities of CaO(SrO, BaO)/MCF in glycolysis of PET processes were thoroughly evaluated. The results showed that CaO/MCF catalyst containing 12 wt% of CaO exhibited higher activity, which was attributed to effective dispersion of CaO and favorable transport of reactants on the 3D open porous structure of MCF. Under optimal conditions, 100% PET conversion and over 80% yield of bis(2-hydroxyethyl) terephthalate with high purity were obtained. For comparison, the activity of 12%CaO/MCF was also superior than 12%CaO/SBA-15 for the glycolysis of PET. Moreover, the 12%CaO/MCF catalyst exhibited excellent stability, and could be reused for five cycles without significant decrease in activity. Combined with the kinetic studies in the presence of 12%CaO/MCF, a possible catalytic mechanism was proposed.

The development of efficient and green protocol for recycling of waste plastics is of great significance in terms of “sustainable society” and “green chemistry” concepts. Several ionic liquids (ILs) with different acidity–basicity and structures were one-step synthesized and characterized. They were applied to alcoholysis of polycarbonate (PC) without metal and solvent. The IL structures and reaction conditions were optimized. Moreover, the alcohol scopes and catalyst reusability were evaluated. The results showed that 100% PC conversion and 99% bisphenol A (BPA) yield were obtained by using [HDBU][LAc] catalyst, and the [HDBU][LAc] could keep high-activity after using for six times under the optimized conditions. Finally, the possible reaction mechanism was proposed via the FT-IR and NMR analysis technique.

A new and environmental friendly route has been developed to hydrogenate α-pinene to cis-pinane. The α-pinene was hydrogenated using ruthenium (Ru) nanoparticles that were stabilized by modified carboxymethyl cellulose in aqueous medium. The conversion of α-pinene reached 96.6% and the selectivity of cis-pinane was 98.4%. Ru nanoparticles could be recycled 18 times. Ru nanoparticles and micelles were characterized by transmission electron microscopy (TEM), confocal laser scanning microscopy (CLSM), dynamic light scattering (DLS), X-ray diffraction (XRD), and other detection techniques. Ru nanoparticles (3.2 nm) had a good stability and uniform distribution, the reaction was divided into micelles that appeared to act as “microreactors”, and the micelle size was increased in the absence of sodium carbonate. The good stability of the Ru nanoparticles could be attributed to electrostatic and steric stabilization.

Fe3O4@C supported ultrasmall and highly monodisperse ruthenium (Ru) nanoparticles (Ru/Fe3O4@C) were prepared as novel nanocatalysts for hydrogenation reactions. The catalysts displayed high activity for the hydrogenation of rosin to form hydrogenated rosin with extraordinary selectivity. The role of controlled carbon size on the catalytic properties of the catalysts was studied. The Ru/Fe3O4@C catalyst can be easily separated from the organic solvent by applying an external magnetic field and the separated Ru/Fe3O4@C can simply and efficiently used in ten consecutive runs without significant decrease in activity. Significantly, Ru/Fe3O4@C nanocatalysts showed a wide substrate scope for hydrogenation reactions under mild conditions.

Abundant natural renewable resource, α-pinene, has been transformed into a reaction mixture containing about 60% its dimers and 40% its isomers via dimerization/isomerization over a novel Bronsted-Lewis double acidic heteropoly inorganic-organic salt, Mn0.5[MIMPS]2PW12O40. The reaction mixture can be treated as a biomass high energy density fuel with a density of 0.90 g/mL (20 °C), a freezing point of −66 °C, a viscosity of 26.5 mm2/s (−10 °C) and a heat value of 39.7 MJ/L. The solid catalyst, Mn0.5[MIMPS]2PW12O40, has been synthesized via the replacement of protons in neat phosphotungstic acid by both metal cations Mn2+ and organic intermediate 3-(N-methylimidazole) propane sulfonates (MIMPS), and characterized by Fourier-transform infrared and pyridine adsorption Fourier-transform infrared spectroscopy, X-Ray Diffraction, Thermal-gravity Analysis, Brunauer-Emmett-Teller (BET) surface area analysis, Inductively Coupled Plasma Atomic Emission Spectroscopy and potentiometric titration technology. In addition, easy recovery and steady reusability of this catalyst have been demonstrated by an eight-run recycling test.

A series of novel polyether-based Bronsted acidic ionic liquids (ILs) have been synthesized, which contain both a polyoxyethylene (POE) chain and a sulfonic group ( SO 3 H). The prepared ILs can well dissolve trifluoromethanesulfonic acid (TfOH), and IL/TfOH mixture has good intermiscibility with the reactants of isobutane and isobutene. Then, a new IL/TfOH catalytic system for the preparation of alkylate gasoline has been developed. The advantages of the new catalytic system are high selectivity for C 8 -alkylate product and the recyclability of TfOH catalyst. Under the optimal catalytic conditions (using the IL with the polymerization degree n = 75, IL/TfOH(v/v) = 5, reaction temperature 60 °C, reaction time 30 min, and stirring rate 800 rpm), the C 8 -selectivity can reach 80%, and above 95% of C 8 -alkylate product is trimethylpentane (TMP). Therefore, the new IL/TfOH catalytic system can afford high-quality alkylate gasoline. In addition, the conversion of isobutene and C 8 -selectivity both have gradually a little drop during 6 recycles, which should attribute to a little loss of TfOH in every recycle.

A deep eutectic solvent with strong Bronsted acidity was prepared easily by choline chloride and trifluoromethanesulfonic acid. The obtained [ChCl][TfOH]2 catalyst which was characterized by FT-IR, 1H NMR and TG, possessed greatly enhanced stability than trifluoromethanesulfonic acid, and exhibited excellent catalytic performance in benzylation with benzyl alcohol. Especially, the prepared [ChCl][TfOH]2 catalyst could dissolve into the reactants to realize homogeneous catalysis, and then self-separate from the organic phase after reaction due to the entire consumption of benzyl alcohol. As a result, the catalyst could be recovered and reused simply for six-runs without noticeable loss of catalytic performance.

Calcium-fuctionalized mesoporous γ-alumina was synthesized for alcoholysis of Polycarbonate (PC). Compared with the traditional homogeneous depolymerization process, such alcoholysis process presents a higher capacity, more time effective and environmental benign. Benefited from such mild condition, the operation can be continuously performed without any equipment corrosion occurring. Such mesoporous γ-alumina composite can be synthesized in one step sol-gel method by utilizing aluminium isopropoxide, calcium nitrate as basic precursors and Pluronic P123 as a structure directing agent. One-pot method can effectively avoid the loss of active components namely Ca species in comparison to conventional impregnation method. As for the reasons leading to such great degradation efficiency, one is the strengthened basicity supplied by the introduction of Ca species, the other is the typical mesoporous nanostructure which is beneficial for improving the kinetic driving force, in other words, the synergistic effects make the superior work efficiency for PC degradation. The operation conditions were optimized including the molar ratio of Ca/Al, temperature, methanol and tetrahydrofuran (THF) dosage and Ca-Al2O3 dosage. Under such optimum conditions, the conversion of PC was approximately 100 wt.% . The catalyst endures a long recycle without any obvious inactive tendency as well as remained mesoporous structure. The transesterification kinetic behaviors were also investigated with an activation energy of 153 kJ/mol. In addition, a plausible catalysis mechanism for the methanolysis of PC was proposed.

Ni-doped spherical mesoporous carbon catalysts (Ni/C n ) were prepared via one-pot hydrothermal carbonization of microcrystalline cellulose (MCC) with nickel acetate as the Ni source. This exhibited a high conversion rate for p-nitrophenol (PNP) hydrogenation to p-aminophenol (PAP). The obtained catalysts contained 0.87–6.84 wt% nickel content that primarily consisted of metallic nickel, with a small amount of nickel oxide. The Ni additive could be beneficial in the formation of the mesoporous structure. The results showed that as the Ni content increased, the mesoporous percentage increased. The doped Ni was monodispersed particles added into the carbon skeleton with an average particle size of 23.6 nm. They were surrounded by ordered striped carbon that exhibited a graphite-like structure. The catalytic hydrogenation reaction took place at normal temperatures and pressure exhibited high catalytic activity. The degradation rate of PNP reached 99.7% when 0.30 g of the Ni/C0.2-900 catalysts was used for a reaction time of 40 min, with corresponding apparent rates constant of 1.68 × 10−3 S−1, apparent activation energy of only 43.25 kJ/mol.

Using a simple one-pot solvothermal method, binary metal oxide, magnetic and hollow ZnFe2O4 nanospheres functionalized with 5,10,15,20-tetrakis(4-carboxylphenyl)-porphyrin (Por–ZnFe2O4 HSs) were prepared and subsequently applied as a substitute for natural peroxidase. The Por–ZnFe2O4 HSs were characterized using powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). In comparison with bare ZnFe2O4 HSs, Por–ZnFe2O4 HSs exhibit enhanced intrinsic peroxidase-like activity. They demonstrate a fast colorimetric response to H2O2 with a detection limit as low as 0.86 μM. The catalytic mechanism of the system was proved to be a hydroxyl radical mechanism using electron spin resonance (ESR). By combining the Por–ZnFe2O4 HSs-catalyzed reaction and the enzymatic oxidation of glucose with glucose oxidase, a colorimetric platform for glucose detection was established. The Por–ZnFe2O4 HSs/glucose oxidase (GOx)/TMB system shows a good response toward glucose with a detection limit of 5.5 μM. Therefore, such nanocomposites have promising applications in biomimetic catalysis and environmental monitoring.

Chemical recycling of bio-based polymer poly(3-hydroxybutyrate) (PHB) by methanolysis was discussed in detail from the perspective of biological refining. The results of methanolysis transformed PHB into ester monomer successfully by using some ionic liquids. PHB was depolymerized into methyl 3-hydroxybutyrare (M3HB) at lower degradation temperatures in the presence of Bronsted-Lewis acidic ionic liquid 1-(3-sulfonic acid)-propyl-3-methylimidazole ferric chloride ([MIMPS]FeCl4) as catalyst. Obtained M3HB from this reaction can be used in many areas, which is consistent with the principles of sustainable development. Then, the influences of reaction parameters on PHB methanolysis were investigated and the optimum conditions were obtained. Under the optimum conditions, the conversion of PHB and yield of M3HB was 98.5% and 87.4%, respectively. This catalyst could be recycled up to 6 times with no apparent decrease in catalytic activity. At the same time, the methanolysis mechanism of PHB is proposed through the experiments. In addition, kinetic study indicated that this reaction was pseudo-first-order reaction with activation energy of 24.74 kJ/mol.

Polyvinyl alcohol (PVA)-stabilized ruthenium nanoparticles in water were synthesized and characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and confocal laser scanning microscope (CLSM). The Ru-PVA catalyst was highly effective for the hydrogenation of α-pinene, exhibiting higher selectivity for cis-pinane as well as high conversion. The selectivity could reach approximately 99%. The catalyst phase could be recycled at least eight times without obvious loss in the catalytic activity and selectivity. Furthermore, both the preparation of catalyst and hydrogenation of α-pinene were under mild experimental conditions. Using water as the reaction medium and PVA as the stabilizing agent made the hydrogenation process environmentally friendly. This catalytic system may also be used to convert a range of cyclenes and long chain alkenes, in particular aromatic compounds to corresponding hydrogenated products.

The alkylation reaction of isobutane with 2-butene to yield C8-alkylates was performed using Bronsted–Lewis acidic ionic liquids (ILs) comprising various metal chlorides (ZnCl2, FeCl2, FeCl3, CuCl2, CuCl, and AlCl3) on the anion. IL 1-(3-sulfonic acid)-propyl-3-methylimidazolium chlorozincinate [HO3S-(CH2)3-mim]Cl-ZnCl2 (x=0.67) exhibited outstanding catalytic performance, which is attributed to the appropriate acidity, the synergistic effect originating from its double acidic sites and the promoting effect of water on the formation and transfer of protons. The Lewis acidic strength of IL played an important role in improving IL catalytic performance. A 100% conversion of 2-butene with 85.8% selectivity for C8-alkylate was obtained under mild reaction conditions. The IL reusability was good because its alkyl sulfonic acid group being tethered covalently, its anion [Zn2Cl5]− inertia to the active hydrogen, and its insolubility in the product. IL [HO3S-(CH2)3-mim]Cl-ZnCl2 had potential applicability in the benzene alkylation reaction with olefins and halohydrocarbons.

A novel Bronsted-Lewis acidic catalyst, Hf0.5[TEAPS]PW12O40, has been prepared by the replacement of protons in neat phosphotungstic acid with both organic and metal cations and characterized by FT-IR, Py-IR, XRD, TG-DTG, ICP-AES, BET, elemental analysis and n-butylamine potentiometeric titration techniques. This hybrid heterogeneous catalyst with both Bronsted and Lewis acidity can efficiently promote the conversion of dibenzyl ether, the self-condensation product of benzyl alcohol, to the benzylation products, as well restrain the polybenzylation of aromatics. As a result, it exhibits excellent catalytic activity and selectivity in the benzylation of p-xylene with clean benzylation reagent benzyl alcohol. Thus, an environmentally friendly route for the benzylation reaction of p-xylene with high atomic economy has been developed by this reusable Hf0.5[TEAPS]PW12O40 catalyst.

Bio-jet fuel synthesis is a promising way to upgrade the value of lignocellulose and contributes to the sustainable development. Presently the property of bio-jet fuel is weakened by single component produced using pure feedstock and water produced in the reaction leading to acid leaching. Therefore, we synthesized a hydrophobic acid resin (R-x) and used it to catalyze lignocellulose-derived mixture upgrading to high-performance bio-jet fuel blending, where R-x shows better activity than Amberlyst-15, Nafion-212 and Hβ with 75.4% of product yield obtained in co-conversion of lignocellulosic derivatives. The better activity of R-x is ascribed to the strong acid, big acid concentration, large surface area and especially super hydrophobicity resulting as R-x recycled steadily in consecutive 5 runs. After hydrodeoxygenation, jet fuel blending with high density and excellent freezing point better than JP-7 was obtained. This work demonstrates an efficient catalyzing method to synthesize high-performance jet fuel by co-conversion of lignocellulosic derivatives.

To increase the yield of iso-hexane and inhibit cracking of isomers in hydroisomerization of n-hexane, hierarchical SAPO-11 was employed to prepare Pt/SAPO-11 catalysts. Hierarchical SAPO-11 was prepared with fluoride ions via an eco-friendly grinding synthesis method. Fluoride ions incorporate into zeolitic framework to form T-F (T = Al and Si) bonds and inhibit the isomorphous substitution of silicon atoms. It endows SAPO-11 intra- and inter-crystalline mesopores and decreases the amount of acid sites. A low diffusion resistance and decreased acidity of catalysts are unfavorable for a subsequent isomerization and cracking of mono-branched iso-hexane. Compared to microporous SAPO-11, catalysts with hierarchical SAPO-11 have a higher selectivity of iso-hexane at a similar conversion. It is reflected as comparable TOFn-C6 = 21.3 h−1 and TOFiso-C6 = 19.9 h−1. Results above propose a facile and green approach to prepare SAPO-11 molecular sieves. The in-situ regulation method of Pt/SAPO-11 is a reference for other types of SAPO supported catalysts.

High density carbon composite (AC3/G) with hierarchical porous structure is prepared by packing biomass-based carbon (ACs) into graphene network (rGO), via microwave-assisted hydrothermal treatment followed by capillary evaporation-induced drying. Graphene oxide is reduced during the treating process and acts as frame network to embed the ACs. ACs are packed into the network with a density up to 1.23 g/cm3 for AC3/G. ACs can prevent the agglomeration of rGO, and channels formed between rGO sheets and ACs facilitate the hierarchical porous structure. When AC3/G is used as a binder and conductive additive-free electrode in the three-electrode system, a high volumetric capacitance of 775 F/cm3 at 0.5 A/g is achieved with excellent cycling stability of 97.05%. When assembled into a flexible solid-state supercapacitor device with lignin hydrogel electrolytes, the high-density electrode delivers high volumetric and gravimetric energy densities of 9.7 W h/L and 7.9 W h/kg, with volumetric capacitance of 326 F/cm3 at 0.5 A/g. Remarkably, the study paves a new idea for preparation of energy devices with high volumetric performance using biomass resources.

2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (BINAP) is a widely used chiral phosphine ligand, and the sulfonated BINAP is one of the important water-soluble BINAP derivatives. In this article, we report an improved oleum sulfonation method for the synthesis of the high-purity 5,5′-disulfonato-(S)-BINAP ligand with an industrially acceptable high yield. By optimizing the sulfonation conditions and improving the workup process, the yield of 5,5′-disulfonated products was enhanced to 73 %. Furthermore, an acetonitrile extraction protocol was developed for the purification of sulfonated products by efficiently removing phosphine oxides, by which the content of phosphine oxide can be controlled below 3 %. The structure of 5,5′-disulfonato-(S)-BINAP was characterized with the elemental analysis, FT-IR, 1H NMR, 13C NMR, 31P NMR, 1H-1H COSY, 1H-13C HSQC, 1H-13C HMBC, and HR-MS, which unambiguously confirmed that the sulfo groups are introduced at the 5,5′-position of the binaphthyl ring skeleton in (S)-BINAP. The prepared high-purity 5,5′-disulfonato-(S)-BINAP was evaluated in the Ru-catalyzed asymmetric hydrogenation of β-keto esters, which exhibited high catalytic activity, enantioselectivity and excellent catalytic stability.

Palladium (Pd) nanoparticles (NPs) stabilized by tri-block copolymer polyoxyethylene–polyoxypropylene–polyoxyethylene (P123) micelles were synthesized in water using a hydrogenation reduction method. Well-dispersed P123 micelles in the aqueous phase favored the stabilization of Pd NPs. The P123–Pd micellar catalyst was first applied in the liquid phase hydrogenation of nitrobenzene (NB), showing excellent catalytic activity, and the only reaction product detected was aniline (AN). Using water as the reaction medium and under mild conditions, both the preparation of catalysts and NB hydrogenation were convenient and environmentally friendly. Under the optimal conditions, the isolated catalyst phase could be recycled at least five times, and the catalytic activity and selectivity remained unchanged. A reaction scheme was suggested. First-order kinetics was determined at 3.0 MPa hydrogen pressure and temperature 30–75 °C, and the activation energy was 40.18 kJ mol−1. This work provides an environmentally benign and effective method for the hydrogenation of NB to AN.

Structural properties and functional groups variations of hydro-products from hydrothermal carbonization (HTC) of loblolly pine at 180, 200, 220, 240 and 260 °C were investigated in this paper. More than 50% fixed carbon content can be obtained in solid products, indicating HTC is a valued carbon sequestration method. The Higher Heating Value (HHV) of the solid residue from 260 °C reached 30.74 MJ/kg, nearly 1.53 times that of untreated pine. Higher temperature benefit for the generation of condensed aromatic structure especially at 240 °C, while 260 °C more conductive to etherification and aryl-condensation substitution reaction. Solid products from HTC were condensed carbon materials consist of lignin/pseudo-lignin and furfural structures with low carbonyl and carboxyl content, protonated carbon percentage in aromatic structure is higher than un-protonated carbon in aromatic structures, methoxy content reduced at higher temperature while aliphatic side-chains content increased; Liquid chemicals were water-soluble products consist of condensed polyaromatic structure with an elevated content of carbonyl and carboxyl groups, un-protonated carbon in aromatic structures show higher percentage, methoxy content increased at higher temperature while aliphatic side-chains content decreased, free phenol hydroxyl are richer than C 5 substituted condensed phenolic OH.

Methanolysis of poly (lactic acid) (PLA) was studied using Lewis acidic ionic liquid [Bmim]FeCl4 as a catalyst and the qualitative analysis indicated that the main product was methyl lactate. Compared with ionic liquid [Bmim]Cl, FeCl3 and other traditional catalysts, the Lewis acidic ionic liquid showed much better catalytic activity in the methanolysis of PLA. Significantly, the conversion of PLA and the yield of methyl lactate were 99.3 and 94.6% respectively with low dosage of catalyst (the molar ratio of [Bmim]FeCl4 to LA unit is 0.0025:1). The lewis acidic ionic liquid [Bmim]FeCl4 could be recycled up to 6 times and FT-IR results showed that the spectrum of the reused catalyst was similar to that of the fresh one. Moreover, a possible mechanism of the methanolysis of PLA catalyzed by [Bmim]FeCl4 was proposed. The kinetics of PLA methanolysis was also investigated under the optimum conditions and the results indicated that it was a first-order kinetic reaction with activation energy of 21.28 kJ mol−1. The methanolysis of poly (lactic acid) (PLA) was studied using Lewis acidic ionic liquid [Bmim]FexCl3x+1 (x>1) as catalyst. The effects of reaction temperature, reaction time, ionic liquid dosage and methanol dosage on methanolysis results were examined. The reusability of ionic liquid in the methanolysis of PLA was investigated, and the results showed that it could be recycled up to 6 times with no apparent decrease in the conversion of PLA and yield of methyl lactate. The reaction mechanism and kinetics of PLA methanolysis catalyzed by [Bmim]FexCl3x+1 were also investigated. Moreover, a possible catalysis mechanism of the methanolysis of PLA was proposed.

The structural characteristics of products derived from the hydrothermal carbonization (HTC) of loblolly pine (LP) and straw grass (SG) were investigated via solid-state cross-polarization/magic angle spinning nuclear magnetic resonance (CP/MAS 13C NMR), heteronuclear single-quantum correlation nuclear magnetic resonance (HSQC-NMR), and solution 13C NMR and 31P NMR techniques. Results revealed that after HTC, hydrochars from both LP and SG mainly consisted of a combination of lignin, furfural, and condensed polyaromatic structures with a high level of fixed carbon content and higher heating value (HHV). Hydrochar from LP exhibited a higher aryl to furan ratio, and those from SG contained more aliphatic functional groups. Solution 13C NMR and HSQC revealed that both liquid chemicals were condensed polyphenolic structures with aliphatic groups that exist mainly in the form of side chains. Although the LP products exhibited a higher proportion of aromatic structures, the types of polyphenol and aliphatic C–H...

In this study, we prepared a new visible light induced photo-catalyst Ag/FeOOH/SBA-15 using a facile deposition–photo-reduction method. Transmission electron-microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and N2 adsorption–desorption isotherm techniques were used to study the morphology form, structure and the valence state of the nano-materials. According to UV–vis absorption spectra, Ag/α-FeOOH/SBA-15 had a better response to visible light than α-FeOOH/SBA-15. Phenol of 20 mg/L was used as a representative organic pollutant to evaluate the photo-catalytic efficiency of Ag/α-FeOOH/SBA-15 and α-FeOOH/SBA-15 catalysts in visible light (λ > 400 nm), 93% and 78% of phenol degradations could be achieved over Ag/α-FeOOH/SBA-15 and FeOOH/SBA-15 catalysts with 5 mmol/L H2O2 in 4 h. Moreover, the mechanism suggested that the high photo-catalytic activity is due to the charge separation, the surface plasmon resonance of metallic Ag particles in the region of visible light and generation of hydroxyl radical. This work is of importance in theory research and practical application of complex nano-composite.

The catalytic hydrogenation of 2-ethylhexenal was investigated over Pd supported on ZrO2, CeO2, Al2O3, MCM-41, MAS-7 and SBA-15. The activities and the selectivities of the catalysts were strongly affected by the nature of the support. Pd/ZrO2 had an excellent catalytic performance for the hydrogenation. The superior dispersion of Pd on the support ZrO2, and the stable structure of active components on ZrO2 as well as the synergistic effect of the bifunctional metal-support interaction enhanced the catalytic performance of Pd/ZrO2. The conversion of 2-ethylhexenal and the selectivity for 2-ethylhexanol were 100 and 99.1% respectively when the reaction was carried out at 240 °C for 7 h. The product was easily separated from the catalyst and the catalyst was of good reusability when it was repeated six times. In addition, the aggregation of Pd nanoparticles and the coking of ZrO2 the catalysts were the main cause for the catalyst deactivation.

The alkylation reaction of thiophenic sulfides with olefin in model fluid catalytic cracking (FCC) gasoline has been carried out over many kinds of organic-inorganic heteropoly acids, H 3 PW 12 O 40 , and AlPW 12 O 40 . The results have showed that organic-inorganic heteropoly acid [Bmim]H 2 PW 12 O 40 exhibits the best catalytic activity for the alkylation of thiophene (T), 2-methyl thiophene (2-MT) and 3-methyl thiophene (3-MT). Many effect factors for the alkylation of thiophenic sulfides catalyzed by [Bmim]H 2 PW 12 O 40 have been fully investigated. Under the optimal reaction conditions (the catalyst dosage 1 wt%, reaction temperature 120 °C, reaction time 40 min and the stirring rate 500 rpm), the conversions of T, 2-MT and 3-MT all can nearly reach up to 100%. [Bmim]H 2 PW 12 O 40 has also exhibited good stability and recyclability. The conversions of thiophenic sulfides nearly remain unchanged during 11 recycles of [Bmim]H 2 PW 12 O 40 . Apparent reaction kinetics for the alkylation of thiophenic sulfides is studied. The alkylations of T, 2-MT and 3-MT all show the pseudo-first-order kinetic characteristics. The order of the reaction rate constants of three thiophenic sulfides is 2-MT > 3-MT > T. However, the calculated apparent activation energies of T, 2-MT and 3-MT are 62, 45.54 and 71.33 kJ/mol, respectively. So, the order of apparent activation energies is 3-MT > T > 2-MT.