Selective Catalytic Epoxidation-Hydration of α-Pinene with Hydrogen Peroxide to Sobrerol by Durable Ammonium Phosphotungstate Immobilized on Imidazolized Activated Carbon.

It is presented that the activated carbon was carboxylated with hydrogen peroxide and then acylated with 2-methylimidazole to prepare the porous carbon support with a surface imidazolated modification. Through the adsorption of phosphotungstic acid on the fundamental site of an imidazolyl group and then adjusting the acid strength with the ammonia molecule, a catalytic carbon material immobilized with ammonium phosphotungstate (AC-COIMO-NH4PW) was obtained, which was used to catalyze a one-pot reaction of convenient α-pinene and hydrogen peroxide to sobrerol. The bifunctional active site originated from the dual property of ammonium phosphotungstate, as the oxidant and acid presenting a cooperatively catalytic performance, which effectively catalyzes the tandem epoxidation-isomerization-hydration of α-pinene to sobrerol, in which the solvent effect of catalysis simultaneously exists. The sobrerol selectivity was significantly improved after the acid strength weakening by ammonia. Monomolecular chemical bonding and anchoring of ammonium phosphotungstate at the basic site prevented the loss of the active catalytic species, and the recovered catalyst showed excellent catalytic stability in reuse. Using acetonitrile as the solvent at 40 °C for 4 h, the conversion of α-pinene could reach 90.6%, and the selectivity of sobrerol was 40.5%. The results of five cycles show that the catalyst presents excellent stability due to the tight immobilization of ammonium phosphotungstate bonding on the imidazolized activated carbon, based on which a catalytic-cycle mechanism is proposed for the tandem reaction.

Recent advances on bifunctional catalysts for one-pot conversion of furfural to γ-valerolactone.

γ-Valerolactone (GVL) is one of the most valuable compounds derived from furfural (FAL), which has been industrially produced from agricultural byproducts like corn cobs. It is extremely challenging to synthesize GVL from FAL efficiently via a one-pot cascade reaction due to the need for multiple active sites in a single pot. By focusing on the aspects of one-pot synthesis of GVL from FAL, the authors aim to shed light on the rational design and utilization of environmentally friendly bifunctional catalysts with high efficiency in this reaction. Perspectives regarding future research opportunities in bi- or multi-functional catalysts for one-pot GVL synthesis are also discussed.

Preparation of Activated Carbon-Based Solid Sulfonic Acid and Its Catalytic Performance in Biodiesel Preparation.

With activated carbon as raw material, AC-Ph-SO3H was prepared after oxidation with nitric acid, modification with halogenated benzene and sulfonation with concentrated sulfuric acid. After modified by 10% bromobenzene with toluene as a solvent for 5 h, followed sulfonation with concentrated sulfuric acid at 150°C, the -SO3H content of prepared AC-Ph-SO3H was 0.64 mmol/g. Acid content test, infrared spectroscopy and Raman spectroscopy detection proved that the surface of AC-Ph-SO3H was successfully grafted with -SO3H group. When used as a catalyst for the methylation of palmitate acid, the catalytic performance of AC-Ph-SO3H was explored. When the reaction time was 6 h, the amount of catalyst acid accounted for 2.5 wt% of palmitic acid, and the molar ratio of methanol/palmitic acid was 40, the esterification rate of palmitic acid was 95.2% and the yield of methyl palmitate was 94.2%, which was much better than those of its precursors AC, AC-O, and AC-Ph (both about 4.5%). AC-Ph-SO3H exhibited certain stability in the esterification reaction system and the conversion rate of palmitic acid was still above 80% after three reuses.

Imidazolized Activated Carbon Anchoring Phosphotungstic Acid as a Recyclable Catalyst for Oxidation of Alcohols With Aqueous Hydrogen Peroxide.

Keggin-type phosphotungstic acid (HPW) supported on imidazolyl-activated carbon (AC-COIMI-HPW) catalysts was prepared, which was used to catalyze the oxidation of benzyl alcohol with aqueous H2O2. In the presence of AC-COIMI-HPW, the benzyl alcohol conversion of 90.2% with 91.8% selectivity of benzaldehyde was obtained at 90°C for 6 h in an acetonitrile aqueous solution. The catalyst exhibited an outstanding performance for the oxidation of various benzyl alcohols and aliphatic alcohols. In addition, the catalyst could be easily recovered and reused five times without significant deactivation. The characterization results showed that HPW was chemically bonded on the surface of the carbon material through an ionic bond. It is proposed that the combination of the imidazole cation with the HPW anion could not only tune the redox catalytic properties of the PW anion but also enhance the compatibility of the catalyst in the reaction medium, thereby improving the catalytic performance.

Sulfuric Acid Immobilized on Activated Carbon Aminated with Ethylenediamine: An Efficient Reusable Catalyst for the Synthesis of Acetals (Ketals).

Through the amination of oxidized activated carbon with ethylenediamine and then the adsorption of sulfuric acid, a strong carbon-based solid acid catalyst with hydrogen sulfate (denoted as AC-N-SO4H) was prepared, of which the surface acid density was 0.85 mmol/g. The acetalization of benzaldehyde with ethylene glycol catalyzed by AC-N-SO4H was investigated. The optimized catalyst dosage accounted for 5 wt.% of the benzaldehyde mass, and the molar ratio of glycol to benzaldehyde was 1.75. After reacting such mixture at 80 °C for 5 h, the benzaldehyde was almost quantitatively converted into acetal; the conversion yield was up to 99.4%, and no byproduct was detected. It is surprising that the catalyst could be easily recovered and reused ten times without significant deactivation, with the conversion yield remaining above 99%. The catalyst also exhibited good substrate suitability for the acetalization of aliphatic aldehydes and the ketalization of ketones with different 1,2-diols.

Titania Nanotubes-Bonded Sulfamic Acid as an Efficient Heterogeneous Catalyst for the Synthesis of n-Butyl Levulinate.

The titania nanotubes-bonded sulfamic acid (TNTs-NHSO3H) catalyst was designed and successfully fabricated by the post-synthesis modification method. The as-prepared catalyst was characterized by a variety of characterization techniques, including Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) analysis, and thermogravimetry-differential thermal gravimetry (TG-DTG). The crystal structure of the TNTs still maintained during the modification process. Although the BET surface area was decreased, the amount of Brønsted acid sites can be efficiently fabricated on the TNTs. The catalytic activity of TNTs-NHSO3H was examined for the synthesis of n-butyl levulinate (BL) from levulinic acid (LA) and furfuryl alcohol (FA). A relatively high selectivity (99.6%) at 99.3% LA conversion was achieved for esterification of levulinic acid owing to the strong Brønsted acidity sites. And also, the TNTs-NHSO3H catalyst exhibited a higher reactivity for alcoholysis of FA and the yield of BL reached 90.4% with 100% FA conversion was obtained under the mild conditions.

Production of the 2,5-Furandicarboxylic Acid Bio-Monomer From 5-Hydroxymethylfurfural Over a Molybdenum-Vanadium Oxide Catalyst.

2, 5-Furandicarboxylic acid (FDCA) is an important bio-monomer that can potentially replace terephthalic acid to synthesize degradable polyesters. Efficient selective oxidation of biomass-based 5-hydroxymethylfurfural (HMF) to FDCA has been a significant but challenging work in the past decades. In this study, a novel molybdenum-vanadium oxide (Mo-V-O) catalyst was prepared by a simple method and showed excellent catalytic activity for converting HMF to FDCA. A high FDCA selectivity of 94.5 and 98.2% conversion of HMF were achieved under the optimal conditions with tert-butyl hydroperoxide as the oxidant. FT-IR, SEM, XRD and TG were applied to investigate the properties of Mo-V-O catalyst. After fitting experimental data with the first-order kinetics equation, the evaluated apparent activation energies of HMF oxidation were obtained. The experimental design and study were carried out by response surface methodology (RSM) to test the effects of reaction conditions on the catalytic process.

Selective Catalytic Isomerization of ß-Pinene Oxide to Perillyl Alcohol Enhanced by Protic Tetraimidazolium Nitrate.

A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of ß-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO3 ]4 under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss.

Ternary catalyst Mn-Fe-Ce/Al2O3 for the ozonation of phenol pollutant: performance and mechanism.

In this study, a novel ternary catalyst Mn-Fe-Ce/Al2O3 was synthesized by co-impregnation method, and was characterized by XRD, SEM, XPS, and FTIR. The catalytic performance of this ternary catalyst was evaluated in the heterogeneous catalytic ozonation of phenol pollutants and it improved the removal rate and mineralization degree of phenol pollutants. The changes of dissolved ozone in water and the TBA experiment proved that the ternary catalyst could accelerate the decomposition of ozone into hydroxyl radicals, thus accelerating the oxidation of phenol. Phosphate experiments and surface hydroxyl density measurements proved that surface hydroxyl was the active site of the catalyst. XPS analysis showed that the ternary catalysts accelerated electron transfer through the redox cycles of Mn2+-Mn3+-Mn4+, Fe2+-Fe3+, and Ce3+-Ce4+, which also contributed to the high catalytic activity. Moreover, the catalyst maintained high catalytic activity after five cycles of use. Therefore, the ternary catalyst was considered an efficient and promising catalyst for catalytic ozonation system.

Efficient synthesis of 5-ethoxymethylfurfural from biomass-derived 5-hydroxymethylfurfural over sulfonated organic polymer catalyst.

Herein, we investigated catalytic potential of a functionalized porous organic polymer bearing sulfonic acid groups (PDVTA-SO3H) to the etherification of 5-hydroxymethylfurfural (HMF) to 5-ethoxymethylfurfural (EMF) under solvent-free conditions. The PDVTA-SO3H material was synthesized via post-synthetic sulfonation of the porous co-polymer poly-divinylbenzene-co-triallylamine by chlorosulfonic acid. The physicochemical properties of the PDVTA-SO3H were characterized by FT-IR, SEM, TG-DTG, and N2 adsorption isotherm techniques. PDVTA-SO3H had high specific surface area (591 m2 g-1) and high density of -SO3H group (2.1 mmol g-1). The reaction conditions were optimized via Box-Behnken response surface methodology. Under the optimized conditions, the PDVTA-SO3H catalyst exhibited efficient catalytic activity with 99.8% HMF conversion and 87.5% EMF yield within 30 min at 110 °C. The used PDVTA-SO3H catalyst was readily recovered by filtration and remained active in recycle runs.

Visible-Light-Triggered Quantitative Oxidation of 9,10-Dihydroanthracene to Anthraquinone by O2 under Mild Conditions.

The development of mild and efficient processes for the selective oxygenation of organic compounds by molecular oxygen (O2 ) is key for the synthesis of oxygenates. This paper discloses an atom-efficient synthesis protocol for the photo-oxygenation of 9,10-dihydroanthracene (DHA) by O2 to anthraquinone (AQ), which could achieve quantitative AQ yield (100 %) without any extra catalysts or additives under ambient temperature and pressure. A yield of 86.4 % AQ was obtained even in an air atmosphere. Furthermore, this protocol showed good compatibility for the photo-oxidation of several other compounds with similar structures to DHA. From a series of control experiments, free-radical quenching, and electron paramagnetic resonance spin-trapping results, the photo-oxygenation of DHA was probably initiated by its photoexcited state DHA*, and the latter could activate O2 to a superoxide anion radical (O2 .- ) through the transfer of its electron. Subsequently, this photo-oxidation was gradually dominated by the oxygenated product AQ as an active photocatalyst obtained from the oxidation of DHA by O2 .- , and was accelerated with the rapid accumulation of AQ. The present photo-oxidation protocol is a good example of selective oxygenation based on the photoexcited substrate self-activated O2 , which complies well with green chemistry ideals.

Direct cyclohexanone oxime synthesis via oxidation-oximization of cyclohexane with ammonium acetate.

An unexpected cascade reaction for oxidation-oximization of cyclohexane with ammonium acetate was developed for the first time to access cyclohexanone oxime with 50.7% selectivity (13.6% conversion). Tetrahedral Ti sites in Ni-containing hollow titanium silicalite can serve as bifunctional catalytic centers in the reaction. This methodology not only provides a direct approach to prepare cyclohexanone oxime, but also simplifies process chemistry. Various available nitrogen sources, such as ammonium salt and even ammonia can be used as starting materials.

Highly-selective solvent-free catalytic isomerization of α-pinene to camphene over reusable titanate nanotubes.

Titanate nanotubes, prepared by the hydrothermal reconstitution and modification with hydrochloric acid, were tested as solid acid catalysts in the isomerization of α-pinene under solvent free conditions. The results showed that titanate nanotubes have better catalytic properties than titanium dioxide nanoparticles, and the camphene was the main product for α-pinene isomerization. The effects of several reaction variables, such as reaction temperature, catalyst dosage, and reaction time, on the conversion of α-pinene and the selectivity to camphene were examined. The highest conversion was up to 97.8% with selectivity to camphene of 78.5% under the mild reaction conditions, and the catalyst also showed outstanding reusability after four runs. It is proposed that appropriate surface acidic sites and opened nanotubular structures are mainly responsible for the excellent catalytic performance of titanate nanotubes materials.

Polymerization mechanism of 4-APN and a new catalyst for phthalonitrile resin polymerization.

The widely used catalysts for phthalonitrile (PN) resin polymerization are aromatic compounds containing -NH2 because of their high catalytic performances. However, the catalytic mechanisms of these catalysts are not very clear. To understand the mechanisms of them, the widely used autocatalytic catalyst 4-(4-aminophenoxy)-phthalonitrile (4-APN) was studied in this paper. The polymerization process of 4-APN was tracked by a multi-purpose method, and ammonia gas was detected during the cross-linking processing for the fist time. Combined with the online IR results of the curing process of 4-APN, the mechanism of ammonia generation was newly proposed. Based on this mechanism, a new catalyst selection strategy was promoted, which is different from the traditional approach to catalyst selection for PN resin polymerization. According to the new strategy, 1,3-diiminoisoindoline (1,3-DII) was selected as a novel catalyst. The results showed that the new catalyst could not only effectively catalyze the polymerization of PN resin, but also has a lower curing temperature than that of organic amine catalysts and can eliminate the release of ammonia gas and the voids in the products caused thereby. Therefore, the results of this study will give important enlightenment to the development of PN catalysts and the development of PN.

Air-Induced Degradation and Electrochemical Regeneration for the Performance of Layered Ni-Rich Cathodes.

Nickel-rich layered oxides are promising cathodes for power batteries owing to their high capacity and low cost. However, during the production, storage, and application of nickel-rich cathodes, especially in case the Ni content exceeds 70%, their surfaces almost inevitably react with ambient air to form electrochemically inert Li2CO3 and LiOH, leading to significant capacity loss and therefore imposing a significant hurdle to practical applications of nickel-rich cathodes. Here, we reveal surface structures and electrochemical properties of the exposed LiNi0.8Co0.15Al0.05O2 (NCA) cathodes and investigate systematically the impact of exposure humidity, temperature, and time on NCA cathodes. We demonstrate that introduction of a 3.0-4.5 V galvanostatic cycling operation at initial cycles can remarkably regenerate the subsequent 3.0-4.3 V battery performances of the exposed cathode. This work represents a facile method to regenerate the battery performance of surface-degraded nickel-rich cathodes, opening up an avenue in fulfilling efficient production, storage, and application of nickel-rich cathode materials.

Selective oxidation of 5-hydroxymethylfurfural into 2,5-diformylfuran over VPO catalysts under atmospheric pressure.

Vanadium phosphate oxide (VPO) heterogeneous catalysts with different V/P molar ratios were prepared and used for selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to produce 2,5-diformylfuran (DFF) in the liquid phase. It was found that the VPO catalyst with V/P molar ratio 0.25 exhibited the best catalytic performance. Then the VPO catalyst was utilized to catalyze the oxidation of HMF in a batch reactor under different conditions, in terms of type of solvent (water and organic), reaction time and temperature. A high DFF yield of 83.6% with HMF conversion of 100% was obtained under atmospheric pressure.

Imidazolyl activated carbon refluxed with ethanediamine as reusable heterogeneous catalysts for Michael addition.

Imidazolyl activated carbon, denoted as AC-N, was prepared via oxidation of AC with HNO3 (AC-O) and then refluxed with ethanediamine under mild conditions. The results showed that the N content of AC-N was 10.3%, and the surface alkali group density of AC-N was 0.96 mmol g-1 from 0.78 mmol g-1 carboxy group of AC-O by Boehm titration. It was revealed that the basic functional groups on the AC-N surface included imidazole and amine groups, from XPS and FT-IR. Evaluated with Michael addition of furfural, the catalytic performance of AC-N showed higher conversion and selectivity than that of commonly used base catalyst such as 2-methylimidazole and KOH. Very remarkably, AC-N showed extraordinary recyclability, in that there was no decline of conversion and selectivity after being recycled 5 times.

Titanate nanotubes-bonded organosulfonic acid as solid acid catalyst for synthesis of butyl levulinate.

In this study, titanate nanotubes-bonded organosulfonic acid (TNTs-SO3H) was prepared and employed as an efficient heterogeneous catalyst for esterification of levulinic acid with n-butanol. Two reaction products pseudo n-butyl levulinate (pseudo-BL) and n-butyl levulinate (BL) were detected by GC-MS. The catalyst showed 86.8% conversion of levulinic acid with 99.7% selectivity towards n-butyl levulinate. TNTs-SO3H exhibited strong acidic sites and high stability even after seven cycles of usage and would be well expected to be a potential candidate for alkyl levulinate production.

Metal-Organic Framework-Derived Materials for Sodium Energy Storage.

Recently, sodium-ion batteries (SIBs) are extensively explored and are regarded as one of the most promising alternatives to lithium-ion batteries for electrochemical energy conversion and storage, owing to the abundant raw material resources, low cost, and similar electrochemical behavior of elemental sodium compared to lithium. Metal-organic frameworks (MOFs) have attracted enormous attention due to their high surface areas, tunable structures, and diverse applications in drug delivery, gas storage, and catalysis. Recently, there has been an escalating interest in exploiting MOF-derived materials as anodes for sodium energy storage due to their fast mass transport resulting from their highly porous structures and relatively simple preparation methods originating from in situ thermal treatment processes. In this Review, the recent progress of the sodium-ion storage performances of MOF-derived materials, including MOF-derived porous carbons, metal oxides, metal oxide/carbon nanocomposites, and other materials (e.g., metal phosphides, metal sulfides, and metal selenides), as SIB anodes is systematically and completely presented and discussed. Moreover, the current challenges and perspectives of MOF-derived materials in electrochemical energy storage are discussed.

One-pot synthesis of trifunctional chitosan-EDTA-ß-cyclodextrin polymer for simultaneous removal of metals and organic micropollutants.

The global contamination of water resources with inorganic and organic micropollutants, such as metals and pharmaceuticals, poses a critical threat to the environment and human health. Herein, we report on a bio-derived chitosan-EDTA-ß-cyclodextrin (CS-ED-CD) trifunctional adsorbent fabricated via a facile and green one-pot synthesis method using EDTA as a cross-linker, for the adsorption of toxic metals and organic micropollutants from wastewater. In this system, chitosan chain is considered as the backbone, and the immobilized cyclodextrin cavities capture the organic compounds via host-guest inclusion complexation, while EDTA-groups complex metals. The thoroughly characterized CS-ED-CD was employed for batch adsorption experiments. The adsorbent displayed a monolayer adsorption capacity of 0.803, 1.258 mmol g-1 for Pb(II) and Cd(II) respectively, while a heterogeneous sorption capacity of 0.177, 0.142, 0.203, 0.149 mmol g-1 for bisphenol-S, ciprofloxacin, procaine, and imipramine, respectively. The adsorption mechanism was verified by FT-IR and elemental mapping. Importantly, the adsorbent perform is effective in the simultaneous removal of metals and organic pollutants at environmentally relevant concentrations. All these findings demonstrate the promise of CS-ED-CD for practical applications in the treatment of micropollutants. This work adds a new insight to design and preparation of efficient trifunctional adsorbents from sustainable materials for water purification.