Conversion Of Benzaldehyde Research Articles

One-pot enantioselective synthesis of chiral phenyllactic acids by combining stereocomplementary d- and l-lactate dehydrogenases with multi-enzyme expression fine-tuning

Chiral phenyllactic acid (PLA) is a new type of antiseptic agent and a valuable precursor for active ingredients in pharmaceuticals and agrochemicals. In this study, we designed a multi-enzyme cascade that combined stereocomplementary d- and l-lactate dehydrogenases with threonine aldolase, phenylserine dehydratase, and formate dehydrogenase for the one-pot conversion of achiral glycine and benzaldehyde to synthesize d-PLA and l-PLA. To overcome the imbalance of multi-enzymes in a single cell, two enzyme modules, overexpressing four enzymes, were assembled in Escherichia coli cells to construct whole-cell catalysis systems (WCCSs). Furthermore, by optimizing reaction conditions and components, recombinant E. coli (WCCS 26) was able to produce 100 mM d-PLA with >99 % ee using a fed-batch strategy, while E. coli (WCCS 60) produced 47.2 mM l-PLA with >99 % ee. This study presents a sustainable and efficient method for synthesizing chiral PLAs from food-grade achiral starting materials.

La(FeCuMnMgTi)O3 High-Entropy Oxide Nanoparticles as Highly Efficient Catalysts for Solvent-Free Aerobic Oxidation of Benzyl Alcohol.

In this work, a solid-state method for the synthesis of perovskite La(FeCuMnMgTi)O3 high-entropy oxide (HEO) nanoparticles is detailed. Additionally, the high performance of these nanoparticles as catalysts in the aerobic and solvent-free oxidation of benzyl alcohol is demonstrated. The structural features of HEO nanoparticles are studied by X-ray diffraction and high-resolution transmission electron microscopy. The La(FeCuMnMgTi)O3 nanoparticles demonstrate excellent benzyl alcohol conversion rates and selectivity for benzaldehyde, reaching 10.6% conversion and 52.8% selectivity after reaction for only 4 h and ≤75.6% conversion after 24 h. In addition, the as-prepared HEO catalyst displays robust stability in benzyl alcohol oxidation. Density functional theory calculations demonstrate that the adsorption energy of benzaldehyde on the HEO surface is lower than that of the benzoic acid. This, in turn, hinders the gradual conversion of benzaldehyde to benzoic acid on the surface of HEO and retains benzaldehyde as the main product.

Multisite Amino‐Allylidene Ligands from Thermal CO Elimination in Diiron Complexes and Catalytic Activity in Hydroboration Reactions

AbstractThe new diiron(I) complexes [Fe2Cp2(μ‐CO){μ‐k3C,kN‐C(R1)C(R2)C(CN)NMe(R)}], 3 a–o (R=alkyl or 4‐C6H4OMe; R1=alkyl, aryl, ferrocenyl (Fc), thiophenyl, CO2Me or SiMe3; R2=H, Me or CO2Me) were synthesized in moderate to high yields from the thermal decarbonylation of the bis‐carbonyl precursors 2 a–o, and were structurally characterized by IR and NMR spectroscopy, and single crystal X‐ray diffraction in four cases. Electrochemical behavior of one complex was also investigated. Complexes 3 a–o comprise a highly functionalized, multisite amino‐(cyano)allylidene ligand, including metal coordination of a tertiary amine group. Selected complexes displayed negligible to moderate catalytic activity in CO2/propylene oxide coupling, working under ambient conditions. Additionally, they were investigated as catalysts for the conversion of benzaldehyde to the corresponding borate ester 6 a, using pinacolborane (HBpin) as the borylating agent. Most complexes achieved good conversions at room temperature with 1 % catalyst loading, and data highlight the significant influence of the multisite ligand substituents on the catalytic performance. Notably, complex 3 m (featuring R=4‐methoxyphenyl, R1=Fc, R2=H) displayed the highest activity and effectively catalyzed the hydroboration of various aldehydes and ketones. A plausible mechanistic cycle involves metal coordination of the carbonyl substrate, its activation being possibly facilitated by intramolecular interactions.

Selective oxidation of styrene to benzaldehyde over mesoporous silica-based silver

An efficient catalyst with silver encapsulated into mesoporous silica (Ag/MS) was prepared via a hydrothermal method. The characterization was done with FT IR, XRD, SEM, BET, and EDX, and the well-organized structure of Ag/MS catalyst has been approved. It is found as an efficient catalyst for the selective oxidation of styrene to benzaldehyde employing hydrogen peroxide as a green and economic oxidant. The effect of various reaction conditions including reaction time, reaction temperature, different kinds of solvents were studied on the catalytic performance. In the optimized reaction conditions, the conversion of benzaldehyde was achieved 72% to 93%.

Catalytical advantages of Hf-MOFs in benzaldehyde acetalization

The potential use of acetals as bioadditives based on sustainable feedstocks in the automotive industry is of great interest. If such feedstock is a residual stream, the process would represent a dual environmental challenge, such as the valorization of glycerol obtained as a by-product of biodiesel to produce acetals. There are just scarce works about this synthetic route due to the challenge in finding efficient catalytic converters for glycerol valorization in a single process. Herein four different Metal-Organic Frameworks (MOFs) are evaluated as heterogeneous catalysts for the acetalization reaction of benzaldehyde with methanol, specifically, two structures, MOF-808 and UiO-66, containing two structural metal ions, zirconium and hafnium. The aim of this work is to investigate the influence of the MOF structure, the metallic active sites and the reaction conditions on the catalytic performance of this acetal production-type reaction. Furthermore, the recyclability of the catalyst is evaluated, and a potential reaction mechanism is suggested. As relevant results, Hf-MOFs showed higher benzaldehyde conversion than Zr-based ones, and significant improvements in reaction conditions were achieved, such as a significant reduction in catalyst loading of 99.6 % using UiO-66-Hf, and an optimization of reagent ratios reducing methanol consumption by 50 % for a 92 % of benzaldehyde conversion. The Brønsted character of UiO-66-Hf seems to enhance the reaction rate more than the metal center accessibility and larger pore volumes offered by MOF-808.

SrCaAl mixed metal oxides derived from LDH precursor as a novel and efficient solid base catalyst for Knoevenagel condensation reaction: Multivariate optimization study

The Knoevenagel condensation reaction is one of the most important reactions in the industry for the synthesis of organic materials, medicinal, and biological compounds. In this work, we have proposed an original and efficient solid-base catalytic system for the Knoevenagel condensation reaction. For the first time, a mixed oxide catalyst derived from hydrotalcite-like Sr0.5Ca2.5Al precursor was synthesized by co-precipitation method and subsequently calcined for 5 h at 850 °C. The catalysts were characterized by various techniques. The Sr0.5Ca2.5Al mixed oxide was also compared with the usual Ca3Al sample in terms of structural characteristics and catalytic activity in the Knoevenagel reaction between active methylene compounds and benzaldehyde. The findings revealed that the Sr0.5Ca2.5Al mixed oxide sample is considerably active in this reaction compared to the Ca3Al sample due to its stronger basicity. The kinetics of the Knoevenagel condensation reaction over the Sr0.5Ca2.5Al catalyst was investigated and indicated that it follows from the second-order model. The stability and reusability of the catalyst sample were studied and it was found that the Sr0.5Ca2.5Al catalyst has high stability and a good lifetime. The effects of reaction time, amount of catalyst, and reaction temperature on benzaldehyde conversion (%) and product selectivity (%) were assessed in this study using the Box-Behnken design. The appropriateness of the quadratic regression model was evaluated through the ANOVA method. Under optimal conditions, the conversion percentage of benzaldehyde and product selectivity reached 97% and 84%, respectively.

Metal-Free Catalytic Conversion of Veratryl and Benzyl Alcohols through Nitrogen-Enriched Carbon Nanotubes

Nitrogen-rich carbon nanotubes NCNT700 and NCNT800 were prepared using the chemical vapor deposition method (CVD). The catalysts were characterized via high-resolution transmission electron microscopy (HRTEM) and X-ray photoelectron spectroscopy (XPS) analysis. Both the catalysts were found to have an inverted cup-stack-like morphology. The XPS analysis revealed that the catalysts are rich in pyridinic sites with variable amounts of nitrogen on their surface. The NCTN700, with a higher nitrogen content and more pyridinic sites on its surface, was found to be a good catalyst for the oxidation of benzyl and veratryl alcohols into respective aldehydes. It was observed that toluene and 4-methyl veratrole were also produced in this reaction. The amount of toluene produced was as high as 21%, with 99% conversion of benzaldehyde in the presence of NCNTs-700. The mechanistic pathway was revealed through DFT studies, where the unusual product formation of aromatic alkanes such as toluene and 4-methyl veratrole was explained during the reaction. It was astonishing to observe the reduced product in the reaction that proceeds in the forward direction in presence of a peroxide (tert-butyl hydroperoxide, TBHP). During the computational analysis, it was revealed that the reduced product observed in the reaction did not appear to proceed through a direct disproportionation reaction. Rather, the benzyl alcohol (the reactant) used in the reaction may undergo oxidation by releasing the hydrogen radicals. The hydrogen atoms released during the oxidation reaction appear to have been trapped on pyrrolic sites on the surface of catalyst and later transferred to the reactant molecules to produce toluene as a side product.

Revealing the roles of the dual active-sites on a polyoxometalate-based metal–organic framework in catalyzing Knoevenagel condensations

The efficient catalysis of Knoevenagel condensations under mild conditions is a significant way for obtaining olefin compounds, which can be used to produce a wide range of biologically active heterocyclic chemicals and fine chemical raw materials. Herein, a novel polyoxometalate-based metal–organic framework (POMOF), [Co(bix)(H2O)]{V2O6} (VMOF-1, bix = 1,4-bis(imidazol-1-ylmethyl)benzene), is synthesized and structurally characterized. After removal of the coordinated water molecules of CoII ions by vacuum drying, VMOF-1a with both Lewis acid and Lewis base catalytic active-centers is achieved. VMOF-1a as the heterogeneous catalyst for the conversion of benzaldehyde and malononitrile to high value-added olefinic compounds under mild conditions, exhibits excellent conversion and selectivity, good recyclability and broad substrate applicability. Experimental and theoretical studies have revealed that CoII ion and {V2O6}2− unit in VMOF-1a synergistically catalyze the Knoevenagel condensation reaction: (1) {V2O6}2− is used as a Lewis base to pull out the proton of the active methylene group on malononitrile; (2) CoII ion acts as a Lewis acid to activate the carbonyl oxygen on benzaldehyde. Furthermore, it is demonstrated for the first time that the Lewis acid sites in POMOF can play the role of stabilize the alcohol hydroxyl anion intermediates generated during the reaction process, which further elucidates the reason for the high catalytic activity of VMOF-1a in the Knoevenagel condensation. This study provides theoretical guidance for the design of efficient and sustainable catalysts for Knoevenagel condensation.

Propylamine Silica-Titania Hybrid Material Modified with Ni(II) as the Catalyst for Benzyl Alcohol to Benzaldehyde Conversion

SiO2-TiO2@propylamine-Ni(II) as the catalyst for the benzyl alcohol oxidation has been synthesized by utilizing rice husk ash as the SiO2 source. This research was started by extracting SiO2 from rice husk ash and continued by synthesizing the SiO2-TiO2 composite using titanium(IV) tetraisopropoxide (TTIP) as TiO2 precursor and PEG-40 as template. The composite functionalization and metal modification were carried out by adding (3-aminopropyl)triethoxysilane (APTES) as the source of propylamine linker and impregnating NiCl2·6H2O as the nickel precursor, respectively. The catalysts were synthesized by varying the ratios between each component within the material. The prepared materials were then characterized using ATR-IR, XRD, XRF, PSA, SAA, AAS, SEM-EDX, HR-TEM, and TGA. The catalyst activity was investigated by applying it to the oxidation reaction of benzyl alcohol to benzaldehyde with H2O2 as the oxidizing agent under sonication system. The obtained products were then analyzed by using GC-MS to quantify the success of the reaction. All characterizations performed in this research generally indicate the success in the synthesis of SiO2-TiO2@propylamine-Ni(II) materials. Under the same condition including at room temperature, 1 h reaction time, and sonication system, the optimal oxidation reaction of benzyl alcohol was reached when SiO2-TiO2@propylamine-Ni(II)5 was used as the catalyst in 98.52% yield.

Solvent-free cross aldol condensation of aldehydes and ketones over SrMo1-xNixO3-δ perovskite nanocrystals as heterogeneous catalysts

Aldol condensation is arguably one of the most fascinating reactions that leads to the formation of C–C bonds. Its use in the pharmaceutical industry to synthesis complex drugs from simple aldehydes and ketones has become of paramount importance. Although this is one reaction that has lured a lot of attention, not enough has been explored in heterogeneous catalysis. In this work we have successfully synthesized multicationic perovskites via the soft-template method and characterized them thoroughly. The synthesized perovskite nanocrystals were found to have small SBET however their catalytic application in the conversion of benzaldehyde (BAL) in the aldol condensation with diethyl ketone (DEK) was found to be astonishing. The synthesis was confirmed using many techniques, from determining the oxidation states of the materials using XPS. This gave access to determine the coordination of the metals in the perovskite lattice and also qualitatively assess the oxygen environments that exist. The oxygen vacancies and SBET were used to assess the activity of the perovskite catalysts in the cross-aldol condensation reaction. The optimal conditions for this aldol condensation were found to be 120 °C after 25 h with no solvent using SrMo0.5Ni0.5O3-δ inorganic perovskite which had the highest amount of oxygen vacant sites which gave a conversion of 88 % and an 82 % selectivity towards the desired cross-aldol condensation product. The use of dimethylformamide (DMF) for this reaction is discouraged as it reacts with BAL to produce a higher amide.

Incorporation of phosphated tin oxide in mesoporous silica nanostructure for high-performance wastewater treatment and synthesis of pharmaceutically significant 14-aryl-14-alkyl-14-H-dibenzoxanthene

Purifying wastewater is critical for mitigating the expected clean water shortage and climate change. Herein, phosphated-SnO2/mesoporous silica nanostructure (SnP2O7/MCM-41) was prepared by skillfully interacting pyrophosphate (P2O7-4) with Sn(OH)4 in the mesopores of MCM-41 via a simple sol-gel approach. TGA and XRD analysis revealed the high thermal stability and crystallinity of the SnP2O7/MCM-41 mesostructure. More importantly, the TEM images and acidity measurements indicated that the SnP2O7 species are homogeneously distributed over the MCM-41 surface, and the acid strength is maximized when the surface is saturated with 35 wt% SnP2O7/MCM-41. Benefiting from the high acidity and plenty of active sites, SnP2O7/MCM-41 catalyzed the conversion of benzaldehyde and β-naphthol to pharmaceutical-significant 14-Aryl-14-alkyl-14-H-dibenzoxanthene with an excellent yield of 97% after 2 h reaction progress under a gentle and solvent-free environment. Moreover, the zeta potential of SnP2O7/MCM-41 catalyst was measured at different pH values and the point of zero charges (PZC) were investigated to determine the best circumstances and make water purification more practicable. The PZC of SnP2O7/MCM-41 was found to be around pH 5.4, and SnP2O7/MCM-41 exhibits 96 % removal of 100 ppm BG dye, which is far higher than SnO2/MCM-41 under the same conditions of pH 8, adsorption contact time (1 h), and adsorbent dosage (0.05 g). The experimental data follows a pseudo-second-order model, providing a good correlation coefficient (R2 = 0.998). In terms of chemical stability, SnP2O7/MCM-41 was reused for 10 cycles without significant performance loss. From the application perspective, our results demonstrate that SnP2O7/MCM-41 has the desired chemical composition for wastewater purification and catalysis applications.

Synthesis of Layered Lead-Free Perovskite Nanocrystals with Precise Size and Shape Control and Their Photocatalytic Activity.

Halide perovskites have attracted enormous attention due to their potential applications in optoelectronics and photocatalysis. However, concerns over their instability, toxicity, and unsatisfactory efficiency have necessitated the development of lead-free all-inorganic halide perovskites. A major challenge in designing efficient halide perovskites for practical applications is the lack of effective methods for producing nanocrystals with precise size and shape control. In this work, a layered perovskite, Cs4ZnSb2Cl12 (CZS), is found from calculations to exhibit size- and facet-dependent optoelectronic properties in the nanoscale, and thus, a colloidal method is used to synthesize the CZS nanoparticles with size-tunable morphologies: zero- (nanodots), one- (nanowires and nanorods), two- (nanoplates), and three-dimensional (nanopolyhedra). The growth kinetics of the CZS nanostructures, along with the effects of surface ligands, reaction temperature, and time were investigated. The optoelectronic properties of the nanocrystals varied with size due to quantum confinement effects and with shape due to anisotropy within the crystals and the exposure of specific facets. These properties could be modulated to enhance the visible-light photocatalytic performance for toluene oxidation. In particular, the 9.7 nm CZS nanoplates displayed a toluene to benzaldehyde conversion rate of 1893 μmol g-1 h-1 (95% selectivity), 500 times higher than the bulk synthesized CZS, and comparable with the reported photocatalysts. This study demonstrates the integration of theoretical calculations and synthesis, revealing an approach to the design and fabrication of novel, high-performance colloidal perovskite nanocrystals for optoelectronic and photocatalytic applications.

Studies of the Solvent-Free Knoevenagel Condensation over Commercial NiO compared with NiO Drived from Hydrotalcites

In this study, we compared the effect of the commercial NiO, synthesis NiAl-HT and NiO-HT drived from hydrotalcite in Knoevenagel condensation reaction. The NiAl-HT sample was synthesized by the coprecipitation method with a molar ratio M2+/M3+ = 2 at constant basic pH. X-ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FTIR) were utilized to identify crystalline phases present in NiAl-HT, NiO-HT and commercial NiO. The chemical composition of the obtained solids was determined by Atomic Absorption Spectroscopy (AAS). Other techniques, such as Thermogravimetric Thermal Analyzer (TGA), Scanning Electron Microscopy (SEM) and Brunauere Emmette Teller Method (BET) were also used. As well as the BET showed the increase of the specific surface for the solid NiO-HT. The performance of the catalysts were studied in Knoevenagel condensation of benzaldehyde with ethyl acetoacetate without solvent to synthesis of organic compounds such as intermediates of dihydropyridines derivatives. The influence of different parameters, such as catalyst amount, reaction temperature and reaction time were optimized for studied the activity, the selectivity and the stability of the solids. Catalytic activity was in its lowest in the presence of NiAl-HT (26% of benzaldehyde conversion) whereas the benzaldehyde conversion increased to 77% in case of NiO-HT which can be explained by the presence of the basic sites of the NiO-HT oxides, a high surface area and a small crystallite size. Therefore, the lower increase in benzaldehyde conversion was noticed using commercial NiO (84%), perhaps owing to its high purity. A reaction mechanism is proposed by using density functional method (DFT). Copyright © 2023 by Authors, Published by BCREC Group. This is an open access article under the CC BY-SA License (https://creativecommons.org/licenses/by-sa/4.0)

Acetalization of Alkyl Alcohols with Benzaldehyde over Cesium Phosphomolybdovanadate Salts

In this work, vanadium-substituted cesium phosphomolybdate salts with general formulae Cs3+nPMo12−nVnO40 (n = 0, 1, 2, and 3) were synthesized and evaluated in the acetalization of benzaldehyde with alkyl alcohols. All the catalysts were characterized through Raman, infrared, and ultraviolet–visible spectroscopies, powder X-ray diffraction patterns, isotherms of N2 desorption/adsorption, and measurements of acidity strength. The catalytic activity of cesium phosphomolybdovanadate salts was evaluated in the acetalization reactions of benzaldehyde with alkyl alcohols. Among the salts tested, the Cs4PMo11V1O40 was the most active and selective catalyst in the conversion of benzaldehyde to methyl benzyl acetal and benzoic acid, which was obtained without the use of an oxidant agent. The impact of the main reaction parameters on the conversion and selectivity was evaluated by varying the content of vanadium per heteropolyanion, catalyst load, temperature, and alkyl alcohols. The greatest activity of the Cs4PMo11V1O40 salt was assigned to the highest Brønsted acidity strength, as demonstrated by the acidity measurements and analysis of their surface properties. This solid catalyst has advantages over traditional liquid homogenous catalysts, such as low corrosiveness, a minimum generation of residues and effluents, and easy recovery/reuse. In addition, its synthesis route is easier and quicker than solid-supported catalysts and comprises a potential alternative route to synthesize acetals.

Conversion of Similar Xenochemicals to Dissimilar Products: Exploiting Competing Reactions in Whole-Cell Catalysis.

Many enzymes have latent activities that can be used in the conversion of non-natural reactants for novel organic conversions. A classic example is the conversion of benzaldehyde to a phenylacetyl carbinol, a precursor for ephedrine manufacture. It is often tacitly assumed that purified enzymes are more promising catalysts than whole cells, despite the lower cost and easier maintenance of the latter. Competing substrates inside the cell have been known to elicit currently hard-to-predict selectivities that are not easily measured inside the living cell. We employ NMR spectroscopic assays to rationally combine isomers for selective reactions in commercial S. cerevisiae. This approach uses internal competition between alternative pathways of aldehyde clearance in yeast, leading to altered selectivities compared to catalysis with the purified enzyme. In this manner, 4-fluorobenzyl alcohol and 2-fluorophenylacetyl carbinol can be formed with selectivities in the order of 90%. Modification of the cellular redox state can be used to tune product composition further. Hyperpolarized NMR shows that the cellular reaction and pathway usage are affected by the xenochemical. Overall, we find that the rational construction of ternary or more complex substrate mixtures can be used for in-cell NMR spectroscopy to optimize the upgrading of similar xenochemicals to dissimilar products with cheap whole-cell catalysts.

Preparation of CuFe2O4 composite metal oxides and selective oxidation of benzyl alcohol

Using iron nitrate and copper nitrate as raw materials, mesoporous material SBA-15 as template agent and n-hexane as solvent, CuFe2O4 samples of mesoporous loaded composite metal oxide catalysts were successfully prepared by calcination at 600 °C. The samples were characterized by X-ray diffraction (XRD), thermogravimetric-differential scanning analysis (TG-DSC), and scanning electron microscopy (SEM). The selective oxidation of benzyl alcohol by CuFe2O4 under different catalytic conditions was investigated using benzyl alcohol as a model compound, and the oxidation products were analyzed by high performance liquid chromatography (HPLC). The results showed that the CuFe2O4 catalyst prepared by calcination at 600°Cwas the best. The best selective oxidation conditions were achieved at a reaction system temperature of 90 °C, a catalyst dosage of 4 g/L, a molar ratio 1:1 of H2O2 dosage to benzyl alcohol, and a reaction time of 4 h. The conversion of benzyl alcohol under this condition was 66.95%, and the selective conversion of benzaldehyde was 96.07%. This indicates that CuFe2O4 is a composite metal oxide with high selective oxidation of benzyl alcohol and has wide application prospects.

Interactions of phenol and benzaldehyde in electrocatalytic upgrading process

Biomass pyrolysis oil can be improved effectively by electrocatalytic hydrogenation (ECH). However, the unclear interactions among different components lead to low bio-oil upgrading efficiency in the conversion process. Herein, benzaldehyde and phenol, as common compounds in bio-oil, were chosen as model compounds. The interactions between the two components were explored in the ECH process by combining experiments and theoretical calculations. Results showed that phenol could accelerate the conversion of benzaldehyde in the ECH. The selectivity of benzyl alcohol was increased from 60.9% of unadded phenol to 99.1% with 30 mmol/L phenol concentration at 5 h. Benzaldehyde inhibited the ECH of phenol. In the presence of benzaldehyde, the conversion rate of phenol was below 10.0% with no cyclohexanone and cyclohexanol formation at 5 h. The density functional theory (DFT) calculations revealed that the phenol could promote the adsorption of benzaldehyde and facilitate the targeted conversion of benzaldehyde on the active site by lowering the reaction energy barrier. The research on the interaction between phenol and benzaldehyde in the ECH provides a theoretical basis for the application of ECH in practical bio-oil upgrading.

Preparation of mespore load composite metal oxide catalyst and selective benzoyl methanol oxide

The CoMn2O4 precursor was prepared by hard template method using mesoporous material SBA-15 as template material, n-hexane as solvent, manganese and cobalt nitrate as raw materials. After calcination at 600 °C, porous composite metal oxide catalyst CoMn2O4 was formed. The samples are characterized by X-Ray Diffraction (XRD), Thermogravimetric Analysis-Differential Scanning Calorimeter (TG-DSC), Scanning Electron Microscopy (SEM), and Energy Dispersive X-Ray Spectroscopy (EDX). Using benzyl alcohol as a model compound, the selective oxidation of benzyl alcohol by CoMn2O4 under different catalytic conditions was studied. The oxidation products are analyzed by High Performance Liquid Chromatography (HPLC). The results show that the pure CoMn2O4 can be prepared at 500 °C to 800 °C, and the samples are spherical particles. The optimal conditions for oxidation are as follows: The amount of catalyst was 4 g/L, the molar ratio of H2O2 to benzyl alcohol was 1:1, the reaction temperature was 80 °C, and the reaction time was 4h. The conversion rate of benzyl methanol is 78.2%, the selective conversion of benzaldehyde is 94.8%. This indicates that the CoMn2O4 is a composite metal oxide with high selective oxidation of benzene methanol.

Preparation of ZSM-5 zeolites by sodium-free method in rotating packed bed

In industry, H-type zeolites are usually synthesized under hydrothermal conditions in the sodium-containing system, in which great deal of ammonia nitrogen wastewater will be produced during the transformation of zeolites from Na-type to H-type. In this work, we prepared ZSM-5 zeolites in the sodium-free system using organic amines in a rotating packed bed (RPB), which can greatly reduce the amount of wastewater. It was found that the ZSM-5 zeolites synthesized by isopropanolamine (MIPA) had the highest acid amount with a value of 2.331 mmol/g compared to that by other three amines, and exhibits the highest conversion of benzaldehyde with a value of 77.63% in the acetal reaction of benzaldehyde and ethylene glycol. More importantly, RPB premixing can improve the transfer of Al into the framework of ZSM-5 zeolites relative to conventional stirring technique. This work provided a new route to prepare ZSM-5 zeolites with high acid amount in sodium-free system.

Waste biomasses as precursors of catalytic supports in benzaldehyde hydrogenation

The optimization of Pd supported on activated biochars as innovative and sustainable catalysts was performed. Four different waste biomasses from vegetal (hazelnut shells (HS), broken rice grains (BR), rice husks (RH)) and animal origin (leather tannery shaving waste (LS)), were pyrolyzed and physically activated (by steam), and a commercial activated carbon was used as the reference support. 0.6 wt% Pd was impregnated onto the supports and all catalysts were characterized and tested for benzaldehyde hydrogenation. The catalytic test showed the highest activity (benzaldehyde conversion of 99%) and selectivity toward toluene (97% and 78%) for Pd/A-RH and Pd/A-HS, respectively. Characterizations of the supports and catalysts confirmed that physicochemical properties of the activated biochars, affected from the origin of initial biomasses, had fundamental influences on the final efficiency of the catalysts.