Kinetics of liquid phase oxidation of benzyl alcohol with hydrogen peroxide over bio-reduced Au/TS-1 catalysts

Zhan, Guowu; Hong, Yaping; Lü, Fenfen; Ibrahim, Abdul‐Rauf; Du, Mingming; Sun, Daohua; Huang, Jiale; Li, Qingbiao; Li, Jun

doi:10.1016/j.molcata.2012.09.026

Cited by 47 publications

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References 30 publications

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“…Investigationi nto the kinetics of the TBHP oxidation of benzyla lcohol using the same calcined Pt/CuClP catalyst ( Fig-ure 1b)r evealed ana ctivation energy of 23.6 kJ mol À1 under reactionconditions identical to those employed for the aerobic oxidation. This is also in agreement with the data obtained for analogouss upported NP materials for peroxide oxidation of benzyla lcohol at 38 [11] and 20 [12] kJ mol À1 ,w hilst surpassing the valueso btained for transition-metal catalysts based on Mo and Wa t8 4a nd 96 kJ mol À1 respectively. [13] The lower activation energy of the peroxide-based oxidation is not surprising;g iven the lower BDE of TBHP relative to that of O 2 ,a nd as reflected in the activity of the catalysta tt emperatures lower than 100 8C.…”

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confidence: 90%

“…[10] As the rate of reactioni sc orrelatedw ith availablea ctive sites on the NP surface and the activation energy directly associated with the rates of reaction, it is noteworthy thatt he activation energies observed in our (partially) activated catalysts compete with those reported in the literature with analogousm aterials. [11,12] Therefore, with an established method for complete extrusion, it should be possible to significantly improve on these values. Further analysis of activation parameters on structural properties and extent of extrusion is currentlyi np rogress.…”

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Utilizing Benign Oxidants for Selective Aerobic Oxidations Using Heterogenized Platinum Nanoparticle Catalysts

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By using platinum nanoparticle catalysts that are generated in situ by extrusion from a porous copper chlorophosphate framework, the role of oxidants in the selective oxidation of benzyl alcohol to benzaldehyde was evaluated, with a view to establishing structure-property relationships. With a detailed 5 study of the kinetic properties of the oxidation reaction, it has been determined that the aerobic oxidation pathways progress with lower levels of product selectivity and higher activation energies (72.4 kJ/mol) than the peroxide-based ones (23.6 kJ/mol); affording valuable insights in the design of solid catalysts for selective 10 oxidation reactions. Furthermore, through the use of X-ray absorption spectroscopy, the effect of calcination temperature on the degree of extrusion and its influence on nanoparticle formation have been evaluated, leading to the establishment of structure-activity correlations between the observed activation energies and the 15 proportion of nanoparticle species generated .Oxidation reactions are ubiquitous in the pharmaceutical and fine-chemical industries, and are fundamentally important to introducing oxygen rich functional groups to organic molecules. For example, aldehyde and ester containing molecules are 20 heavily employed as flavouring and fragrance agents due to their volatility and distinctly aromatic nature that are often pleasing to smell and taste.[1] Benzaldehyde is a key component for most almond-based flavourings, although it finds other uses as precursors for plastic additives and as a pharmaceutical 25 intermediate toward antibiotic drugs such as chloramphenicol and ampicillin, as well as stimulants like ephedrine.[2] Industrially, it is synthesized by the hydrolysis of benzal chloride, however the dehydrogenative oxidation of benzyl alcohol is a viable, chloride free and environmentally benign alternative. [2] 30 Traditionally, industrial oxidation reactions are based on the use of stoichiometric quantities of inorganic metal-based oxidizing agents such as MnO2 or CrO3, or harsh mineral acids like H2SO4 and HNO3, which result in hazardous, corrosive and toxic operating conditions as well as leading to the generation of 35 large quantities of polluting waste by-products.[3] Due to the heightened socio-economic demand for the chemical and related industries to reduce their negative impact on the environment, there is a significant drive to find alternative economic and sustainable oxidation reagents and synthetic 40 protocols.[3] The abundance of molecular oxygen, its high atomeconomy in oxidation reactions, low costs and mild reaction conditions make it an appealing candidate as an oxidant, [4] although high-pressure and relatively high reaction temperatures are often required, owing to the gaseous nature of the reaction. 45 Similarly, simple peroxides such as H2O2 and tert-butyl hydroperoxide (TBHP), are often considered as alternative green oxidants.[4] Although, this often leads to the generation of larger quantities of by-products in compa...

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Utilizing Benign Oxidants for Selective Aerobic Oxidations Using Heterogenized Platinum Nanoparticle Catalysts

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“…306 Therefore, the Au NPs with negative charges can be fully adsorbed on the TS-1 support by the electrostatic attractive forces. 311 By fitting the kinetic data using the power-rate law model, the orders of the reaction with respect to benzyl alcohol, H 2 O 2 , benzaldehyde and catalyst were found to be 0.55, 0.22, À0.35 and 1.06, respectively, with an activation energy of 38.2 kJ mol À1 from an Arrhenius plot. 306 Compared to the Au/TS-1 catalysts without IL, the Au/TS-1-IL catalysts showed enhancement of catalytic performance, as shown in Fig.…”

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Bio-inspired synthesis of metal nanomaterials and applications

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“…ρ cat is the density of catalysts, given as 1000 kg/m 3 [47]. D eff is the effective diffusion coefficient whose order of magnitude is approximately evaluated to 10 −9 m 2 /s [50]. C As is the surface concentration of BzOH, whose order of magnitude was once measured as 1 mol/L [51].…”

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The Steric Effect in Green Benzylation of Arenes with Benzyl Alcohol Catalyzed by Hierarchical H-beta Zeolite

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Wang

et al. 2019

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For decades the steric effect was still ambiguously understood in catalytic benzylation reactions of arenes with benzyl alcohol, which limited the green synthesis of phenylmethane derivates in industrial scale. This research applies a series of silica–alumina beta zeolites to systematically evaluate factors like catalyst porosity, reactants molecule size, and reaction temperature on catalytic benzylation. First, a suitable hierarchical beta zeolite catalyst was screened out by X-ray powder diffraction, N2 adsorption−desorption, and probe benzylation with p-xylene. In the following substrates expanding study, for a typical benzylation of benzene, it showed extraordinary performance among literature reported ones that the conversion was 98% while selectivity was 90% at 353 K only after 10 min. The steric effect of aromatics with different molecular sizes on benzylation was observed. The reaction activities of four different aromatics followed the order: benzene > toluene > p-xylene > mesitylene. Combined with macroscopic kinetic analysis, this comprehensive study points out for the first time that the nature of this steric effect was dominated by the relative adsorption efficiency of different guest aromatic molecules on the host zeolite surface.

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Kinetics of liquid phase oxidation of benzyl alcohol with hydrogen peroxide over bio-reduced Au/TS-1 catalysts

Cited by 47 publications

References 30 publications

Utilizing Benign Oxidants for Selective Aerobic Oxidations Using Heterogenized Platinum Nanoparticle Catalysts

Utilizing Benign Oxidants for Selective Aerobic Oxidations Using Heterogenized Platinum Nanoparticle Catalysts

Bio-inspired synthesis of metal nanomaterials and applications

The Steric Effect in Green Benzylation of Arenes with Benzyl Alcohol Catalyzed by Hierarchical H-beta Zeolite

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