Abstract

CoxOy–manganese carbonate (X%)(CoxOy–MnCO3 catalysts (X = 1–7)) were synthesized via a straightforward co-precipitation strategy followed by calcination at 300 °C. Upon calcination at 500 °C, these were transformed to CoxOy–dimanganese trioxide i.e., (X%)CoxOy–Mn2O3. A relative catalytic evaluation was conducted to compare the catalytic efficiency of the two prepared catalysts for aerial oxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) using O2 molecule as a clean oxidant without utilizing any additives or alkalis. Amongst the different percentages of doping with CoxOy (0–7% wt./wt.) on MnCO3 support, the (1%)CoxOy–MnCO3 catalyst exhibited the highest catalytic activity. The influence of catalyst loading, calcination temperature, reaction time, and temperature and catalyst dosage was thoroughly assessed to find the optimum conditions of oxidation of benzyl alcohol (BzOH) for getting the highest catalytic efficiency. The (1%)CoxOy–MnCO3 catalyst which calcined at 300 °C displayed the best effectiveness and possessed the largest specific surface area i.e., 108.4 m2/g, which suggested that the calcination process and specific surface area play a vital role in this transformation. A 100% conversion of BzOH along with BzH selectivity >99% was achieved after just 20 min. Notably, the attained specific activity was found to be considerably larger than the previously-reported cobalt-containing catalysts for this transformation. The scope of this oxidation reaction was expanded to various alcohols containing aromatic, aliphatic, allylic, and heterocyclic alcohols without any further oxidation i.e., carboxylic acid formation. The scanning electron microscope (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and Brunauer–Emmett–Teller (BET) specific surface area analytical techniques were used to characterize the prepared catalysts. The obtained catalyst could be easily regenerated and reused for six consecutive runs without substantial decline in its efficiency.

Highlights

  • Catalytic oxidation of compounds, especially oxidation of organic alcohols to respective carbonyls, has extremely important organic synthetic transformation and industrial applications [1]

  • The oxidation of benzyl alcohol (BzOH) into BzH with gaseous O2 as an eco-friendly oxidant acted as a template reaction to examine the activities of the as-synthesized catalysts (Scheme 2)

  • The results indicated that conversion of BzOH increases with raising catalyst quantity, while BzH selectivity was found to be same (>99%)

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Summary

Introduction

Especially oxidation of organic alcohols to respective carbonyls, has extremely important organic synthetic transformation and industrial applications [1]. Carbonyls (e.g., aldehydes and ketones) are extensively applied as high value raw materials in pharmacology, perfumery, plastic additives, biofuels, confectionery, odorants, cosmetics, pesticides, flame-retardants, dyestuffs, and agrochemical industries [2] This transformation is conventionally performed employing stoichiometric quantities of NaClO, CrO3, SeO2, RuO4, Br2, and Cr2O7, which are relatively costly, highly toxic, and corrosive in nature [3]. Molecular O2 has been widely employed for the catalytic oxidation of alcohol This possesses several merits including the abundance of oxygen and its inexpensive and eco-friendly nature, in addition to the formation of water as the only by-product [5]. (S(SXXcc%%hhee))CmmCooeexxO1O1..yy–AA–MMppnnii2cc2OttOoo3r3raiiaataltl5i50ill00lluu0°ssC◦ttCrr.aa.ttiioonn ffoorr tthhee ffaabbrriiccaattiioonn ooff((XX%%))CCooxxOOyy––MMnnCCOO33 ccaallcciinneedd aatt 330000 ◦°CC aanndd

Catalyst Fabrication
Catalytic Performance Results
Influence of Dosage of Catalyst
Recovery Tests
Conclusions
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