Highly Active and Recyclable Cu_xFe_3‐xO₄ NPs for Selective Oxidation of Benzyl Alcohol using TBHP as an Oxidant

Abstract

Herein, we report the synthesis of CuxFe3‐xO4 nanoparticles (NPs) via a novel, facile, cost‐effective, and eco‐benign method using a water‐soluble egg‐white. The characterization studies confirmed that the fabricated CuxFe3‐xO4 NPs are crystalline and possess super‐paramagnetic behavior. The fabricated magnetic CuxFe3‐xO4 NPs also exhibited excellent catalytic performance towards the selective oxidation of benzyl alcohol to benzaldehyde using tetra‐butyl hydroperoxide (TBHP) as an oxidant under solvent‐free conditions. It was found that the addition of egg‐white during the synthesis significantly enhanced both the crystallinity and catalytic activity. Among the prepared ratios, Cu1.5Fe1.5O4 demonstrated the highest conversion (>73 %) and complete selectivity (100 %) to benzaldehyde under lenient oxidation conditions. The novelty of the work lies in achieving the magnetically recoverable CuxFe3‐xO4 NPs in the absence of any base or other organic reagents and is highly selective for the production of benzaldehyde under the mild reaction condition.

Nanoporous Au/Ag Catalyzed Benzylic sp3C−H Oxidation of 9H‐Fluorene Derivatives and Similar Molecules with TBHP

“…Usually, these catalysts often contain a transition metal or metal oxide species as the catalytically active center (For a compilation of catalysts used in 9H‐fluorene oxidation with TBHP, see SI, Table S2). They range from homogenous catalysts, such as complexes [10,11j,k,12d] or salts, [11h,i,l] to heterogenous catalysts, like various nanoparticles, [12b,c,e,g] nanostructures or MOFs [17] . Gold, whether in the form of a KAuCl 4 [11l] salt or as supported nanoparticle, [12c,f,18] serves both as a homogeneous and heterogeneous catalyst in the oxidation of benzylic sp 3 ‐carbon positions or benzylic alcohols with TBHP.…”

Recent Progress of Amorphous Porous Organic Polymers as Heterogeneous Photocatalysts for Organic Synthesis

“…The selective oxidative conversion of alcohols to aldehydes or ketones is a common organic synthesis reaction, especially benzaldehyde, an important chemical widely used in the pharmaceutical, dye, and fragrance industries. [97] However, few amorphous POP materials are available for photocatalytic reaction. Guo et al [98] synthesized an interesting heptazine-based porous organic polymer (POP-HE) from 2,5,8-trichloro-s-heptazine and 4,4′,4″,4‴-(ethene-1,1,2,2-tetrayl) tetraaniline (Figure 16a).…”

“…The selective oxidative conversion of alcohols to aldehydes or ketones is a common organic synthesis reaction, especially benzaldehyde, an important chemical widely used in the pharmaceutical, dye, and fragrance industries. [ 97 ] However, few amorphous POP materials are available for photocatalytic reaction. Guo et al.…”

Ultrasonic irradiation-assisted MnFe2O4 nanoparticles catalyzed solvent-free selective oxidation of benzyl alcohol to benzaldehyde at room temperature

“…To minimize the environmental hazards and cost, several research groups have developed heterogeneous catalysts based selective oxidation of benzyl alcohol using low-toxic oxidants such as O 2 , tert-butyl hydroperoxide (TBHP), H 2 O 2 , and so forth. [22][23][24][25][26] However, most of the reported methods required high temperatures, prolonged reaction time and solvents which are again not benecial for technological applications. Further, the recovery of the conventional catalyst for reuse is a daunting task in most cases because of the loss of the catalyst during purication by conventional ltration or centrifugation methods.…”

“…14,16 Accordingly, several research groups have reported the use of ferrite-based magnetic NPs for selective oxidation of benzyl alcohol using low-toxicity oxidants such as O 2 , TBHP, H 2 O 2 , etc. [22][23][24][25]28 However, the use of a high amount of catalyst, low selectivity of benzaldehyde, high reaction time as well as temperature are the main drawbacks in some of the reported methods. 23,24,29 So, a systematic study is required to further simplify the existing protocols and develop an active, selective, and recyclable catalyst that can work efficiently under solventfree conditions for the selective oxidation of benzyl alcohols into corresponding benzaldehyde with high conversion.…”