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Oxidations of Aldehydes and Ketones to Carboxylic Acids01:15

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Oxidation of aldehydes and ketones results in the formation of carboxylic acids. Aldehydes, bearing hydrogen next to the carbonyl group, are easily oxidized compared to ketones. This is because an aldehydic proton can easily be abstracted during oxidation.
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Esters to Carboxylic Acids: Acid-Catalyzed Hydrolysis01:13

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Hydrolysis of esters under acidic conditions proceeds through a nucleophilic acyl substitution. In the presence of excess water, the reaction proceeds in a reversible manner, forming carboxylic acids and alcohols.
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In this lesson, the oxidation of alcohols is discussed in depth. The various reagents used for oxidation of primary and secondary alcohols are detailed, and their mechanism of action is provided.
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Baeyer–Villiger oxidation converts aldehydes to carboxylic acids and ketones to esters. The reaction uses peroxy acids or peracids and is often catalyzed by acid. The reaction is named after its pioneers, Adolf von Baeyer and Victor Villiger. The reaction is achieved by a wide range of peracids such as m-chloroperoxybenzoic acid (mCPBA), perbenzoic acid (C6H5COOOH), peracetic acid (CH3COOOH), hydrogen peroxide (H2O2), and tert-butyl hydroperoxide (t-BuOOH).
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Pd-loaded modulated MOF-808: a bifunctional solid-acid catalyst for one-pot oxidation-acetalization.

Zipeng Li1,2, Jiaxin Geng1,2, Li Sun1,2

  • 1State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, P. R. China. yingya.liu@dlut.edu.cn.

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|November 11, 2025
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Summary

This study developed a bifunctional palladium/MOF-808 catalyst for efficient one-pot benzyl alcohol oxidation and acetalization. The engineered catalyst demonstrates high performance and stability for green chemistry applications.

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Area of Science:

  • Catalysis
  • Materials Science
  • Green Chemistry

Background:

  • Growing demand for fine chemicals necessitates efficient and sustainable catalytic processes.
  • Designing multifunctional solid catalysts for tandem reactions remains a significant challenge.
  • Catalytic cascade reactions offer operational efficiency and high atom economy.

Purpose of the Study:

  • To rationally design a bifunctional palladium/MOF-808 catalyst for one-pot tandem oxidation-acetalization.
  • To tailor the acidic properties of MOF-808 through defect engineering for enhanced catalytic performance.
  • To investigate the synergy between metallic and acidic sites in the bifunctional catalyst.

Main Methods:

  • Synthesis of MOF-808 variants using different modulating agents for defect engineering.
  • Structural characterization (XPS, TEM) to confirm MOF structure and Pd nanoparticle dispersion.
  • Immobilization of palladium nanoparticles via double-solvent impregnation.
  • Testing the bifunctional catalyst for benzyl alcohol oxidation and acetalization.

Main Results:

  • Engineered MOF-808-H2O/HAc/HCl exhibited enhanced acidity while preserving the microporous framework.
  • Optimal Pd/MOF-808-H2O/HAc/HCl achieved 99.9% benzyl alcohol conversion and 82.8% acetal selectivity.
  • The catalyst outperformed traditional zeolite-supported Pd catalysts and demonstrated excellent stability over six cycles without leaching.

Conclusions:

  • Rational design of bifunctional Pd/MOF-808 catalysts enables efficient tandem catalysis.
  • Tailored moderate acidity of the MOF-808 support is crucial for directing selectivity in acetalization.
  • The catalyst exhibits high stability and recyclability, highlighting its potential for sustainable fine chemical synthesis.