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Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism01:13

Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Mechanism

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Carboxylic acids react with alcohols to yield esters via an acid-catalyzed condensation reaction called Fischer esterification. This is a nucleophilic acyl substitution reaction that proceeds via a tetrahedral intermediate, where a water molecule is eliminated as the leaving group.
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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.
During hydrolysis, the ester is first activated towards nucleophilic attack through the protonation of the carboxyl oxygen atom by the acid catalyst. The protonation makes the ester carbonyl carbon more electrophilic. In the next step, water acts as a nucleophile and adds to the...
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Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation01:22

Reactions of Aldehydes and Ketones: Baeyer–Villiger Oxidation

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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).
The carbonyl center is activated by...
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Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview01:20

Carboxylic Acids to Esters: Acid-Catalyzed (Fischer) Esterification Overview

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The Fischer esterification reaction was developed by the German chemist Emil Fischer in 1895. It is a condensation reaction between carboxylic acids and alcohols in an acidic medium to give esters and water.
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Aldehydes and Ketones to Alkenes: Wittig Reaction Overview01:19

Aldehydes and Ketones to Alkenes: Wittig Reaction Overview

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The Wittig reaction is the conversion of carbonyl compounds-aldehydes and ketones-to alkenes using phosphorus ylides, or the Wittig reagent. The reaction was pioneered by Prof. Georg Wittig, for which he was awarded the Nobel Prize in Chemistry.
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Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism01:14

Aldehydes and Ketones to Alkenes: Wittig Reaction Mechanism

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The Wittig reaction, which converts aldehydes or ketones to alkenes using phosphorus ylides, proceeds through a nucleophilic addition‒elimination process.
The reaction begins with the nucleophilic addition between a phosphorus ylide and the carbonyl compound. Due to its carbanionic character,  phosphorus ylide acts as a strong nucleophile and attacks the electrophilic carbonyl group. This generates a charge-separated dipolar intermediate called betaine. The negatively charged oxygen atom and...
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Selective Vapor-Phase Formic Acid Decomposition Over Carbon-Supported Rhenium Catalysts with Metallic, Carbide, and

Claudio Contreras-Díaz1,2, Verónica Naharro-Ovejero3, Claudio Araya-López1,2

  • 1Departamento de Ingeniería Química y Bioprocesos, Pontificia Universidad Católica de Chile, Avenida Vicuña Mackenna 4860, Macul, Santiago, Chile.

Chemistryopen
|September 23, 2025
PubMed
Summary

Formic acid decomposition for hydrogen production is efficient using rhenium carbide catalysts on graphite supports. Rhenium carbide demonstrates superior activity and selectivity under mild conditions, outperforming metallic and oxide rhenium phases.

Keywords:
Re phasescarbon supportsdecompositionformic acidheterogeneous catalysisrhenium

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Area of Science:

  • Catalysis
  • Materials Science
  • Chemical Engineering

Background:

  • Formic acid (FA) serves as a liquid organic hydrogen carrier due to its low decomposition temperature.
  • Hydrogen production from FA offers a sustainable energy pathway under mild conditions.
  • Noble metal catalysts are crucial for efficient FA decomposition.

Purpose of the Study:

  • To investigate the vapor-phase decomposition of formic acid.
  • To compare the catalytic activity of different rhenium phases (metal, carbide, oxide) supported on graphite and carbon nanotubes.
  • To identify the most effective rhenium phase and support for efficient hydrogen production.

Main Methods:

  • Catalytic decomposition experiments in a fixed-bed reactor.
  • Characterization of catalysts using N2 adsorption-desorption, H2-temperature-programmed reduction, TEM, TPD-NH3, TPR-methanol, XRD, and XPS.
  • Analysis of reaction products for activity and selectivity.
  • Determination of intrinsic activity per active site.

Main Results:

  • Graphite-supported rhenium catalysts exhibited higher activity than those supported on carbon nanotubes.
  • Rhenium carbide supported on graphite (ReC/G) showed superior performance at lower temperatures per active site.
  • All catalysts demonstrated high selectivity toward CO2, with ReC/G being the most active phase.

Conclusions:

  • Rhenium carbide is a more active phase for formic acid decomposition than metallic or oxide rhenium.
  • Graphite is a superior support material compared to carbon nanotubes for rhenium catalysts in this application.
  • The findings highlight the potential of ReC/G for efficient hydrogen production from formic acid under mild conditions.