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Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...

Reduction of Alkenes: Catalytic Hydrogenation

Reduction of Alkenes: Catalytic Hydrogenation

Alkenes undergo reduction by the addition of molecular hydrogen to give alkanes. Because the process generally occurs in the presence of a transition-metal catalyst, the reaction is called catalytic hydrogenation.
Metals like palladium, platinum, and nickel are commonly used in their solid forms — fine powder on an inert surface. As these catalysts remain insoluble in the reaction mixture, they are referred to as heterogeneous catalysts.
The hydrogenation process takes place on the...

Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation

Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation

Unlike the easy catalytic hydrogenation of an alkene double bond, hydrogenation of a benzene double bond under similar reaction conditions does not take place easily. For example, in the reduction of stilbene, the benzene ring remains unaffected while the alkene bond gets reduced. Hydrogenation of an alkene double bond is exothermic and a favorable process. In contrast, to hydrogenate the first unsaturated bond of benzene, an energy input is needed; that is, the process is endothermic. This is...

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

Introduction
Like alkenes, alkynes can be reduced to alkanes in the presence of transition metal catalysts such as Pt, Pd, or Ni. The reaction involves two sequential syn additions of hydrogen via a cis-alkene intermediate.

Structural Isomerism

Structural Isomerism

Isomerism in Complexes
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...

Catalysis

Catalysis

The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.

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Updated: Jun 18, 2025

Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production

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Regulating Second-Shell Coordination in Cobalt Single-Atom Catalysts toward Highly Selective Hydrogenation.

Yunxia Duan, Yongming Xia, Yuxuan Ling

|July 31, 2024

Summary

This study developed cobalt single-atom catalysts (Co-SACs) with sulfur in the second coordination shell for selective hydrogenation. These catalysts show superior activity and durability, highlighting the importance of the second-shell atom for catalyst performance.

Keywords:

high-value chemicals non-noble metal catalysts p-chloronitrobenzene second-shell coordination atom single-atom catalysts

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Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes

Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes

Published on: June 24, 2022

Area of Science:

Catalysis
Materials Science
Surface Chemistry

Background:

Single-atom catalysts (SACs) offer high atom efficiency and tunable properties.
The local coordination environment of metal centers is crucial for catalyst performance.
Developing efficient SACs for selective hydrogenation remains a challenge.

Purpose of the Study:

To design and synthesize cobalt single-atom catalysts (Co-SACs) with sulfur atoms in the second coordination shell.
To investigate the effect of the second-shell sulfur atoms on the selective hydrogenation of halo-nitrobenzene.
To elucidate the structure-activity relationship in Co-SACs for enhanced catalytic performance.

Main Methods:

Synthesis of nitrogen-doped carbon matrix supported Co-SACs with second-shell sulfur.
Synchrotron-based X-ray absorption spectroscopy (XAS) for structural characterization.
Density functional theory (DFT) calculations for mechanistic insights.
In situ characterization techniques to monitor catalytic processes.

Main Results:

Co-SACs with second-coordination shell S atoms were successfully synthesized and characterized.
The catalysts exhibited excellent activity and durability for selective hydrogenation of halo-nitrobenzene.
Performance surpassed that of many precious metal-based catalysts.
Identification of a beneficial Co-O bond formation at Co1N4-S active sites.

Conclusions:

The presence of sulfur atoms in the second coordination shell significantly enhances the activity and selectivity of Co-SACs.
The Co-O bond formation and reduced energy barriers at Co1N4-S moieties are key to the observed high performance.
This work establishes a clear correlation between the second-shell coordination environment and the catalytic performance of SACs.