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Related Concept Videos

Catalysis02:50

Catalysis

30.0K
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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Woodward–Hoffmann Selection Rules and Microscopic Reversibility01:34

Woodward–Hoffmann Selection Rules and Microscopic Reversibility

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Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
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Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

3.8K
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...
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Regioselectivity and Stereochemistry of Hydroboration02:36

Regioselectivity and Stereochemistry of Hydroboration

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A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
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Thermal and Photochemical Electrocyclic Reactions: Overview01:26

Thermal and Photochemical Electrocyclic Reactions: Overview

2.9K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
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Chemisorption Can Reverse Defect-Defect Interaction on Heterogeneous Catalyst Surfaces.

Liping Yu1, Adrienn Ruzsinszky2, Qimin Yan2

  • 1Department of Physics and Astronomy , University of Maine , Orono , Maine 04469 , United States.

The Journal of Physical Chemistry Letters
|November 12, 2019
PubMed
Summary
This summary is machine-generated.

Defect interactions in molybdenum disulfide (MoS2) surfaces influence hydrogen bonding. Sulfur vacancy interactions switch from repulsive to attractive upon hydrogen adsorption, impacting catalytic performance for hydrogen evolution reactions.

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Area of Science:

  • Materials Science
  • Catalysis
  • Surface Chemistry

Background:

  • Understanding defect-defect interactions is key for designing advanced catalysts.
  • Molybdenum disulfide (MoS2) is a promising nonprecious catalyst for hydrogen evolution.
  • Defect engineering is crucial for optimizing catalyst performance.

Purpose of the Study:

  • To elucidate the microscopic mechanism of sulfur vacancy-vacancy interactions during hydrogen adsorption on MoS2 surfaces.
  • To explain the influence of these interactions on hydrogen bonding and adsorption energy.
  • To provide insights for improving MoS2-based catalysts through defect control.

Main Methods:

  • First-principles calculations were employed to study defect interactions.
  • Analysis of in-gap vacancy states and their coupling.
  • Investigation of hydrogen adsorption on MoS2 surfaces with varying sulfur vacancy concentrations.

Main Results:

  • Sulfur vacancy-vacancy interactions are initially repulsive due to antibonding-like coupling of occupied in-gap states.
  • Upon hydrogen adsorption, these interactions become attractive.
  • This transition reduces hydrogen adsorption energy, correlating with increased vacancy concentration.

Conclusions:

  • The study reveals a dynamic shift in vacancy-vacancy interactions upon adsorbate binding.
  • This mechanism explains the observed decrease in hydrogen adsorption energy with higher defect densities.
  • Findings offer guidance for defect engineering to enhance catalytic activity.