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Related Concept Videos

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

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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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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.
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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

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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.
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If a set of reactants can yield multiple constitutional isomers, but one of the isomers is obtained as the major product, the reaction is said to be regioselective. In such reactions, bond formation or breaking is favored at one reaction site over others.
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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...
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Catalysis02:50

Catalysis

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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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Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
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Controlling CO2 Hydrogenation Selectivity by Metal-Supported Electron Transfer.

Xiaoyu Li1,2, Jian Lin1, Lin Li1

  • 1CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 116023, Dalian, China.

Angewandte Chemie (International Ed. in English)
|July 16, 2020
PubMed
Summary

Controlling carbon dioxide (CO2) hydrogenation selectivity is key for producing valuable chemicals. Researchers found that altering titanium dioxide (TiO2) crystal phases or metal loadings reverses selectivity by changing electron transfer and hydrogen spillover.

Keywords:
CO2crystal phaseelectron transferhydrogen spilloverselectivity

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Area of Science:

  • Catalysis
  • Materials Science
  • Chemical Engineering

Background:

  • Controlling selectivity in carbon dioxide (CO2) hydrogenation is crucial for synthesizing value-added chemicals and fuels.
  • A lack of fundamental understanding hinders effective catalyst design for CO2 hydrogenation.
  • Developing catalysts with tunable selectivity remains a significant challenge in the field.

Purpose of the Study:

  • To investigate methods for completely reversing selectivity in ambient pressure CO2 hydrogenation.
  • To elucidate the underlying mechanism controlling selectivity based on catalyst properties.
  • To establish a rational design strategy for efficient catalyst development.

Main Methods:

  • Utilizing different crystal phases of titanium dioxide (TiO2) supports (anatase and rutile).
  • Varying metal loadings on anatase-TiO2 catalysts.
  • Employing operando spectroscopy and ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) for in-situ analysis.

Main Results:

  • Complete reversal of CO2 hydrogenation selectivity was achieved by changing TiO2 crystal phases or metal loadings.
  • Electron transfer from the metal to the support, influenced by hydrogen spillover, was identified as the key factor.
  • This electron transfer affects the adsorption and activation of carbon monoxide (CO) intermediates.

Conclusions:

  • Catalyst selectivity in CO2 hydrogenation can be precisely tuned by manipulating TiO2 crystal phases and metal loadings.
  • Understanding electron transfer and hydrogen spillover provides a pathway for rational catalyst design.
  • This approach offers potential for optimizing other catalytic reactions beyond CO2 hydrogenation.