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Reduction of Alkenes: Catalytic Hydrogenation02:13

Reduction of Alkenes: Catalytic Hydrogenation

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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.
The hydrogenation process takes place on the...
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Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation02:24

Reduction of Alkynes to cis-Alkenes: Catalytic Hydrogenation

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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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Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation01:28

Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation

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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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Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

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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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Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide02:44

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Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
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Hydroboration-Oxidation of Alkenes03:08

Hydroboration-Oxidation of Alkenes

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In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
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Multifunctional Au/Hydroxide Interface toward Enhanced C-C Coupling for Solar-Driven CO2 Reduction into C2H6.

Lei Lu1,2, Yu Cheng1, Zhiping Liang1

  • 1School of Materials Science and Engineering, Jiangsu University, Zhenjiang212013, China.

Inorganic Chemistry
|February 2, 2023
PubMed
Summary

This study introduces a novel gold/hydroxide interface to overcome kinetic limitations in CO2 photoreduction, significantly enhancing C2+ product selectivity. The Au/ZnSn(OH)6 catalyst boosts ethane (C2H6) formation by optimizing electron transfer and hydroxyl availability.

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Area of Science:

  • Materials Science
  • Catalysis
  • Photochemistry

Background:

  • Photoreduction of carbon dioxide (CO2) to valuable chemical products is a key area in sustainable energy research.
  • Achieving high selectivity for C2+ products, such as ethane (C2H6), is challenging due to kinetic bottlenecks in C-C coupling reactions.
  • Existing catalysts often struggle to efficiently facilitate the multi-electron transfer required for C2+ formation.

Purpose of the Study:

  • To develop a multifunctional interface catalyst for enhanced CO2 photoreduction to C2+ products.
  • To investigate the role of metal-support electronic interactions and defect engineering in improving C-C coupling.
  • To achieve high selectivity towards ethane (C2H6) via CO2 photoreduction.

Main Methods:

  • Synthesis of a gold (Au) / ZnSn(OH)6 composite material.
  • Characterization of the catalyst's electronic structure and surface properties.
  • Photocatalytic evaluation of CO2 reduction under simulated solar irradiation, with product analysis using gas chromatography.

Main Results:

  • The Au/ZnSn(OH)6 catalyst demonstrated significantly enhanced selectivity for C2H6, utilizing approximately 50% of electrons for its formation.
  • Strong metal-support electronic interactions at the Au/ZnSn(OH)6 interface created an electric field, accelerating electron transfer for C-H and C-C bond formation.
  • Lattice hydroxyls (Sn-OH, Zn-OH) acted as H+ and oxygen vacancy (OV) donors, facilitated by hole-induced oxidation, further boosting C2H6 production.
  • Synergistic effects between OVs and Au sites promoted efficient CO hydrogenation to methyl (*CH3) and ethyl (*CH3*CH3) intermediates, leading to C2H6.

Conclusions:

  • The multifunctional Au/hydroxide interface, exemplified by Au/ZnSn(OH)6, effectively overcomes kinetic limitations in CO2 photoreduction.
  • The catalyst design promotes C-C coupling through enhanced electron transfer, H+ and OV supply, and synergistic catalytic sites.
  • This approach offers a promising strategy for selectively producing high-value C2+ hydrocarbons from CO2.