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Oxidation-Reduction Reactions03:11

Oxidation-Reduction Reactions

Oxidation–Reduction Reactions
Reduction of Alkenes: Catalytic Hydrogenation02:13

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.
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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.
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Heterogeneous Catalysis01:22

Heterogeneous Catalysis

Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...

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Updated: Jul 6, 2026

Synthesis and Performance Characterizations of Transition Metal Single Atom Catalyst for Electrochemical CO2 Reduction
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Mechanistic Promiscuity in Cobalt-Mediated CO2 Reduction Reaction: One- Versus Two-Electron Reduction Process.

Ayan Bera1, Sarah Bimmermann2, Philipp Gerschel2

  • 1Institut für Chemie, Humboldt-Universität zu Berlin, Brook-Taylor-Str. 2, 12489, Berlin, Germany.

Angewandte Chemie (International Ed. in English)
|May 21, 2025
PubMed
Summary

Researchers compared two cobalt complexes for carbon dioxide reduction (CO2RR). One complex selectively produced CO, while the other favored hydrogen evolution, highlighting the impact of subtle structural changes on CO2RR selectivity.

Keywords:
CO2 reductionElectrocatalysisH‐bondingOxalateRedox non‐innocent ligands

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Area of Science:

  • Electrochemistry
  • Catalysis
  • Coordination Chemistry

Background:

  • Electrocatalytic reduction of carbon dioxide (CO2RR) is crucial for sustainable energy.
  • Cobalt complexes with bipyridine ligands are promising CO2RR electrocatalysts.
  • Understanding the factors influencing CO2RR selectivity is essential for catalyst design.

Purpose of the Study:

  • To compare the CO2RR activity and selectivity of two cobalt complexes: [(Hbbpya)CoII]2+ and [(Mebbpya)CoII]2+.
  • To elucidate the molecular origin of differences in product selectivity between the two complexes.
  • To investigate the mechanistic pathways governing CO2 reduction.

Main Methods:

  • Electrocatalytic experiments were performed.
  • Spectroscopic methods were used to trap reactive intermediates.
  • Kinetic and theoretical studies were conducted to analyze reaction mechanisms.

Main Results:

  • [(Hbbpya)CoII]2+ exhibited high selectivity for carbon monoxide (CO) production.
  • [(Mebbpya)CoII]2+ showed higher hydrogen evolution activity and low CO selectivity.
  • A proton relay mechanism via the -NH group facilitated two-electron CO2 reduction in [(Hbbpya)CoII]2+.
  • One-electron chemistry prevailed for [(Mebbpya)CoII]2+, forming a CO2 radical anion intermediate.

Conclusions:

  • Subtle electronic and protonation changes significantly control CO2RR product selectivity.
  • The -NH moiety in [(Hbbpya)CoII]2+ enables efficient CO2 to CO conversion.
  • The -NCH3 moiety in [(Mebbpya)CoII]2+ leads to different reaction pathways and lower CO selectivity.