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Metal ions can be separated from one another by complexation with organic ligands–the chelating agent– to form uncharged chelates. Here, the chelating agent must contain hydrophobic groups and behave as a weak acid, losing a proton to bind with the metal. Since most organic ligands used in this process are insoluble or undergo oxidation in the aqueous phase, the chelating agent is initially added to the organic phase and extracted into the aqueous phase. The metal-ligand complex is...
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The hemoglobin in the blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes.
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During the electron transport chain, electrons from NADH and FADH2 are first transferred to complexes I and II, respectively. These two complexes then transfer the electrons to ubiquinol, which carries them further to complex III. Complex III passes the electrons across the intermembrane space to Cyt c, which carries them further to complex IV. Complex IV donates electrons to oxygen and reduces it to water. As electrons pass through complexes I, III, and IV, the energy released aids the pumping...
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A type of Lewis acid-base chemistry involves the formation of a complex ion (or a coordination complex) comprising a central atom, typically a transition metal cation, surrounded by ions or molecules called ligands. These ligands can be neutral molecules like H2O or NH3, or ions such as CN− or OH−. Often, the ligands act as Lewis bases, donating a pair of electrons to the central atom. These types of Lewis acid-base reactions are examples of a broad subdiscipline called coordination...
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Electrodeposition is a technique used to separate an analyte from interferents by electrochemical processes. Here, the analyte is a metal ion that can be deposited on an electrode immersed in the sample solution. The electrochemical setup consists of an anode and a cathode. When an electric current is applied to the setup, oxidation occurs at the anode. At the cathode, which consists of a large metal surface, metal ions undergo reduction and deposit onto the surface.
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Mediating CO2 Electroreduction Activity and Selectivity over Atomically Precise Copper Clusters.

Li-Juan Liu1, Zhi-Yuan Wang1, Zhao-Yang Wang1

  • 1Henan Key Laboratory of Crystalline Molecular Functional Materials, Henan International Joint Laboratory of Tumor Theranostical Cluster Materials, Green Catalysis Center, College of Chemistry, Zhengzhou University, Zhengzhou, 450001, China.

Angewandte Chemie (International Ed. in English)
|June 8, 2022
PubMed
Summary
This summary is machine-generated.

Structurally precise copper (Cu) clusters are key for electrocatalytic carbon dioxide (CO2) reduction. Ditetrahedron-shaped Cu8 clusters show higher selectivity and efficiency for CO2 reduction than cube-shaped isomers.

Keywords:
Atomically PreciseCO2 ReductionCopper ClustersStructure-Activity Relationships

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • Atomically precise copper clusters are promising catalysts for electrocatalytic CO2 reduction.
  • Understanding structure-activity relationships is crucial but hindered by synthesis challenges.
  • Systematic studies comparing Cu cluster isomers for CO2 reduction are scarce.

Purpose of the Study:

  • To synthesize and investigate structurally precise Cu8 cluster isomers with distinct core structures (cube and ditetrahedron).
  • To evaluate their performance in electrocatalytic CO2 reduction.
  • To elucidate the structure-activity relationships governing CO2 reduction selectivity and activity.

Main Methods:

  • Synthesis of structurally precise Cu8 cluster isomers with cube and ditetrahedron core structures.
  • Electrocatalytic measurements to assess CO2 reduction performance (Faradaic efficiency, selectivity).
  • Theoretical investigations to understand reaction mechanisms and intermediate binding energies.

Main Results:

  • The ditetrahedron-shaped Cu8 cluster demonstrated significantly higher Faradaic efficiency for formic acid (≈92%) at -1.0 V compared to the cube-shaped isomer.
  • The ditetrahedron-shaped Cu8 cluster exhibited enhanced selectivity for CO2 reduction.
  • Theoretical studies indicated reduced competition from hydrogen evolution and lower free energies for HCOO* intermediates on the ditetrahedron-shaped cluster.

Conclusions:

  • The core structure of Cu8 clusters critically influences their electrocatalytic performance for CO2 reduction.
  • Ditetrahedron-shaped Cu8 clusters are superior catalysts for selective and efficient CO2 to formic acid conversion.
  • Computational insights support the experimental findings, highlighting the role of intermediate binding and competing reactions.