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Related Concept Videos

Metal-Ligand Bonds02:51

Metal-Ligand Bonds

21.3K
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.
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
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Extraction: Advanced Methods00:56

Extraction: Advanced Methods

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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...
506
Complexation Equilibria: Factors Influencing Stability of Complexes01:09

Complexation Equilibria: Factors Influencing Stability of Complexes

442
In complexation reactions, metal cations are the electron pair acceptors, and the ligands are the electron pair donors. The stability of the metal complexes depends primarily on the complexing ability of the central metal ion and the nature of the ligands. Generally, the complexing ability of the metal ion depends on the size and charge of the ion. As the metal ion size increases, the stability of the metal complexes decreases, provided that the valency of the metal ion and the ligands remain...
442
Electrodeposition01:08

Electrodeposition

691
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.
Electrodeposition can...
691
Complexation Equilibria: Overview01:23

Complexation Equilibria: Overview

764
Complexation reactions take place when dative or coordinate covalent bonds form between metal ions and ligands. The compounds formed in these reactions are called coordination compounds. The number of bonds formed between the metal ion and the ligands is called its coordination number. Generally, most metal ions in an aqueous solution are solvated by water molecules and thus exist as aqua complexes.
The equilibrium constant of the complexation reaction is represented as the formation constant...
764
Complexation Equilibria: The Chelate Effect01:19

Complexation Equilibria: The Chelate Effect

588
In complexation reactions, metal atoms or cations interact with ligands to form donor-acceptor adducts called metal complexes. Ligands that bind through one donor site are monodentate, ligands with two donor sites are bidentate, and those with more than two donor sites are polydentate ligands. For example, ethylene diamine is a bidentate ligand that binds through two nitrogen donor atoms, forming a five-membered ring. EDTA is a polydentate ligand that binds through four oxygen and two nitrogen...
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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
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Stabilizing copper sites in coordination polymers toward efficient electrochemical C-C coupling.

Yongxiang Liang1, Jiankang Zhao1, Yu Yang2

  • 1Hefei National Research Center for Physical Sciences at the Microscale, CAS Key Laboratory of Strongly-Coupled Quantum Matter Physics, Key Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education Institutes, Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.

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|January 29, 2023
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Stable single-site copper coordination polymers catalyze carbon dioxide electroreduction to ethylene with enhanced selectivity. These catalysts maintain structural integrity, enabling efficient multi-carbon product formation for net-zero emissions.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • Electrochemical reduction of carbon dioxide (CO2) using renewable electricity is crucial for achieving net-zero carbon emissions.
  • Single-site catalysts are key for carbon-carbon coupling to produce valuable multi-carbon (C2+) products, but often degrade into metallic agglomerations under reaction conditions.

Purpose of the Study:

  • To develop a stable single-site catalyst for efficient CO2 electroreduction.
  • To investigate the mechanism of C-C coupling and the role of catalyst structure in CO2 conversion.

Main Methods:

  • Synthesis and characterization of a stable single-site copper coordination polymer (Cu(OH)BTA).
  • In-situ/operando X-ray absorption, Raman, and infrared spectroscopies to study catalyst stability.
  • Electrochemical analysis, kinetic isotope effect studies, and computational calculations to elucidate the reaction mechanism.

Main Results:

  • The Cu(OH)BTA catalyst demonstrated a 1.5 times increase in C2H4 selectivity compared to metallic copper at 500 mA cm-2.
  • The catalyst remained structurally stable during the reaction, without transforming into metallic agglomerations.
  • Neighboring copper sites in the polymer facilitate the formation of an *OCCHO intermediate, promoting C-C coupling.
  • Stable operation of a full-device CO2 electrolysis cell at 1 ampere for 67 hours was achieved.

Conclusions:

  • Stable single-site copper coordination polymers can effectively catalyze CO2 electroreduction to C2+ products.
  • The designed catalyst structure prevents degradation and promotes efficient C-C coupling through dual-site activation.
  • This work offers a promising strategy for designing robust molecular catalysts for electrochemical CO2 conversion.