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Coordination Number and Geometry02:57

Coordination Number and Geometry

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For transition metal complexes, the coordination number determines the geometry around the central metal ion. Table 1 compares coordination numbers to molecular geometry. The most common structures of the complexes in coordination compounds are octahedral, tetrahedral, and square planar.
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Coordination Compounds and Nomenclature02:54

Coordination Compounds and Nomenclature

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In most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 1a). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a...
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Metallic Solids02:37

Metallic Solids

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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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.
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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Lattice Centering and Coordination Number02:33

Lattice Centering and Coordination Number

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The structure of a crystalline solid, whether a metal or not, is best described by considering its simplest repeating unit, which is referred to as its unit cell. The unit cell consists of lattice points that represent the locations of atoms or ions. The entire structure then consists of this unit cell repeating in three dimensions. The three different types of unit cells present in the cubic lattice are illustrated in Figure 1.
Types of Unit Cells
Imagine taking a large number of identical...
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Bonding in Metals02:32

Bonding in Metals

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Metallic bonds are formed between two metal atoms. A simplified model to describe metallic bonding has been developed by Paul Drüde called the “Electron Sea Model”. 
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Synthesis and Characterization of Functionalized Metal-organic Frameworks
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Metal-Organic Frameworks Mediate Cu Coordination for Selective CO2 Electroreduction.

Dae-Hyun Nam1, Oleksandr S Bushuyev1, Jun Li1,2

  • 1Department of Electrical and Computer Engineering , University of Toronto , 10 King's College Road , Toronto , Ontario M5S 3G4 , Canada.

Journal of the American Chemical Society
|August 17, 2018
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Researchers developed a new method using metal-organic frameworks (MOFs) to create copper (Cu) clusters. This strategy enhances the electrochemical carbon dioxide reduction reaction (CO2RR) for producing valuable multi-carbon products like ethylene.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • The electrochemical carbon dioxide reduction reaction (CO2RR) is crucial for converting CO2 into valuable chemicals.
  • Copper (Cu) clusters are promising catalysts for CO2RR, but controlling their selectivity, especially for multi-carbon products, remains challenging.
  • Surface coordination number (CN) of Cu active sites significantly influences CO2RR outcomes.

Purpose of the Study:

  • To develop a strategy for regulating Cu cluster formation using metal-organic frameworks (MOFs) to enhance CO2RR towards multi-carbon products.
  • To promote undercoordinated Cu sites by controlling the structure of Cu dimers, precursors to Cu clusters.
  • To establish a structure-activity relationship between Cu cluster CN and CO2RR selectivity.

Main Methods:

  • Utilized HKUST-1, a metal-organic framework (MOF), as a template for Cu cluster formation.
  • Thermally treated HKUST-1 to distort symmetric Cu dimers into asymmetric motifs, creating undercoordinated sites.
  • Employed electron paramagnetic resonance (EPR) and in situ X-ray absorption spectroscopy (XAS) to characterize the Cu clusters and their electronic states.
  • Investigated the effect of varying material processing conditions on Cu dimer structure and CO2RR performance.

Main Results:

  • Successfully promoted the formation of Cu clusters with low coordination numbers (CN) from distorted Cu dimers within HKUST-1.
  • Achieved a record 45% Faradaic efficiency (FE) for C2H4 (ethylene) production using these MOF-derived Cu cluster catalysts.
  • Demonstrated that tuning the Cu-Cu CN in Cu clusters is key to controlling CO2RR selectivity.

Conclusions:

  • The MOF-regulated synthesis strategy effectively controls Cu cluster formation and promotes undercoordinated active sites.
  • This approach offers a pathway to selectively produce multi-carbon products from CO2 electroreduction.
  • The established structure-activity relationship provides insights for designing advanced Cu catalysts for CO2RR.