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Related Concept Videos

Valence Bond Theory02:42

Valence Bond Theory

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Coordination compounds and complexes exhibit different colors, geometries, and magnetic behavior, depending on the metal atom/ion and ligands from which they are composed. In an attempt to explain the bonding and structure of coordination complexes, Linus Pauling proposed the valence bond theory, or VBT, using the concepts of hybridization and the overlapping of the atomic orbitals. According to VBT, the central metal atom or ion (Lewis acid) hybridizes to provide empty orbitals of suitable...
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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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The presence of electron-donating, electron-withdrawing, or conjugating groups adjacent to a radical center, imparts electronic stabilization to the radicals. Examples of such electronically-stabilized radicals are triphenylmethyl, tetramethylpiperidine‐N‐oxide, and 2,2‐diphenyl‐1‐picrylhydrazyl. These radicals are remarkably stable and are known as persistent radicals. Some of the persistent radicals can even be isolated and purified.
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Coordination Number and Geometry02:57

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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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Catalysis02:50

Catalysis

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The presence of a catalyst affects the rate of a chemical reaction. A catalyst is a substance that can increase the reaction rate without being consumed during the process. A basic comprehension of a catalysts’ role during chemical reactions can be understood from the concept of reaction mechanisms and energy diagrams.
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Complexation Equilibria: Overview01:23

Complexation Equilibria: Overview

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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...
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Catalytic Reactions at Amine-Stabilized and Ligand-Free Platinum Nanoparticles Supported on Titania During Hydrogenation of Alkenes and Aldehydes
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Digging Its Own Site: Linear Coordination Stabilizes a Pt1/Fe2O3 Single-Atom Catalyst.

Ali Rafsanjani-Abbasi1, Florian Buchner2, Faith J Lewis1

  • 1Institute of Applied Physics, TU Wien, Vienna AT 1040, Austria.

ACS Nano
|September 18, 2024
PubMed
Summary

Platinum atoms on iron oxide support form a unique linear structure, reconfiguring the surface for enhanced catalytic activity. This finding is crucial for designing better single-atom catalysts.

Keywords:
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Area of Science:

  • Materials Science
  • Catalysis
  • Surface Chemistry

Background:

  • Accurate modeling of single-atom catalysts (SACs) requires understanding active site coordination.
  • Current methods often rely on idealized support surfaces, potentially misrepresenting real-world catalyst behavior.

Purpose of the Study:

  • Investigate the binding and coordination of platinum (Pt) atoms on the α-Fe2O3 (11̅02) facet.
  • Determine the preferred atomic configuration of Pt on this common SAC support material.

Main Methods:

  • Combined experimental techniques: scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS).
  • Extensive computational modeling using an evolutionary search algorithm based on density functional theory (DFT).

Main Results:

  • Pt atoms induce significant reconfiguration of the α-Fe2O3 surface.
  • A pseudolinear O-Pt-O coordination is energetically favored (0.84 eV) over configurations on an unperturbed surface.
  • This involves breaking Fe-O bonds, highlighting the dynamic nature of the active site.

Conclusions:

  • The linear coordination of Pt on α-Fe2O3 is a stable and reactive configuration.
  • This geometry likely balances thermal stability with reactant adsorption in Pt-based SACs.
  • Comprehensive structural searches are essential for accurate single-atom catalysis modeling.