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Metal-Ligand Bonds02:51

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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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Transition metals are defined as those elements that have partially filled d orbitals. As shown in Figure 1, the d-block elements in groups 3–12 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals.
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Crystal Field Theory
To explain the observed behavior of transition metal complexes (such as colors), a model involving electrostatic interactions between the electrons from the ligands and the electrons in the unhybridized d orbitals of the central metal atom has been developed. This electrostatic model is crystal field theory (CFT). It helps to understand, interpret, and predict the colors, magnetic behavior, and some structures of coordination compounds of transition metals.
CFT focuses on...
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Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
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Electrochemistry is the science involved in the interconversion of electrical and chemical reactions. Such reactions are called reduction-oxidation, or redox reactions. These important reactions are defined by changes in oxidation states for one or more reactant elements and include a subset of reactions involving the transfer of electrons between reactant species. Electrochemistry as a field has evolved to yield sufficient insights on the fundamental principles of redox chemistry and multiple...
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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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Atomic-Layer IrO Enabling Ligand Effect Boosts Water Oxidation Electrocatalysis.

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Researchers developed ultrathin iridium oxide (IrO2) layers on intermetallic IrVMn nanoparticles for enhanced oxygen evolution reaction (OER) electrocatalysis. This design improves catalytic activity and stability, crucial for efficient energy conversion.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Catalysis

Background:

  • The oxygen evolution reaction (OER) is critical for energy conversion technologies.
  • Iridium-based materials are promising OER electrocatalysts, but their efficiency is limited by the formation of active IrO2 layers.
  • Controlling the thickness and properties of these IrO2 layers is challenging.

Purpose of the Study:

  • To design and synthesize intermetallic IrVMn nanoparticles that induce the in situ formation of an ultrathin IrO2 layer.
  • To investigate the electronic interactions and surface reconstruction dynamics in the O-IrVMn/IrO2 system.
  • To evaluate the electrocatalytic performance and stability of the O-IrVMn/IrO2 catalyst for OER.

Main Methods:

  • Synthesis of intermetallic IrVMn nanoparticles.
  • In situ characterization using X-ray absorption near edge spectra (XANES) and extended X-ray absorption fine structure (EXAFS).
  • X-ray photoelectron spectroscopy (XPS) for surface analysis.
  • Density functional theory (DFT) calculations for theoretical validation.

Main Results:

  • The O-IrVMn/IrO2 catalyst exhibited an ultrathin IrO2 layer with lower Ir oxidation states and unsaturated oxygen coordination.
  • Achieved superior OER performance with an overpotential of 279 mV at 10 mA cm-2 and a mass activity of 2.3 A mg-1.
  • Demonstrated excellent catalytic stability with significantly reduced Ir dissolution compared to disordered catalysts.

Conclusions:

  • The intermetallic IrVMn strategy effectively induces the formation of an ultrathin IrO2 layer, enhancing the ligand effect for OER.
  • The ordered atomic arrangement in O-IrVMn/IrO2 minimizes metal leaching and stabilizes the active sites.
  • This approach offers a promising pathway for developing highly active and stable Ir-based OER electrocatalysts.