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Radical Oxidation of Allylic and Benzylic Alcohols01:21

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Activated manganese(IV) oxide can selectively oxidize allylic and benzylic alcohols via a radical intermediate mechanism. Primary allylic alcohols are oxidized to aldehydes, while secondary allylic alcohols yield ketones. The redox reaction of potassium permanganate with an Mn(II) salt such as manganese sulfate (under either alkaline or acidic conditions), followed by thorough drying, yields the oxidizing agent: activated MnO2. While MnO2 is insoluble in the solvents used for the reaction, the...
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The degradation of metals due to natural electrochemical processes is known as corrosion. Rust formation on iron, tarnishing of silver, and the blue-green patina that develops on copper are examples of corrosion. Corrosion involves the oxidation of metals. Sometimes it is protective, such as the oxidation of copper or aluminum, wherein a protective layer of metal oxide or its derivatives forms on the surface, protecting the underlying metal from further oxidation. In other cases, corrosion is...
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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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Synthesis and Evaluation of a Ruthenium-based Mitochondrial Calcium Uptake Inhibitor
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Active and durable R2MnRuO7 pyrochlores with low Ru content for acidic oxygen evolution.

Dmitry Galyamin1, Jorge Torrero2, Isabel Rodríguez1

  • 1Grupo de Energía y Química Sostenibles, Instituto de Catálisis y Petroleoquímica, CSIC. C/Marie Curie 2, 28049, Madrid, Spain.

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Summary

Low-ruthenium pyrochlores show high activity and durability for the oxygen evolution reaction (OER) in acidic media. These advanced electrocatalysts offer a promising alternative to iridium for green hydrogen production.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Green Chemistry

Background:

  • The oxygen evolution reaction (OER) is a key bottleneck in green hydrogen production using water electrolyzers.
  • Current state-of-the-art OER electrocatalysts rely heavily on iridium (Ir), a precious and scarce metal.
  • Ruthenium (Ru)-based catalysts present a viable alternative if their performance can be significantly enhanced.

Purpose of the Study:

  • To investigate the potential of low-ruthenium pyrochlores (R₂MnRuO₇) as highly active and durable electrocatalysts for the OER in acidic media.
  • To understand the structure-performance relationship governing the OER activity of these novel materials.
  • To evaluate the performance of these Ru-based catalysts in a functional water electrolyzer.

Main Methods:

  • Synthesis and characterization of low-Ru-content pyrochlores (R₂MnRuO₇, where R = Y, Tb, Dy).
  • Electrochemical evaluation of OER activity and durability in acidic media using techniques like linear sweep voltammetry and chronoamperometry.
  • Computational modeling (e.g., DFT) and experimental analysis to elucidate the catalytic mechanism.
  • Testing of the most promising catalyst (Y₂MnRuO₇) in a water electrolyzer setup.

Main Results:

  • Low-Ru-content pyrochlores, particularly Y₂MnRuO₇, demonstrated high activity and excellent durability for the OER.
  • Y₂MnRuO₇ exhibited a potential of 1.5 V at 10 mA cm⁻² and maintained stability for 40 hours or 5000 cycles up to 1.7 V.
  • Computational and experimental data indicated that the superior performance originates from Ru sites within RuMnOₓ surface layers.
  • A water electrolyzer utilizing Y₂MnRuO₇ (0.2 mgRu cm⁻²) achieved 1 A cm⁻² at 1.75 V and remained stable at 200 mA cm⁻² for over 24 hours.

Conclusions:

  • Low-ruthenium pyrochlores are highly effective electrocatalysts for the OER, offering a promising alternative to iridium.
  • The incorporation of Ru sites within RuMnOₓ surface layers is crucial for the enhanced OER performance.
  • Partial substitution of Ru with inexpensive cations in Ru-based catalysts warrants further investigation for improved OER efficiency in green hydrogen production.