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Related Concept Videos

Catalysis02:50

Catalysis

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.
Catalysis01:27

Catalysis

Catalysis influences the rate of chemical reactions by providing an alternative reaction pathway with lower activation energy. A catalyst speeds up a reaction, but it is not consumed during the process. The fundamental principle of catalysis is the ability of a catalyst to alter the reaction mechanism, often introducing a more efficient pathway than the uncatalyzed process.In a catalyzed reaction, the catalyst participates directly in the reaction mechanism. It interacts with reactants to form...
Introduction to Mechanisms of Enzyme Catalysis01:13

Introduction to Mechanisms of Enzyme Catalysis

For many years, scientists thought that enzyme-substrate binding took place in a simple "lock-and-key" fashion. This model stated that the enzyme and substrate fit together perfectly in one instantaneous step. However, current research supports a more refined view scientists call induced fit. The induced-fit model expands upon the lock-and-key model by describing a more dynamic interaction between enzyme and substrate. As the enzyme and substrate come together, their interaction causes a mild...
Introduction to Mechanisms of Enzyme Catalysis01:13

Introduction to Mechanisms of Enzyme Catalysis

For many years, scientists thought that enzyme-substrate binding took place in a simple "lock-and-key" fashion. This model stated that the enzyme and substrate fit together perfectly in one instantaneous step. However, current research supports a more refined view scientists call induced fit. The induced-fit model expands upon the lock-and-key model by describing a more dynamic interaction between enzyme and substrate. As the enzyme and substrate come together, their interaction causes a mild...
Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids02:04

Oxidation of Alkenes: Anti Dihydroxylation with Peroxy Acids

Diols are compounds with two hydroxyl groups. In addition to syn dihydroxylation, diols can also be synthesized through the process of anti dihydroxylation. The process involves treating an alkene with a peroxycarboxylic acid to form an epoxide. Epoxides are highly strained three-membered rings with oxygen and two carbons occupying the corners of an equilateral triangle. This step is followed by ring-opening of the epoxide in the presence of an aqueous acid to give a trans diol.
Heterogeneous Catalysis01:22

Heterogeneous Catalysis

Heterogeneous catalysis involves a catalyst in a different phase from the reactants. It is a process where the catalyst and the reactants are in distinct phases, typically solid and gas or liquid.Most heterogeneous catalysts are metals, metal oxides, or acids. The list includes transition metals like iron (Fe), cobalt (Co), nickel (Ni), palladium (Pd), platinum (Pt), chromium (Cr), manganese (Mn), tungsten (W), silver (Ag), and copper (Cu). These metals possess partially vacant d orbitals that...

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[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
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Acid-induced mechanism change and overpotential decrease in dioxygen reduction catalysis with a dinuclear copper

Dipanwita Das1, Yong-Min Lee, Kei Ohkubo

  • 1Department of Bioinspired Science, Ewha Womans University, Seoul 120-750, Korea.

Journal of the American Chemical Society
|February 28, 2013
PubMed
Summary

A dinuclear copper complex efficiently catalyzes the four-electron reduction of oxygen to water using ferrocene derivatives. Protonation activates the complex, lowering the reduction potential for efficient catalysis.

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Area of Science:

  • Inorganic Chemistry
  • Catalysis
  • Electrochemistry

Background:

  • Efficient catalytic reduction of molecular oxygen (O2) to water is crucial for energy conversion technologies.
  • Ferrocene (Fc) derivatives are common one-electron reductants, but their use in O2 reduction often requires strong driving forces.

Purpose of the Study:

  • To investigate the catalytic four-electron reduction of O2 using a dinuclear copper(II) complex.
  • To elucidate the mechanism and key intermediates involved in the catalytic cycle.

Main Methods:

  • Utilized a dinuclear copper(II) complex with a specific dinucleating ligand (XYLO).
  • Employed ferrocene (Fc) and 1,1'-dimethylferrocene (Me2Fc) as reductants in the presence of perchloric acid (HClO4).
  • Conducted kinetic studies and low-temperature detection of intermediates to clarify the reaction mechanism.

Main Results:

  • The dinuclear copper(II) complex [Cu(II)2(XYLO)(OH)](2+) efficiently catalyzes O2 reduction in acetone at 298 K.
  • Protonation with HClO4 shifts the reduction potential, enabling the use of weak reductants like Fc and Me2Fc.
  • Identified key intermediates, including a hydroperoxo complex, and elucidated the proton-coupled electron-transfer (PCET) pathway.

Conclusions:

  • The study demonstrates an efficient catalytic system for O2 reduction to water.
  • Protonation of the copper complex is key to lowering the overpotential and enabling catalysis with weak reductants.
  • The mechanistic insights provide a foundation for designing advanced electrocatalysts.