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Processes at Electrodes

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The electrode interacts with ions in the electrolyte solution at its interface. The rate of oxidation and reduction depends on the speed at which electrons can transfer through this interface. As ions attach to or leave the electrode surface, the electrode acquires a charge, and an electrical potential forms across the interface, making the process more difficult to reach equilibrium. The charge on the electrode affects the local ion concentrations in the solution, though thermal motion...
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Electrochemical cells are systems that convert chemical energy into electrical energy or use electrical energy to drive chemical reactions. They consist of two electrodes in contact with an electrolyte, where redox reactions enable electron transfer. Most electrochemical cells include two half-cells connected by an external wire for electron flow and a salt bridge for ion flow. The salt bridge contains an electrolyte solution and maintains charge neutrality by allowing ions—not...
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The final stage of cellular respiration is oxidative phosphorylation that consists of two steps: the electron transport chain and chemiosmosis. The electron transport chain is a set of proteins found in the inner mitochondrial membrane in eukaryotic cells. Its primary function is to establish a proton gradient that can be used during chemiosmosis to produce ATP and generate electron carriers, such as NAD+ and FAD, that are used in glycolysis and the citric acid cycle.
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Electrochemical systems provide a fascinating insight into the dynamic interplay of charged species within various phases. One notable example is the interaction between a membrane permeable to K⁺ ions but not to Cl⁻ ions, separating an aqueous KCl solution from pure water. As K⁺ ions diffuse through the membrane, they generate net charges on each phase, leading to a potential difference between them.Similarly, when a piece of Zn is immersed in an aqueous ZnSO₄ solution,...
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Electrochemistry is the branch of chemistry that studies the relationship between electrical quantities and chemical reactions, particularly oxidation and reduction. Oxidation is the loss of electrons from a substance, whereas reduction refers to the gain of electrons. A substance with a strong electron affinity is called an oxidizing agent (oxidant), and a reducing agent (reductant) is a species that donates electrons. Oxidation and reduction processes are pivotal to electrochemical reactions,...
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Electrocatalysis by Mass-Selected Ptn Clusters.

Alexander von Weber1, Scott L Anderson1

  • 1Chemistry Department, University of Utah , 315 S. 1400 E., Salt Lake City, Utah 84112, United States.

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|October 18, 2016
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Summary
This summary is machine-generated.

Size-selected platinum clusters exhibit size-dependent electrocatalytic activity for oxygen reduction and ethanol oxidation. Electronic structure, not just size, dictates activity, with small clusters potentially causing support corrosion.

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Area of Science:

  • Materials Science
  • Electrochemistry
  • Surface Science

Background:

  • Understanding nanoparticle catalysis is crucial for energy applications.
  • Platinum (Pt) clusters are key electrocatalysts, but their size-dependent properties require detailed study.
  • Controlling cluster size and studying their behavior without air exposure is essential for accurate mechanistic insights.

Purpose of the Study:

  • To prepare and characterize size-selected platinum (Pt) clusters (n ≤ 14) on glassy carbon (GC) and indium tin oxide (ITO) supports.
  • To investigate the electrocatalytic activity of these Pt clusters for oxygen reduction and ethanol oxidation reactions.
  • To elucidate the relationship between Pt cluster size, electronic structure, and catalytic performance, and compare it to nanoparticles and bulk Pt.

Main Methods:

  • Mass-selected Ptn+ ion deposition in ultrahigh vacuum (UHV) to create size-controlled electrodes.
  • In situ electrochemical characterization without significant air exposure.
  • Analysis of catalytic activity for oxygen reduction and ethanol oxidation reactions.
  • Correlation of activity with Pt 4d core level binding energies.

Main Results:

  • Strong cluster size effects were observed for both reactions, with activity varying nonmonotonically for ethanol oxidation.
  • Pt clusters showed significantly higher mass activity than Pt nanoparticles for ethanol oxidation.
  • Oxygen reduction selectivity (water vs. hydrogen peroxide) strongly depended on cluster size on ITO.
  • Unusual, highly efficient oxidation of the GC support by small Pt clusters was observed, raising concerns about electrode corrosion.

Conclusions:

  • Electrocatalytic activity of Pt clusters is strongly influenced by their size and electronic structure, not solely geometric factors.
  • Small Pt clusters can exhibit unique catalytic behaviors, including support oxidation, which differs from larger Pt nanoparticles.
  • Careful control of cluster size and minimizing air exposure are critical for studying and optimizing Pt-based electrocatalysts.