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Related Concept Videos

Interfacial Electrochemical Methods: Overview01:06

Interfacial Electrochemical Methods: Overview

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Interfacial electrochemical methods focus on the phenomena occurring at the boundary between an electrode and a solution, as opposed to bulk methods that concentrate on the solution's overall properties. These interfacial methods are classified as either static or dynamic based on the presence of a nonzero current in the electrochemical cell and the consistency of analyte concentrations. Static methods, such as potentiometry, measure the cell's potential without any significant current...
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Colloidal precipitates01:09

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The high insolubility of some precipitates can result in an unfavorable relative supersaturation. This can lead to colloidal particles with a large surface-to-mass ratio, where adsorption is promoted. For instance, in the precipitation of silver chloride, silver ions are adsorbed on the surface of the colloidal particles, forming a primary layer. This layer attracts ions of opposite charge (such as nitrate ions), forming a diffuse secondary layer of adsorbed ions. This electric double layer...
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Leveling Effect01:29

Leveling Effect

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In acid-base chemistry, the leveling effect refers to the limitation imposed by the solvent on the strength of acids and bases in solution. When a base stronger than the solvent's conjugate base is used, it deprotonates the solvent until the base is entirely consumed, making it ineffective against weaker acids. Conversely, an acid stronger than the solvent's conjugate acid protonates the solvent until the acid is depleted, rendering it ineffective against weaker bases. Essentially, the...
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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.
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Formation of Complex Ions03:45

Formation of Complex Ions

26.4K
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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Solvating Effects

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An understanding of the solvating effect helps rationalize the relation between solvation and acidity of the compound. In addition, this also explains the relative stability of conjugate bases for compounds with different pKa values. This lesson details, in-depth, the principle of solvating effects. The strength of an acid and the stability of its corresponding conjugate base are determined using pKa values. This observed relationship is a consequence of solvation, which is the interaction...
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Updated: Feb 27, 2026

In situ FTIR Spectroscopy as a Tool for Investigation of Gas/Solid Interaction: Water-Enhanced CO2 Adsorption in UiO-66 Metal-Organic Framework
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In situ FTIR Spectroscopy as a Tool for Investigation of Gas/Solid Interaction: Water-Enhanced CO2 Adsorption in UiO-66 Metal-Organic Framework

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Interfacial Adsorbate Competition Regulates Intermediate Stabilization and Onset Potential in Acidic CO2

Adrián Pinilla-Sánchez1, Suraj Panja2,3, Bárbara Polesso1

  • 1ICFO - Institut de Ciències Fotòniques, the Barcelona Institute of Science and Technology, Castelldefels Barcelona 08860, Spain.

Journal of the American Chemical Society
|February 26, 2026
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Summary

Anion interactions significantly impact electrochemical CO2 reduction (CO2R) selectivity in acidic media. Sulfate adsorption inhibits CO2R, while hydroxyl coadsorption enables intermediate formation, guiding catalyst design for improved performance.

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Area of Science:

  • Electrochemistry
  • Catalysis
  • Surface Science

Background:

  • Electrochemical CO2 reduction (CO2R) is crucial for carbon utilization but faces selectivity challenges, especially from the hydrogen evolution reaction (HER) in acidic conditions.
  • While proton source and cation concentration effects are known, the influence of anions on CO2R selectivity remains largely unexplored.

Purpose of the Study:

  • To investigate the role of anionic species in copper-catalyzed CO2R under acidic conditions.
  • To elucidate the mechanisms by which anions affect CO2R selectivity and intermediate formation at relevant current densities.

Main Methods:

  • In situ surface-enhanced Raman spectroscopy (SERS) was employed during CO2R on copper gas diffusion electrodes.
  • Theoretical simulations were combined with experimental data to analyze anion interactions and reaction pathways.

Main Results:

  • Sulfate adsorption was found to inhibit CO2R at low pH by delaying the formation of key intermediates.
  • Hydroxyl species coadsorption was observed to enable intermediate formation, influencing CO stabilization and coverage.
  • Anion competition was identified as a critical factor regulating the selectivity towards multicarbon products.

Conclusions:

  • Anion interactions play a pivotal role in governing CO2R selectivity in acidic electrolytes.
  • Understanding these interactions provides essential guidance for designing advanced catalyst-electrolyte interfaces to optimize CO2R performance and minimize HER.