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Potentiometry: Membrane Electrodes01:15

Potentiometry: Membrane Electrodes

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Membrane electrodes, also known as p-ion electrodes, use membranes that selectively interact with free analyte ions, generating a potential difference across the membrane. The resulting membrane potential, known as the asymmetry potential, is not zero even when analyte concentrations on both sides of the membrane are equal. The membrane's response is typically not selective to a single analyte but proportional to the concentration of all ions in the sample solution capable of interacting at...
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Ions as Acids and Bases02:54

Ions as Acids and Bases

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Salts with Acidic Ions
Salts are ionic compounds composed of cations and anions, either of which may be capable of undergoing an acid or base ionization reaction with water. Aqueous salt solutions, therefore, may be acidic, basic, or neutral, depending on the relative acid-base strengths of the salt’s constituent ions. For example, dissolving the ammonium chloride in water results in its dissociation, as described by the equation:
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Lewis Acids and Bases02:33

Lewis Acids and Bases

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In 1923, G. N. Lewis proposed a generalized definition of acid-base behavior in which acids and bases are identified by their ability to accept or to donate a pair of electrons and form a coordinate covalent bond.
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Ion Exchange01:17

Ion Exchange

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Ion exchange chromatography separates charged molecules from a solution by reversibly exchanging them with mobile, or 'active', ions associated with the oppositely charged stationary phase. This method can be used to separate ions, soften and deionize water, and purify solutions. The polymers comprising the ion-exchange column are high-molecular-weight and chemically stable polymers, crosslinked to be porous and essentially insoluble. They are also functionalized with either acidic or...
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Polyprotic Acids03:38

Polyprotic Acids

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Acids are classified by the number of protons per molecule that they can give up in a reaction. Acids such as HCl, HNO3, and HCN that contain one ionizable hydrogen atom in each molecule are called monoprotic acids. Their reactions with water are:
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Metal-Ligand Bonds02:51

Metal-Ligand Bonds

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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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Proton-donating cations enable efficient and stable acidic CO2 reduction in membrane electrode assemblies.

Shijia Feng1,2, Ziang Liu2, Dongfang Cheng3

  • 1National Laboratory of Solid State Microstructures, School of Sustainable Energy and Resources, Jiangsu Key Laboratory of Artificial Functional Materials, Collaborative Innovation Center of Advanced Microstructures, Frontiers Science Center for Critical Earth Material Cycling, Nanjing University, Nanjing 210008, China.

National Science Review
|September 29, 2025
PubMed
Summary

Ammonium (NH4+) improves electrochemical CO2 reduction (CO2R) in acidic systems by enhancing selectivity and lowering voltage. This novel approach offers a stable and efficient pathway for sustainable chemical production.

Keywords:
NH3/NH4+ recirculationacidic CO2 reductioncationic effectsmembrane electrode assembliesproton-donating effects

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Area of Science:

  • Electrochemistry
  • Catalysis
  • Sustainable Chemistry

Background:

  • Electrochemical CO2 reduction (CO2R) in acidic membrane electrode assemblies (MEAs) is promising for sustainable chemical production but faces challenges in selectivity, cell voltage, and stability.
  • Current methods using alkali cations improve selectivity but suffer from high overpotential and precipitation due to water's weak proton-donating ability, leading to operational issues.
  • Addressing these limitations is crucial for advancing CO2R technology towards practical applications.

Purpose of the Study:

  • To introduce and evaluate ammonium (NH4+) as a dual-function cation and proton donor in acidic MEAs for electrochemical CO2 reduction.
  • To demonstrate how NH4+ can simultaneously enhance selectivity, reduce overpotential, and improve operational stability.
  • To overcome the limitations of traditional proton donors like water in CO2R processes.

Main Methods:

  • Utilizing NH4+ as both a cation and proton donor in acidic MEAs with a CoPc@CNT-NH2 catalyst.
  • Investigating the electromigration of NH4+ to the catalyst surface to stabilize intermediates and manage local proton concentration.
  • Analyzing the proton-donating ability of NH4+ compared to water under limited proton transport conditions.
  • Assessing the effect of NH4+ on bicarbonate decomposition and precipitate management.
  • Operating the system under specific conditions (100 mA cm-2, 60°C) and evaluating performance over 110 hours.

Main Results:

  • NH4+ demonstrated enhanced CO2 intermediate stabilization and reduced localized proton concentration, leading to high selectivity.
  • The superior proton-donating ability of NH4+ decreased the protonation barrier, lowering the CO2R overpotential and cell voltage.
  • NH4+ promoted efficient bicarbonate decomposition at lower temperatures, facilitating precipitate removal and enabling stable NH3/NH4+ recirculation.
  • Achieved an average CO2-to-CO selectivity of 86% at 100 mA cm-2 and 60°C.
  • Demonstrated stable operation for over 110 hours at an average cell voltage of 2.84 V, with 40.6% energy efficiency.

Conclusions:

  • Ammonium (NH4+) effectively functions as a proton-donating cation in acidic MEAs, simultaneously improving CO2R selectivity, reducing overpotential, and enhancing operational stability.
  • This strategy overcomes key limitations of water as a proton donor, paving the way for more efficient and practical electrochemical CO2 reduction.
  • The findings represent a significant advancement in acidic MEA-based CO2R, moving the technology closer to real-world implementation.