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Related Concept Videos

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Electrochemistry is the science involved in the interconversion of electrical and chemical reactions. Such reactions are called reduction-oxidation, or redox reactions. These important reactions are defined by changes in oxidation states for one or more reactant elements and include a subset of reactions involving the transfer of electrons between reactant species. Electrochemistry as a field has evolved to yield sufficient insights on the fundamental principles of redox chemistry and multiple...
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Electron carriers can be thought of as electron shuttles. These compounds can easily accept electrons (i.e., be reduced) or lose them (i.e., be oxidized). They play an essential role in energy production because cellular respiration is contingent on the flow of electrons.
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A solution containing appreciable amounts of a weak conjugate acid-base pair is called a buffer solution, or a buffer. Buffer solutions resist a change in pH when small amounts of a strong acid or a strong base are added. A solution of acetic acid and sodium acetate is an example of a buffer that consists of a weak acid and its salt: CH3COOH (aq) + CH3COONa (aq). An example of a buffer that consists of a weak base and its salt is a solution of ammonia and ammonium chloride: NH3 (aq) + NH4Cl...
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Buffer capacity is the quantitative measure of a buffer to resist the change in pH. As shown in the following equation, the buffer capacity, denoted by 'beta', is expressed as the number of moles of acid or base needed to change the pH of a one-liter buffer solution by 1 unit. Here, Ca and Cb indicate the number of moles of acid and base, respectively. Note that dpH represents the change in pH.
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Tuning Redox Active Polyoxometalates for Efficient Electron-Coupled Proton-Buffer-Mediated Water Splitting.

Jie Lei1, Jun-Jie Yang1, Ting Liu1

  • 1State Key Laboratory for Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical Engineering, iChem (Collaborative Innovation Center of Chemistry for Energy Materials), Xiamen University, Xiamen, Fujian, 361005, P. R. China.

Chemistry (Weinheim an Der Bergstrasse, Germany)
|July 17, 2019
PubMed
Summary

We enhanced water splitting using a novel polyoxometalate cluster, H6ZnW12O40. This redox mediator enables efficient, on-demand hydrogen generation with high decoupling and energy efficiency.

Keywords:
H2 storage and transportationelectron-coupled proton bufferpolyoxometalateswater splitting

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Area of Science:

  • Materials Chemistry
  • Electrochemistry
  • Catalysis

Background:

  • Water splitting is crucial for sustainable hydrogen production.
  • Polyoxometalates (POMs) are explored as redox mediators for water splitting.
  • Tuning POM redox properties is key to improving efficiency.

Purpose of the Study:

  • To enhance electron-coupled proton-buffer-mediated water splitting.
  • To investigate the role of heteroatom substitution in Keggin-type POMs.
  • To achieve on-demand hydrogen generation with high efficiency and decoupling.

Main Methods:

  • Synthesized and characterized Keggin-type polyoxometalate clusters, focusing on H6ZnW12O40.
  • Tuned redox properties by heteroatom substitution in the POM structure.
  • Evaluated performance in an electrolytic cell for water splitting and hydrogen generation.

Main Results:

  • H6ZnW12O40 demonstrated a doubled electron and proton transfer capacity (4e/4H) compared to traditional POMs.
  • Achieved 95.5% decoupling efficiency and 83.3% electrochemical energy efficiency for hydrogen generation.
  • Exhibited excellent cycling stability with near 100% H2-mediated capacity retention over 200 cycles and >92% coulombic efficiency.

Conclusions:

  • Heteroatom substitution in POMs effectively tunes redox properties for enhanced water splitting.
  • H6ZnW12O40 is a high-performance redox mediator for efficient and on-demand hydrogen production.
  • The developed strategy offers a promising pathway for advanced electrochemical energy conversion.