Self-assembled monolayers for electrostatic electrocatalysis and enhanced electrode stability in thermogalvanic cells

Waste heat is ubiquitous; as such, sustainable and long-lasting devices are required to convert it into more useful forms of energy that can make use of this abundant potential resource. Thermogalvanic cells (or thermocells) can use the thermoelectrochemical properties of redox couples to achieve th...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2024-05, Vol.15 (18), p.6958-6964
Main Authors: Laws, Kristine, Buckingham, Mark A, Aldous, Leigh
Format: Article
Language:English
Subjects:
Chemistry
Electrocatalysis
Electrodes
Energy conversion
Gold
Monolayers
Nanomaterials
Potassium ferricyanide
Rechargeable batteries
Redox reactions
Self-assembled monolayers
Self-assembly
Stability
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Summary:Waste heat is ubiquitous; as such, sustainable and long-lasting devices are required to convert it into more useful forms of energy that can make use of this abundant potential resource. Thermogalvanic cells (or thermocells) can use the thermoelectrochemical properties of redox couples to achieve this; entropy-driven redox reactions allow them to act as liquid thermoelectrics. However, excellent electrocatalysis at the electrode surface is required for optimum conversion efficiency. Serendipitous observation of Nafion-based electrocatalysis prompted the exploration of electrostatically charged self-assembled monolayers (SAMs) inside a thermocell. Both electrostatic electrocatalysis and improved electrode stability were observed; in an aqueous K 3 [Fe(CN) 6 ]/K 4 [Fe(CN) 6 ]-based cell, modification with (3-trimethylammonium bromide)thiopropane resulted in higher electrical power, and protection against [Fe(CN) 6 ] 3−/4− -induced gold passivation, relative to bare gold. Molecular-based electrostatic electrocatalysis could be an alternative to precious metal-based nanomaterial electrocatalysis, and could be integrated with (nano)carbon-based electrodes to further enhance the ability of thermogalvanic and other electrochemical energy conversion devices, e.g. redox flow batteries. Thermogalvanic cells can convert temperature gradients ( e.g. waste heat) into electricity; here we demonstrate how electrostatically charged self-assembled monolayers can act as molecular electrocatalysts, plus reduce electrode passivation.
ISSN:2041-6520
2041-6539
DOI:10.1039/d3sc06766a