Fine tuning of electrosynthesis pathways by modulation of the electrolyte solvation structure

Abstract

Electrosynthesis is a method of choice for designing new synthetic routes owing to its ability to selectively conduct reactions at controlled potentials, high functional group tolerance, mild conditions and sustainability...

Introducing the use of a recyclable solid electrolyte for waste minimization in electrosynthesis: preparation of 2-aryl-benzoxazoles under flow conditions

“…Electrochemical synthesis requires electrolyte additives that dissolve in the reaction medium allowing the transmission of electrons in solution. 14 These electrolytes are generally non-recoverable species and used in large amounts. Even when used in catalytic amounts, they and their byproducts formed during the reaction must be separated from the final reaction mixture.…”

Correlating substrates reactivity at electrified interfaces with electrolyte structure in synthetically relevant organic solvent/water mixtures

“…Nevertheless, the past few years have seen a growing interest being paid to the role of non-covalent interactions in liquid electrolytes and at electrochemical interfaces, with numerous demonstrations of their role in governing the outcome of electrocatalytic and electrosynthetic reactions. [1][2][3] Hence, both the kinetics and selectivity of aqueous electrocatalytic reactions have been tuned by electrolyte engineering approaches, in particular through the use of tailored supporting salt ions. Pivotal results were obtained for the hydrogen evolution reaction (HER), 4,5 the oxygen evolution reaction (OER) 6,7 and the CO2 and N2 reduction reactions.…”

“…23,26 These mixtures constitute a novel class of electrolytes and offer a formidable playground to tune electrocatalytic and electrosynthetic reactions via the modulation of the electrolyte nano/microstructure. 1 Indeed, https://doi.org/10.26434/chemrxiv-2024-g1jhk-v2 ORCID: https://orcid.org/0000-0003-2300-7582 Content not peer-reviewed by ChemRxiv. License: CC BY-NC-ND 4.0 while binary mixtures of water and water-soluble organic solvents are macroscopically homogeneous, bulk heterogeneity can occur at different length scales depending on the molar fraction of water and the nature of the organic solvent.…”

Correlating Substrate Reactivity at Electrified Interfaces with the Electrolyte Structure in Synthetically Relevant Organic Solvent/Water Mixtures

“…The field of electrocatalysis has long been driven by the design of ever better electrocatalysts with optimal adsorption energy for reaction intermediates, allowing researchers to steer the selectivity and kinetics of various reactions. Nevertheless, the past few years have seen a growing interest being paid to the role of noncovalent interactions in liquid electrolytes and at electrochemical interfaces, with numerous demonstrations of their role in governing the outcome of electrocatalytic and electrosynthetic reactions. − Hence, both the kinetics and selectivity of aqueous electrocatalytic reactions have been tuned by electrolyte engineering approaches, in particular, through the use of tailored supporting salt ions. Pivotal results were obtained for the hydrogen evolution reaction (HER), , the oxygen evolution reaction (OER), , and the CO 2 and N 2 reduction reactions. − This strategy was also successfully adopted for electrosynthetic reactions in aqueous electrolytes, including to control the competition between the HER and the electrohydrodimerization of acrylonitrile. , In organic electrosynthesis, beyond the nature of supporting salt ions, the solvent itself can impact the selectivity.…”

“…In the quest toward greener reactants, mixtures of an organic solvent and water with a supporting salt (denoted as “hybrid electrolytes”) are currently investigated to harness water either as the oxygen atom source in anodic reactions − or as the proton/deuterium source in electrochemical protonation/deuteration of alkyl, aryl, and benzylic halides ,− and alkynes. , These mixtures constitute a novel class of electrolytes and offer a formidable playground to tune electrocatalytic and electrosynthetic reactions via the modulation of the electrolyte nano/microstructure . Indeed, while binary mixtures of water and water-soluble organic solvents are macroscopically homogeneous, bulk heterogeneity can occur at different length scales depending on the molar fraction of water and the nature of the organic solvent.…”