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    Isomerization and Redox Tuning: Reorganizing the Maya Blue Puzzle from Synthetic, Spectral, and Electrochemical Issues

    Autor: 
    Doménech-Carbó, Antonio
    ;
    Costero, Ana María
    ;
    Gil, Salvador
    ;
    Montoya, Noemí
    ;
    López-Carrasco, Alejandro
    ;
    Sáez, José A.
    ;
    Arroyo, Pau
    ;
    Doménech-Carbó, María Teresa
    Fecha: 
    2021
    Palabra clave: 
    electrochemistry; electrolytic reduction; isomerization; isomers; organic-inorganic materials; spectroscopic analysis; supersaturation; tuning; Scopus; WOS(2)
    Tipo de Ítem: 
    article
    URI: 
    https://reunir.unir.net/handle/123456789/13250
    DOI: 
    https://doi.org/10.1021/acs.jpcc.1c07932
    Dirección web: 
    https://pubs.acs.org/doi/10.1021/acs.jpcc.1c07932
    Open Access
    Resumen:
    A new approach to describe the composition of Maya blue (MB), an ancient organic-inorganic hybrid material, is presented. It is based on the analysis of attenuated total reflection-Fourier transform infrared (ATR-FTIR), Raman spectroscopy, UV-visible (vis) spectroscopic, and electrochemical data for indigo and dehydroindigo plus palygorskite hybrids, including a novel methodology using electrocatalytic effects on the oxygen reduction reaction. As a result, it is concluded that MB results from the tautomerization of indigo-to-indigo hemienol and the subsequent oxidation of these isomeric forms to dehydroindigo, all associated with the palygorskite clay framework, at temperatures above 100 °C. This model is also consistent with13C NMR data on indigo plus sepiolite hybrids. A consistent set of thermochemical parameters is obtained from ATR-FTIR, solid-state electrochemistry, and UV-vis diffuse reflectance spectra for the successive isomerization and redox tuning processes experienced by palygorskite-associated indigo.
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