Air-oxidation of phenolic resin aerogels: backbone reorganization, formation of ring-fused pyrylium cations, and the effect on microporous carbons with enhanced surface areas

Hojat Majedi Far, Suraj Donthula, Tahereh Taghvaee, Adnan Malik Saeed, Zachary Garr, Chariklia Sotiriou-Leventis, Nicholas Leventis
  • RSC Advances, January 2017, Royal Society of Chemistry
  • DOI: 10.1039/c7ra10958j

phenolic resin aerogels and microporous carbons with enhanced surface areas

Why is it important?

This paper is a thorough investigation of the chemical transformations during pyrolytic conversion of phenolic resins to carbons, and reports that all carbons obtained from main-stream phenolic resins including phloroglucinol–formaldehyde (FPOL), phloroglucinol–terephthalaldehyde (TPOL), resorcinol–formaldehyde (RF), and phenol–formaldehyde (PF) contain fused pyrylium rings and charge-compensating phenoxides. Those four phenolic resins were prepared via a fast HCl-catalyzed process as low-density nanostructured solids classified as aerogels, which, owing to their open porosity, allowed air circulation through their bulk. In that regard, the first step of this study was the air-oxidation of those phenolic resin aerogels at 240 C. In FPOL and TPOL aerogels, that air-oxidation step kicked off a cascade of reactions leading to ring-fusion aromatization and formation of pyrylium O+-heteroaromatic rings in every repeat unit of the polymeric backbone. Despite the complexity of the process, those structural forms were well-defined, and were retained through pyrolytic carbonization (800 C). Under the same conditions (240 C/air), RF and PF aerogels did not undergo aromatization; instead, they just went through an autooxidation-like process that converted the –CH2– bridges between phenolic moieties into carbonyls (C]O). Importantly, however, upon further stepwise pyrolysis under Ar, by 600 C all four systems (TPOL, FPOL, RF and PF), irrespective of whether they had been previously oxidized or not, converged to a common chemical composition. Thereby, carbon produced by pyrolysis of phenolic resins at 800 C always contains fused pyrylium rings. All chemical analysis relied on FTIR, solid-state 13C NMR, XPS and CHN analysis. The only and significant difference made by the low-temperature (240 C) air-oxidation step was identified with the surface areas of carbons from aromatizable systems (TPOL and FPOL), which were higher than those from direct pyrolysis of as-prepared aerogels. Upon further reactive etching with CO2, those surface areas went as high as 2778 209 m2 g 1. Those findings are directly relevant to high surface area carbons for gas sorption (e.g., capture and sequestration of CO2) and ion exchange materials.

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The following have contributed to this page: Mr Hojat Majedi Far