[EN] MOLECULARLY TUNABLE HETEROGENEOUS CATALYSTS BY EDGE FUNCTIONALIZATION OF GRAPHITIC CARBONS [FR] CATALYSEURS HÉTÉROGÈNES MODIFIABLES MOLÉCULAIREMENT PAR UNE FONCTIONNALISATION TERMINALE DE CARBONES GRAPHITIQUES
[EN] MOLECULARLY TUNABLE HETEROGENEOUS CATALYSTS BY EDGE FUNCTIONALIZATION OF GRAPHITIC CARBONS [FR] CATALYSEURS HÉTÉROGÈNES MODIFIABLES MOLÉCULAIREMENT PAR UNE FONCTIONNALISATION TERMINALE DE CARBONES GRAPHITIQUES
Molecularly tunable heterogeneous catalysts by edge functionalization of graphitic carbons
申请人:Massachusetts Institute of Technology
公开号:US11005108B2
公开(公告)日:2021-05-11
Disclosed are surface immobilized (electro)catalysts that may be prepared by a condensation reaction that generates an aromatic unit that is robust to acid and base and elevated temperatures. Among their many desirable characteristics, the catalysts are far less prone to the bimolecular deactivation pathways commonly observed for homogeneous catalysts, and may be used in solvents with a range of polarities and dielectric strengths. The catalysts are suitable for a wide array of thermal catalytic reactions (polymerization, oxidation, hydrogenation, cross-coupling etc.) and as anodes and/or cathodes in fuel cells, electrolyzers, and in batteries and supercapacitors.
Condensation of ortho-phenylenediamine derivatives with ortho-quinone moieties at edge planes of graphitic carbon generates graphite-conjugated pyrazines (GCPs) that are active for oxygen reduction electro-catalysis in alkaline aqueous electrolyte. Catalytic rates of oxygen reduction are positively correlated with the electrophilicity of the active site pyrazine unit and can be tuned by over 70-fold by appending electron-withdrawing substituents to the phenylenediamine precursors. Discrete molecular analogs containing pyrazine moieties display no activity above background under identical conditions. This simple bottom up method for constructing molecularly well-defined active sites on ubiquitous graphitic solids enables the rational design of tunable heterogeneous catalysts.
Barraclough, Paul; Collard, David; Gillam, Janet, Journal of Chemical Research, Miniprint, 1996, # 9, p. 2316 - 2335
作者:Barraclough, Paul、Collard, David、Gillam, Janet、King, W. Richard、Smith, Steven
DOI:——
日期:——
MOLECULARLY TUNABLE HETEROGENEOUS CATALYSTS BY EDGE FUNCTIONALIZATION OF GRAPHITIC CARBONS
申请人:Massachusetts Institute of Technology
公开号:US20170047592A1
公开(公告)日:2017-02-16
Disclosed are surface immobilized (electro)catalysts that may be prepared by a condensation reaction that generates an aromatic unit that is robust to acid and base and elevated temperatures. Among their many desirable characteristics, the catalysts are far less prone to the bimolecular deactivation pathways commonly observed for homogeneous catalysts, and may be used in solvents with a range of polarities and dielectric strengths. The catalysts are suitable for a wide array of thermal catalytic reactions (polymerization, oxidation, hydrogenation, cross-coupling etc.) and as anodes and/or cathodes in fuel cells, electrolyzers, and in batteries and supercapacitors.