Post-synthetic efficient functionalization of polyaniline with phosphorus-containing groups. Effect of phosphorus on electrochemical properties. (October 2019)

• Record Type: Journal Article
• Authors: Quílez-Bermejo, Javier; Ghisolfi, Alessio; Grau-Marín, Daniel; San-Fabián, Emilio; Morallón, Emilia; Cazorla-Amorós, Diego
• Is Part Of: European polymer journal. Volume 119(2019)
• Page Start: 272
• Page End: 280
• Publication Date: 2019-10
• Subjects: Polyaniline -- Phosphorus -- Post-modification -- Electrochemical properties -- Modified polyaniline; Polymers -- Periodicals; Polymerization -- Periodicals; Polymères -- Périodiques; Polymérisation -- Périodiques; Polymerization; Polymers; Periodicals; Electronic journals; 547.705
• DOI: 10.1016/j.eurpolymj.2019.07.048
• Languages: English
• ISSNs: 0014-3057

Abstract

Graphical abstract: Highlights: Efficient methodology for post-synthetic functionalization of polyaniline with phosphorus-containing compounds. The electroactivity of modified polyaniline depends on the phosphorus precursor. DFT results proved that the reaction occurs through the imine groups and the phosphorus atoms. Abstract: P-postmodified polyaniline was obtained by reacting phosphorus trichloride (PCl3 ) and chlorodiphenylphosphine (PPh2 Cl) and polyaniline (PANI), under mild conditions. The reaction was found to be very selective, as only the imine groups were involved in the P-functionalization, and efficient as well, affording a P-loading of 3 at.% and 5 at.% for PPh2 Cl and PCl3, respectively. All the polymers were characterized by different techniques and the results were endorsed by theoretical calculations. Experimental and Density Functional Theory results proved that the reaction occurs through the imine groups and the phosphorus atoms, generating NP bonds. The electrochemical properties of the NP modified materials were evaluated and the catalytic activity towards oxygen reduction reaction was measured. It was found that a high concentration of phenyl groups from PPh2 Cl (about 3 at.%) affected negatively the activity of the catalyst since they prevented the access of the oxygen molecules to the catalytic active sites. However, a lower amount of PPh2 groups (1 at.%) or the use of PCl3 avoided this hindrance and resulted in an improved catalytic activity with respect to pristine PANI.