Stöber synthesis of salen-formaldehyde resin polymer- and carbon spheres with high nitrogen content and application of the corresponding Mn-containing carbon spheres as efficient electrocatalysts for the oxygen reduction reaction.

Abstract

Salen-formaldehyde (SF) resin polymer spheres were synthesized by the Stöber method from 4,4′-dihydroxysalen (N,N′-bis-(4-hydroxysalicylidene)-ethylenediamine; a tetradentate N2O2 Schiff base ligand) and formaldehyde. The salen precursor was prepared by condensation of ethylenediamine with 2,4-dihydroxybenzaldehyde in methanol. The SF resin colloidal spheres were also prepared by using Pluronic F127 and ammonia as a porogenic agent and catalyst, respectively (SF-P). In addition, corresponding Mn(ii)-coordinated polymer spheres of the SF-P were synthesized (SF-P-Mn(ii)). Corresponding monodispersed carbon spheres of all of the abovementioned samples were also obtained by pyrolysis technique. All of the products were characterized with conventional microscopic and spectroscopic techniques, as well as other physical methods such as BET analysis. It was found that carbonization of the SF resin spheres results in carbon spheres with specific surface areas in the range of 499–528 m2 g−1 and average pore sizes in the range of 2.58–3.08 nm. Nitrogen content of the SF-MWHT (obtained hydrothermally in a methanol/water mixture), and SF-P-C@Mn (obtained from carbonization of SF-P-Mn(ii)) samples were as high as 27.5 wt% and 35.02 wt%, respectively. Finally, a glassy carbon electrode (GCE) modified with SF-P-C@Mn (SF-P-C@Mn/GCE) was prepared and its electrocatalytic activity was evaluated for oxygen reduction reaction (ORR) by linear sweep voltammetry (LSV). The LSV results showed that the SF-P-C@Mn/GCE has a higher current density and a lower negative potential in the ORR compared to GCE.