Carbon materials slightly doped with heteroatoms such as nitrogen (N‐RFC) or sulfur (S‐RFC) are investigated as active catalysts for the electrochemical bielectronic oxygen reduction reaction (ORR) to H2O2. Mesoporous carbons with wide, accessible pores were prepared by pyrolysis of a resorcinol‐formaldehyde resin using a PEO‐b‐PS block copolymer as a sacrificial templating agent and the nitrogen and sulfur doping were accomplished in a second thermal treatment employing 1,10‐phenanthroline and dibenzothiophene as nitrogen and sulfur precursors, respectively. The synthetic strategy allowed to obtain carbon materials with very high surface area and mesopore volume without any further physicochemical post treatment. Voltammetric rotating ring‐disk measurements in combination with potentiostatic and galvanostatic bulk electrolysis measurements in 0.5 m H2SO4 demonstrated a pronounced effect of heteroatom doping and mesopores volume on the catalytic activity and selectivity for H2O2. N‐RFC electrode was employed as electrode material in a 45 h electrolysis showing a constant H2O2 production of 298 mmol g−1 h−1 (millimoles of H2O2 divided by mass of catalyst and electrolysis time), with a faradic efficiency (FE) up to 61 % and without any clear evidence of degradation. The undoped carbon RFC showed a lower production rate (218 mmol g−1 h−1) but a higher FE of 76 %, while the performances drastically dropped when S‐RFC (production rate 11 mmol g−1 h−1 and FE=39 %) was used.
Highly accessible surface area and heteroatom-doping are desired properties for carbon electrode materials to be used in electrochemical supercapacitors. In this paper, nitrogen and sulfur doped carbon materials with wide mesopores (13-14 nm) were synthetized according to a hard template approach by pyrolysis of sucrose, 1,10-phenanthroline or dibenzothiophene as carbon, nitrogen-carbon or sulfur-carbon precursors, respectively. The morphology and dimension of mesopores were induced by sacrificial SiO2 nanoparticles (10-20 nm), which are removed at the end of synthesis by an etching solution to reveal a network of hemispherical pores. The interconnected pore structure was confirmed by scanning electron microscopy and transmission electron microscopy. X-ray photoemission spectroscopy and elemental analysis confirmed the presence of nitrogen and sulfur functional groups. The prepared materials were fully characterized by cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy in 0.5 M H2SO4. Notwithstanding the small surface (200 m2g-1) determined by BET method, the nitrogen doped mesoporous carbon showed high specific gravimetric (∼170 F g-1) and surface (∼835 F m-2) capacitances that are comparable to those of materials with much higher surface area (5-10-fold higher)
In this paper, nitrogen doped carbon materials with mesopores 4–8 nm‐wide and a high surface area of ca.1100 m2 g−1 were synthesized according to an innovative hard template method. Sucrose was used as carbon source and propylamine functionalized silica acted as both nitrogen source and templating agent. The novel doped carbons were compared with mesoporous carbons featuring similar texture properties (pore size and surface area) but obtained by the pyrolysis of sucrose or 1,10‐phenantholine and employing non‐functionalized silica as a templating agent. The interest of this investigation is to understand how doping occurs when a functionalized silica is employed, and whether the nitrogen doping remains a surface property or it is extended also to the bulk of the material, influencing the morphological and the electrical properties of the resulting carbon. X‐ray photoemission spectroscopy, elemental analysis, and EDX confirmed the doping action of the functionalized silica and the electrochemical characterization allowed to compare the different performances as supercapacitor materials.
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