Insights into the Electrocatalytic Activity of Fe,N-Glucose/Carbon Nanotube Hybrids for the Oxygen Reduction Reaction

Abstract

Glucose-derived carbon hybrids were synthesized by hydrothermal treatment in the presence of oxidized carbon nanotubes. Additionally, iron and nitrogen functionalities were incorporated into the carbon structure using different methodologies. The introduction of iron and nitrogen in a single step under a H2 atmosphere favored the formation of quaternary nitrogen and oxidized nitrogen, whereas the incorporation of nitrogen under an N2 atmosphere after doping the hybrids with iron mainly produced pyridinic nitrogen. The samples were characterized by scanning electron microscopy, X-ray spectroscopy, adsorption isotherms, inductively coupled plasma optical emission spectrometry, and Raman spectroscopy. The presence of iron and nitrogen in the carbons increases the onset potential toward oxygen reduction in KOH 0.1 mol L−1 by 130 mV (0.83 V), in comparison to carbonized glucose, whereas the reaction mechanism shifts closer to a direct pathway and the formation of HO2− decreases to 25% (3.5 electrons). The reaction rate also increased in comparison to the carbonized glucose, as observed by the decrease in the Tafel slope value from 117 to 61 mV dec−1. Furthermore, the incorporation of iron and nitrogen in a single step enhanced the short-term performance of the prepared electrocatalysts, which may also be due to the higher relative amount of quaternary nitrogen.