A highly active iron-nitrogen-doped carbon nanotube catalyst for the oxygen reduction reaction (ORR) is produced by employing vertically aligned carbon nanotubes (VA-CNT) with a high specifi c surface area and iron(II) phthalocyanine (FePc) molecules. Pyrolyzing the composite easily transforms the adsorbed FePc molecules into a large number of iron coordinated nitrogen functionalized nanographene (Fe-N-C) structures, which serve as ORR active sites on the individual VA-CNT surfaces. The catalyst exhibits a high ORR activity, with onset and halfwave potentials of 0.97 and 0.79 V, respectively, versus reversible hydrogen electrode, a high selectivity of above 3.92 electron transfer number, and a high electrochemical durability, with a 17 mV negative shift of E 1/2 after 10 000 cycles in an oxygen-saturated 0.5 M H 2 SO 4 solution. The catalyst demonstrates one of the highest ORR performances in previously reported any-nanotube-based catalysts in acid media. The excellent ORR performance can be attributed to the formation of a greater number of catalytically active Fe-N-C centers and their dense immobilization on individual tubes, in addition to more effi cient mass transport due to the mesoporous nature of the VA-CNTs.
Nitrogen-doped graphene materials with abundant pyridinic and quaternary nitrogen species were selectively synthesized by thermal surface polymerization of nitrogen-containing aromatic molecules. Catalytic studies revealed that the oxygen reduction by nitrogen-doped graphene, containing pyridinic and quaternary nitrogen species, proceeds via a four- and two-electron reduction pathway, respectively, in alkali-based solutions.
Fluorine-doped carbon has a higher electrocatalytic oxygen evolution activity than pristine carbon black in alkaline media. The activity of oxygen evolution and characteristics of carbon to fluorine bond are controlled by pyrolysis temperature of Nafion.
Oxygen evolution reactions (OER) are important reactions for energy conversion. Metal-free carbon-based catalysts potentially contribute to the catalytic materials for OER. However, it has been difficult to understand the intrinsic catalytic activity of carbon materials, due to catalyst decomposition over the course of long-term reactions. Here, we report high oxygen evolution reaction catalytic activity of F-doped carbon in alkaline media. Intrinsic OER activity was evaluated from a combination of measurements using a rotating disk electrode and O2 sensor. The F-doped carbon catalyst is a highly active catalyst, comparable to state-of-the-art precious-metal-based catalysts such as RuO2.
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