Details

Autor(en) / Beteiligte

• Palaniselvam, Thangavelu
• Biswal, Bishnu P.
• Banerjee, Rahul
• Kurungot, Sreekumar

Titel

Zeolitic Imidazolate Framework (ZIF)-Derived, Hollow-Core, Nitrogen-Doped Carbon Nanostructures for Oxygen-Reduction Reactions in PEFCs

Ist Teil von

• Chemistry : a European journal, 2013-07, Vol.19 (28), p.9335-9342

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2013

Quelle

Wiley-Blackwell Journals

Beschreibungen/Notizen

• The facile synthesis of a porous carbon material that is doped with iron‐coordinated nitrogen active sites (FeNC‐70) is demonstrated by following an inexpensive synthetic pathway with a zeolitic imidazolate framework (ZIF‐70) as a template. To emphasize the possibility of tuning the porosity and surface area of the resulting carbon materials based on the structure of the parent ZIF, two other ZIFs, that is, ZIF‐68 and ZIF‐69, are also synthesized. The resulting active carbon material that is derived from ZIF‐70, that is, FeNC‐70, exhibits the highest BET surface area of 262 m2 g−1 compared to the active carbon materials that are derived from ZIF‐68 and ZIF‐69. The HR‐TEM images of FeNC‐70 show that the carbon particles have a bimodal structure that is composed of a spherical macroscopic pore (about 200 nm) and a mesoporous shell. X‐ray photoelectron spectroscopy (XPS) reveals the presence of Fe‐N‐C moieties, which are the primary active sites for the oxygen‐reduction reaction (ORR). Quantitative estimation by using EDAX analysis reveals a nitrogen content of 14.5 wt. %, along with trace amounts of iron (0.1 wt. %), in the active FeNC‐70 catalyst. This active porous carbon material, which is enriched with Fe‐N‐C moieties, reduces the oxygen molecule with an onset potential at 0.80 V versus NHE through a pathway that involves 3.3–3.8 e− under acidic conditions, which is much closer to the favored 4 e− pathway for the ORR. The onset potential of FeNC‐70 is significantly higher than those of its counterparts (FeNC‐68 and FeNC‐69) and of other reported systems. The FeNC‐based systems also exhibit much‐higher tolerance towards MeOH oxidation and electrochemical stability during an accelerated durability test (ADT). Electrochemical analysis and structural characterizations predict that the active sites for the ORR are most likely to be the in situ generated NFeN2+2/C moieties, which are distributed along the carbon framework. Rabbit‐proof FeNC: FeN‐doped porous carbon (FeNC) materials were prepared by annealing [Fe(Phen)3]2+ that was embedded in ZIFs (ZIF‐68, ZIF‐69, and ZIF‐70) and electrochemically examined for their activity in oxygen‐reduction reactions in polymer electrolyte fuel cells (PEFCs) (see figure).