FeN_x/FeS_x-Anchored Carbon Sheet–Carbon Nanotube Composite Electrocatalysts for Oxygen Reduction

Abstract

Even though various Pt-free electrocatalysts for oxygen reduction reaction (ORR) have been introduced, many of them are found to be active only in alkaline conditions. Considering Nafion, phosphoric acid-doped polybenzimidazole (PBI), and so on as the prominent ionomer membranes, used in the commercially available polymer electrolyte membrane fuel cells (PEMFCs), it becomes important that any development on the Pt-free catalysts should ensure the better ORR performance under acidic conditions. The present work effectively tackles this issue, where an ORR-based catalyst could be prepared with simultaneous incorporation of both Fe−N and Fe−S active sites on in situ generated carbon sheets which are spatially separated by the carbon nanotube (CNT) network. This catalyst shows ability to perform under both acidic and basic conditions. This has been achieved by growing a polyethylenedioxythiophene polymer network in the presence of CNT and melamine followed by its pyrolysis under an inert atmosphere. The catalyst formed at 900 °C (PMCNT-900) displays 0.94 V onset potential for ORR under acidic electrolyte conditions, which corresponds to 60 mV overpotential compared to its 40 wt % Pt/C counterpart. Interestingly, in single cell demonstration of Nafion-based PEMFC with PMCNT-900 as the cathode catalyst, the system delivered a maximum power density (PD) of 500 and 275 mW/cm 2 at 60 °C under H 2 −O 2 and H 2 −air feed conditions, respectively. On the other hand, in a single cell test in the anion exchange membrane fuel cell (AEMFC) mode, a maximum power density of 65 mW/cm 2 at 50 °C could be achieved with the same cathode catalyst, which is a comparable value obtained while employing Pt/C as the cathode. These results, thus, infer to the efficiency of the catalyst to facilitate ORR under the extreme pH conditions, and particularly its performance under acidic condition reveals its prospect as a potential Pt-free electrocatalyst to serve in the Nafion-based systems.

A Facile “Double‐Catalysts” Approach to Directionally Fabricate Pyridinic NB‐Pair‐Doped Crystal Graphene Nanoribbons/Amorphous Carbon Hybrid Electrocatalysts for Efficient Oxygen Reduction Reaction

“…In the electrochemical impedance spectroscopy (EIS) spectra, the BNC-1 has a high slope in the low frequency, indicating faster ion diffusion, which can be attributed to the existence of porous structure (Figure S11, Supporting Information). [57,58] The electrochemical active surface area (ECSA) was measured to characterize the active sites density, and the ECSA of BNC-1 is 27 times higher than that of the NC indicating the dramatically increasing number of active sites (Figure S12, Supporting Information). Inductively coupled plasma optical emission spectra (ICP-OES) in Table S3 (Supporting Information) were completed and the results show the negligible Fe impurity (<0.5 ppm) in all samples.…”

“…Actually, the enhancing function of high crystal carbon on electron transport has been widely demonstrated such as CNTs doped into carbon sheets, graphitic shells doped into porous carbon. [58,62] Due to low carbon crystal degree, the BNC-2 and BNC-3 show amorphous structure and form more micropores (Figure S18, Supporting Information), which leads to high BET surface area (1349.1 m 2 g −1 for BNC-2, 1093.6 m 2 g −1 for BNC-2) in Figure 4f. The abundant porous structure is beneficial to the ion/mass transport as demonstrated by the high slope at low frequency in the EIS spectra (Figure S19, Supporting Information).…”