Synthesis of nitrogen-doped onion-like carbon and its use in carbon-based CoFe binary non-precious-metal catalysts for oxygen-reduction

• Published in: Carbon (New York) 2011-10, Vol.49 (12), p.3972-3982
• Main Authors: Wu, Gang, Nelson, Mark, Ma, Shuguo, Meng, Hui, Cui, Guofeng, Shen, Pei Kang
• Format: Article
• Language: English
• Subjects: Applied sciences; Carbon; Catalysis; Catalysts; Chemistry; Cross-disciplinary physics: materials science; rheology; Durability; Electrochemistry; Energy; Energy. Thermal use of fuels; Equipments for energy generation and conversion: thermal, electrical, mechanical energy, etc; Exact sciences and technology; Fuel cells; Fullerenes and related materials; diamonds, graphite; General and physical chemistry; Iron; Kinetics and mechanism of reactions; Materials science; Nanostructure; Performance enhancement; Physics; Specific materials; Synthesis; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0008-6223; 1873-3891
• DOI: 10.1016/j.carbon.2011.05.036

Nitrogen-doped onion-like carbon-rich materials were synthesized by heat treatment of a “hybrid” containing hexamethylene diamine complex in the presence of Co and Fe species while preparing non-precious metal electrocatalyst for oxygen-reduction. As demonstrated by electrochemical rotating disk electrode and fuel cell tests, the binary CoFe-based catalyst containing graphitized onion-like carbon nanostructures provides for improved performance relative to the single Fe-based catalyst in which no such carbon structure was observed. In the binary catalysts, variation of the ratios of Co to Fe and the total metal loading during the synthesis leads to a markedly different activity and four-electron selectivity for oxygen reduction. The optimized binary catalyst was studied in fuel cell lifetime tests using both constant current and voltage models, showing a good combination of activity and durability. Possible reasons for the improved performance of the CoFe-based binary catalyst are discussed. The graphitized onion-like carbon structure exclusively derived from Co in this work may be providing a robust matrix to host non-precious metal active sites, which would prevent water flooding of them, and increase the resistance to oxidative attack in the oxygen cathode, thereby leading to an improvement in performance durability.