Dioxygen Adsorption and Dissociation on Nitrogen Doped Carbon Nanotubes from First Principles Simulation

The electronic and materials properties of carbon nanotubes (CNTs), like those of recent discovered graphene and earlier found fullerenes, attracted lots of research interests due to their appealing applications1 in the field of molecular electronics or for the refinement of materials, such as antistatic paints and shieldings, sensor, and catalytic functionality in fuel cells, etc. Like its two/three dimensional siblings graphene and graphite, CNTs consist sp2 hybridized carbon atoms and are either semiconducting or metallic depending on their helicity. CNTs can be considered in structure as rolling up a single sheet of graphene into a cylinder. Polymer electrolyte membrane fuel cells (PEMFCs) are the best candidates for automobile propulsion owing to their zero emissions, low temperature, and high efficiency. Precious platinum (Pt) catalyst is a key ingredient in fuel cells, which produce electricity and water as the only byproduct from hydrogen fuel.2 However, platinum is rare and expensive. Reducing the amount of Pt loading by identifying new catalysts is one of the major targets in the current research for the large-scale commercialization of fuel cells. Specifically, developing alternative catalysts to substitute platinum for the oxygen reduction reaction (ORR) in the fuel cell cathodes is essential because the slow kinetics of this reaction causes significant efficiency losses in the fuel cells. Recent intensive research efforts in reducing or replacing Pt-based electrode in fuel cells have led to the development of new ORR electrocatalysts, including carbon nanotube–supported metal particles.3,4 In 2006, Ozkan and coworkers reported that nitrogen-containing nanostructured carbons and nanotubes have promising catalytic activity towards ORR.5,6 In a 2008 report, Yang et al. at Argonne National Laboratory showed that the vertically-aligned CNT arrays, which are functionalized through nitrogen and iron doping by a chemical vapor deposition (CVD) process, can be electrocatalytically active toward ORR.7 The functionalized CNTs show promise properties as an alternative non-Pt electrocatalyst with a unique nano-architecture and advantageous material properties for the cathode of PEMFC. They further identified FeN4 sites, which are incorporated into the graphene layers of aligned carbon nanotubes, being electrocatalytic active towards ORR, by their X-ray absorption spectroscopy and other characterization techniques.