Conflicting Roles of Nitrogen Doping in Carbon Nanotubes As Anode and Cathode Catalyst Support for Direct Methanol Fuel Cells

Abstract

Nitrogen doping in carbon nanotubes (CNTs) is of great interest because it endows the inherently inert surface of CNTs with a variety of chemical functionalities. For instance, nitrogen-doped carbon nanotubes (NxCNTs) have been shown a promising electrode catalyst support for polymer electrolyte membrane fuel cells because the doped nitrogen atoms can promote a high dispersion of the metal catalyst nanoparticles on the NxCNT surface, which is essential for achieving a high utilization and thus high catalytic performance. However, beyond the role in nanoparticle dispersion, how nitrogen doping affects the catalytic performance in the anode and in the cathode of a realistic membrane-electrode-assembly (MEA), still remains elusive. In this report, we performed a comparative study of NxCNTs at three different N doping levels as the anode and cathode catalyst support in both rotating disk electrode (RDE) and realistic direct methanol fuel cell (DMFC) test. Our results show that nitrogen doping can play significantly conflicting roles in the anode and cathode performance: (i) A very low doping level (1at.%) is sufficient to induce a homogenous distribution of both anode (PtRu) and cathode (Pt) catalyst nanoparticles. (ii) In RDE test, while nitrogen doping can substantially increase the specific activity of the anodic methanol oxidation, it brings no specific activity enhancement in the cathodic oxygen reduction reaction (ORR), suggesting that nitrogen doping can hardly affect the ORR electrocatalysis on the Pt surface. (iii) In MEA test, a low nitrogen doping level at 1 at.% in NxCNTs as anode catalyst support resulted in a higher power density compared to non-doped CNT support at both 30 and 60°; increasing nitrogen-doping content decreased the power density, likely due to a decreased electron conduction. In contrast, at the cathode, NxCNTs support mainly showed a lower power density, particularly at 60°, which is rationalized by the increased hydrophicility and thus unflavored removal of the water. Taken together, our results provide important guidelines for application of NxCNT support at the appropriate electrode of DMFCs.