Carbon xerogels as Pt catalyst supports for polymer electrolyte membrane fuel-cell applications

Carbon xerogels prepared by the resorcinol-formaldehyde (RF) sol–gel method with ambient-pressure drying were explored as Pt catalyst supports for polymer electrolyte membrane (PEM) fuel cells. Carbon xerogel samples without Pt catalyst (CX) were characterized by the N2 sorption method (BET, BJH, others), and carbon xerogel samples with supported Pt catalyst (Pt/CX) were characterized by thermogravimetry (TGA), powder X-ray diffraction (XRD), electron microscopy (SEM, TEM) and ex situ cyclic voltammetry for thin-film electrode samples supported on glassy carbon and studied in a sulfuric acid electrolyte. Experiments on Pt/CX were made in comparison with commercially obtained samples of Pt catalyst supported on a Vulcan XC-72R carbon black support (Pt/XC-72R). CX samples had high BET surface area with a relatively narrow pore size distribution with a peak pore size near 14 nm. Pt contents for both Pt/CX and Pt/XC-72R were near 20 wt % as determined by TGA. Pt catalyst particles on Pt/CX had a mean diameter near 3.3 nm, slightly larger than for Pt/XC-72R which was near 2.8 nm. Electrochemically active surface areas (ESA) for Pt as determined by ex situ CV measurements of H adsorption/desorption were similar for Pt/XC-72R and Pt/CX but those from CO stripping were slightly higher for Pt/XC-72R than for Pt/CX. Membrane-electrode assemblies (MEAs) were fabricated from both Pt/CX and Pt/XC-72R on Nafion 117 membranes using the decal transfer method, and MEA characteristics and single-cell performance were evaluated via in situ cyclic voltammetry, polarization curve, and current-interrupt and high-frequency impedance methods. In situ CV yielded ESA values for Pt/XC-72R MEAs that were similar to those obtained by ex situ CV in sulfuric acid, but those for Pt/CX MEAs were smaller (by 13–17%), suggesting that access of Nafion electrolyte to Pt particles in Pt/CX electrodes is diminished relative to that for Pt/XC-72R electrodes. Polarization curve analysis at low current density (0.9 V cell voltage) reveals slightly higher intrinsic catalyst activity for the Pt/CX catalyst which may reflect the fact that Pt particle size in these catalysts is slightly higher. Cell performance at higher current densities is slightly lower for Pt/CX than the Pt/XC-72R sample, however after normalization for Pt loading, performance is slightly higher for Pt/CX, particularly in H2/O2 and at lower cell temperatures (50 °C). This latter finding may reflect a possible lower mass-transfer resistance in the Pt/CX sample.