The effect of ionomer distribution on the oxygen mass transport resistance, the proton resistivity of the cathode catalyst layer, and the H₂/air fuel cell performance was investigated for catalysts with surface modified carbon supports. By introducing nitrogen containing surface groups, it was shown that the ionomer distribution in the cathodic electrode can be optimized to decrease mass transport related voltage losses at high current density. The in house prepared catalysts were fully characterized by TEM, TGA, elemental analysis, and XPS. Thin-film rotating disk electrode measurements showed that the carbon support modification did not affect the oxygen reduction activity of the catalysts, but exclusively affects the ionomer distribution in the electrode during electrode preparation. Limiting current measurements were used to determine the pressure independent oxygen transport resistance – primarily attributed to oxygen transport in the ionomer film – which decreases for catalysts with surface modified carbon support. Systematically lowering the ionomer to carbon ratio (I/C) from 0.65 to 0.25 revealed a maximum performance at I/C = 0.4, where an optimum between ionomer thickness and proton conductivity within the catalyst layer is obtained. From this work, it can be concluded that not only ionomer film thickness, but more importantly ionomer distribution is the key to high performance low Pt loaded electrodes.

Mixed precious-group metal–organic frameworks [Ru _x Rh _3−x (BTC) ₂ ] of the HKUST-1-type were synthesized and characterized (PXRD, BET, IR, Raman, XPS, TGA, SS-UV/VIS, EA, and HR-TEM).