To endow catalyst support with excellent stability and cocatalytic activity toward methanol, oxidation reaction (MOR) is an effective way to strengthen the electrocatalytic activity of Pt-based catalysts. Tungsten phosphide/3D-corrugated porous carbon (WP/C) composite as Pt-support and cocatalyst for MOR is prepared via a synchronous synthesis method. Porous 3D-tufted structure and high surface area of WP/C with abundant oxygen-containing groups (such as C-O-C, C-O-H, or C-OH) can significantly improve the exposure of active sites, which enlarge the contact area with electrolyte and facilitate the mass transfer and absorption of methanol for promoting the MOR activity in acidic electrolyte. Pt-WP/C exhibits a considerably higher mass activity (1559.3 mA mgPt-1) for MOR than that of Pt/C (488.2 mA mgPt-1), owing to the special activity of Wδ+ and Pδ- sites for the decomposition reaction of water. With the introduction of W species, more available P species (passivated or not) are activated for further enhancing the cocatalytic activity of WP for MOR. Furthermore, the CO tolerance and durability of Pt-WP/C are also remarkable, which should benefit from the fast surface transport of adsorbed CO on different crystalline faces of WP and the extremely stable WP-C structure originating from the existence of P-P chains between the adjacent WP particles, respectively. The design of the porous structure and cocatalytic effect of this catalyst support (WP/C) provides a promising method to drastically enhance MOR activity.
Keywords: cocatalytic action; electrocatalytic activity; methanol oxidation reaction; platinum catalyst support; tungsten phosphide.