Small-sized tungsten nitride anchoring into a 3D CNT-rGO framework as a superior bifunctional catalyst for the methanol oxidation and oxygen reduction reactions

The application of direct methanol fuel cells (DMFC) is hampered by high cost, low activity, and poor CO tolerance by the Pt catalyst. Herein, we designed a fancy 3D hybrid by anchoring tungsten nitride (WN) nanoparticles (NPs), of about 3 nm in size, into a 3D carbon nanotube-reduced graphene oxide framework (CNT-rGO) using an assembly route. After depositing Pt, the contacted and strongly coupled Pt–WN NPs were formed, resulting in electron transfer from Pt to WN. The 3D Pt–WN/CNT-rGO hybrid can be used as a bifunctional electrocatalyst for both methanol oxidation reaction (MOR) and oxygen reduction reaction (ORR). In MOR, the catalysts showed excellent CO tolerance and a high mass activity of 702.4 mA·mg_Pt^–1, 2.44 and 3.81 times higher than those of Pt/CNT-rGO and Pt/C(JM) catalysts, respectively. The catalyst also exhibited a more positive onset potential (1.03 V), higher mass activity (151.3 mA·mg_Pt^–1), and better cyclic stability and tolerance in MOR than ORR. The catalyst mainly exhibited a 4e-transfer mechanism with a low peroxide yield. The high activity was closely related to hybrid structure. That is, the 3D framework provided a favorable path for mass-transfer, the CNT-rGO support was favorable for charge transfer, and strongly coupled Pt–WN can enhance the catalytic activity and CO-tolerance of Pt. Pt–WN/CNT-rGO represents a new 3D catalytic platform that is promising as an electrocatalyst for DMFC because it can catalyze both ORR and MOR in an acidic medium with good stability and highly efficient Pt utilization.