Stable CuO with variable valence states cooperated with active Co²⁺ as catalyst/co-catalyst for oxygen...

Catalysts/co-catalysts for cathodic oxygen reduction and anodic methanol oxidation reactions (ORR/MOR) play the major roles in promoting the commercialization of direct methanol fuel cells. Herein, bimetallic zeolite-imidazolate-frameworks (CoZn-ZIFs) is used as precursor to synthesize Co₃O₄@NPC/CuO composites as catalysts for ORR and Pt supports/co-catalysts for MOR. The ORR activity (E_1/2 = 0.83 V) and long-term stability (activity retention of 85.5% after 30,000 s) of Co₃O₄@NPC/CuO-400 (400 °C) dodecahedron are better than those of commercial Pt/C (10 wt%) in alkaline electrolytes. The surface CuO with variable valence states (Cu⁰ and Cu²⁺) can be used as both the active component for ORR and the protective layer for Co₃O₄ to enhance catalytic stability. Partial removal of CoO_x from carbon framework promotes the exposure of highly active sites (Co²⁺) on the Co₃O₄. For MOR, the mass activity of Pt-Co₃O₄@NPC/CuO-400 (5 wt%) (1947 mA mg_Pt^-1) is much higher than that of Pt/C (751 mA mg_Pt^-1), mainly attributing to that the Pt active sites are uniformly dispersed on Co₃O₄@NPC/CuO support. The strong interaction between Pt and CuO can reduce the bond strength of Pt-CO to enhance CO resistance. Co₃O₄ can activate H₂O molecules to provide sufficient OH^- species to promote MOR. This study provides a new idea for preparation of active ORR catalysts and MOR co-catalyst from bimetallic ZIFs.