Palladium Nanoparticles Anchored on Anatase Titanium Dioxide-Black Phosphorus Hybrids with Heterointerfaces: Highly Electroactive and Durable Catalysts for Ethanol Electrooxidation

Designing high-performance palladium (Pd) supports with enhanced ethanol oxidation reaction (EOR) activity has consistently been a challenge. Here, a novel anatase titanium dioxide nanosheets-black phosphorus (ATN-BP) hybrid is fabricated as a support for Pd nanoparticles used in the EOR. The direct ball-milling of BP nanoflakes and ATN under argon protection lead to the formation of ATN-BP hybrids with BP nanoflakes interconnected by cataclastic ATN with P  O  Ti bonds. The structure of ATN-BP not only is beneficial for improving the electrolyte penetration and electron transportation but also has a strong influence on the stripping of reactive intermediates through the synergistic interaction between Pd and ATN-BP. The results demonstrate that the Pd/ATN-BP hybrids with heterointerfaces of Pd, BP, and ATN exhibit ultrahigh electroactivity and durability. In the EOR, the Pd/ATN-BP catalyst can achieve an electrochemically active surface area of ≈462.1 m 2 g Pd −1 and a mass peak current density of 5023.8 mA mg Pd −1 , which are 11.67 and 6.87 times greater, respectively, than those of commercial Pd/C. The Pd/ATN-BP catalysts also show remarkable stability with a retention rate of the peak current density of ≈30.6% after a durability test of 3600 s.