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

Abstract 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.