Black Phosphorus–Graphene Heterostructure-Supported Pd Nanoparticles with Superior Activity and Stability for Ethanol Electro-oxidation

Rational design supporting material for palladium (Pd)-based catalyst can maximize its electrocatalytic performance for ethanol oxidation reaction (EOR) catalyst in alkaline condition. Utilizing the unique two-dimensional structures and outstanding physicochemical property of graphene and black phosphorus (BP), herein, we proposed and designed a black phosphorus-graphene heterostructure for supporting Pd nanoparticles. Through merely ball-milling of activated graphene (AG) and black phosphorus (BP), the AG-BP hybrid with a linkage of P-C bonding is used as supports of Pd. The obtained Pd/AG-BP hybrid exhibits ultrahigh electrochemical activity toward EOR. Remarkably, it can achieve a high mass peak current density of ∼6004.53 and ∼712.03 mA mg_Pd^-1 before and after the durability tests of 20 000s on EOR, which are ∼7.19 and 80 times higher than those of commercial Pd/C. The experimental analysis and density-functional-theory calculation show that Pd becomes more positive with electrons transfer from Pd to AG-BP supports and is liable to absorb the OH radicals for removing CO_ads intermediate to release active sites on EOR, together with the excellent ability to generate additional OH militants after combining with the AG-BP heterostructure.