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 mgPd-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 COads intermediate to release active sites on EOR, together with the excellent ability to generate additional OH militants after combining with the AG-BP heterostructure.