Phosphorus‐Modified Tungsten Nitride/Reduced Graphene Oxide as a High‐Performance, Non‐Noble‐Metal Electrocatalyst for the Hydrogen Evolution Reaction

Abstract Phosphorus‐modified tungsten nitride/reduced graphene oxide (P‐WN/rGO) is designed as a high‐efficient, low‐cost electrocatalyst for the hydrogen evolution reaction (HER). WN (ca. 3 nm in size) on rGO is first synthesized by using the H 3 PO 4 (W 3 O 9 ) 4 cluster as a W source. Followed by phosphorization, the particle size increase slightly to about 4 nm with a P content of 2.52 at %. The interaction of P with rGO and WN results in an obvious increase of work function, being close to Pt metal. The P‐WN/rGO exhibits low onset overpotential of 46 mV, Tafel slope of 54 mV dec −1 , and a large exchange current density of 0.35 mA cm −2 in acid media. It requires overpotential of only 85 mV at current density of 10 mA cm −2 , while remaining good stability in accelerated durability testing. This work shows that the modification with a second anion is powerful way to design new catalysts for HER.