Intermediate Modulation on Noble Metal Hybridized to 2D Metal-Organic Framework for Accelerated Water Electrocatalysis

The rational modulation of reaction intermediates is critical to achieving high-performance heterogeneous catalysis. However, practical realization remains challenging. Using water electrocatalysis as a model reaction, we report an interfacial-bond-induced intermediate modulation to accelerate the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) by hybridizing a 2D nickel metal-organic framework (MOF) and Pt nanocrystals into a heterostructure. The design is initially verified via theoretical calculations, indicating charge relocation on newly formed Ni-O-Pt interfacial bonds for increased OH* adsorption energy together with reduced H* adsorption energy. Experimental findings confirm the formation of the Ni-O-Pt bonds, which electronically modify the heterostructure to increase electron density for Pt and the high-energy Ni 3d state for the MOF, optimizing the adsorption for H* and OH*, respectively. This hybridized material delivered HER activity of 7.92 mA mu g(-1) Pt, which is among the best reported for alkaline electrocatalysts, and an improved OER activity.