Directional electronic tuning of Ni nanoparticles by interfacial oxygen bridging of support for catalyzing alkaline hydrogen oxidation.

Metallic nickel (Ni) is a promising candidate to substitute Pt-based catalysts for hydrogen oxidation reaction (HOR), but huge challenges still exist in precise modulation of the electronic structure to boost the electrocatalytic performances. Herein, we present the use of single-layer TiCT MXene to deliberately tailor the electronic structure of Ni nanoparticles via interfacial oxygen bridges, which affords Ni/TiCT electrocatalyst with exceptional performances for HOR in an alkaline medium. Remarkably, it shows a high kinetic current of 16.39 mA cm at the overpotential of 50 mV for HOR [78 and 2.7 times higher than that of metallic Ni and Pt/C (20%), respectively], also with good durability and CO antipoisoning ability (1,000 ppm) that are not available for conventional Pt/C (20%) catalyst. The ultrahigh conductivity of single-layer TiCT provides fast transmission of electrons for Ni nanoparticles, of which the uniform and small sizes endow them with high-density active sites. Further, the terminated -O/-OH functional groups on TiCT directionally capture electrons from Ni nanoparticles via interfacial Ni-O bridges, leading to obvious electronic polarization. This could enhance the Ni-O interaction and weaken Ni-H interaction of Ni sites in Ni/TiCTenabling a suitable H-/OH-binding energy and thus enhancing the HOR activity.