Physics

Electron transfer

Engineering

Electron

Computational chemistry

Physical chemistry

Density functional theory

Catalysis

Nanotechnology

Tafel equation

Electrode

Organic chemistry

Chemistry

Overpotential

Metallurgy

Materials science

Phosphide

Chemical engineering

Electrochemistry

Metal

Quantum mechanics

Polaron

Exchange current density

Advanced Materials

Heterointerface engineering can be used to develop excellent catalysts through electronic coupling effects between different components or phases. As one kind of promising Pt-free electrocatalysts for hydrogen evolution reaction (HER), pure-phased metal phosphide exhibits the unfavorable factor of strong or weak H*-adsorption performance. Here, 6 nm wall-thick Ni2P–NiP2 hollow nanoparticle polymorphs combining metallic Ni2P and metalloid NiP2 with observable heterointerfaces are synthesized. It shows excellent catalytic performance toward the HER, requiring an overpotential of 59.7 mV to achieve 10 mA cm−2 with a Tafel slope of 58.8 mV dec−1. Density functional theory calculations verify electrons' transfer from P to Ni at the heterointerfaces, which decreases the absolute value of H* adsorption energy and simultaneously enhance electronic conductivity. That is, the heterojunctions balance the metallic Ni2P and the metalloid NiP2 to form an optimized phosphide polymorph catalyst for the HER. Furthermore, this polymorph combination is used with NiFe-LDH nanosheets to form an alkaline electrolyzer. It shows highly desirable electrochemical properties, which can reach 10 mA cm−2 in 1 m KOH at 1.48 V and be driven by an AAA battery with a nominal voltage of 1.5 V. The work about interfacial charge transfer might provide an insight into designing excellent polymorph catalysts.

Interfacial Electron Transfer of Ni<sub>2</sub> P-NiP<sub>2</sub> Polymorphs Inducing Enhanced Electrochemical Properties

Interfacial Electron Transfer of Ni2 P-NiP2 Polymorphs Inducing Enhanced Electrochemical Properties

Interfacial Electron Transfer of Ni₂ P-NiP₂ Polymorphs Inducing Enhanced Electrochemical Properties