Highly Crystalline Iridium-Nickel Nanocages with Subnanopores for Acidic Bifunctional Water Splitting Electrolysis.

Developing efficient bifunctional materials is highly desirable for overall proton membrane water splitting. However, the design of iridium materials with high overall acidic water splitting activity and durability, as well as an in-depth understanding of the catalytic mechanism, is challenging. Herein, we successfully developed subnanoporous Ir3Ni ultrathin nanocages with high crystallinity as bifunctional materials for acidic water splitting. The subnanoporous shell enables Ir3Ni NCs optimized exposure of active sites. Importantly, the nickel incorporation contributes to the favorable thermodynamics of the electrocatalysis of the OER after surface reconstruction and optimized hydrogen adsorption free energy in HER electrocatalysis, which induce enhanced intrinsic activity of the acidic oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Together, the Ir3Ni nanocages achieve 3.72 A/mgIr(η=350 mV) and 4.47 A/mgIr(η=40 mV) OER and HER mass activity, which are 18.8 times and 3.3 times higher than that of commercial IrO2 and Pt, respectively. In addition, their highly crystalline identity ensures a robust nanostructure, enabling good catalytic durability during the oxygen evolution reaction after surface oxidation. This work provides a new revenue toward the structural design and insightful understanding of metal alloy catalytic mechanisms for the bifunctional acidic water splitting electrocatalysis.

Epitaxial Growth of Ultrathin Highly Crystalline Pt-Ni Nanostructure on a Metal Carbide Template for Efficient Oxygen Reduction Reaction.

Structure engineering strategies such as core-shell and hollow nanostructures are effective pathways to improve the utilization of noble metals for catalysis. However, nowadays materials design based on these strategies still largely rely on precious metal templates. Herein, the epitaxial growth of highly crystalline Pt3 Ni overlayer on earth-abundant nickel carbide is reported, forming Ni3 C@Pt3 Ni core-shell nanoparticles with a well-defined interface through a new lattice-match-directed synthetic strategy. Derived from such core-shell nanostructures, ultrathin highly crystalline Pt3 Ni nanocages have an advantageous configuration of oxygen reduction reaction (ORR)-favored facets and inherently high active surface area for the ORR, bringing high mass activity and specific activity as much as 4.71 A mgPt -1 and 5.14 mA cm-2 , which are 26 and 20 times to that of commercial Pt/C, respectively. This novel epitaxial growth of platinum opens up new avenues to rationally design highly active and economical electrocatalysts.