Surface Phase Engineering Modulated Iron‐Nickel Nitrides/Alloy Nanospheres with Tailored d‐Band Center for Efficient Oxygen Evolution Reaction

Abstract

The oxygen evolution reaction (OER) plays a key role in many electrochemical energy conversion systems, but it is a kinetically sluggish reaction and requires a large overpotential to deliver appreciable current, especially for the non‐noble metal electrocatalysts. In this study, the authors report a surface phase engineering strategy to improve the OER performance of transition metal nitrides (TMNs). The iron‐nickel nitrides/alloy nanospheres (FeNi3‐N) wrapped in carbon are synthesized, and the optimized FeNi3‐N catalyst displays dual‐phase nitrides on the surface induced by atom migration phenomenon, resulting from the different migration rates of metal atoms during the nitridation process. It shows excellent OER performance in alkaline media with an overpotential of 222 mV at 10 mA cm−2, a small Tafel slope of 41.53 mV dec−1, and long‐term durability under high current density (>0.5 A cm−2) for at least 36 h. Density functional theory (DFT) calculations further reveal that the dual‐phase nitrides are favorable to decrease the energy barrier, modulate the d‐band center to balance the absorption and desorption of the intermediates, and thus promote the OER electrochemical performance. This strategy may shed light on designing OER and other catalysts based on surface phase engineering.

Transition Metal Nitrides for Electrocatalytic Application: Progress and Rational Design

“…As a kind of non-noble metal material, TMNs exhibit similar surface and adsorption properties to the VIII group of precious metals (such as Pt and Pd) because the atomic distance between metal atoms increases and the d-band center downshifts after the incorporation of nitrogen atoms [ 21 , 22 ]. Combined with attractive electrical conductivity, robust chemical stability, and remarkable mechanical robustness, TMNs have great potential as high-efficiency catalysts in various areas such as electrocatalysis, hydrogenation/desulfurization of fuel oil, synthesis/decomposition of ammonia, and other fields [ 23 , 24 , 25 , 26 ]. Moreover, their impressive chemical inertness and high corrosion resistance allow TMNs to be applied in a wide array of pH conditions for long periods, expanding the electrocatalytic application in various mediums [ 27 , 28 ].…”

Ultrathin hollow hemisphere-carbon-anchored Ni3FeN nanoparticles as nanoreactors facilitating the formation of NiCx with long-term durability for the oxygen evolution reaction

“…To date, RuO 2 and Ir are considered as the most effective electrocatalysts for the OER. [1][2][3][4] However, these noble-metal electrocatalysts are unsuitable for practical application due to their high cost, insufficient reserves, and poor catalytic durability. 5,6 Therefore, it is an urgent challenge for the scientic community to develop earth-abundant and highefficiency OER electrocatalysts.…”

“…In particular, Ni 3 FeN has recently attracted much attention as a bimetallic nitride electrocatalyst. 1,5,[15][16][17] At present, there are two main ways to prepare Ni 3 FeN: one is to synthesize it via a simple nitridation reaction with the corresponding layered double hydroxide nanosheets (FeNi LDHs); 5,18,19 the other is realized using Ni and Fe precursors to obtain Ni 3 FeN nanoparticles on bulk or sheet graphene aer carbonization and ammonization. 15,20,21 However, these strategies are not ideal for synthesizing nanoscale Ni 3 FeN and they barely achieve satisfactory electrocatalytic stability due to agglomeration and detachment.…”

Corrosion-Engineered Morphology and Crystal Structure Regulation toward Fe-Based Efficient Oxygen Evolution Electrodes

“…Recently, transition metals and corresponding derivatives (e.g., chalcogenides [7], carbides [8], nitrides [9], phosphides [10], borides [11], etc.) have come to the foreground in the field of water splitting for their enormous natural resources.…”