Composition‐Tunable Antiperovskite Cu_xIn_1−xNNi₃ as Superior Electrocatalysts for the Hydrogen Evolution Reaction

Abstract

A group of newly reported antiperovskite nitrides CuxIn1−xNNi3 (0≤x≤1) with tunable composition are employed as electrocatalysts for the hydrogen evolution reaction (HER). Cu0.4In0.6NNi3 shows the highest intrinsic performance among all developed catalysts with an overpotential of merely 42 mV at 10 mA cmgeo−2. Stability tests at a high current density of 100 mA cmgeo−2 show its super‐stable performance with only 7 mV increase in overpotential after more than 60 hours of measurement, surpassing commercial Pt/C (increase of 170 mV). By partial substitution, the derived antiperovskite nitride achieves a smaller kinetic barrier of water dissociation compared to the unsubstituted InNNi3 and CuNNi3, revealed by first‐principle calculations. It is found that the partially substituted CuxIn1−xNNi3 possesses a thermal neutral and desirable Gibbs free energy of hydrogen for HER, ascribed to the tailoring of the energy of d‐band center arose by the A‐site (A=Cu or In) substitution and a resulting optimization of adsorbate interactions.

Fe3+-Preactivated Ni/ Co-Based Antiperovskite Nitrides for Boosting Oxygen Evolution: Surface Tuning and Catalytic Mechanism

“…The obtained ZnNNi 3 NS was immersed in FeCl 3 solution to realize the preactivation, which is schematically shown in Figure a. As revealed by previous studies, , the transition metals in antiperovskite nitrides feature metallic properties. This preactivation is thus similar to the reaction of Fe 3+ with metallic Cu in the conventional printed circuit board .…”

“…19,21−24 For instance, the CuNNi 3 antiperovskite exhibits 3 orders of magnitude higher electronic conductivity than that of Nibased perovskite oxide (LaNiO 3 ). 23 antiperovskite nitrides have been identified to be active for OER in alkaline media, but their intrinsic activities are insufficient for practical application. Thus, some potential strategies including composition tuning and surface modification should be taken into consideration to enhance the OER activities of antiperovskite nitrides.…”

“…In recent years, a class of Ni/Co-based antiperovskite nitrides (ANM 3 : A = Cu, Zn, In, Cd; M = Co, Ni; e.g., CuNNi 3 and CuNCo 3 ) has been proven to be a promising alternative to metal oxide-based electrocatalysts due to the excellent conductivity of those antiperovskite nitrides. ,− For instance, the CuNNi 3 antiperovskite exhibits 3 orders of magnitude higher electronic conductivity than that of Ni-based perovskite oxide (LaNiO 3 ) . Most Ni/Co-based antiperovskite nitrides have been identified to be active for OER in alkaline media, but their intrinsic activities are insufficient for practical application.…”

Electrocatalytic hydrogen evolution: From principle to application

“…在过渡金属内的原子与原子间存在间隙， 当氮原 子插入这些间隙时，就得到了过渡金属氮化物 [14] 。由 于氮原子带负电荷， 氮原子的插入使金属晶格发生畸 变，金属的 d 带变宽，导致 d 带收缩增大，改变了费 米能级附近的态密度， 从而使过渡金属氮化物的电子 结构发生改变， 使其具备类似于铂和钯等贵金属的催 化活性。因而，金属氮化物成为最有潜力的能够取代 贵金属的催化剂。目前，HER 过渡金属氮化物基催 化剂主要包括钴 [15] 、镍 [16][17][18][19][20][21][22] 、铁 [23] 、钼 [24,25] 、钨 [26,27] 、 铜 [28] [29] The Gibbs free energy of Had on the (100) plane of CuNNi3, InNNi3, and Cu0.5In0.5NNi3 is calculated [30] .…”

“…(c) 计算得到了 CuNNi3、InNNi3 和 Cu0.5In0.5NNi3 的 (100)面上的氢吸附 Gibbs 自由能[30] Figure4(a) The calculation model of InNNi3, CuNNi3, and Cu0.5In0.6NNi3. (b) The total energy of different steps in the process of hydrolysis and dissociation of the intermediate.…”