Composition‐Tunable Antiperovskite CuxIn1−xNNi3 as Superior Electrocatalysts for the Hydrogen Evolution Reaction. Issue 40 (11th August 2020)

• Record Type: Journal Article
• Authors: Zhang, Jiaxi; Zhang, Longhai; Du, Li; Xin, Huolin L.; Goodenough, John B.; Cui, Zhiming
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 40(2020)
• Page Start: 17488
• Page End: 17493
• Publication Date: 2020-08-11
• Subjects: antiperovskite nitride -- CuxIn1−xNi3 -- electrocatalyst -- hydrogen evolution -- water dissociation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202007883
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: A group of newly reported antiperovskite nitrides Cu x In1− x NNi3 (0≤ x ≤1) with tunable composition are employed as electrocatalysts for the hydrogen evolution reaction (HER). Cu0.4 In0.6 NNi3 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 Cu x In1− x NNi3 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. Abstract : A composition tuning strategy is employed to develop a group of ANNi3 antiperovskite nitrides (A=In or Cu). By partial substitution of the A site in the pristine antiperovskite nitride, a remarkable enhancement of the hydrogen evolution reaction (HER) performance is achieved on the derived Cu x In1− x NNi3 electrocatalysts. This is ascribed to the lowered kinetic barrier and optimal hydrogen adsorption free energy by the compositional adjustment.