Regulating the Interfacial Electronic Coupling of Fe₂N via Orbital Steering for Hydrogen Evolution Catalysis

Abstract

The capability of manipulating the interfacial electronic coupling is the key to achieving on‐demand functionalities of catalysts. Herein, it is demonstrated that the electronic coupling of Fe2N can be effectively regulated for hydrogen evolution reaction (HER) catalysis by vacancy‐mediated orbital steering. Ex situ refined structural analysis reveals that the electronic and coordination states of Fe2N can be well manipulated by nitrogen vacancies, which impressively exhibit strong correlation with the catalytic activities. Theoretical studies further indicate that the nitrogen vacancy can uniquely steer the orbital orientation of the active sites to tailor the electronic coupling and thus benefit the surface adsorption capability. This work sheds light on the understanding of the catalytic mechanism in real systems and could contribute to revolutionizing the current catalyst design for HER and beyond.

The Heterostructure of Ru2P/WO3/NPC Synergistically Promotes H2O Dissociation for Improved Hydrogen Evolution

“…As shown in the Supporting Information, Figure S8c,t he obtained C dl of Ru 2 P@NPC was 1.76 times higher than that of Ru 2 P/WO 3 @NPC;h owever, the current density of Ru 2 P/ WO 3 @NPC at ap otential of 0.1 V( vs.R HE) was 2.6 times higher than that of Ru 2 P@NPC,i ndicating that the excellent activity of Ru 2 P/WO 3 @NPC originates from its intrinsic catalytic activity. [28] Thec alculated electrochemically active surface areas (ECSA)s are 37.3 cm 2 and 231.2 cm 2 for Ru 2 P/ WO 3 @NPC and Ru 2 P@NPC,r espectively.T he ECSA normalized LSV curves of Ru 2 P/WO 3 @NPC and Ru 2 P@NPC are shown in the Supporting Information, Figure S9. Thei nterfacial charge-transfer kinetics of the four typical electrocatalysts were also studied via electrochemical impedance spectroscopy in the range of 100 kHz-0.1 Hz (Supporting Information, Figure S10).…”

The Electronic Metal–Support Interaction Directing the Design of Single Atomic Site Catalysts: Achieving High Efficiency Towards Hydrogen Evolution

“…[1,2] Among many methods of producing hydrogen, the electrolysis of water has been proved to be a feasible way. [3][4][5][6][7][8][9][10][11][12] However, it wastes a large amount of energy and results in a poor cost-performance, which are the main reason why it still hasnt come into practice until now. [13][14][15][16] Therefore, it is essential to achieve high efficiency and stability at practical current density of the catalysts for hydrogen evolution reaction (HER).…”

V-doped Ni3N/Ni heterostructure with engineered interfaces as a bifunctional hydrogen electrocatalyst in alkaline solution: Simultaneously improving water dissociation and hydrogen adsorption

“…Thus, the requirement of moderate hydrogen adsorption and water dissociation free energies restricts the activities of alkaline HER/HOR electrocatalysts. In this regard, extensive efforts have been devoted to regulating the structures of catalysts for optimizing GH*, including cation/anion doping [37][38][39], defects engineering [40,41] and size confinement [42]. For TMNs, recent studies show that high valence-state metal ions doping can modulate the d-band centers, which accordingly adjust the GH* to reach a thermo-neutral point [14,43].…”