Neglected Sulfidic Interfacial Layer as a Key Modulator in Nickel Nitride‐Zinc Indium Sulfide Core‐Shell Photocatalysts

ABSTRACT

Constructing core‐shell heterostructures is widely regarded as an efficient strategy for photocatalyst design. However, the interfacial reconstruction and associated chemical transition layer between the core and shell components are often oversimplified or overlooked. Here, we construct a Ni ₃ N‐ZnIn ₂ S ₄ core‐shell photocatalyst and systematically reveal a previously neglected sulfidic interfacial layer within the core‐shell architecture, elucidating its critical roles in electronic regulation and reaction pathway modulation. Acting as an active electronic regulator, this interfacial layer reconstructs local coordination environments, induces stepwise electron migration pathways, and amplifies the interfacial built‐in electric field strength. The formation origin and dynamic evolution mechanism of this sulfidic interfacial layer are systematically elucidated. Benefiting from the synergistic interfacial regulation effect, the Ni ₃ N‐ZnIn ₂ S ₄ catalyst delivers efficient disulfide production in thiol coupling reactions, achieving a maximum reaction rate of 26.38 mmol g ⁻¹  h ⁻¹ , together with good substrate generality, scalable potential, and significant value increment under real solar irradiation. This work provides a new interfacial engineering paradigm and theoretical basis for designing high‐performance photocatalytic reaction interfaces.