Constructive Strategy of Amine Functionalization on Cu−In−Zn−S With N→Cu Coordination for Efficacious Photocatalytic Hydrogen Evolution

Abstract

Functionalization has emerged as a pivotal endeavor to tailor the surface properties of photocatalysts. We propose a facile amine functionalization strategy to establish a Cu−In−Zn−S (CIZS)/NiS_x hybrid with covalent bonds using individual ethylenediamine (EDA) molecules. Our approach witnesses a remarkable photocatalytic hydrogen evolution (PHE) competence of 65.93 mmol g⁻¹ h⁻¹ driven by visible light, the highest value yielded by CIZS to date. X-ray absorption spectra of CIZS and density functional theory (DFT) calculations confirm the crucial amine N→Cu coordination after amine functionalization. The new emerging coordination via lone-pair electron donation profitably accesses the regulation of the coordination environment, electronic structures, and carrier behavior. Moreover, individual EDA molecule with two-terminal −NH₂ group serves as a molecular bridge to hybrid CIZS and NiS_x cocatalyst via N→Cu and N→Ni coordination, favorably promoting efficient charge transport. This study provides advances in practical functionalizing photocatalysts.

Keywords

amine functionalization / coordination / Cu−In−Zn−S / molecular bridges / photocatalytic hydrogen evolution

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