High-Entropy Nitride Photocatalysts for Visible-Light Antibiotic Degradation: Structural Stability, In Situ Interfacial Visualization, and Molecular-Level Mechanistic Insights

Abstract

High-entropy nitrides (HENs) have emerged as a promising class of advanced materials with tunable electronic structures, high stability, and abundant active sites. The incorporation of nitrogen enhances visible-light absorption, promotes efficient charge separation, and improves structural robustness, making these materials highly suitable for photocatalytic applications. In this study, (MnFeCoNiCu)N-based HEN nanoparticles (NPs) were synthesized as visible-light-assisted photocatalysts for the degradation of antibiotics, including sulfamethoxazole (SME) and tetracycline (TCL). The catalyst exhibited excellent performance, achieving 96% degradation of SME and 94% removal of TCL within 2 h of visible-light irradiation. The photocatalytic activity was systematically evaluated under varying operational parameters, including solution pH, catalyst dosage, pollutant concentration, and the presence of coexisting ions. Notably, the catalyst maintained high efficiency in real water matrices, demonstrating its practical applicability. The entropy-stabilized nitride framework exhibited negligible metal leaching, excellent thermal and structural stability as confirmed by temperature-dependent synchrotron angle-dispersive X-ray diffraction, and stable performance over multiple reuse cycles. Furthermore, in situ liquid-cell transmission electron microscopy provided real-time insight into catalyst-pollutant interactions, while complementary molecular simulations revealed the structural stability of the HEN NPs during molecular adsorption and the distinct interaction modes of the two antibiotics. Phytotoxicity tests using Vigna radiata confirmed the effective detoxification of treated solutions. Overall, this work establishes (MnFeCoNiCu)N HENs as efficient and durable visible-light-driven photocatalysts for the removal of antibiotics from complex aqueous environments.