Slow-release synthesis of Cu single-atom catalysts with the optimized geometric structure and density of state distribution for Fenton-like catalysis

• Published in: Proceedings of the National Academy of Sciences - PNAS 2023-10, Vol.120 (43), p.e2311585120-e2311585120
• Main Authors: Gu, Chao-Hai, Wang, Song, Zhang, Ai-Yong, Liu, Chang, Jiang, Jun, Yu, Han-Qing
• Format: Article
• Language: English
• Subjects: Binding; Carbon nitride; Catalysis; Catalysts; Chemical synthesis; Contaminants; Controllability; Copper; Mass transfer; Metals; Microenvironments; Montmorillonite; Physical Sciences; Precursors; Reaction kinetics; Reaction mechanisms; Single atom catalysts; Supply & demand
• ISSN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.2311585120

Single-atom Fenton-like catalysis has attracted significant attention, yet the quest for controllable synthesis of single-atom catalysts (SACs) with modulation of electron configuration is driven by the current disadvantages of poor activity, low selectivity, narrow pH range, and ambiguous structure-performance relationship. Herein, we devised an innovative strategy, the slow-release synthesis, to fabricate superior Cu SACs by facilitating the dynamic equilibrium between metal precursor supply and anchoring site formation. In this strategy, the dynamics of anchoring site formation, metal precursor release, and their binding reaction kinetics were regulated. Bolstered by harmoniously aligned dynamics, the selective and specific monatomic binding reactions were ensured to refine controllable SACs synthesis with well-defined structure-reactivity relationship. A copious quantity of monatomic dispersed metal became deposited on the C N /montmorillonite (MMT) interface and surface with accessible exposure due to the convenient mass transfer within ordered MMT. The slow-release effect facilitated the generation of targeted high-quality sites by equilibrating the supply and demand of the metal precursor and anchoring site and improved the utilization ratio of metal precursors. An excellent Fenton-like reactivity for contaminant degradation was achieved by the Cu /C N /MMT with diminished toxic Cu liberation. Also, the selective ·OH-mediated reaction mechanism was elucidated. Our findings provide a strategy for regulating the intractable anchoring events and optimizing the microenvironment of the monatomic metal center to synthesize superior SACs.