Jin Zhang,Hanxuan Zeng,Lingjun Bu,Shiqing Zhou,Zhou Shi,Lin Deng
In this study, zero valent copper (Cu 0 ) was incorporated into ZIF-67 to construct Cu 0 and cobalt/nitrogen doped carbonaceous frameworks x -Cu@Co N C y . The obtained Cu@Co N C was employed to activate PMS to degrade naproxen (NPX) in aqueous phase. Influencing factors on NPX degradation were investigated, including mole ratio of Cu/Co, pyrolysis temperature, pH, catalyst dosage, PMS concentration, and coexisting inorganic anions. In the presence of 0.5 mM PMS and 25 mg/L 1:3-Cu@Co N C 900, complete degradation of NPX (50 μM) could be achieved in 20 min within a wide pH range of 3 to 10. The superior catalytic activity of Cu@Co N C 900 for PMS activation was related to the increased surface –OH groups, accelerated electron transfer rate induced by Cu 0 with strong conductivity, formed surface PMS complexes with high oxidation activity, and synergistic effect between Cu and Co. EPR analysis, radical scavenging and probe tests excluded the participation of SO 4 − and OH in NPX degradation. Nonradical pathways of electron transfer from NPX to PMS and 1 O 2 oxidation contributed to the excellent degradation. The 1:3-Cu@Co N C 900 demonstrated a decent degradation performance even after five consecutive recycles with low cobalt and copper ions leaching due to the encapsulation of Co and Cu on N -doped porous carbon. Further, the intermediates of NPX degradation were identified, and three possible degradation pathways were proposed. Overall, this work provides a feasible strategy to improve the stability and catalytic activity of ZIF-67 by the incorporation of Cu 0 .
This study pioneers a sustainable “waste-to-wealth” strategy for fabricating a high-performance, pH-universal Fenton-like catalyst (FeCu 2 @BC T4 ) through the one-step co-pyrolysis of acid-precipitated black liquor (APBL) and Fenton sludge with a copper precursor. The innovation lies in the precise engineering of a Fe 0 /Fe 3 O 4 heterojunction synergistically coupled with Cu 0 nanoparticles on a functional APBL-derived biochar. By tuning the Cu/Fe mass ratio and pyrolysis time, the phase composition and electron-transfer properties were optimized. The resulting catalyst exhibits exceptional activity and stability across a broad pH range (3–9), achieving >92.3% methylene blue degradation within 60 min, and demonstrates superior removal efficiency toward various cationic dyes (rhodamine B, crystal violet, malachite green) and an anionic dye (methyl orange). Mechanistic investigations reveal a clear pH-governed transition of reactive oxygen species (ROS) pathways: under acidic conditions (pH 3), •OH-dominated homogeneous–heterogeneous catalysis prevails; under neutral conditions, the system shifts to a heterogeneous process driven by synergistic •OH/ 1 O 2 oxidation. This unique ROS switch is sustained by efficient electron mediation from the biochar matrix, coupled with robust electron supply and transfer enabled by the Fe 0 /Fe 3 O 4 heterojunction and Fe Cu galvanic coupling. This work provides a novel paradigm for converting industrial solid wastes into advanced catalytic materials with a well-elucidated mechanism, effectively overcoming the critical pH limitation of conventional Fenton technologies and showing broad application prospects for organic wastewater remediation.
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