CoNi alloy anchored onto N-doped porous carbon for the removal of sulfamethoxazole: Catalyst, mechanism, toxicity analysis, and application. (December 2022) - Liu, Zhibin
Abstract: Developing highly efficient, stable, recyclable, and application value heterogeneous catalysts in advanced oxidation processes has essential application value in the degradation of refractory pollutants. In this paper, the CoNi alloy anchored onto N-doped porous carbon (CoNi-600@NC) catalyst was prepared using bimetallic doped metal-organic frameworks as precursors. The magnetic CoNi-600@NC can activate peroxymonosulfate (PMS) to degrade sulfamethoxazole (SMX). Therefore, SMX can be removed 100% within 25 min. CoNi-600@NC/PMS has a broad pH (3–9) application range, good applicability, and repeatability. Radical quenching, quantitative and electrochemical experiments proved that the degradation of SMX was dominated by free radical (Superoxide anions) and non-free radical pathways (surface-bound radicals). Mechanistic analysis showed that the interaction between Co-Nx /pyridine N-sites and graphitized carbon with PMS induced the formation of surface-bound active species. Moreover, CoNi nanoparticles promoted the redox cycle of metals. The synergistic catalytic mechanisms between the CoNi alloy and the abundant functional groups gave CoNi-600@NC excellent catalytic properties and applicability. Using density functional theory predicted the reaction sites of SMX and proposed four degradation pathways. The toxicity of intermediates was comprehensively evaluated. In addition, a CoNi-600@NC continuous flow reactor was constructed with a daily treatment capacity of 45 L and 100% SMX removal. This study expands the application of persulfate advanced oxidation technology by synthesizing recyclable magnetic catalysts and provides new synergistic degradation mechanisms for removing refractory organics. Graphical abstract: Image 1 Highlights: Magnetic CoNi@NC600 was synthesized using a self-sacrificing method. The synergistic mechanism of PMS activated by CoNi@NC600 composite was elucidated. ECOSAR evaluation and toxicity test of the degraded solution was conducted. Degradation pathways of SMX were proposed combined by DFT and LC-QQQ-TOF. SMX was effectively removed in both batch and continuous flow processes.