Ultrasmall copper-metal organic framework (Cu-MOF) quantum dots decorated on waste derived biochar for enhanced removal of emerging contaminants: Synergistic effect and mechanistic insight.

ABSTRACT

This study proposes a novel one-pot hydrothermal impregnation strategy for surface decoration of waste derived pisum sativum biochar with zero‒dimensional Cu‒MOF Quantum dots (PBC‒HK), with an average particle size of 5.67 nm, for synergistic removal of an emerging sulfur containing drug pantoprazole (PTZ) and Basic Blue 26 (VB) dye within 80 min and 50 min of visible-light exposure, respectively. The designed Integrated Photocatalytic Adsorbent (IPA) presented an enhanced PTZ removal efficiency of 95.23% with a catalyst loading of 0.24 g/L and initial PTZ conc. 30 mg/L at pH 7, within 80 min via synergistic adsorption and photodegradation under visible-light exposure. While, on the other hand, 96.31% VB removal efficiency was obtained in 50 min with a catalyst dosage of 0.20 g/L, initial VB conc. 60 mg/L at pH 7 under similar irradiation conditions. An in-depth analysis of the synergistic adsorption and photocatalysis mechanism resulting in the shortened time for the removal of contaminants in the synergistic integrated model has been performed by outlining the various advantageous attributes of this strategy. The first-order degradation rate constant for PTZ was found to be 0.04846 min-1 and 0.04370 min-1 for PTZ and VB, respectively. Adsorption of contaminant molecules on the biochar (PS‒BC) surface can facilitate photodegradation by accelerating the kinetics, and photodegradation promotes regeneration of adsorption sites, contributing to an overall reduction in operation time for removal of contaminants. Besides enhancing the adsorption of targeted pollutants, the carbon matrix of IPAs serves as a surface for adsorption of intermediates of degradation, thereby minimizing the risk of secondary pollution. The photogenerated holes present in the VB is responsible for the generation of •OH radicals. While, the photogenerated electrons present in the CB are captured by Cu2+ of the MOF metal center, reducing it to Cu+, which is subsequently oxidized to produce additional •OH species in the aqueous medium. This process leads to effective charge separation of the photogenerated charge carriers and minimizes the probability of charge recombination as evident from photoluminescence (PL) analysis. Meanwhile, PL studies, EPR and radical trapping experiments indicate the predominant role of •OH radicals in the removal mechanism of PTZ and VB. The investigation of the degradation reaction intermediates was confirmed by HR‒LCMS, on the basis of which the plausible degradation pathway was elucidated in detail. Moreover, effects of pH, inorganic salts, other organic compounds and humic acid concentration have been investigated in detail. The environmental impact of the proposed method was comprehensively evaluated by ICP-OES analysis and TOC and COD removal studies. Furthermore, the economic feasibility and the cost-effectiveness of the catalyst was assessed to address the potential for large scale commercialization. Notably, this research not only demonstrates a rational design strategy for the utilization of solid waste into treasure via the fabrication of IPAs based on MOF Quantum dots (QDs) and waste-derived biochar, but also provides a practical solution for real wastewater treatment systems for broader industrial applications.