Efficient removal of emerging organic contaminants via photo-Fenton process over micron-sized Fe-MOF sheet
Graphical abstract
Introduction
Organic pollutants in water environment might exert great potential threat to environment due to their persistence and biotoxicity. Unfortunately, these organic pollutants, such as pharmaceutical and personal care products (PPCPs) and antibiotic, are difficult to efficiently remove via traditional process [1], [2]. Advanced oxidation processes (AOPs) like photocatalysis [3], [4], [5], [6], persulfate activation [7], [8], Fenton-like and so on [9], [10] have been proved to be highly efficient and eco-friendly, which are widely used in organic pollutants degradation.
Recently, increasing researchers focus on heterogeneous Fenton-like reaction for degrading organic contaminants into less toxic molecules and even mineralizing them into CO2 and H2O [8], [11]. It is expected to overcome the typical drawbacks of traditional homogeneous Fenton reaction, including but not limited to operation in the narrow pH range (<3) and producing huge amount of sludge. However, the application of heterogenous Fenton reaction is hampered by slow Fe2+ generation rate from Fe3+ and high H2O2 consumption [12]. Hou et al. introduced a reductive agent NH2OH to goethite for surface Fenton reaction, which significantly accelerated Fe2+ generation from Fe3+ [13]. Zhu et al. demonstrated that Fe3+/Fe2+ cycle could be greatly promoted by combining ferrihydrite with carbon nanotubes (CNTs), since CNTs not only accelerated the electron transfer, but also decreased Fe3+/Fe2+ redox potential [14]. As well, coupling technologies like photo-Fenton [15], electro-Fenton [16] and ultrasound-Fenton [17] are efficient approaches to promote Fe3+/Fe2+ cycles and decomposition of H2O2 [18], [19], [20]. Xing et al. demonstrated that the metal sulfide (like MoS2 [10], [21] and WS2 [22]) cocatalyst greatly promoted Fe3+/Fe2+ conversion, which resulted in high H2O2 decomposition efficiency.
Metal-organic frameworks (MOFs) have attracted increasing attentions due to their diverse structures and versatile potential applications in separation [23], [24], catalysis [25], [26], photocatalysis [11], [27], and so on [28], [29], [30], [31], [32]. Fe-MOFs, their composites as well as derivatives exhibited huge potential in environmental remediation, especially for heterogenous Fenton-like reaction [33], [34], [35]. MIL-88A, a 3D Fe-MOF constructed by fumaric acid and Fe3+, is considered as an eco-friendly catalyst, which have received wide interest in photo-Fenton process [36]. For example, our group demonstrated that 100% bisphenol A (BPA) was degraded over MIL-88A within 80 min under the illuminance of visible light [37], whereas the complete BPA removal could be accomplished within 30 min over polyaniline@MIL-88A composite under white light [38]. Actually, the photoinduced charges transfer rate of MIL-88A is slow because of its low conductivity. In comparison, 2D MOFs possess higher aspect ratio, more exposed activated sites, faster mass transfer rate and quicker photoinduced charges transfer rate, leading to higher photocatalytic activities [39], [40], [41], [42]. At this point, 2D MOF nanosheets have been studied in the field of photocatalysis. Ding et al. reported in-situ growth of 2D Ni-MOF nanosheet on nickel foam (Ni-MOF/NF) without extra metal source, linked by 2-methylimidazole [43]. The as-prepared Ni-MOF/NF possessed abundant active sites and outstanding light absorption activity, which exhibited excellent photocatalytic volatile organic compounds (VOCs) degradation under visible light. Xiao et al prepared a 2D Mn-MOF (Mn-TBAPy, TBAPy = 1,3,6,8-tetrakis(p-benzoic acid)pyrene) nanosheet with average thickness of 9.5 nm by sonication exfoliation [44]. The H2 evolution rate on the nanosheet was 11 times higher than that on bulk Mn-MOF, which resulted from short charge transfer distance and fast charge separation on Mn-MOF nanosheet. However, the water stability of 2D MOFs nanosheets should be further concerned [45]. Accordingly, it is desired to develop 2D micron-sized MOF sheets with high catalytic activity, good water stability and low biotoxicity for environmental remediation.
Herein, a micron-sized MOF sheet, namely BUC-21(Fe), was synthesized from Fe2+ nodes and two ligands (1,3‐dibenzyl‐2‐imidazolidone‐4,5‐dicarboxylic acid (H2L) and 4,4′‐bipyridine (bpy)) with low toxicity (Table S1). Within this paper, chloroquine phosphate (CQ) was selected as the target emerging organic pollutant model to test the photo-Fenton performance of BUC-21(Fe). It was deemed that CQ, one of important drugs for treating malaria [46], might exert toxic effects to the non-target organisms, especially in higher pH conditions [47], [48]. Within this paper, the influences of H2O2 dosage, initial pH and co-existing inorganic anions on photo-Fenton degradation of CQ were investigated, and the role of the surface Fe ions in the reaction was studied. The oxidation state and content of Fe were determined by X-ray absorption fine structure (XAFS). The concentration of generated ·OH and the H2O2 consumption under different pH were monitored. Density functional theory (DFT) was introduced to clarify the band gap of BUC-21(Fe) and the transfer pathway of the charge carriers. As well, different organic contaminants including sulfamethoxazole (SMX) and bisphenol A (BPA) were selected to test the university of BUC-21(Fe) as photo-Fenton catalyst for organic pollutants degradation.
Section snippets
Materials and methods
The information of materials, characterizations and the DFT calculation were proved in the supplementary information (SI).
Characterizations of BUC-21(Fe)
The scanning electronic microscopy (SEM) images (Fig. 1a and Fig. S2a) demonstrated that BUC-21(Fe) displayed rough sheet morphology with size of ca. 60 μm length, 60 μm width and 5 μm thick. The single crystal structure analysis revealed that BUC-21(Fe) is constructed from Fe2+, L2− and bpy (Fig. 1b). Detailly, the Fe1 was coordinated with two oxygen atoms from two different L2− ligands, two oxygen atoms from two water molecules, and two nitrogen atoms from two bpy ligands (Fig. 1c), and the
Conclusion
A micron-sized 2D MOF BUC-21(Fe) sheet was synthesized, which displayed excellent heterogeneous photo-Fenton activity and high stability in water. CQ, as emerging organic pollutant model, was degraded efficiently within 30 min at pH = 5.0. The high efficiency might be contributed to the following: (i) Fast mass transport rate (H2O2 and organic pollutants) and easy accessibility of the active sites because of the unique 2D structure; (ii) The inhibited recombination of electron and hole due to
CRediT authorship contribution statement
Fu-Xue Wang: Data curation, Investigation, Visualization, Writing – original draft. Chong-Chen Wang: Conceptualization, Funding acquisition, Supervision, Project administration, Writing – review & editing. Xuedong Du: Methodology, Validation. Yang Li: Resources, Software. Fei Wang: Data curation, Investigation. Peng Wang: Resources.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by National Natural Science Foundation of China (51878023, 22176012), Beijing Natural Science Foundation (8202016), Great Wall Scholars Training Program Project of Beijing Municipality Universities (CIT&TCD20180323), Beijing Talent Project (2020A27) and The Fundamental Research Funds for Beijing University of Civil Engineering and Architecture (X20147/X20141/X20135/X20146).
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