Original Research PaperMIL-88A grown in-situ on graphitic carbon nitride (g-C3N4) as a novel sorbent: Synthesis, characterization, and high-performance of tetracycline removal and mechanism
Graphical abstract
Introduction
Tetracycline (TC) is a broad-spectrum antibiotic, which can inhibit most Gram-positive and Gram-negative bacteria. Due to its low cost and high antibacterial activity, TC ranks second in the production and use of antibiotics worldwide [1]. As such, the heavy use of TC has accumulated in the environment, inducing microorganisms to gradually become resistant. This has resulted in the enrichment of drug-resistant flora and a generation of resistance genes that are now serious environmental problems [2]. Currently, methods for treating wastewater containing tetracycline antibiotics include microbial treatment, membrane separation, chemical oxidation, and adsorption [3], [4], [5]. Among such methods, adsorption is widely used because of it’s high efficiency, easy utilization, lack of byproducts, and low cost [6], [7].
The metal-organic framework (MOF) is an excellent adsorbent due to its high specific surface area and adjustable pore parameters [8], [9], [10]. In recent years, iron-based porous MOFs have attracted attention because of their environmentally protective qualities and low cost of Fe-containing raw materials [11], [12]. However, most MOFs require a high reaction temperature and long synthesis time, which increases manufacturing costs significantly [13]. Therefore, it is necessary to find a feasible preparation method with low energy consumption and short preparation time. Existing research has reported that the MIL-88A synthesis temperature is as low as 65 °C, and the synthesis time is just 4 h. Compared with some reported MOF materials (Table S1), the MIL-88A synthesis temperature and time are both lower, effectively reducing energy consumption [14], [15], [16], [17], [18], [19], [20]. MIL-88A has a three-dimensional flexible frame based on the Fe(III) octahedral oxygen core trimer connected by fumaric acid, forming interconnected holes and cages, and the open channel that runs along the c axis [21]. This structure provides a large specific surface area and high porosity, which enables pollutants to absorb efficiently [22]. Graphite carbon nitride (g-C3N4) is a material with excellent photoelectron bond structure, good thermal stability, and chemical stability [23], [24]. It also has strong electron-withdrawing properties of pyridine N atoms, as well as basic NH and NH2 functional groups on the edges, contributing to electrostatic interaction with target pollutants [25]. Moreover, g-C3N4-based composite materials have been extensively studied in the field of adsorption, thus effectively improving their adsorption capacity [26], [27], [28].
In this study, MIL-88A was grown in-situ on g-C3N4 through a very simple and energy-saving one-step hydrothermal method, and the micro-nanoscale MIL-88A/g-C3N4 adsorption material was successfully prepared. MIL-88A/g-C3N4 was used as an adsorbent for tetracycline in water for the first time. By studying the zeta potential of MIL-88A/g-C3N4, identifying the potential functional groups, and analyzing the kinetics and thermodynamics, the adsorption mechanism is proposed. The study of an MIL-88A/g-C3N4 adsorbent provides a theoretical basis and a new prospect for the development of novel efficient and energy-saving adsorption materials.
Section snippets
Chemicals
Melamine (C3H6N6, 99.0%), ferric chloride hexahydrate (FeCl3·6H2O, 99.0%), ethanol (C2H5OH, ≥99.7 wt%), hydrochloric acid (HCl), sodium hydroxide (NaOH), methanol (CH3OH), formaldehyde (CH2O), and formic acid (CH2O2) were purchased from the Sinopharm Chemical Reagent Co., Ltd. Fumaric acid (C4H4O4, ≥99.0 wt%) and tetracycline (C22H24N2O8, ≥99.0 wt%) were obtained from the Shanghai Macklin Chemical Reagent Co., Ltd. N,N-dimethylformamide (DMF, C4H9NO, ≥99.0%) was obtained from the Shanghai
Morphology of the materials
The SEM image in Fig. 1(a) shows that the well-crystallized, rod-like MIL-88A morphology was successfully synthesized by our simple and low-cost hydrothermal synthesis method, and the average length and width were 730.2 and 201.3 nm, respectively [Fig. S1(a)-(b)]. Fig. 1(b) shows that g-C3N4 has a lamellar structure with a rougher surface that can provide more growth sites for the MIL-88A. Fig. 1(c)–(e) are the SEM images of MIL-g-0.1, MIL-g-0.2, and MIL-g-0.3, respectively, and the overall
Conclusions
In this study, MIL-88A/g-C3N4 micro-nano particles with a large specific surface area, porous structure, and large pore diameter were prepared by a simple, one-step hydrothermal method with low energy consumption (65 °C for 4 h). SEM, TEM, elemental analysis, FTIR, XRD, and XPS characterization methods suggest the MIL-88A/g-C3N4 adsorbent was successfully prepared. At a pH of 7.0, the MIL-88A/g-C3N4 reaches maximum TC adsorption capacity (154.51 mg·g−1) at room temperature. The study of
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.
Acknowledgments
The National Key Research and Development Program of China (2019YFC0408304), the Fundamental Research Funds for the Central Universities of China (No. 2232020G-04), and the Fundamental Research Funds for the Central Universities and Graduate Student Innovation Fund of Donghua University (CUSF-DH-D-2020073) supported this work.
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