MIL-88A grown in-situ on graphitic carbon nitride (g-C3N4) as a novel sorbent: Synthesis, characterization, and high-performance of tetracycline removal and mechanism

doi:10.1016/j.apt.2020.09.011

Advanced Powder Technology

Volume 31, Issue 10, October 2020, Pages 4344-4353

https://doi.org/10.1016/j.apt.2020.09.011 Get rights and content

Highlights

•
MIL-88A/g-C₃N₄ was successfully prepared by a simple one-step hydrothermal method.
•
The combination of MIL-88A and g-C₃N₄ greatly improved the adsorption of TC.
•
The electrostatic interaction plays an important role in the adsorption process.
•
COOH and NH₂ groups are involved in TC adsorption through ion exchange.

Abstract

The extensive and accumulative use of tetracycline (TC) in the environment has become a serious problem. In this study, MIL-88A/g-C₃N₄ micro-nano particles were successfully prepared through a simple, low-cost, one-step hydrothermal method for TC adsorption in water. At a pH of 7.0, the maximum adsorption capacity (154.51 mg·g⁻¹) of MIL-88A/g-C₃N₄ is reached at room temperature. Owing to its porous structure and large pore size (>2.06 nm) of MIL-88A/g-C₃N₄, TC can be adsorbed on both external and internal surfaces. Kinetic and thermodynamic studies have shown that the pseudo-second-order kinetic and the Langmuir-Freundlich model can be used to describe the adsorption process, which is a spontaneous endothermic process. The mechanism study reveals that the TC adsorption process by MIL-88A/g-C₃N₄ is mainly through electrostatic interaction and the ion exchange of single bond COOH and NH₂ groups on MIL-88A/g-C₃N₄ to TC. After simple pickling and water washing, MIL-88A/g-C₃N₄ can still reach 83.1% of the original adsorption capacity after five cycles, which proves that MIL-88A/g-C₃N₄ can be a promising adsorbent.

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 single bond 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.

References (65)

R. Pulicharla et al.
Tetracyclines metal complexation: significance and fate of mutual existence in the environment
Environ. Pollut.
(2017)
J. Jia et al.
Characterization of tetracycline effects on microbial community, antibiotic resistance genes and antibiotic resistance of Aeromonas spp. in gut of goldfish Carassius auratus Linnaeus
Ecotoxicol. Environ. Saf.
(2020)
Z. Zhang et al.
Enhancing anaerobic digestion and methane production of tetracycline wastewater in EGSB reactor with GAC/NZVI mediator
Water Res.
(2018)
R. Abejon et al.
Large-scale enzymatic membrane reactors for tetracycline degradation in WWTP effluents
Water Res.
(2015)
G. Tan et al.
A comparative study of arsenic(V), tetracycline and nitrate ions adsorption onto magnetic biochars and activated carbon
Chem. Eng. Res. Des.
(2020)
Y. Guo et al.
Removal of tetracycline from aqueous solution by MCM-41-zeolite A loaded nano zero valent iron: Synthesis, characteristic, adsorption performance and mechanism
J. Hazard. Mater.
(2017)
D. Jiang et al.
The application of different typological and structural MOFs-based materials for the dyes adsorption
Coord. Chem. Rev.
(2019)
R. Wang et al.
High-quality Al@Fe-MOF prepared using Fe-MOF as a micro-reactor to improve adsorption performance for selenite
J. Hazard. Mater.
(2019)
Z. Chang et al.
Selective and efficient adsorption of Au (III) in aqueous solution by Zr-based metal-organic frameworks (MOFs): an unconventional way for gold recycling
J. Hazard. Mater.
(2020)
S. Ploychompoo et al.
Fast and efficient aqueous arsenic removal by functionalized MIL-100(Fe)/rGO/δ-MnO₂ ternary composites: adsorption performance and mechanism
J. Environ. Sci.
(2020)

W. Huang et al.

Integration of plasmonic effect into spindle-shaped MIL-88A(Fe): steering charge flow for enhanced visible-light photocatalytic degradation of ibuprofen

Chem. Eng. J.

(2018)

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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

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Chemicals

Morphology of the materials

Conclusions

Declaration of Competing Interest

Acknowledgments

Environ. Pollut.

Ecotoxicol. Environ. Saf.

Water Res.

Water Res.

Chem. Eng. Res. Des.

J. Hazard. Mater.

Coord. Chem. Rev.

J. Hazard. Mater.

J. Hazard. Mater.

J. Environ. Sci.

Appl. Surf. Sci.

J. Power Sources.

Colloids Surf., A.

Sci. Total Environ.

Chemosphere

Mater. Sci. Eng., C.

Mater. Sci. Semicond. Process.

Ultrason. Sonochem.

Sci. Total Environ.

Chem. Eng. Res. Des.

Appl. Catal., B.

Appl. Surf. Sci.

Chem. Eng. J.

Appl. Catal., B.

Sci. Total Environ.

J. Hazard. Mater.

Bioresour. Technol.

Chem. Eng. J.

J. Hazard. Mater.

Mater. Res. Bull.

Mater. Chem. Phys.

Chem. Eng. J.

Original Research Paper
MIL-88A grown in-situ on graphitic carbon nitride (g-C₃N₄) as a novel sorbent: Synthesis, characterization, and high-performance of tetracycline removal and mechanism