Research Paper
Preparation of multivariate zirconia metal-organic frameworks for highly efficient adsorption of endocrine disrupting compounds

https://doi.org/10.1016/j.jhazmat.2021.127559Get rights and content

Highlights

  • A series MTV Zr-MOFs termed as TCPP@MOF-808s was prepared via mix-ligands strategy.

  • The 57%TCPP@MOF-808 present good crystallinity and exceptional stability.

  • The 57%TCPP@MOF-808 as sorbent demonstrates ideal adsorption performance to EDCs.

Abstract

Owing to their structural and functional tunability, the preparation of multivariate metal-organic frameworks (MTV-MOFs) and investigation of their potential application has become a hot topic in fields of environment and energy. To achieve more adsorption and removal performance, a series of multivariate Zr-MOFs (TCPP@MOF‐808s) were prepared via mixed-ligands strategy for the first time. The morphology, as well as adsorption and removal properties of TCPP@MOF‐808s can be controlled by adjusting ratio of the linkers. 57%TCPP@MOF-808 could provide ideal appearance with excellent stability. By using 57%TCPP@MOF-808 as sorbent, a dispersive solid-phase extraction (dSPE) was developed for extraction of endocrine disrupting compounds (EDCs) including BPA, 17β-E2, 17α-E2, E1, and HEX from environmental water prior to HPLC analysis. The pseudo-second-order model can describe the adsorption kinetic data well. Using Langmuir isotherm model, the maximum adsorption capacities of BPA, 17β-E2, 17α-E2, and E1 were calculated as 94.34, 104.17, 109.89, and 121.95 mg·g−1, respectively. The LODs for the analysis of EDCs with HPLC-DAD by using 57%TCPP@MOF-808 as sorbent were achieved in the range of 0.01–0.03 ng·mL−1. The recoveries were obtained in the range of 74.63–98.00%. Enrichment factors were calculated in the range of 146–312. This work provides an effective strategy for design and preparation of multifunctional nanomaterials to improve their potential applications in the detection of environmental pollutants.

Introduction

The strategy for preparing multivariate metal-organic frameworks (MTV-MOFs) by incorporating two or more functional groups in MOF structure attracted considerable attention since it was first introduced by Deng and co-workers in 2010 (Deng et al., 2010). The adsorption capacity and selectivity of MTV-MOFs are usually dramatically increased with forming plenty of pore environments by introducing multiple ligands (Yu et al., 2019). Due to special pore structures and synergistic effect of different functional ligands, MTV-MOFs have broad application prospects in the fields of gas adsorption (Fan et al., 2020), drug release (Dong et al., 2017), and heterogeneous catalysis (Feng et al., 2018). However, the introduction of complex functional groups or linkers into single-phase crystalline materials to prepare “heterogeneity within order” of MOFs are still a challenge, because linkers with different sizes and connectivity often form different domains rather than a unified phase (Furukawa et al., 2015).

Among known MOF materials, zirconia metal-organic frameworks (Zr-MOFs) are foreseen as one of promising materials because of precisely controllable pore structures as well as exceptional thermal and chemical stability (Bai et al., 2016). Moreover, Zr-MOFs have strong tolerance to structural defects of missing linkers (Yuan et al., 2017). Since ideal coordination number of Zr-MOFs ligand is 12, the decrease of coordination number (down to 6 or 8) can form inherent defects of MOFs. In addition, the defects of Zr-MOFs can be reasonably controlled by changing number or type of linkers to achieve large pore volume and specific surface area (Zhao et al., 2017). Fortunately, previous studies have proved that the crystal structure of Zr-MOFs can be maintained even with a great deal of defects (Wu et al., 2013). However, it is still difficult to synthesize secondary ligands with different topologies by one-pot synthesis strategy.

As a representative of Zr-MOF, UiO-66 has good crystallinity and toleration to introduce ligands with different topologies and functions (Sun et al., 2016). The defects of UiO-66 have been found to provide positive impact on heterogeneous catalysis (Liang et al., 2021), gas capture (Li et al., 2019), and heavy metal removal (Boix et al., 2020). Recently, MOF-808 as Zr6-oxoaggregates that is similar to UiO-66 received widespread concern (Cha et al., 2020, Chen et al., 2020a, Chen et al., 2020b). In MOF-808 structure, each cluster is connected by six trimeric linkers, while other coordination sites of Zr ions are saturated by bridging formic acid molecules (Furukawa et al., 2014). These formic acid molecules can be removed by simple solvent washing or mild heat treatment, thus leaving two coordination vacancies at each metal site which occupied by an -OH group and an unstable H2O molecule, respectively. As a 6-coordinated MOF material, MOF-808 has more open Zr sites and better spatial accessibility than 12-coordinated UiO-66 (Mautschke et al., 2018). Therefore, these characteristics provide great possibility for MOF-808 to tolerate ligands with different topologies and functions.

Endocrine disrupting compounds (EDCs), also known as environmental estrogens or environmental hormones, are organic pollutants released into environment during human production and living activities, which can lead to genital disorders, behavioral abnormalities, reduced reproductive capacity, larval mortality, and even extinction (Ma et al., 2021, Giulivo et al., 2016, Jiang et al., 2020). EDCs are widely distributed in various environmental media and have difficulty to degradation (Gmurek et al., 2017). Even if the concentration in environment is very low, they can accumulate in biological cells and can be transferred step by step along food chain, and finally enter human and higher animals with extremely high concentration. Among them, estradiol (E2), estrone (E1), estradiol valerate (EV), diethylstilbestrol (DES), and bisphenol A (BPA) are considered as typical estrogenic compounds (Čelić et al., 2020). These substances have strong reproductive and developmental toxicity at low doses and have become one of the hot topics in the field of environmental toxicology (Gmurek et al., 2017). However, the analysis and detection of trace EDCs is still facing great challenging because of complexity of environmental samples. Therefore, developing simple, sensitive, and reliable analytical methods for detecting EDCs has become an urgent technique in study their toxicological characteristics.

HPLC-DAD is one of the most widely used equipments in environmental analysis. However, the sensitivity is not sufficient to detect trace pollutants. High-efficient sample pretreatment method is usually considered as complementary technique to overcome this drawback. As we all know, the adsorption material is the core of sample pretreatment. Herein, a series MTV Zr-MOFs (TCPP@MOF-808s) was designed and prepared by one-pot hydrothermal method. The morphology, as well as adsorption and removal properties of TCPP@MOF-808s can be adjusted by changing ratio of linkers. Experimental results demonstrated that 57%TCPP@MOF-808 presented the best performance to recognize and extract EDCs including BPA, 17β-E2, 17α-E2, E1, and HEX in water sample prior to HPLC-DAD analysis. In addition, the effects of adsorption kinetics and isotherm on adsorption were studied. As far as we know, this is the first study to investigate defect-controlled TCPP@MOF-808 on original framework and use as sorbent in sample pretreatment. The as-prepared 57%TCPP@MOF-808 may be presented potential applicability in sample pretreatment, pollutant removal, and actual water treatment.

Section snippets

Preparation of MOF-808

In a typical synthesis, ZrCl4 (175 mg) and H3BTC (52.8 mg) were dissolved in 8 mL formic acid and 8 mL DMF with sonication in water bath (Biswas et al., 2021). After being sonicated for 0.5 h, the mixture was transformed into reaction tube with a capacity of 50 mL. The reaction tube was maintained at 120 °C for 24 h, and then naturally cooled to room temperature. Finally, the obtained samples were washed with DMF and acetone to remove the impurities and dried at 80 ℃ in a vacuum drying oven.

Preparation of TCPP@MOF-808s

The

Characterization of adsorbents

The MTV-MOFs (TCPP@MOF-808s) with combination of desired functionality and exceptional stability, were synthesized through mixed-ligand strategy (Fig. 1a). During the synthesis process, TCPP was incorporated and limited into the framework of MOF-808 because of small pore structures of MOF-808. As can be seen from Fig. 2a, the color of prepared MOF-808 gives white. The solutions of freshly synthesized TCPP@MOF-808s present green (Fig. S1). After washing with DMF and acetone, the product remains

Conclusion

In summary, the new Zr-MOFs termed as TCPP@MOF-808s were successfully synthesized based on the mixed-ligands strategy. TCPP ligand was successfully integrated into MOF-808, and good crystallinity and exceptional stability were maintained. The performance of TCPP@MOF-808s were affected by the modification of the connection ratio. The missing-linker defects caused by additional TCPP could effectively enhance the adsorption capacity of the modified materials for EDCs. The results demonstrated

CRediT authorship contribution statement

Lizhen Han: Conceptualization, Methodology, Investigation, Data curation, Writing – original draft. Xiaojing Liu: Resources, Validation. Xiaowan Zhang: Formal analysis. Mengyuan Li: Data curation, Visualization. Dan Li: Resources. Shufang Tian: Writing – review & editing. Peige Qin: Resources, Data curation. Minghua Lu: Supervision, Funding acquisition. Zongwei Cai: Project administration.

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 sponsored by the National Natural Science Foundation of China (22076038), and Natural Science Foundation of Henan Province, China (202300410044).

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