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. 2024 Jul 30;14(1):17607.
doi: 10.1038/s41598-024-67986-8.

Cu-Co bimetallic organic framework as effective adsorbents for enhanced adsorptive removal of tetracycline antibiotics

Jiayuan Yue  1 , Qi Zheng  1 , Shushu Ding  1   2 , Yujian Yin  1 , Xiaodan Zhang  1 , Liyun Wang  1 , Yipeng Gu  1 , Jiejia Li  3 , Yuhan Zhang  1 , Yurou Shi  1 , Yuetan Dong  1 , Qing Zhu  4   5 , Huixiao Duo  6   7
Affiliations

Cu-Co bimetallic organic framework as effective adsorbents for enhanced adsorptive removal of tetracycline antibiotics

Jiayuan Yue et al. Sci Rep. .

Abstract

In this study, the removal effect of a new MOF-on MOF adsorbent based on Cu-Co bimetallic organic frameworks on tetracycline antibiotics (TCs) in water system was studied. The adsorbent (Cu-MOF@Co-MOF) were synthesized by solvothermal and self-assembly method at different concentrations of Co2+/Cu2+. The characterization results of SEM, XRD, XPS, FTIR and BET indicated that the MOF-on MOF structure of Cu-MOF@Co-MOF exhibited the best recombination and physicochemical properties when the molar ratio of Co2+: Cu2+ is 5:1. In addition, the Cu-MOF@Co-MOF have a high specific surface area and bimetallic clusters, which can achieve multi-target synergistic adsorption of TCs. Based on above advantages, Cu-MOF@Co-MOF provided a strong affinity and could efficiently adsorb more than 80% of pollutants in just 5 to 15 min using only 10 mg of the adsorbent. The adsorption capacity of tetracycline and doxycycline was 434.78 and 476.19 mg/g, respectively, showing satisfactory adsorption performance. The fitting results of the experimental data were more consistent with the Langmuir isotherm model and pseudo-second-order kinetic model, indicating that the adsorption process of TC and DOX occurred at the homogeneous adsorption site and was mainly controlled by chemisorption. Thermodynamic experiments showed that Cu-MOF@Co-MOF was thermodynamically advantageous for the removal of TCs, and the whole process was spontaneous. The excellent adsorption capacity and rapid adsorption kinetics indicate the prepared MOF-on MOF adsorbent can adsorb TCs economically and quickly, and have satisfactory application prospects for removing TCs in practical environments. The results of the study pave a new way for preparing novel MOFs-based water treatment materials with great potential for efficient removal.

Keywords: Antibiotics removal; Cu-MOF@Co-MOF; MOF-on MOF; Water purification.

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Conflict of interest statement

The authors declare no competing interests.

Figures

Figure 1
Figure 1
The procedure for synthesis of Cu-MOF@Co-MOF and removal process of TCs over Cu-MOF@Co-MOF adsorbent via DSPE.
Figure 2
Figure 2
SEM images of (a) Cu-MOF; (b) Co-MOF@Co-MOF-3.75; (c) Co-MOF@Co-MOF-5; (d) Co-MOF@Co-MOF-7.
Figure 3
Figure 3
Characterization results of (a) XRD patterns; (b) FTIR spectra; (c) XPS spectra; and (d) N2 adsorption–desorption isotherms.
Figure 4
Figure 4
Isotherms fitting curves of TCs on Cu-MOF@Co-MOF: (a) Langmuir model and (b) Freundlich model.
Figure 5
Figure 5
The kinetic models fitting curves of the Cu-MOF@Co-MOF for TCs: (a) Pseudo-first-order model; (b) Pseudo-second-order model; (c) Elovich model; and (d) Liquid film diffusion model.
Figure 6
Figure 6
(a) FTIR spectra; (b) XRD spectra; and (c–f) XPS spectra: (c) XPS Survey, (d) Cu2p, (e) Co2p, (f) C1s of Cu-MOF@Co-MOF before and after adsorption.
Figure 7
Figure 7
The adsorption mechanism of TCs on Cu-MOF@Co-MOF.
See this image and copyright information in PMC

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