Adsorptive Removal of Neonicotinoid Pesticides in Water by MOF-525 Composite Sponge Designed by Perspective of Molecular Interactions

doi:10.19894/j.issn.1000-0518.250072

Chinese Journal of Applied Chemistry ›› 2025, Vol. 42 ›› Issue (8): 1144-1154.DOI: 10.19894/j.issn.1000-0518.250072

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Adsorptive Removal of Neonicotinoid Pesticides in Water by MOF-525 Composite Sponge Designed by Perspective of Molecular Interactions

Xin-Yu ZHANG¹^,², Jian-Hui HUANG¹^,², Lei HUANG¹^,², Da-Ming ZHANG²^,³, Fei XU¹^,², Xiu-Xiu WU¹^,²()

^1.School of Health Science and Engineering，University of Shanghai for Science and Technology，Shanghai 200093，China
^2.Shanghai Engineering Research Center of Food Rapid Detection，Shanghai 200093，China
^3.Shanghai Ruixin Technology Instrument Co. ，Ltd. ，Shanghai 200331，China

Received:2025-02-24 Accepted:2025-06-16 Published:2025-08-01 Online:2025-08-11
Contact: Xiu-Xiu WU
About author:xiuxiuwu@usst.edu.cn
Supported by:
the Program of Shanghai Academic/Technology Research Leader(22XD1434700);the National Natural Science Foundation of China(32302219)

Abstract

Abstract:

Porphyrin based-metal organic framework （MOF） with strong affinity for neonicotinoid pesticide molecules were screened based on intermolecular interactions. Neonicotinoid pesticide molecules bind to meso-tetrakis（4-carboxyphenyl）porphyrin （H₄TCPP） ligands mainly through weak interactions such as π-π interactions， CH…π and Cl…π. MOF-525 was prepared by solvothermal method using zirconium chloride octahydrate， meso-tetra（4-carboxyphenyl）porphin， and benzoic acid as the raw materials. MOF-525 was immobilized on a melamine sponge （MS） by poly （vinyl alcohol）（PVA） to obtain MOF-525 composite melamine sponge （MOF-525@MS）. The structure of MOF-525@MS was characterized by using scanning electron microscopy （SEM）， energy dispersive X-ray spectroscopy （EDS）， X-ray diffraction （XRD）， Fourier-transform infrared spectroscopy （FT-IR）， and thermogravimetric （TG）， respectively. MOF-525@MS was used as an adsorbent for the optimization of adsorption experimental conditions， determination of actual samples and determination of reusability of four neonicotinoid pesticides （nitenpyram， thiamethoxam， acetamiprid and imidacloprid） in water. The results showed that the removal rate of MOF-525@MS for the above four neonicotinoid pesticides was over 87.49% at pH=5， adsorption time of 15 min and 8% NaCl. Three kinds of water samples from Huangpu River， field water and lake water were spiked with different concentrations of pesticides （100， 200 and 300 mg/L）， and MOF-525@MS showed 80.61%~97.82% removal of pesticides in all three kinds of water samples. Finally， the removal rate was still 75.41%~81.20% after five cycles of adsorption-elution-drying-re-adsorption repetition， which has good reusability and is a good adsorbent material that can be used for the removal of neonicotinoid pesticides in water.

Key words: Metal-organic framework, Composite materials, Neonicotinoid pesticides, Adsorptive removal

CLC Number:

O647.3

Xin-Yu ZHANG, Jian-Hui HUANG, Lei HUANG, Da-Ming ZHANG, Fei XU, Xiu-Xiu WU. Adsorptive Removal of Neonicotinoid Pesticides in Water by MOF-525 Composite Sponge Designed by Perspective of Molecular Interactions[J]. Chinese Journal of Applied Chemistry, 2025, 42(8): 1144-1154.

Figures/Tables 11

Fig.1 Chemical structures of four neonicotinoid pesticides and the ligand meso-tetra（4-carboxyphenyl） porphine （H4TCPP） of MOF-525

Fig.2 Schematic of the synthesis flow of MOF-525@MS

Fig.3 The electrostatic potential diagrams of four neonicotinoid pesticides and the ligand H4TCPP of MOF-525

Fig.4 The IGMH and binding energy （ΔE）of neonicotinoid pesticides with the ligand H4TCPP

Fig.5 SEM of MOF-525 （A）， MS （B） and MOF-525@MS （C）； SEM mappings （D） and EDS （E） of MOF-525@MS

Fig.6 XRD （A）， FT-IR （B） and thermogravimetry curves （C） of MOF-525， MS， MOF-525@MS

Fig.7 Standard curves of four neonicotinoid pesticides

Table 1 Standard equations and R2 of four neonicotinoid pesticides

Pesticides	Standard equations	R²	LOD/（mg·L^-1）	RSD/%
Nitenpyram	y=25587.66x-33952.41	0.999 0	0.042 1	1.43
Thiamethoxam	y=44439.14x-35652.92	0.999 6	0.053 2	2.09
Acetamiprid	y=47040.26x-47425.61	0.999 2	0.023 4	4.69
Imidaclo	y=51678.63x-43019.07	0.999 0	0.092 5	2.46

Fig.8 Effect of number of MOF-525@MS particles used （A）， adsorption time （B）， pH （C） and mass concentration of NaCl （D） on removal of neonicotinoid pesticides

Fig.9 Determination of the removal rate of four neonicotinoid pesticides spiked in real water samples by MOF-525@MS

Fig.10 Reusability of MOF-525@MS

References 24

[1]	ALAMMAR A， PARK S H， IBRAHIM I， et al. Architecting neonicotinoid-scavenging nanocomposite hydrogels for environmental remediation［J］. Appl Mater Today， 2020， 21： 100878.
[2]	YAN X T， CAI Y Y， ZHANG Q Q， et al. Neonicotinoid insecticides in a large-scale agricultural basin system-use， emission， transportation， and their contributions to the ecological risks in the Pearl River Basin， China［J］. Sci Total Environ， 2024， 948： 174392.
[3]	LIAO L， FENG S， ZHAO D， et al. Neonicotinoid insecticides in well-developed agricultural cultivation areas： seawater occurrence， spatial-seasonal variability and ecological risks［J］. J Hazard Mater， 2024， 473： 134621.
[4]	GOEDJEN G J， CAPEL P D， BARRY J D， et al. Occurrence and distribution of neonicotinoids and fiproles within groundwater in Minnesota： effects of lithology， land use and geography［J］. Sci Total Environ， 2024， 954： 176411.
[5]	ZHANG X， CAO Y， ZHANG Z， et al. Residues of neonicotinoid insecticides in artificial waterways of the Eastern Route of the South-to North Water Diversion Project， China： implications for environmental risks and human health［J］. Environ Pollut， 2024， 363： 125132.
[6]	WANG J， YUAN M， CAO N， et al. In situ boron-doped cellulose-based biochar for effective removal of neonicotinoids： adsorption mechanism and safety evaluation［J］. Int J Biol Macromol， 2023， 237： 124186.
[7]	LI X， FAN C， ZHENG J， et al. Facile synthesis of Ag@AgCl/ZnAl-LDH sesame balls nanocomposites with enhanced photocatalytic performance for the degradation of neonicotinoid pesticides［J］. Chem Eng J， 2022， 446： 136485.
[8]	ZHANG X， HUANG Y， CHEN W J， et al. Environmental occurrence， toxicity concerns， and biodegradation of neonicotinoid insecticides［J］. Environ Res， 2023， 218： 114953.
[9]	MA M， ZHOU A， HONG T， et al. Tailored porous structure and CO₂ adsorption capacity of Mg-MOF-74 via solvent polarity regulation［J］. Chem Eng J， 2023， 476： 146845.
[10]	WANG X， CHEN Y， LI W， et al. Ultramicroporous zinc-aminotriazole MOF with customized alkaline pore environments for highly efficient capture of CO₂ from flue gas［J］. Chem Eng J， 2024， 498： 155338.
[11]	GAO Y， LIU Q， ZENG Y， et al. Synthesis of a novel microplastic trap with abundant oxime groups based on MOF-545 post-engineering for the environmental pollution control and water remediation［J］. J Cleaner Prod， 2023， 430： 139678.
[12]	SHEN H M， WANG X， HUANG H， et al. Staged oxidation of hydrocarbons with simultaneously enhanced conversion and selectivity employing O₂ as oxygen source catalyzed by 2D metalloporphyrin-based MOFs possessing bimetallic active centers［J］. Chem Eng J， 2022， 443： 136126.
[13]	MONDOL M M H， JHUNG S H. Adsorptive removal of pesticides from water with metal-organic framework-based materials［J］. Chem Eng J， 2021， 421： 129688.
[14]	ZHANG Q， ZHAO J， XIE R， et al. A simple and efficient method for determining the pyrethroid pesticide residues in freshly squeezed fruit juices using a water stable metal-organic framework［J］. Microchem J， 2023， 187： 108392.
[15]	HUANG H， LI N， CHEN Y， et al. Synthesis of multiwalled carbon nanotubes/metal-organic framework composite for the determination of neonicotinoid pesticides in medicine and food homology products［J］. Food Chem， 2024， 434： 137354.
[16]	WANG Z， GU X， ZHANG X， et al. New easily recycled carrier based polyurethane foam by loading Al-MOF and biochar for selective removal of fluoride ion from aqueous solutions［J］. Sci Total Environ， 2023， 901： 166312.
[17]	CATALA-ICARDO M， GOMEZ-BENITO C， MARTINEZ-PEREZ-CEJUELA H， et al. Green synthesis of MIL53（Al）-modified paper-based analytical device for efficient extraction of neonicotinoid insecticides from environmental water samples［J］. Anal Chim Acta， 2024， 1316： 342841.
[18]	XIA J， GAO Y， YU G. Tetracycline removal from aqueous solution using zirconium-based metal-organic frameworks （Zr-MOFs） with different pore size and topology： adsorption isotherm， kinetic and mechanism studies［J］. J Colloid Interface Sci， 2021， 590： 495-505.
[19]	CHEN D， ZHANG Y， LV B， et al. Dietary exposure to neonicotinoid insecticides and health risks in the Chinese general population through two consecutive total diet studies［J］. Environ Int， 2020， 135： 105399.
[20]	CHEN B， LI Y， LI M， et al. Rapid adsorption of tetracycline in aqueous solution by using MOF-525/graphene oxide composite［J］. Microporous Mesoporous Mater， 2021， 328： 111457.
[21]	ZHAO H， LI T， ZHANG M， et al. Enhanced removal of Pb²⁺ and Congo red from aqueous solutions using hierarchically porous melamine sponge/polyvinyl alcohol/Zr-MOF composites［J］. J Environ Chem Eng， 2024， 12（2）： 112361.
[22]	WU X， HUANG L， YANG Q， et al. Effective extraction of pyrethroid pesticides from cabbages using Fe₃O₄@NU-1000 and adsorption mechanism： an experimental and theoretical study［J］. Microchem J， 2024， 204： 110979.
[23]	YU K， LEE Y R， SEO J Y， et al. Sonochemical synthesis of Zr-based porphyrinic MOF-525 and MOF-545： enhancement in catalytic and adsorption properties［J］. Microporous Mesoporous Mater， 2021， 316： 110985.
[24]	ZHOU Y， WANG J， YANG J， et al. Mesoporous silica-confined MOF-525 for stable adsorption of tetracycline over a wide pH application range［J］. ACS Appl Nano Mater， 2024， 7（4）： 3806-3816.

Adsorptive Removal of Neonicotinoid Pesticides in Water by MOF-525 Composite Sponge Designed by Perspective of Molecular Interactions

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