Highly Efficient Removal of Neonicotinoid Insecticides by Thioether-Based (Multivariate) Metal–Organic Frameworks

Abstract

Circumventing the impact of agrochemicals on aquatic environments has become a necessity for health and ecological reasons. Herein, we report the use of a family of five eco-friendly water-stable isoreticular metal–organic frameworks (MOFs), prepared from amino acids, as adsorbents for the removal of neonicotinoid insecticides (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) from water. Among them, the three MOFs containing thioether-based residues show remarkable removal efficiency. In particular, the novel multivariate MOF {Sr II Cu II 6 [( S,S )-methox] 1.5 [( S,S )-Mecysmox] 1.50 (OH) 2 (H 2 O)}·36H 2 O ( 5 ), featuring narrow functional channels decorated with both −CH 2 SCH 3 and −CH 2 CH 2 SCH 3 thioalkyl chains—from l -methionine and l -methylcysteine amino acid-derived ligands, respectively—stands out and exhibits the higher removal efficiency, being capable to capture 100% of acetamiprid and thiacloprid in a single capture step under dynamic solid-phase extraction conditions—less than 30 s. Such unusual combination of outstanding efficiency, high stability in environmental conditions, and low-cost straightforward synthesis in 5 places this material among the most attractive adsorbents reported for the removal of this type of contaminants.

Multivariate Metal–Organic Framework/Single-Walled Carbon Nanotube Buckypaper for Selective Lead Decontamination

“…The gram-scale preparation of 1 follows a previously reported experimental procedure (see Experimental Section in Supporting Information). 50 The experimental PXRD pattern of 1 is identical to the calculated one ( Figure S2 ), which confirms the homogeneity of the bulk sample and its isostructurality to the single-crystals selected for SCXRD (see below). As a preliminary step to the preparation of MTV-MOF/SWCNT-BP , we evaluated the behavior of MTV-MOF 1 in the removal of Pb 2+ from water (see the Supporting Information for details on preparation of 1 ).…”

High Performance of Ionic-Liquid-Based Materials to Remove Insecticides

“…In contrast, AC was able to obtain significantly lower adsorption efficiencies ranging from 5 to 48% for the same neonics [ 25 ]. Negro et al [ 26 ] showed the ability of MOFs to adsorb acetamiprid and thiacloprid from aqueous solutions of 100 mg L −1 , in less than 30 s. The achieved removal efficiencies were 60% and 30% for imidacloprid and thiamethoxam, respectively, and the q max for all the pesticides in the study ranged from 400 and 500 mg g −1 . Ma et al [ 27 ] used potassium hydroxide activated magnetic microporous loofah sponge biochar to remove imidacloprid, registering a maximum adsorption capacity of 738 mg g −1 , whereas when a potassium hydroxide activated magnetic microporous sugarcane bagasse biochar was used as adsorbent for the same insecticide, a lower maximum adsorption capacity of 313 mg g −1 was achieved [ 28 ].…”

“…Several materials have been reported in the literature as adsorbents for a variety of insecticides, for instance, porous AC [ 19 ], granular AC [ 21 ], a combination of AC and florisil [ 22 ], DMPIS [ 23 ], chitin-derived three-dimensional nanomaterials [ 24 ], MOFs [ 26 ], POCIS [ 25 ], potassium hydroxide activated magnetic microporous loofah sponge biochar [ 27 ], and potassium hydroxide activated magnetic sugarcane bagasse biochar [ 28 ]. Mohammad et al [ 19 ] studied the application of micro- and mesoporous activated carbon (TPAC) to remove acetamiprid, in which a maximum adsorption capacity of 35.7 mg g −1 was achieved at the equilibrium time of 240 min.…”

“…In addition to activated carbon, Dummy Template Surface Molecularly Imprinted Polymers (DMIPs) have been used to adsorb imidacloprid and acetamiprid [ 23 ], whereas chitin-derived three-dimensional nanomaterials have been used as adsorbents to remove acetamiprid [ 24 ]. Other types of materials include Polar Organic Chemical Integrative Sampler (POCIS), applied to adsorb imidacloprid, acetamiprid, thiacloprid, thiamethoxam, clothianidin, dinotefuran, and nitenpyram [ 25 ], and Metal-Organic Frameworks (MOFs) containing thioether-based residues to remove acetamiprid and thiacloprid from aqueous solutions [ 26 ]. Potassium hydroxide activated magnetic microporous loofah sponge biochar [ 27 ] and potassium hydroxide activated magnetic microporous sugarcane bagasse biochar [ 28 ] have also been applied as adsorbents to remove imidacloprid.…”

Insights into Paraben Adsorption by Metal–Organic Frameworks for Analytical Applications

“…However, in the case of the adsorption of relatively large molecules (drugs, cosmetics, pesticides, etc.) from liquids for applications in drug delivery, pollutants removal, or analytical chemistry, there are fewer studies dedicated to the analysis of the adsorption processes and the mechanisms involved. ,,,− Considering that these applications benefit from the adsorption of large amounts of target molecules from liquids, they all should share in a comprehensive manner the efforts in the analysis of adsorption of target molecules by MOFs. Essentially because these target molecules are frequently the same, they are sometimes delivered as drugs to the organism, they need to be removed from water for being pollutants, or it is important to monitor their concentration in water, food, and/or biological samples.…”