Publications

[1]. A Hybrid {Silk@Zirconium MOF} Material as Highly Efficient As III-sponge

Exposure of humans to Arsenic from groundwater drinking sources is an acute global public health problem, entailing the urgent need for highly efficient/low-cost Arsenite (AsIII) up-taking materials. Herein we present an innovative hybrid-material, ZrMOF@SFd operating like an “AsIII-sponge” with unprecedented efficiency of 1800 mg AsIII gr−1. ZrMOF@SFd consists of a neutral Zirconium Metal-Organic Framework [ZrMOF] covalently grafted on a natural silk-fiber (SFd). ZrMOF itself exhibits AsIII adsorption of 2200 mg gr−1, which supersedes any -so far- known AsIII-sorbent. Using XPS, FTIR, BET-porosimetry data, together with theoretical Surface-Complexation-Modeling (SCM), we show that the high-AsΙΙΙ-uptake is due to a sequence of two phenomena:[i] at low AsIII-concentrations, surface-complexation of H3AsO3 results in AsIII-coated voids of ZrMOF, [ii] at increased AsIII-concentrations, the AsIII-coated voids of ZrMOF are filled-up by H3AsO3 via a partitioning-like mechanism. In a more general context, the present research exemplifies a mind-changing concept, i.e. that a “partitioning-like” mechanism can be operating for adsorption of metalloids, such as H3AsO3, by metal oxide materials. So far, such a mechanism has been conceptualized only for the uptake of non-polar organics by natural organic matter or synthetic polymers.

[2]. Alkylamino-terephthalate ligands stabilize 8-connected Zr4+ MOFs with highly efficient sorption for toxic Se species

Zirconium(IV) metal organic frameworks (MOFs) with low net connectivity and available intra-framework sorption sites constitute excellent sorbents for toxic anions. To expand this family of highly promising sorbents, it would be desired to develop new synthetic strategies aiming towards such materials. Here we show that the utilization of terephthalate ligands with small to medium size alkyl-amino functional groups comprises an effective approach towards microporous Zr4+ MOFs with 8-connected frameworks. The new MOFs were proved the most effective Se(IV) and Se(VI) sorbents ever reported, with exceptional sorption capacities (up to 272 mg Se(IV) g−1 and 290 mg Se(VI) g−1), reusability, rapid sorption kinetics (≤3 min) and capability to sorb efficiently these anions in a very wide pH range (1–10), even in the presence of various competitive anions. The MOFs also display highly efficient sorption capability for the particularly toxic SeCN−, with such property demonstrated for the first time for MOF materials.

[3]. Robust Al3+ MOF with Selective As(V) Sorption and Efficient Luminescence Sensing Properties toward Cr(VI)

Herein, we report the synthesis and characterization of a new robust Al3+ metal–organic framework MOF, [Al(OH)(PATP)]·solvent (Al-MOF-1, with PATP2– = 2-((pyridin-2-ylmethyl)amino)terephthalate). Al-MOF-1 exhibits excellent stability from highly acidic (pH = 2) to basic (pH = 12) aqueous solutions or in the presence of oxoanionic species [As(V) and Cr(VI)]. On the contrary, the related MIL-53(Al) MOF (Al(OH) (BDC), with BDC2– = terephthalate) shows a partial structure collapse under these conditions, signifying the superior chemical robustness of Al-MOF-1. Al-MOF-1 was proved to be an effective sorbent toward As(V) with efficient sorption capacity (71.9 ± 3.8 mg As/g), rapid sorption kinetics (equilibrium time ≤1 min), and high selectivity in the presence of various competing anions.

Furthermore, Al-MOF-1 revealed high sorption capacities for Cr(VI) species in both neutral (124.5 ± 8.6 mg Cr/g) and acidic (63 ± 2 mg Cr/g) aqueous media, combining fast kinetics and relatively good selectivity. The limited porosity (BET = 38 m2/g) and small pores (2–3 Å) of the material indicate that the sorption process occurs exclusively on the external surface of Al-MOF-1 particles. The driving force for the capture of oxoanions by Al-MOF-1 is the strong electrostatic interactions between the oxoanionic species and the positively charged surface of MOF particles. Aiming at a practical wastewater treatment, we have also immobilized Al-MOF-1 on a cotton substrate, coated with polydopamine.

The fabric sorbent exhibited highly effective removal of the toxic oxoanionic species from aqueous media under either batch or dynamic (continuous flow) conditions. In addition, Al-MOF-1 was found to be a promising luminescence sensor for detecting trace amounts of Cr(VI) in real water samples, with Cr(VI) being successfully detected at concentrations well below the acceptable limits (<50 ppb). Moreover, Al-MOF-1 was demonstrated to be a sufficient water sensor in organic solvents (LOD ≤0.25% v/v). All the above indicate that Al-MOF-1 represents a multifunctional material with a multitude of potential applications, such as environmental remediation, industrial wastewater treatment, chemical analysis, and water determination in biofuels.

[4]. Zirconium(IV) Metal Organic Frameworks with Highly Selective Sorption for Diclofenac under Batch and Continuous Flow Conditions

Diclofenac (DCF) is among the most effective non-steroidal anti-inflammatory drugs (NSAIDs) and at the same time one of the most consumed drugs worldwide. Since the ever-increasing use of diclofenac poses serious threats to ecosystems, its substantial removal is crucial. To address this issue, a variety of sorbents have been employed. Herein we present the diclofenac removal properties of two metal organic frameworks, namely [Zr6O4(OH)4(NH2BDC)6]·xH2O (MOR-1) and H16[Zr6O16(H2PATP)4]·xH2O (MOR-2). Batch studies revealed fast sorption kinetics for removal of DCF− from water as well as particularly high selectivity for the drug vs. common competitive species. Moreover, the composite MOR-1-alginic acid material was utilized in a sorption column, displaying remarkable removal efficiency towards DCF− anions. Significantly, this is the first time that column sorption data for removal of NSAIDs using MOF-based materials is reported.

[5]. Cotton fabric decorated by a Zr4+ MOF for selective As(V) and Se(IV) removal from aqueous media

In this work we describe a new method for the fabrication of a bulk sorbent material composed of the metal-organic framework (MOF) [Zr6O4(OH)4(NH2BDC)6]·xH2O (MOR-1) supported on cotton textiles and demonstrate its ability to remove toxic oxyanions from the aquatic environment. The new sorbent shows exceptional capability for both individual and competitive sorption of As(V) and Se(IV) oxyanionic species from aqueous media, due to the strong binding of these species to the Zr4+ metal ions, the high permeability and large contact surface area of the fabric. The sorption capacities of MOR-1@cotton fabric for As(V) (459 mg g−1) and Se(IV) (325 mg g−1) largely exceed those of previous reported sorbents. In addition, MOR-1@cotton fabric showed excellent sorption efficiency in a wide pH range (3−7) as well as high selectivity for As(V) and Se(IV) against several competitive anionic species. Finally, the fabric sorbent was examined for its efficiency in the removal of As(V) and Se(IV) from genuine water samples (lake, river and well water) under realistic conditions with very satisfactory results. These data, along with the fact that the bulk MOR-1@cotton fabric can be easily retrieved from water after use (in contrast to sorbents being in powder form), pledges on the potential use of the material for real water treatment applications.

[6]. Zr4+-terephthalate MOFs with 6-connected structures, highly efficient As(iii/v) sorption and superhydrophobic properties

The use of terephthalate ligands with CnH2n+1NH-chains (n ≥ 6) led to the isolation of the first examples of Zr4+-terephthalate MOFs with 6-connected frameworks. The material with hexyl-amino functional groups has been proved to be an exceptional sorbent for the removal of As(III/V) toxic species from aqueous media, whereas MOFs with heptyl to dodecyl-amino moieties are superhydrophobic with promising oil–water separation properties.

[7]. Highly efficient sorption and luminescence sensing of oxoanionic species by 8-connected alkyl-amino functionalized Zr4+ MOFs

In the present study we provide the sorption properties of four 8-connected Zr4+ MOFs with the general formula H16[Zr6O16(RNH-BDC)4]·solvent (RNH-BDC2− = 2-alkyl-amine-terephthalate; R = ethyl-, ET-MOF; R = propyl-, PROP-MOF; R = isobutyl-, SBUT-MOF; R = n-butyl, BUT-MOF) towards toxic Cr(VI) and radionuclide-related ReO4− oxoanions. These MOFs represent superior sorbents for the removal of oxoanionic species, in terms of kinetics, sorption isotherms, selectivity and regeneration/reusability. The excellent sorption capability of the MOFs is due to a combination of surface and intra-framework sorption phenomena. The latter process proceeds via replacement of terminal water/hydroxyl ligands from the Zr6 clusters and subsequent binding of oxonanions to the Zr4+ centers, a fact that was proved via Rietveld PXRD analysis for the anion-loaded BUT-MOF. Importantly, BUT-MOF demonstrated an exceptional sorption capacity for Cr2O72− (505 mg g−1) and was further utilized in a sorption column in the form of MOF/calcium alginate beads, displaying remarkable removal efficiency towards industrial (chrome-plating) wastewater. Furthermore, the luminescence Cr(VI) sensing properties of BUT-MOF were explored in detail, presenting high sensitivity (detection limits as low as 9 ppb) and selectivity for these species against various competitive anions.

[8]. Composite Materials Based on a Zr4+ MOF and Aluminosilicates for the Simultaneous Removal of Cationic and Anionic Dyes from Aqueous Media

Environmental pollution has been a reality for many decades, with its contamination intensifying daily due to rapid urbanization and the ever-increasing world population. Dyes, and especially synthetic ones, constitute a category of pollutants that not only affect the quality of water but also exhibit high toxicity toward living organisms. This study was thoroughly planned to explore the removal of two toxic dyes, namely the methylene blue (MB) and methyl orange (MO) compounds from contaminated aqueous media. For this purpose, we designed and synthesized two new composite materials based on ammonium-functionalized Zr4+ MOF (MOR-1 or UiO-66-NH3+) and naturally occurring sorbents, such as bentonite and clinoptilolite. The composite materials displayed exceptional sorption capability toward both MB+ and MO− ions. A key finding of this study was the high efficiency of the composite materials to simultaneously remove MB+ and MO− under continuous flow conditions, also showing regeneration capability and reusability, thus providing an alternative to well-known mixed bed resins.

[9]. Development of a New Method to Estimate the Water Purification Efficiency of Bulk-Supported Nanosorbents under Realistic Conditions

The direct use of nanosorbents for water purification is limited due to their aggregation and the lack of techniques for their recovery from natural waters. To overcome these problems, the affixation of nanomaterials onto bulk, non-mobile supports has been proposed. However, a method to simulate the efficiency of these sorbents under realistic conditions is still not available. To address this need, this work describes a method for evaluating the sorption efficiency of nanosorbent materials incorporated on bulk supports under non-equilibrium conditions. The method combines the principles of passive sampling, an environmental monitoring technique that is based on passive diffusion of dissolved contaminants from water to a sorbent, with batch sorption experiments that measure sorption under equilibrium conditions, to determine the parameters associated with water purification. These parameters are the maximum sorption capacity of the sorbent and the sampling rate, which is the volume of contaminated water treated per unit of time. From these variables, the deployment time of the sorbent until reaching saturation is proposed as an alternative indicator of sorbent efficiency. As proof-of-principle, the removal of oxyanions from a Zr-metal-organic framework (MOR−1) immobilized on cotton textiles was investigated. The results show that the sorption capacity under passive diffusion uptake conditions, is approximately 20 mg/g for As(VI) and 36 mg/g Se(IV), which is 10 to 30 times lower compared to that determined in batch sorption studies, indicating that conventional equilibrium sorption overestimates the efficiency of the sorbents under realistic conditions. The application of the method to a worst-case scenario, involving the severe contamination of freshwaters with arsenate species, is also demonstrated.

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