Versatile Covalent Postsynthetic Modification of Metal Organic Frameworks via Thermal Condensation for Fluoride Sensing in Waters.

Having access to safe drinking water is one of the 17 sustainable development goals defined by the United Nations (UN). However, many settlements around the globe have limited access to drinkable water due to non-anthropogenic pollution of the water sources. One of those pollutants is fluoride, which can induce major health problems. In this manuscript, we report on a post synthetic functionalization of metal organic frameworks for the sensing of fluoride in water. The proposed thermal condensation methodology allows for a high yield of functionalization using few steps, reducing reagent costs and generating minimal by-products. We identified a Rhodamine B functionalized Al-BDC-NH2 metal organic framework as one particularly suitable for fluoride detection in water.

Effect of the Ethanol/BTC Ratio on the Methane Uptake of Mechanochemically Synthesized MOF-199.

We report on a detailed textural analysis of mechanochemically synthesized MOF-199 including N2 adsorption-desorption and CO2 adsorption isotherms data at 77 K and 273 K (up to atmospheric pressure), respectively, and CH4 adsorption data at 298 K (up to 35 bar). We used the isotherm adsorption data to determine the micropore volume of the MOF-199 structures, to establish their methane uptake capacity and to understand how these properties depended on the Ethanol/BTC ratio used during the synthesis. The maximum methane uptake capacity for our specimens was recorded at 130 v/v at 35 bars. These results open an avenue for a better understanding of alternative manufacturing processes of MOF structures for gas storage applications.

The Long and Bright Path of a Lanthanide MOF: From Basics towards the Application.

The development of portable, reliable, and low-cost sensors for assessing the quality of natural water sources is of high relevance in developing countries as they can serve as an intermediate solution prior to the building of permanent potable water distribution infrastructure. These sensors should be simple to operate by non-trained operators and easy to manufacture locally. Lanthanide-based metal-organic frameworks (MOFs) offer a trustable platform due to their intense emission in regions of the visible spectra and their high sensitivity to fluorides in water. Cotton was chosen as a substrate due to its high hydrophilicity which, together with the highly porous nature of the MOF, allows for shorter reaction times. The modified cotton was characterized by XRD, SEM as well as XAFS, hence probing the presence of [Tb(BTC)6 (H2 O)] (Tb-BTC) attachment to cotton. Changes in the emission when Tb-BTC modified cotton was exposed to water and aqueous fluoride solutions were monitored as a function of time. Crystalline phase changes were identified that correlated to structural information. Finally, the Tb-BTC modified cotton was used to build a fluoride demonstrator sensor with a linear response of up to 10 mg L-1 and a limit of detection of 0.8 mg L-1 , making it suitable for drinking water analysis under international regulations.

Open-Source Portable Device for the Determination of Fluoride in Drinking Water.

The prolonged exposure to fluorides results in the development of several diseases, from dental fluorosis to crippling deformities of the spine and major joints. The population exposed to high fluoride concentration is located in developing countries where the assurance of water quality is difficult to perform. Addressing this challenge, an open-source system for the determination of fluoride in natural water was developed using the equilibrium between the red Fe-SCN complex and the colorless Fe-F. The reaction develops in cotton substrates to reduce the manipulation of liquid reagents and reduce the errors by nontrained operators. The system was optimized by image analysis and implemented in an open-source Arduino-based device and data was acquired through the serial port of a cell phone, which is also used as a power source, avoiding the use of a battery and reducing production costs. The device showed a detection limit of 0.7 mg L-1 and a linear range of up to 8 mg L-1. This extended detection limit makes the device useful for the application in regions where the fluoride concentration in drinking water is far higher than the United Nations limit (1.5 mg L-1), e.g., the United Republic of Tanzania, where the upper limit of F- was extended to 4 mg L-1 or in USA, where the Environmental Protection Agency established the Maximum Contaminant Level of F- in drinking water at 4 mg L-1. The method was tested with natural waters from the Arusha region in the northeast of Tanzania and validated against the results from ion chromatography showing a good correlation. The developed device exhibits chemical stability of 5 days, allowing it to be manufactured and distributed in local areas and, also, modified according to the requirements of the water composition due to Industry 4.0 concepts used in the design.

Evaluation of performance of three different hybrid mesoporous solids based on silica for preconcentration purposes in analytical chemistry: From the study of sorption features to the determination of elements of group IB.

Several studies involving the physicochemical interaction of three silica based hybrid mesoporous materials with metal ions of the group IB have been performed in order to employ them for preconcentration purposes in the determination of traces of Cu(II), Ag(I) and Au(III). The three solids were obtained from mesoporous silica functionalized with 3-aminopropyl (APS), 3-mercaptopropyl (MPS) and N-[2-aminoethyl]-3-aminopropyl (NN) groups, respectively. Adsorption capacities for Au, Cu and Ag were calculated using Langmuir's isotherm model and then, the optimal values for the retention of each element onto each one of the solids were found. Physicochemical data obtained under thermodynamic equilibrium and under kinetic conditions - imposed by flow through experiments - allowed the design of simple analytical methodologies where the solids were employed as fillings of microcolumns held in continuous systems coupled on-line to an atomic absorption spectrometry. In order to control the interaction between the filling and the analyte at short times (flow through conditions) and thus, its effect on the analytical signal and the presence of interferences, the initial adsorption velocities were calculated using the pseudo second order model. All these experiments allowed the comparison of the solids in terms of their analytical behaviour at the moment of facing the determination of the three elements. Under optimized conditions mainly given by the features of the filling, the analytical methodologies developed in this work showed excellent performances with limits of detection of 0.14, 0.02 and 0.025 microg L(-1) and RSD % values of 3.4, 2.7 and 3.1 for Au, Cu and Ag, respectively. A full discussion of the main findings on the interaction metal ions/fillings will be provided. The analytical results for the determination of the three metals will be also presented.

Non-chromatographic determination of ultratraces of V(V) and V(IV) based on a double column solid phase extraction flow injection system coupled to electrothermal atomic absorption spectrometry.

In this work, a non-chromatographic procedure for the on-line determination of ultratraces of V(V) and V(IV) is presented. The method involves a solid phase extraction-flow injection system coupled to electrothermal atomic absorption spectrometry (SPE-FI-ETAAS). The system holds two microcolumns (MC) set in parallel and filled with lab-made mesoporous silica functionalized with 3-aminopropyltriethoxy silane (APS) and mesoporous silica MCM-41, respectively. The pre-concentration of V(V) is performed by sorption onto the first MC (C1) filled with APS at pH 3, whilst that of V(IV) is performed by sorption onto the second column (C2) filled with mesoporous silica MCM-41 at pH 5. Aqueous samples containing both analytes are loaded and, after pre-concentration (pre-concentration factor PCF=10, sorption flow rate=1 mL min(-1), sorption time=10 min), they are eluted in separate vessels with hydroxylammonium chloride (HC) 0.1 mol L(-1) in HCl 0.5 mol L(-1) (elution volume=1 mL, elution flow rate=0.5 mL min(-1)). Afterwards, both analytes are determined through ETAAS with graphite furnace. Under optimized conditions, the main analytical figures of merit for V(V) and V(IV) are, respectively: detection limits (3s): 0.5 and 0.6 microg L(-1), linear range: 2-100 microg L(-1) (both analytes), sensitivity: 0.015 and 0.013 microg(-1)L and sample throughput: 6h(-1) (both analytes). Recoveries of both species were assayed in different water samples. Validation was performed through certified reference materials for ultratraces of total vanadium in river water.