Catalytic hydrodehalogenation activity and selectivity of polyiodinated phenolic disinfection byproducts at ambient conditions.

Iodo-phenolic disinfection byproducts (DBPs) widely occur in disinfected water, posing potential risks to human health and the ecosystem as they possess higher toxicity than the bromo- and chloro-analogs. Herein, we elucidated the catalytic hydrodehalogenation (HDH) activity and selectivity of polyiodinated phenolic DBPs on supported noble metal catalysts at ambient conditions. Both 2,4,6-triiodophenol and 4-chloro-2,6-diiodophenol can be efficiently eliminated on Pd/TiO2 and Rh/TiO2 within 20 min, with Pd/TiO2 exhibiting higher turnover frequency. The HDH reactions proceeded in both stepwise and concerted pathways on Pd/TiO2, while they were dominantly stepwise on Rh/TiO2. Experimental results and theoretical calculations revealed that the HDH selectivity depends on the position and the bond energy of halo-substitutions. For the HDH of 2,4,6-triiodophenol, the para-substituted iodine was more favorable to be dehalogenated than the ortho-substituted ones due to the steric hindrance of the hydroxyl group. For the HDH of 4-chloro-2,6-diiodophenol, the ortho-substituted iodine was removed before the para-substituted chlorine as CI bond had higher reactivity than CCl bond. Significant catalyst deactivation was observed for the HDH of 4-chloro-2,6-diiodophenol on Pd/TiO2 due to iodine poisoning, resulting in 4-chlorophenol as the dominant product. In contrast, Rh/TiO2 can completely hydrodehalogenate 4-chloro-2,6-diiodophenol into cyclohexanone with little iodine poisoning. Our results suggest that HDH is an efficient process for abating iodo-phenolic DBPs. Rh/TiO2 is a more promising HDH catalyst for iodinated DBP removal than Pd/TiO2 with excellent resistance to iodine poisoning.

Multiple-Emitting Luminescent Metal-Organic Framework as an Array-on-a-MOF for Rapid Screening and Discrimination of Nitroaromatics.

Fluorescence array technologies have attracted great interest in the sensing field because of their high sensitivity, low cost, and capability of multitarget detection. However, traditional array sensing relies on multiple independent sensors and thus often requires time-consuming and laborious measurement processes. Herein, we introduce a novel fluorescence array strategy of the array-on-a-metal-organic framework (MOF), which integrates multiple array elements into a single MOF matrix to achieve facile sensing and discrimination of multiple target analytes. As a proof-of-concept system, we constructed a luminescent MOF containing three different emitting channels, including a lanthanide ion (europium/Eu3+, red emission), a fluorescent dye (7-hydroxycoumarin-4-acetic acid/HCAA, blue emission), and the MOF itself (UiO-66-type MOF, blue-violet emission). Five structurally similar nitroaromatic compounds (NACs) were chosen as the targets. All three channels of the array-on-a-MOF displayed rapid and stable fluorescence quenching responses to NACs (response equilibrium achieved within 30 s). Different responses were generated for each channel against each NAC due to the various quenching mechanisms, including photoinduced electron transfer, energy competition, and the inner filter effect. Using linear discriminant analysis, the array-on-a-MOF successfully distinguished the five NACs and their mixtures at varying concentrations and demonstrated good sensitivity to quantify individual NACs (detect limit below the advisory concentration in drinking water). Moreover, the array also showed feasibility in the sensing and discrimination of multiple NACs in real water samples. The proposed "array-on-a-MOF" strategy simplifies multitarget discrimination procedures and holds great promise for various sensing applications.

Robust Activity and Stability of P-Doped Fe-Carbon Composites Derived from MOF for Bromate Reduction.

Iron-based materials are effective for the reductive removal of the disinfection byproduct bromate in water, while the construction of highly stable and active Fe-based materials with wide pH adaptability remains greatly challenging. In this study, highly dispersed iron phosphide-decorated porous carbon (Fe2P(x)@P(z)NC-y) was prepared via the thermal hydrolysis of Fe@ZIF-8, followed by phosphorus doping (P-doping) and pyrolysis. The reduction performances of Fe2P(x)@P(z)NC-y for bromate reduction were evaluated. Characterization results showed that the Fe, P, and N elements were homogeneously distributed in the carbonaceous matrix. P-doping regulated the coordination environment of Fe atoms and enhanced the conductivity, porosity, and wettability of the carbonaceous matrix. As a result, Fe2P(x)@P(1.0)NC-950 exhibited enhanced reactivity and stability with an intrinsic reduction kinetic constant (kint) 1.53-1.85 times higher than Fe(x)@NC-950 without P-doping. Furthermore, Fe2P(0.125)@P(1.0)NC-950 displayed superior reduction efficiency and prominent stability with very low Fe leaching (4.53-22.98 µg L-1) in a wide pH range of 4.0-10.0. The used Fe2P(0.125)@P(1.0)NC-950 could be regenerated by phosphating, and the regenerated Fe2P(0.125)@P(1.0)NC-950 maintained 85% of its primary reduction activity after five reuse cycles. The study clearly demonstrates that Fe2P-decorated porous carbon can be applied as a robust and stable Fe-based material in aqueous bromate reduction.

Efficient Catalytic Oxidation of Ethylene at 0 °C on an in Situ Carbon Modified Pt Catalyst Supported on SBA-15.

The design of efficient catalysts for catalytic ethylene (C2H4) oxidation is of crucial importance for extending the shelf life of fruits and vegetables. Herein, a carbon modified SBA-15 supported Pt catalyst (Pt/CSBA-15) was prepared in situ by a facile solid phase grinding-infiltration-inert atmosphere calcination method. Characterization results reveal that in the Pt/CSBA-15 catalysts thin carbon layers are successfully formed in the hexagonal pores of SBA-15. Additionally, Pt particles are well dispersed in the channels of SBA-15, and Pt/CSBA-15 has a smaller Pt particle size than the catalyst without carbon modification (i.e., Pt/SBA-15). O2 is more feasibly adsorbed and activated on small-sized Pt particles, and in situ formed carbon species enhance the hydrophobicity of catalysts. As a result, both 3Pt/CSBA-15 and 5Pt/CSBA-15 are able to maintain 100% conversion of 50 ppm of C2H4 for more than 7 h at 0 °C. 3Pt/CSBA-15 even achieves 81.5% C2H4 conversion and 71.6% CO2 yield after 20 h, exhibiting much more prominent catalytic performances than 3Pt/SBA-15. DFT calculations and in situ FTIR measurements confirm that small-sized Pt particles possess strong O2 affinity to promote O2 adsorption, and in situ formed hydrophobic carbon layers efficiently suppress competitive H2O adsorption. Such a unique one-step catalyst preparation method for regulating the size of metal particles and the hydrophobicity of catalysts can be perfectly utilized to develop simple and efficient hydrophobic catalysts applied in low-temperature oxidation of C2H4.

In situ biosynthesized polyphosphate nanoparticles/reduced graphene oxide composite electrode for highly sensitive detection of heavy metal ions.

The development of an effective sensing platform is critical for the electrochemical detection of heavy metal ions (HMIs) in water. In this study, we fabricated a newly designed sensor through the in situ assembly of reduced graphene oxide (rGO) and polyphosphate nanoparticles (polyP NPs) on a carbon cloth electrode via microorganism-mediated green biochemical processes. The characterization results revealed that the rGO produced via microbial reduction had a three-dimensional porous structure, serving as an exceptional scaffold for hosting polyP NPs, and the polyP NPs were evenly distributed on the rGO network. In terms of detecting HMIs, the numerous functional groups of polyP NPs play a major role in the coordination with the cations. This electrochemical sensor, based on polyP NPs/rGO, enabled the individual and simultaneous determination of lead ion (Pb2+) and copper ion (Cu2+) with detection limits of 1.6 nM and 0.9 nM, respectively. Additionally, the electrode exhibited outstanding selectivity for the target analytes in the presence of multiple interfering metal ions. The fabricated sensor was successfully used to determine Pb2+/Cu2+ in water samples with satisfactory recovery rates ranging from 92.16% to 104.89%. This study establishes a facile, cost-effective, and environmentally friendly microbial approach for the synthesis of electrode materials and the detection of environmental pollutants.

Ni12P5 Confined in Mesoporous SiO2 with Near-Unity CO Selectivity and Enhanced Catalytic Activity for CO2 Hydrogenation.

CO2 hydrogenation via the reverse water gas shift (RWGS) reaction is a promising strategy for CO2 utilization while constructing Ni-based catalysts with high catalytic activity and perfect CO selectivity remains a great challenging. Here, we demonstrate that the product selectivity for CO2 hydrogenation can be significantly tuned from CH4 to CO by phosphating of SiO2-supported Ni catalysts due to the geometric effect. Interestingly, nickel phosphide catalysts with different crystalline phases (Ni12P5 and Ni2P) differ sharply in CO2 conversion, and Ni12P5 is remarkably more active. Furthermore, we developed a facile strategy to confine small Ni12P5 nanoparticles in mesoporous SiO2 channels (Ni12P5@SBA-15). Enhanced activity is exhibited on Ni12P5@SBA-15, ascribed to the highly effective confinement effect. The in situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory calculations unveil that catalytic CO2 hydrogenation follows a direct CO2 dissociation route with adsorbed CO as the key intermediate. Notably, strong multibonded CO (threefold and bridge-bonded CO) is feasibly formed on the Ni catalyst accounting for CH4 as the dominant product whereas only weak linearly bonded CO exists on nickel phosphide catalysts resulting in almost 100% CO selectivity. The present results indicate that Ni12P5@SBA-15 combining the geometric effect and the confinement effect can achieve near-unity CO selectivity and enhanced activity for CO2 hydrogenation.

Hierarchical porous loofah-like carbon with sulfhydryl functionality for electrochemical detection of trace mercury in water.

Mercury is a common contaminant found in natural waters, which is highly toxic to human health. Thus, the facile and reliable monitoring of mercury in waters is of great significance. In this study, we fabricated a novel loofah-like hierarchical porous carbon with sulfhydryl functionality (S-LHC), and applied it as an ultrasensitive sensor for the electrochemical detection of mercury in water. The S-LHC was prepared through the direct pyrolysis of a triazole-rich metal-organic framework (MOF), followed by chemical modification using thioglycolic acid. The highly conductive N-doped carbon framework of S-LHC facilitated the electron transfer in mercury electrochemical sensing. Meanwhile, the open hierarchical pore structure and abundant sulfhydryl groups allowed the fast diffusion and effective enrichment of mercury ions. Consequently, the S-LHC sensor exhibited an exceptionally high sensitivity for mercury ions, with the mercury detection limit (0.36 nM) orders of magnitude lower than the regulated values in drinking water (typically 10∼30 nM). The constructed sensor also afforded good anti-interference ability and excellent stability for long-term detection of mercury in a variety of complex real water samples. The present study provides not only a facile method for mercury detection, but also a new idea for the construction of highly sensitive electrochemical sensors.

Amino-Functionalized Hierarchical Porous Carbon Derived from Zeolitic Imidazolate Frameworks for Ultrasensitive Electrochemical Sensing of Heavy Metals in Water.

Electrochemical sensing provides a feasible avenue to monitor heavy metal ions (HMIs) in water, whereas the construction of highly sensitive and selective sensors remains challenging. Herein, we fabricated a novel amino-functionalized hierarchical porous carbon by the template-engaged method using ZIF-8 as the precursor and polystyrene sphere as the template, followed by carbonization and controllable chemical grafting of amino groups for efficient electrochemical detection of HMIs in water. The amino-functionalized hierarchical porous carbon features an ultrathin carbon framework with a high graphitization degree, excellent conductivity, unique macro-, meso-, and microporous architecture, and rich amino groups. As a result, the sensor exhibits prominent electrochemical performance with significantly low limits of detection for individual HMIs (i.e., 0.93 nM for Pb2+, 2.9 nM for Cu2+, and 1.2 nM for Hg2+) and simultaneous detection of HMIs (i.e., 0.62 nM for Pb2+, 1.8 nM for Cu2+, and 0.85 nM for Hg2+), which are superior to most reported sensors in the literature. Moreover, the sensor displays excellent anti-interference ability, repeatability, and stability for HMI detection in actual water samples.

A nanozyme-like colorimetric sensing strategy based on persulfate activation on Co-based metal-organic frameworks.

A nanozyme-like colorimetric sensing strategy based on persulfate activation on Co-based metal-organic frameworks is developed for biomolecule detection in solution and on paper strips. By switching from H2O2 activation on nanozymes to catalytic persulfate activation, this general strategy provides higher sensitivity, faster speed, and wider application ranges for detection.

ZnO Nanorod-Immobilized Pt Single-Atoms as an Ultrasensitive Sensor for Triethylamine Detection.

Triethylamine (TEA) is a flammable and highly toxic gas, and the fast, accurate, and sensitive detection of gas TEA remains greatly challenging. Herein, we report a ZnO nanorod anchored with a single-atom Pt catalyst (Pt1/ZnO) as a gas sensor for TEA detection. The sensor shows high selectivity and high response to gas TEA with a response value of 4170 at 200 °C, which is 92 times higher than that of pure ZnO. Moreover, the Pt1/ZnO sensor has very short response and recovery times of only 34 and 76 s, respectively, and also has a high response to ppb-level TEA gas (100 ppb-21.6). The gas-sensing enhancement mechanism of the Pt1/ZnO sensor to gas TEA was systematically investigated using band structure analysis, in situ diffuse reflectance infrared Fourier transformation spectroscopy, and density functional theory calculations. The results show that the oxygen vacancies on Pt1/ZnO can effectively activate the adsorbed oxygen. Moreover, chemical bonds can be formed between Pt single atoms and N atoms in TEA to achieve effective adsorption and activation of TEA molecules, facilitating the reaction between TEA and the adsorbed oxygen on Pt1/ZnO, and thereby obtaining high gas-sensing performance. This work highlights the crucial role of Pt single-atom in improving the sensing performance for gas TEA detection, paving the way for developing more advanced gas sensors.

Insight into phase structure-dependent soot oxidation activity of K/MnO2 catalyst.

In the present study, two nanosized MnO2 with ß and δ phase structures and potassium loaded MnO2 catalysts with varied K loading amounts (denoted as K/MnO2) were prepared. Temperature programmed oxidation and isothermal reactions in loose contact modes were employed to examine the soot oxidation activity of the as-prepared catalysts. Characterization results show that as compared with ß-MnO2, δ-MnO2 has larger surface area and higher content of hydroxyl groups. Upon K loading, abundant hydroxyl groups in δ-MnO2 effectively sequestrate K cation to form bound K species and free K species are available only at K loading above 3.0 wt.%. In contrast, the majority of K species present as free state in ß-MnO2 even at a K loading of 1.0 wt.% due to its very low hydroxyl group content. The O2 temperature-programmed desorption (O2-TPD) demonstrates that the catalysts with free K species exhibit strong ability in activating gaseous O2, whereas the catalysts only having bound K display minor O2 activation capability. As a result, despite of slightly lower activity of ß-MnO2 than δ-MnO2, the K/ß-MnO2 catalysts exhibit substantially higher activities than K/δ-MnO2 catalysts with identical K loadings. The finding in this study clearly demonstrates that for MnO2 based catalysts, the enhancement of catalytic activity for soot oxidation is highly K loading amount dependent and the dependency is strongly associated with the phase structure of MnO2.

Polyaniline coated Pt/CNT as highly stable and active catalyst for catalytic hydrogenation reduction of Cr(VI).

Liquid phase catalytic hydrogenation reduction is a feasible method to eliminate Cr(VI) in water, while supported noble metal catalysts are liable to deactivation. In this study, carbon nanotube supported Pt catalyst (Pt/CNT) coated by polyaniline (Pt/CNT@PANI) was prepared and applied in the liquid phase catalytic hydrogenation of Cr(VI). Characterization results disclose that after coating Pt/CNT is completely wrapped by PANI layers and active Pt particles are no longer accessible. Despite complete embedment of Pt particles by PANI layers, Pt/CNT@PANI remains highly active for Cr(VI) reduction in liquid phase catalytic hydrogenation. The catalytic Cr(VI) reduction on Pt/CNT@PANI can be described by a PANI oxidation-reduction mechanism, by which PANI is first oxidized by Cr(VI) to form Cr(III), and oxidized PANI is reduced by catalytic hydrogenation. The Cr(VI) reduction on Pt/CNT@PANI complies with the Langmuir-Hinshelwood model, reflecting the pivotal role of Cr(VI) adsorption. Furthermore, the catalytic activity of Pt/CNT@PANI differs with PANI layer thickness and Cr(VI) reduction is positively correlated with reaction temperature. Catalyst recycling results show that after 4 cycles Pt/CNT loses 92.4% of catalytic activity, while the initial activity of Pt/CNT@PANI slightly decreases by 11.6%, demonstrating its high catalyst stability.

Effective catalytic hydrodechlorination removal of chloroanisole odorants in water using palladium catalyst confined in zeolite Y.

Chloroanisoles is a class of odorous pollutants commonly identified in drinking water. In the present study, we confined noble metal palladium (Pd) in the micropores of zeolite Y (ie-Pd@Y) using an ion exchange method, and applied it for the catalytic hydrodechlorination removal of chloroanisoles (represented by 2,4,6-trichloroanisole/TCA) in water. Pd supported on zeolite Y surface (im-Pd/Y, prepared by conventional impregnation method) was used as the benchmarking catalyst. The characterization results revealed that ie-Pd@Y had smaller Pd particle size and higher Pdn+/Pd0 ratio than im-Pd/Y. The catalytic hydrodechlorination of TCA followed a concerted dechlorination pathway and the Langmuir-Hinshelwood model. The ie-Pd@Y catalysts with different Pd loadings exhibit excellent catalytic activities with more than 95% of TCA removed within 30 min, which is far superior to the im-Pd/Y catalysts (27-70%). Moreover, due to the confinement effect of zeolite Y, ie-Pd@Y displayed enhanced catalytic stability as compared with im-Pd/Y. The initial activity of ie-Pd@Y was more than 20 times higher than that of im-Pd/Y after five reaction cycles. Additionally, with the assistance of sieving effect, ie-Pd@Y displayed much stronger capability against the interference from dissolved organic matter than im-Pd/Y. The present results demonstrate that the confined catalysts ie-Pd@Y can be applied in liquid phase catalytic hydrogenation to effectively eliminate halogenated odorants in waters.

Synergistic effects boost electrocatalytic reduction of bromate on supported bimetallic Ru-Cu catalyst.

Bromate is a commonly identified carcinogenic and genotoxic disinfection byproduct in water. In the present work, bimetallic Ru-Cu catalyst supported on carbon nanotube (RuCu/CNT) was prepared and the structural properties of the catalysts were characterized. The results show that the presence of Ru enhances the dispersion and reduction of Cu particles in the RuCu/CNT catalyst in comparison with the monometallic Cu catalyst supported on CNT (Cu/CNT). For electrocatalytic reaction on Cu/CNT, bromate is reduced on metallic Cu surface via a redox process. For Ru/CNT, highly active H* radicals are generated on metallic Ru surface via the Volmer process and are used for bromate reduction. As for the RuCu/CNT, bromate is reduced through two main pathways, including direct redox reaction on metallic Cu and indirect reduction by active H* radicals on Ru surface. Accordingly, RuCu/CNT exhibits the highest catalytic activity, ascribed to the synergistic effect between metallic Ru and Cu. Furthermore, the bimetallic catalyst displays much higher catalytic efficiency as compared with previously reported results. The pH, initial bromate concentration, in-situ electrochemical reduction of the electrodes and working potential have strong impacts on the removal efficiency of bromate on RuCu/CNT.

Mechanism for selective binding of aromatic compounds on oxygen-rich graphene nanosheets based on molecule size/polarity matching.

Selective binding of organic compounds is the cornerstone of many important industrial and pharmaceutical applications. Here, we achieved highly selective binding of aromatic compounds in aqueous solution and gas phase by oxygen-enriched graphene oxide (GO) nanosheets via a previously unknown mechanism based on size matching and polarity matching. Oxygen-containing functional groups (predominately epoxies and hydroxyls) on the nongraphitized aliphatic carbons of the basal plane of GO formed highly polar regions that encompass graphitic regions slightly larger than the benzene ring. This facilitated size match-based interactions between small apolar compounds and the isolated aromatic region of GO, resulting in high binding selectivity relative to larger apolar compounds. The interactions between the functional group(s) of polar aromatics and the epoxy/hydroxyl groups around the isolated aromatic region of GO enhanced binding selectivity relative to similar-sized apolar aromatics. These findings provide opportunities for precision separations and molecular recognition enabled by size/polarity match-based selectivity.

Highly effective electrocatalytic reduction of N-nitrosodimethylamine on Ru/CNT catalyst.

N-Nitrosodimethylamine (NDMA) is a commonly identified carcinogenic and genotoxic pollutant in water. In this study, we prepared Ru catalysts supported on carbon nanotube (Ru/CNT) and studied the electrocatalytic reduction of N-nitrosamines on Ru/CNT electrode in a three-electrode system. The results show that Ru-based catalyst exhibits a high activity of 793.3 µmol L-1 gCat-1 h-1 for electrochemical reduction of NDMA. Reaction mechanism study discloses that the electrocatalytic reduction of NDMA is accomplished by both direct electron reduction and atomic H* mediated indirect reduction pathways. Further product analysis indicates that NDMA is finally reduced to dimethylamine (DMA) and ammonia. The reduction efficiency of NDMA strongly relies on cathode potential, initial NDMA concentration and solution pH. To verify the universality of Ru/CNT electrode, electrocatalytic reduction of three dialkyl N-nitrosamines with different alkyl groups was performed and Ru catalyst has high catalytic activities for the three N-nitrosamines, while the catalytic efficiency differs with their structures. Simultaneous electrochemical reduction of the three N-nitrosamines indicates that the reduction rates of N-nitrosamines follow the same order in the multiple-component system as that in the single-component system. Catalyst recycling results demonstrate that after 5 consecutive recycling runs Ru/CNT electrode remains almost identical catalytic activity to the fresh catalyst, manifesting the high catalytic stability of Ru/CNT electrode.

One-step elimination of Cr(VI) by catalytic hydrogenation of Cr(VI) and simultaneous Cr(OH)3 recovery on Pt catalysts encapsulated in N-doped mesoporous carbon.

Hexavalent chromium Cr(VI) is a highly toxic heavy metal, which is commonly eliminated by stepwise reduction at acidic pH and precipitation of Cr(OH)3 at alkaline pH. A unique Pt catalyst with Pt particles embedded in the framework of N-doped mesoporous carbon CMK-3 (denoted as Pt@NCMK-3) was designed and fabricated to one-step eliminate Cr(VI) pollution at near neutral pH via simultaneous Cr(VI) reduction by catalytic hydrogenation and Cr(OH)3 recovery. Structural characterization showed that Pt particles of Pt@NCMK-3 were effectively embedded in the carbon rods of NCMK-3. Batch experiments revealed that Pt@NCMK-3 exhibited a higher catalytic activity and stability than other test catalysts. Fixed-bed column reaction results indicated that under the experimental conditions Pt@NCMK-3 had better breakthrough performances than other catalysts. Additionally, after 4 treatment-recovery cycles Pt@NCMK-3 maintained nearly identical breakthrough performance, whereas other catalysts displayed markedly decreased breakthrough bed volumes, reflecting a substantially higher stability of Pt@NCMK-3.

Rapid detoxification of Microcystin-LR by selective catalytic hydrogenation of the Adda moiety using TiO2-supported Pd catalysts.

The hepatotoxicity of Microcystin-LR (MC-LR) is mainly caused by its Adda moiety. In this study, we used TiO2-supported Pd catalysts to selectively hydrogenate the CC bonds in the Adda moiety, achieving rapid detoxification of MC-LR in water under ambient conditions. MC-LR was removed within 5 min by catalytic hydrogenation on Pd(1.0)/TiO2 with a catalyst dosage normalized rate constant of 1.3 × 10-2 L mgcat-1 min-1, significantly more efficient than other catalytic treatment methods. The reactions proceeded in a highly selective manner towards catalytic hydrogenation at the CC bond of the Mdha moiety and subsequently the conjugated double bond of the Adda moiety, yielding two intermediates and one final product. Upon catalytic hydrogenation for 30 min on Pd(0.07)/TiO2, the toxicity of MC-LR (assessed by protein phosphatase 2A activity assay) drastically decreased by 90.8%, demonstrating effective detoxification. The influence of catalyst support, Pd content, initial MC-LR concentration, reaction pH, and catalytic stability were examined. Surface adsorption and the cationic Pd played a crucial role in the reaction kinetics. Our results suggest that catalytic hydrogenation is a highly effective and safe strategy for detoxifying MC-LR by selective reactions.

Metal-organic framework-101 grafted with amino groups as solid-phase extraction adsorbent coupled with liquid chromatography for the determination of phenoxycarboxylic acids in environmental samples.

Metal-Organic Framework (MOF) MIL-101 and three amino-modified MIL-101s were synthesized and used as adsorbents for solid-phase extraction of trace-level polar phenoxycarboxylic acids (PCAs) from environmental water samples for quantification by liquid chromatography. The four MOFs were characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, N2 adsorption-desorption isotherm, pore structure analysis and powder X-ray diffraction analysis. Parameters which play important roles in the process of solid phase extraction were optimized. MIL-101-ethylenediamine (ED) was chosen as the optimum adsorbent for the extraction of PCAs due to electron donation of alkyl groups in aliphatic amino groups and the smaller steric hindrance. The extraction efficiency using MIL-101-ED compacted column was compared with three commercial columns and the influence of humic acid (HA) on extraction was investigated. The merits of newly-built SPE-LC method based on MIL-101-ED are as follows: (a) low limits of detection (0.052-0.160 ng mL-1), (b) wide linear ranges (0.5-1000 ng mL-1), (c) good repeatabilities (1.33-3.35%) and reproducibilities (2.51-3.49%) and (d) excludability of HA. This method has been applied to the determination of PCAs in environmental water samples successfully.

Screening and Discrimination of Perfluoroalkyl Substances in Aqueous Solution Using a Luminescent Metal-Organic Framework Sensor Array.

The extensive production and large-scale use of perfluoroalkyl substances (PFASs) have raised their presence in aquatic environments worldwide. Thus, the facile and reliable screening of PFASs in aqueous systems is of great significance. Herein, we designed a novel fluorescent sensor array for the rapid screening and discrimination of multiple PFASs in water. The sensor array comprised three highly stable zirconium porphyrinic luminescent metal-organic frameworks (i.e., PCNs) with different topological structures. The sensing mechanism was based on the static fluorescence quenching of PCNs by PFASs upon their adsorptive interactions. The fluorescence response patterns were characteristic for each PFAS because of their different adsorption affinities toward different PCNs. Through the interpretation of response patterns by statistical methods, the proposed PCN array successfully discriminated six different kinds of PFASs, each PFAS at different concentrations and PFAS mixtures at different molar ratios. The practicability of this array was further verified by effectively discriminating PFASs in two real water samples. Remarkably, the PCN sensors exhibited a very short response time toward PFASs (within 10 s) due to the ordered pore structure allowing fast PFAS diffusion. This study not only provides a facile method for rapid PFAS screening in waters but also broadens the application of luminescent metal-organic frameworks and array techniques in sensing fields.