Pd(OAc)2@SBA‐15/PrEn nanoreactor: a highly active,reusable and selective phosphine‐free catalyst for Suzuki–Miyaura cross‐coupling reaction in aqueous media

A series of ordered mesoporous organic–inorganic hybrid material was designed by using the amine‐functionalized SBA‐15 (PdX₂@SBA‐15/N_Y, Y = 1, 2) as solid support for palladium complexes. Among them, the Pd(OAc)₂/ethylenediamine complex encapsulated into SBA‐15 (Pd(OAc)₂@SBA‐15/PrEn or Pd(OAc)₂@SBA‐15/PrNHEtNH₂) exhibits higher activity and selectivity toward Suzuki cross‐coupling reaction under aerobic conditions and water solvent mixture. The SBA‐15/PrEn supported palladium pre‐catalyst could be separated easily from reaction products and used repetitively several times, showing its superiority over homogeneous catalysts for industrial and chemical applications. Copyright © 2013 John Wiley & Sons, Ltd.     

Solid‐phase extraction of phenoxyacetic acid herbicides in complex samples with a zirconium(IV)‐based metal–organic framework

A zirconium(IV)‐based metal–organic framework material (MOF‐808) has been synthesized in a simple way and used for the extraction of phenoxyacetic acids in complex samples. The material has good thermal and chemical stability, large specific surface area (905.36 m²/g), and high pore size (22.18 Å). Besides, it contains a large amount of Zr‐O groups, easy‐to‐form Zr‐O‐H bond with carboxyl groups of phenoxyacetic acids, and possesses biphenyl skeleton structure, easy to interact with compounds through π‐π and hydrophobic interactions. These characteristics make the material very suitable for the extraction of certain compounds with a high extraction efficiency and excellent selectivity. The extraction conditions were optimized, and then an analytical method was successfully established and applied for analysis of actual samples. The solid‐phase extraction method based on prepared material had a wide linear range of 0.2–250 μg/L and a low detection limit of 0.1–0.5 μg/L for four phenoxyacetic acid compounds including 2,4‐dichlorophenoxyacetic acid, 2‐(2,4‐dichlorophenoxy) propionic acid, 4‐chlorophenoxyacetic acid, and dicamba. The relative standard deviations of intra‐ and interday precision were 1.8–3.8 and 4.3–6.9%, and the recoveries after spiking were between 77.1 and 109.3%. The results showed that the material is a desired substituent for the extraction of compounds with benzene ring structure containing carboxyl groups.     

A Novel Hybrid Metal–Organic Framework–Polymeric Monolith for Solid‐Phase Microextraction

This study describes the fabrication of a novel hybrid metal–organic framework– organic polymer (MOF–polymer) for use as a stationary phase in fritless solid‐phase microextraction (SPME) for validating analytical methods. The MOF–polymer was prepared by using ethylene dimethacrylate (EDMA), butyl methacrylate (BMA), and an imidazolium‐based ionic liquid as porogenic solvent followed by microwave‐assisted polymerization with the addition of 25 % MOF. This novel hybrid MOF–polymer was used to extract penicillin (penicillin G, penicillin V, oxacillin, cloxacillin, nafcillin, dicloxacillin) under different conditions. Quantitative analysis of the extracted penicillin samples using the MOF–organic polymer for SPME was conducted by using capillary electrochromatography (CEC) coupled with UV analysis. The penicillin recovery was 63–96.2 % with high reproducibility, sensitivity, and reusability. The extraction time with the proposed fabricated SPME was only 34 min.     

Porous carbon derived from a metal–organic framework as an efficient adsorbent for the solid‐phase extraction of phthalate esters

A porous carbon designated as MOF‐5‐C was prepared by directly carbonizing a metal–organic framework (MOF‐5). The morphology and microstructure of MOF‐5‐C were characterized by scanning electron microscopy, N₂ adsorption, and powder X‐ray diffraction. The MOF‐5‐C retained the original porous structures of MOF‐5, and showed a high Brunauer–Emmett–Teller surface area (1808 m² g^?1) and large pore volume (3.05 cm³ g^?1). To evaluate its adsorption performance, the MOF‐5‐C was used as an adsorbent for the solid‐phase extraction of four phthalate esters from bottled water, peach juice, and soft drink samples followed by high‐performance liquid chromatographic analysis. Several parameters that could affect the extraction efficiencies were investigated. Under the optimum conditions, a good linearity was achieved in the concentration range of 0.1–50.0 ng mL^?1 for bottled water sample and 0.2–50.0 ng mL^?1 for peach juice and soft drink samples. The limits of detection of the method (S/N = 3) were 0.02 ng mL^?1 for bottled water sample, and 0.04–0.05 ng mL^?1 for peach juice and soft drink samples. The results indicated that the MOF‐5‐C exhibited an excellent adsorption capability for trace levels of phthalate esters, and it could be a promising adsorbent for the preconcentration of other organic compounds.     

Synthesis of layered zinc hydroxide intercalated with dodecyl sulfate organic–inorganic hybrid nanocomposite as a fiber coating for the headspace solid‐phase microextraction of aromatic hydrocarbons from water

We describe the synthesis of a layered zinc hydroxide‐dodecyl sulfate organic–inorganic hybrid nanocomposite as a new solid‐phase microextraction fiber. The fiber coating can be prepared easily in a short time and the reaction is at room temperature; it is mechanically stable and exhibits relatively high thermal stability. The synthesized layered zinc hydroxide‐dodecyl sulfate nanocomposite was successfully prepared and immobilized on a stainless steel wire and evaluated for the extraction of aromatic compounds from aqueous sample solutions in combination with gas chromatography and mass spectrometry. The method yields good results for some validation parameters. Under optimum conditions (extraction time: 15 min, extraction temperature: 50°C, desorption time: 1 min, desorption temperature: 250°C, salt concentration: 0.5 g/mL), the limit of detection and dynamic linear range were 0.69–3.2 ng/L and 10–500 ng/L, respectively. The method was applied to the analyses of benzene, toluene, ethylbenzene, and o‐, p‐, and m‐xylenes in two real water samples collected from the Aji river and Mehran river, Tabriz, Iran. Under optimum conditions, the repeatability and reproducibility for one fiber (n = 3), expressed as the relative standard deviation, was 3.2–7.3% and 4.2–11.2% respectively. The fibers are thermally stable and yield better recoveries than conventional methods of analysis.     

Extra‐Framework Aluminum Species of Zeolite that Surrogate the Growth of Metal Organic Framework from Zeolite Matrix

Constructing a robust hybrid material with a porous inorganic and a porous organic framework is highly intriguing owing to its diverse functionality and porosity. However, the line of synthesis is not straightforward, since their nucleation and crystal growth processes are incompatible. Here, a simple method for the fabrication of hybrid zeolite/metal–organic framework of different framework structures is developed wherein the less‐useful extra‐framework aluminum species present in the zeolite surrogate the growth of metal organic framework (MOF) from the zeolite matrix in the presence of organic linkers of the corresponding MOF. An NMR study confirms that all the octahedral Al species are converted to Al‐MOF. TGA analysis shows that 32 % Al of H‐Beta is converted to Al‐MOF. Furthermore, NH₃ TPD analysis shows that most of the weak acid sites disappear but strong acid sites are preserved suggesting the utilization of weakly bound Al species of H‐Beta in the growth of Al‐MOF. The synthesis strategy is successfully demonstrated using H‐Beta, H‐ZSM‐5, and H‐Y zeolites for the growth of MIL‐53 and MIL‐96 MOFs from the zeolite matrix. This synthesis strategy enables application‐based engineering of the framework structures, functionality, and porosity of the materials.     

An Ultrahydrophobic Fluorous Metal–Organic Framework Derived Recyclable Composite as a Promising Platform to Tackle Marine Oil Spills

Derived from a strategically chosen hexafluorinated dicarboxylate linker aimed at the designed synthesis of a superhydrophobic metal–organic framework (MOF), the fluorine‐rich nanospace of a water‐stable MOF ( UHMOF‐100 ) exhibits excellent water‐repellent features. It registered the highest water contact angle (≈176°) in the MOF domain, marking the first example of an ultrahydrophobic MOF. Various experimental and theoretical studies reinforce its distinctive water‐repellent characteristics, and the conjugation of superoleophilicity and unparalleled hydrophobicity of a MOF material has been coherently exploited to achieve real‐time oil/water separation in recyclable membrane form, with significant absorption capacity performance. This is also the first report of an oil/water separating fluorinated ultrahydrophobic MOF‐based membrane material, with potential promise for tackling marine oil spillages.     

Fabrication of carboxymethylated cellulose fibers supporting Ag NPs@MOF‐199s nanocatalysts for catalytic reduction of 4‐nitrophenol

In this work, we prepared high‐performance and recyclable nanocatalysts that consist of small and well‐dispersed silver nanoparticles (Ag NPs) immobilized onto Cu‐ based metal–organic framework (MOF‐199 s) supported by carboxymethylated cellulose fibers (CCFs). The as‐prepared green nanohybrid catalysts, namely Ag NPs@ MOF‐199 s/CCFs, were characterized using SEM, TEM, XRD and FT‐IR techniques. The catalytic performances showed that Ag NPs@ MOF‐199 s/CCFs catalysts exhibited a very high catalytic efficiency towards the reduction of 4‐nitrophenol to 4‐aminophenol. The enhanced catalytic performances are attributed to the improved dispersity, small particles of Ag NPs stabilized by the MOF‐199 s, and the porous catalyst structures. The introduction of cellulose fiber further facilitates the reuse and sustainability of the nanohybrid catalysts, showing a stable and high reusability (more than 91% of catalytic activity) even after five runs.     

Metal–organic framework UiO‐67‐coated fiber for the solid‐phase microextraction of nitrobenzene compounds from water

A sol–gel coating technique was applied for the preparation of a solid‐phase microextraction fiber by coating the metal–organic framework UiO‐67 onto a stainless‐steel wire. The prepared fiber was explored for the headspace solid‐phase microextraction of five nitrobenzene compounds from water samples before gas chromatography with mass spectrometric detection. The effects of the extraction temperature, extraction time, sample solution volume, salt addition, and desorption conditions on the extraction efficiency were optimized. Under the optimal conditions, the linearity was observed in the range of 0.015–12.0 μg/L for the compounds in water samples, with the correlation coefficients (r) of 0.9945–0.9987. The limits of detection of the method were 5.0–10.0 ng/L, and the recoveries of the analytes from spiked water samples for the method were in the range of 74.0–102.0%. The precision for the measurements, expressed as the relative standard deviation, was less than 11.9%.     

Metathesis of 1‐Butene to Propene over Mo/Al2O3@SBA‐15: Influence of Alumina Introduction Methods on Catalytic Performance

A series of Mo‐based catalysts for 1‐butene metathesis to propene were prepared by supporting Mo species on SBA‐15 premodified with alumina. The effects of the method of introduction of the alumina guest to the host SBA‐15 on the location of the Mo species and the corresponding metathesis activity were studied. As revealed by N₂ adsorption isotherms and TEM results, well‐dispersed alumina was formed on the pore walls of SBA‐15 if the ammonia/water vapor induced hydrolysis (NIH) method was employed. The Mo species preferentially interacted with alumina instead of SBA‐15, as evidenced by X‐ray photoelectron spectroscopy, time‐of‐flight secondary‐ion mass spectrometry, and IR spectroscopy of adsorbed pyridine. Furthermore, new Brønsted acid sites favorable for the dispersion of the Mo species and low‐temperature metathesis activity were generated as a result of the effective synergy between the alumina and SBA‐15. The Mo/Al₂O₃@SBA‐15 catalyst prepared by the NIH method showed higher metathesis activity and stability under the conditions of 120 °C, 0.1 MPa, and 1.5 h^?1 than catalysts prepared by other methods.     

A novel nano‐size lanthanum metal–organic framework based on 5‐amino‐isophthalic acid and phenylenediamine: Photoluminescence study and sensing applications

In this paper, a novel lanthanum metal–organic framework La‐MOF was prepared via hydrothermal and reflux methods. The La‐MOF was achieved through the reaction of a 5‐amino‐isophthalic acid with 1, 2‐phenylenediamine and lanthanum chloride. The prepared La‐MOF structure was confirmed by XRD, mass spectrometry, IR, UV–Vis and elemental analysis, whereas the size, and morphology was examined by FE‐SEM/EDX and HR‐TEM. The results indicated that the La‐MOF prepared via both methods have the same structure and composition. Meanwhile, the MOF yield, reaction time, morphology, physiochemical and sensing properties were highly depended on the used preparation method. The photoluminescence (PL) study was carried out for the La‐MOF, and the results showed that La‐MOF exhibits strong emission at 558 nm after excitation at 369 nm. Moreover, the PL data indicating that the La‐MOF has highly selective sensing properties for iron (III) competing with different metal ions. The Stern‐Völmer graph shows a linear calibration curve which achieved over a concentration range 1.0–500 μM of Fe³⁺ with a correlation coefficient, detection, and quantitation limits 0.998, 1.35 μM and 4.08 μM, respectively. According to the remarkable quenching of the PL intensity of La‐MOF using various concentrations of Fe³⁺, it was successfully used as a sensor for Fe³⁺detecting in different water resources (pure and waste) samples. The quenching mechanism was studied and it has a dynamic type and due to efficient energy transfer between the La‐MOF and Fe³⁺.     

Metal Oxide Assisted Preparation of Core–Shell Beads with Dense Metal–Organic Framework Coatings for the Enhanced Extraction of Organic Pollutants

Dense and homogeneous metal–organic framework (MOF) coatings on functional bead surfaces are easily prepared by using intermediate sacrificial metal oxide coatings containing the metal precursor of the MOF. Polystyrene (PS) beads are coated with a ZnO layer to give ZnO@PS core–shell beads. The ZnO@PS beads are reactive in the presence of 2‐methylimidazole to transform part of the ZnO coating into a porous zeolitic imidazolate framework‐8 (ZIF‐8) external shell positioned above the internal ZnO precursor shell. The obtained ZIF‐8@ZnO@PS beads can be easily packed in column format for flow‐through applications, such as the solid‐phase extraction of trace priority‐listed environmental pollutants. The prepared material shows an excellent permeance to flow when packed as a column to give high enrichment factors, facile regeneration, and excellent reusability for the extraction of the pollutant bisphenol A. It also shows an outstanding performance for the simultaneous enrichment of mixtures of endocrine disrupting chemicals (bisphenol A, 4‐tert‐octylphenol and 4‐n‐nonylphenol), facilitating their analysis when present at very low levels (<1 μg L^?1) in drinking waters. For the extraction of the pollutant bisphenol A, the prepared ZIF‐8@ZnO@PS beads also show a superior extraction and preconcentration capacity to that of the PS beads used as precursors and the composite materials obtained by the direct growth of ZIF‐8 on the surface of the PS beads in the absence of metal oxide intermediate coatings.     

Nylon–MOF Composites through Postsynthetic Polymerization

Hybridization of metal–organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF–polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench‐top approach to covalently tethered nylon–MOF polymer composite materials through an interfacial polymerization technique. The copolymerization of a modified UiO‐66‐NH₂ MOF with a growing polyamide fiber (PA‐66) during an interfacial polymerization gave hybrid materials with up to around 29 weight percent MOF. The covalent hybrid material demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl‐4‐nitrophenyl phosphate, DMNP) compared to MOFs that are non‐covalently, physically entrapped in nylon, thus highlighting the importance of MOF–polymer hybridization.     

Dehydrogenation of Isobutane to Isobutene with Carbon Dioxide over SBA‐15‐Supported Chromia‐Ceria Catalysts

A series of SBA‐15‐supported chromia‐ceria catalysts with 3% Cr and 1%–5% Ce (3Cr‐Ce/SBA) were prepared using an incipient wetness impregnation method. The catalysts were characterized by XRD, N₂ adsorption, SEM, TEM‐EDX, Raman spectroscopy, UV–vis spectroscopy, XPS and H₂‐TPR, and their catalytic performance for isobutane dehydrogenation with CO₂ was tested. The addition of ceria to SBA‐15‐supported chromia improves the dispersion of chromium species. 3Cr‐Ce/SBA catalysts are more active than SBA‐15‐supported chromia (3Cr/SBA), which is due to a higher concentration of Cr⁶⁺ species present on the former catalysts. The 3Cr‐3Ce/SBA catalyst shows the highest activity, which gives 35.4% isobutane conversion and 89.6% isobutene selectivity at 570 °C after 10 min of the reaction.     

Preparation of restricted‐access material precolumns by grafting δ‐gluconolactone onto a hybrid silica monolithic column for on‐line solid‐phase extraction of tetracycline residues from milk

A restricted‐access material–hybrid monolithic column was prepared based on single‐component organosiloxane and dynamic grafting of δ‐gluconolactone for on‐line solid phase extraction of tetracycline antibiotic residues from milk. The hybrid monolithic column was prepared in a stainless‐steel chromatographic column using methyltrimethoxysilane as the single precursor. δ‐Gluconolactone was covalently coupled to aminopropyl derivatized hybrid monolithic column, which formed hydrophilic structures on the surface of the pore of the restricted‐access material–hybrid monolithic column. The columns were characterized by scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared spectroscopy, nitrogen adsorption, contact angle analysis, dynamic adsorption, and chromatographic performance evaluation. The restricted‐access material–hybrid monolithic column was applied to the on‐line extraction of tetracycline residues from milk. An enrichment factor of 15.8 and a good sample clean‐up effect were obtained under the optimized conditions. The recoveries of the three spiked milk samples were between 81.7 and 102.5% with relative standard deviations (n = 3) in the range of 2–5%. The limits of detection (S/N = 3) for target compounds were in the range of 3.80–9.03 μg/kg. The results show that the on‐line extraction using the restricted‐access material–hybrid monolithic column was powerful for food sample pretreatment with high selectivity and good clean‐up effect.     

Direct Air Capture of CO2 by Physisorbent Materials

Sequestration of CO₂, either from gas mixtures or directly from air (direct air capture, DAC), could mitigate carbon emissions. Here five materials are investigated for their ability to adsorb CO₂ directly from air and other gas mixtures. The sorbents studied are benchmark materials that encompass four types of porous material, one chemisorbent, TEPA‐SBA‐15 (amine‐modified mesoporous silica) and four physisorbents: Zeolite 13X (inorganic); HKUST‐1 and Mg‐MOF‐74/Mg‐dobdc (metal–organic frameworks, MOFs); SIFSIX‐3‐Ni , (hybrid ultramicroporous material). Temperature‐programmed desorption (TPD) experiments afforded information about the contents of each sorbent under equilibrium conditions and their ease of recycling. Accelerated stability tests addressed projected shelf‐life of the five sorbents. The four physisorbents were found to be capable of carbon capture from CO₂‐rich gas mixtures, but competition and reaction with atmospheric moisture significantly reduced their DAC performance.     

原位配体功能化策略制备共价金属有机骨架促进其析氢反应

新型多孔材料在诸多领域具有广阔的应用前景,其发展引起了研究者较大关注.在过去的十年中,大量的先进多孔材料被设计并应用于不同领域.其中,共价有机骨架(COFs)和金属有机骨架(MOFs)材料由于具有结构多样、孔隙可调以及功能多样等独特性质,得到了广泛研究.为了有效地结合各个组分的优点以获得最优性能,科研工作者投入了大量的...     

Atypical Hybrid Metal–Organic Frameworks (MOFs): A Combinative Process for MOF‐on‐MOF Growth,Etching, and Structure Transformation

The structural, compositional, and morphological features of metal–organic frameworks (MOFs) govern their properties and applications. Construction of hybrid MOFs with complicated structures, components, or morphologies is significant for the development of well‐organized MOFs. An advanced route is reported for construction of atypical hybrid MOFs with unique morphologies and complicated components: 1) MOF‐on‐MOF growth of a 3D zeolitic imidazolate framework (ZIF) on a ZIF‐L template, 2) etching of a part of the 2D ZIF‐L template, and 3) structural transformation of 2D ZIF‐L into 3D ZIF. The formation of core–shell‐type MOF rings and plates is controlled by regulating the three processes. The formation route for the core–shell‐type MOF rings and plates was monitored by tracking changes in morphology, structure, and composition. Carbon materials prepared from the pyrolysis of the core–shell‐type hybrid MOFs displayed enhanced oxygen reduction reaction activities compared to their monomeric counterparts.     

Layer‐by‐layer self‐assembly of a novel covalent organic frameworks microextraction coating for analyzing polycyclic aromatic hydrocarbons from aqueous solutions via gas chromatography

In this study, a new covalent organic framework, consisting of tetra(4‐aminophenyl)porphyrin and tris(4‐formyl phenyl)amine, was layer‐by‐layer immobilized on stainless‐steel wire as a coating for microextraction. The fabrication process was easy and controllable under mild conditions. The as‐grown fiber was applied to extract polycyclic aromatic hydrocarbons in aqueous solution via head‐space solid‐phase microextraction. Furthermore, it was analyzed by gas chromatography with a flame ionization detector. A wide linear range (0.1–50 µg/L), low limits of detection (0.006–0.024 µg/L, signal‐to‐noise ratio = 3), good repeatability (intra‐fiber, n = 6, 3.1–8.50%), and reproducibility (fiber to fiber; n = 3, 5.79–9.98%), expressed as relative standard deviations, demonstrate the applicability of the newly developed coating. This new material was successfully utilized in real sample extraction with a satisfactory result. Potential parameters affecting the extraction efficiency, including extraction temperature and extraction time, salt concentration, agitation speed, sample volume, desorption temperature, and time, were also optimized and discussed.     

Evaluation of metal‐organic framework 5 as a new SPE material for the determination of polycyclic aromatic hydrocarbons in environmental waters

Metal‐organic frameworks, a new class of materials with high surface area and great porosity, have been widely applied in gas sorption. It is generally known that metal‐organic framework 5 cannot be applied in aqueous phase since it is water sensitive. However, this work reveals that the derived material of metal‐organic framework 5 is a good SPE sorbent that can be applied to aqueous phases. Metal‐organic framework 5 was prepared and used as a SPE sorbent for the determination of polycyclic aromatic hydrocarbons in environmental matrices coupling with HPLC. The water treatment induced changes in the properties were investigated in detail. Even though metal‐organic framework 5 is conversed to a second phase after water treatment, it still shows high extraction ability. Under the optimized experimental conditions, good sensitivity levels were achieved with low LODs ranging from 0.4 to 4.0 ng L^?1 and a linearity of 0.004–20 μg L^?1 (R² > 0.996) for the investigated polycyclic aromatic hydrocarbons. The method has been validated in the analysis of real water samples with recoveries in the range of 80.2–120.2% and RSDs in the range of 0.5–11.7%.