Multi‐responses optimization of simultaneous adsorption of methylene blue and malachite green dyes in binary aqueous system onto Ni:FeO(OH)‐NWs‐AC using experimental design: derivative spectrophotometry method

In this research, response surface methodology (RSM) approach using Central Composite Design (CCD) coupled by derivative spectrophotometry method was applied to develop mathematical model and optimize process parameters for simultaneous adsorption of methylene blue (MB) and malachite green (MG) from aqueous solution using Ni:FeO(OH) ‐ NWs‐AC. The optimal conditions to adsorption of MB and MG in binary mixture solution from aqueous solution were found at pH 8.0, MB concentration 20 mg L^‐1, MG concentration 20 mg L^‐1, adsorbent dosage 0.033 g and contact time 40 min. At these conditions, high adsorption efficiency (99.39% and 100.0% for MB and MG, respectively) was achieved. Among experimental equilibrium, Langmuir isotherm model fitted well with maximum monolayer adsorption capacity of 28.6 and 29.8 mg g^‐1 for MB and MG, respectively. The adsorption kinetic data followed pseudo second‐order kinetics for MB and MG dyes.     

Characterization and Mechanism Elucidation of Dye Adsorption Using Cuprous Selenide Nanoparticles from Aqueous Solutions

The removal of cationic dyes, methylene blue(MB) and rhodamine B(RB), and anionic dyes, methyl or-ange(MO) and eosin Y(EY), from aqueous solutions by adsorption using Cu₂Se nanoparticles(Cu₂SeNPs) was studied. The effects of the initial pH values, adsorbent doses, contact time, initial dye concentrations, salt concentrations, and operation temperatures on the adsorption capacities were investigated. The adsorption process was better fitted the Langmuir equation and pseudo-second-order kinetic model, and was spontaneous and endothermic as well. The adsorption mechanism was probably based on the electrostatic interactions and π-π interactions between Cu₂SeNPs and dyes. For an adsorbent of 0.4 g/L of Cu₂SeNPs, the adsorption capacities of 23.1(MB), 22.9(RB) and 23.9(EY) mg/g were achieved, respectively, with an initial dye concentration of 10 mg/g(pH=8 for MB and pH=4 for RB and EY) and a contact time of 120 min. The removal rate of MB was still 70.4% for Cu₂SeNPs being reused in the 5th cycle. Furthermore, the recycled Cu₂SeNPs produced from selenium nanoparticles adsorbing copper were also an effective adsorbent for the removal of dyes. Cu₂SeNPs showed great potential as a new adsorbent for dyes removal due to its good stability, functionalization and reusability.     

Enhancing CO2 Separation Ability of a Metal–Organic Framework by Post‐Synthetic Ligand Exchange with Flexible Aliphatic Carboxylates

A series of porous metal–organic frameworks having flexible carboxylic acid pendants in their pores (UiO‐66‐ADn: n=4, 6, 8, and 10, where n denotes the number of carbons in a pendant) has been synthesized by post‐synthetic ligand exchange of terephthalate in UiO‐66 with a series of alkanedioic acids (HO₂C(CH₂)_n?2CO₂H). NMR, IR, PXRD, TEM, and mass spectral data have suggested that a terephthalate linker in UiO‐66 was substituted by two alkanedioate moieties, resulting in free carboxyl pendants in the pores. When post‐synthetically modified UiO‐66 was partially digested by adjusting the amount of added HF/sample, NMR spectra indicated that the ratio of alkanedioic acid/terephthalic acid was increased with smaller amounts of acid, implying that the ligand substitution proceeded from the outer layer of the particles. Gas sorption studies indicated that the surface areas and the pore volumes of all UiO‐66‐ADns were decreased compared to those of UiO‐66, and that the CO₂ adsorption capacities of UiO‐66‐ADn (n=4, 8) were similar to that of UiO‐66. In the case of UiO‐66‐AD6, the CO₂ uptake capacity was 34 % higher at 298 K and 58 % higher at 323 K compared to those of UiO‐66. It was elucidated by thermodynamic calculations that the introduction of flexible carboxyl pendants of appropriate length has two effects: 1) it increases the interaction enthalpy between the host framework and CO₂ molecules, and 2) it mitigates the entropy loss upon CO₂ adsorption due to the formation of multiple configurations for the interactions between carboxyl groups and CO₂ molecules. The ideal adsorption solution theory (IAST) selectivity for CO₂ adsorption over that of CH₄ was enhanced for all of the UiO‐66‐ADns compared to that of UiO‐66 at 298 K. In particular, UiO‐66‐AD6 showed the most strongly enhanced CO₂ uptake capacity and significantly increased selectivity for CO₂ adsorption over that of CH₄ at ambient temperature, suggesting that it is a promising material for sequestering CO₂ from landfill gas.     

Adsorptive removal of malachite green and Rhodamine B dyes on Fe3O4/activated carbon composite

This study demonstrates the adsorption experiments of toxic dyes malachite green (MG) and Rhodamine B (RB) on Fe₃O₄-loaded activated carbon (AC). AC, which is known to be a high-capacity adsorbent, was aimed to be easily separated from aqueous media by loading it with Fe₃O₄. Fe₃O₄-loaded AC was prepared by the coprecipitation method and named magnetic activated carbon (M-AC), and the produced M-AC was characterized by x-ray diffraction (XRD), thermogravimetric analysis (TGA), and pH_pzc analyses. MG and RB adsorption by the M-AC was performed separately by batch technique and the effects of adsorbent amount, solution pH, and initial dye concentration on the adsorption were explored. Maximum removal efficiencies were found to be 96.11% for MG and 98.54% for RB, and the Langmuir isotherm model was the most fitted isotherm model for the adsorption. The kinetic and thermodynamic studies showed that the adsorption proceeded via the pseudo-second-order kinetic model and endothermic in-nature for both dyes.     

Combination of Optimization and Metalated‐Ligand Exchange: An Effective Approach to Functionalize UiO‐66(Zr) MOFs for CO2 Separation

The strategy to functionalize water‐stable metal–organic frameworks (MOFs) in order to improve their CO₂ uptake capacities for efficient CO₂ separation remains limited and challenging. We herein present an effective approach to functionalize a prominent water‐stable MOF, UiO‐66(Zr), by a combination of optimization and metalated‐ligand exchange. In particular, by systematic optimization, we have successfully obtained UiO‐66(Zr) of the highest BET surface area reported so far (1730 m² g^?1). Moreover, it shows a hybrid Type I/IV N₂ isotherm at 77 K and a mesopore size of 3.9 nm for the first time. The UiO‐66 MOF underwent a metalated‐ligand‐exchange (MLE) process to yield a series of new UiO‐66‐type MOFs, among which UiO‐66‐(COONa)₂‐EX and UiO‐66‐(COOLi)₄‐EX MOFs have both enhanced CO₂ working capacity and IAST CO₂/N₂ selectivity. Our approach has thus suggested an alternative design to achieve water‐stable MOFs with high crystallinity and gas uptake for efficient CO₂ separation.     

Evaluation of UiO‐66 metal organic framework as an effective sorbent for Curcumin's overdose

Metal organic frameworks (MOFs) UiO‐66 (UiO stands for University of Oslo) and NH₂‐UiO‐66 were prepared and characterized as sorbent (antidotal agents) for curcumin (CUR) adsorption. The structure of products were characterized by X‐ray powder diffraction (XRD), Field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), Attenuated Total Reflectance‐Fourier transform infrared spectroscopy (ATR‐FTIR), and N₂ adsorption–desorption measurements. FESEM showed NH₂‐UiO‐66 displayed symmetrical crystals with triangular base pyramid morphology, with the particle size around 100 nm and uniform size distribution. Adsorption capacities of CUR/MOFs with different mass ratios in the feed were investigated in the present study, and this investigation revealed that when the CUR/MOFs with mass ratio was around 0.4, the absorption capacity of NH₂‐UiO‐66 had tended to maximum. Although, functionalization reduced the specific surface area and free volume, introducing polar amine groups could improve the affinity of NH₂‐UiO‐66 respect to CUR. Kinetic studies showed that the kinetic data are well fitted with the pseudo‐ second‐order model. MTT assay revealed that MOFs at the concentration range of 0–560 μg/ml had no cytotoxic effect on the Human Foreskin Fibroblast normal cell line (HFF‐2). These results suggest that these MOFs could be safe as sorbent for adsorb CUR from the body.     

Nanosized Functional MOFs Loading Ag/AgBr with Throughout‐Visible‐Light Absorption for High‐Efficiency Photocatalysis

Porous metal‐organic frameworks (MOFs) loading metal nanoparticles to form a composite photocatalyst demonstrated unique advantages. Modification of the electron donating group on the aromatic linkers of MOFs could increase the absorption range of light, thereby increasing the photocatalytic activity. In this study, we prepared a composite photocatalyst using a stable NH₂‐functionalized MOF (UiO‐66‐NH₂) to load semiconductor Ag/AgBr nanoparticles, and the resultant composites have intense optical absorption throughout visible light range. The greatly enhanced optical absorption and the unique hetero‐junction between Ag/AgBr and UiO‐66‐NH₂ render efficient separation and utilization of photogenerated electron‐hole pairs. Therefore, Ag/AgBr@UiO‐66‐NH₂ showed much more excellent photocatalytic activity, compared with unmodified UiO‐66 loading Ag/AgBr (Ag/AgBr@UiO‐66) and reported AgX@MOF catalysts. Moreover, the composite photocatalysts showed excellent stability during cycling experiment.     

An Evaluation of UiO‐66 for Gas‐Based Applications

In addition to its high thermal stability, repetitive hydration/dehydration tests have revealed that the porous zirconium terephthalate UiO‐66 switches reversibly between its dehydroxylated and hydroxylated versions. The structure of its dehydroxylated form has thus been elucidated by coupling molecular simulations and X‐ray powder diffraction data. Infrared measurements have shown that relatively weak acid sites are available while microcalorimetry combined with Monte Carlo simulations emphasize moderate interactions between the UiO‐66 surface and a wide range of guest molecules including CH₄, CO, and CO₂. These properties, in conjunction with its significant adsorption capacity, make UiO‐66 of interest for its further evaluation for CO₂ recovery in industrial applications. This global approach suggests a strategy for the evaluation of metal–organic frameworks for gas‐based applications.     

Metal–Organic Gel Material Based on UiO‐66‐NH2 Nanoparticles for Improved Adsorption and Conversion of Carbon Dioxide

Metal–organic frameworks (MOFs) including the UiO‐66 series show potential application in the adsorption and conversion of CO₂. Herein, we report the first tetravalent metal‐based metal–organic gels constructed from Zr^IV and 2‐aminoterephthalic acid (H₂BDC‐NH₂). The ZrBDC‐NH₂ gel materials are based on UiO‐66‐NH₂ nanoparticles and were easily prepared under mild conditions (80 °C for 4.5 h). The ZrBDC‐NH₂‐1:1‐0.2 gel material has a high surface area (up to 1040 m² g^?1) and showed outstanding performance in CO₂ adsorption (by using the dried material) and conversion (by using the wet gel) arising from the combined advantages of the gel and the UiO‐66‐NH₂ MOF. The ZrBDC‐NH₂‐1:1‐0.2 dried material showed 38 % higher capture capacity for CO₂ at 298 K than microcrystalline UiO‐66‐NH₂. It showed high ideal adsorbed solution theory selectivity (71.6 at 298 K) for a CO₂/N₂ gas mixture (molar ratio 15:85). Furthermore, the ZrBDC‐NH₂‐1:1‐0.2 gel showed activity as a heterogeneous catalyst in the chemical fixation of CO₂ and an excellent catalytic performance was achieved for the cycloaddition of atmospheric pressure of CO₂ to epoxides at 373 K. In addition, the gel catalyst could be reused over multiple cycles with no considerable loss of catalytic activity.     

Preparation and evaluation of open‐tubular capillary column combining a metal–organic framework and a brush‐shaped polymer for liquid chromatography

In this work, an open‐tubular capillary liquid‐phase column was prepared by modifying chain polymer on the inner surface of capillary and chemical bonding of metal organic frameworks, NH₂‐UiO‐66, to the brushes of chain polymer (poly(glycidyl methacrylate)). Besides advantages of facial preparation and good permeability, the chain polymer effectively increases the modification amount of NH₂‐UiO‐66 nanoparticles to increase the phase ratio of open‐tubular capillary column and enhance the interactions with analytes. The results of scanning electron microscope energy‐dispersive X‐ray spectra indicated that NH₂‐UiO‐66 nanoparticles were successfully bonded to the chain polymer. Because of the hydrophobic interaction and hydrogen bonding interaction between the analytes and the ligand of NH₂‐UiO‐66, different analytes were well separated on the NH₂‐UiO‐66‐modified poly(glycidyl methacrylate) capillary (1.12 m × 25 μm id × 365 μm od) with the high absolute column efficiency reaching 121 477 plates, benefiting from an open‐tubular column and low mass transfer resistance provided by polymer brush and metal–organic framework crystal. The relative standard deviations of the retention time for run‐to‐run, day‐to‐day, and column‐to‐column (n = 3) runs are below 4.28%, exhibiting good repeatability. Finally, the column was successfully applied to separation of flavonoids in licorice.     

Boosting Photocatalytic Hydrogen Production of a Metal–Organic Framework Decorated with Platinum Nanoparticles: The Platinum Location Matters

Improving the efficiency of electron–hole separation and charge‐carrier utilization plays a central role in photocatalysis. Herein, Pt nanoparticles of ca. 3 nm are incorporated inside or supported on a representative metal–organic framework (MOF), UiO‐66‐NH₂, denoted as Pt@UiO‐66‐NH₂ and Pt/UiO‐66‐NH₂, respectively, for photocatalytic hydrogen production via water splitting. Compared with the pristine MOF, both Pt‐decorated MOF nanocomposites exhibit significantly improved yet distinctly different hydrogen‐production activities, highlighting that the photocatalytic efficiency strongly correlates with the Pt location relative to the MOF. The Pt@UiO‐66‐NH₂ greatly shortens the electron‐transport distance, which favors the electron–hole separation and thereby yields much higher efficiency than Pt/UiO‐66‐NH₂. The involved mechanism has been further unveiled by means of ultrafast transient absorption and photoluminescence spectroscopy.     

Fluorocarbon Separation in a Thermally Robust Zirconium Carboxylate Metal–Organic Framework

Fluorocarbons have important applications in industry, but are environmentally unfriendly, and can cause ozone depletion and contribute to the global warming with long atmospheric lifetimes and high global warming potential. In this work, the metal–organic framework UiO‐66(Zr) is demonstrated to have excellent performance characteristics to separate fluorocarbon mixtures at room temperature. Adsorption isotherm measurements of UiO‐66(Zr) display high fluorocarbon sorption uptakes of 5.0 mmol g^?1 for R22 (CHClF₂), 4.6 mmol g^?1 for R125 (CHF₂CF₃), and 2.9 mmol g^?1 for R32 (CH₂F₂) at 298 K and 1 bar. Breakthrough data obtained for binary (R22/R32 and R32/R125) and ternary (R32/R125/R134a) mixtures reveal high selectivities and capacities of UiO‐66(Zr) for the separation and recycling of these fluorocarbon mixtures. Furthermore, the UiO‐66(Zr) saturated with R22 and R125 can be regenerated at temperatures as low as 120 °C with excellent desorption–adsorption cycling stabilities.     

Molecularly imprinted polymer coating on metal‐organic frameworks for solid‐phase extraction of fluoroquinolones from water

In this work, a novel surface molecularly imprinted polymer with high adsorption capacity, high adsorption rate, and high selectivity for fluoroquinolones was prepared on the surface of UiO‐66‐NH₂, which is a kind of metal‐organic framework. The surface morphology and adsorption properties of this molecularly imprinted polymer were investigated. The maximum adsorption capacity was 99.19 mg/g, and adsorption equilibrium was achieved within 65 s. Combined with reversed‐phase high‐performance liquid chromatography, the molecularly imprinted polymer was used to selectively enrich, separate and analyze fluoroquinolones present in lake water. The results showed that the recoveries of the four fluoroquinolones were 92.6–100.5%, and the relative standard deviations were 2.9–6.4% (n = 3). The novel molecularly imprinted polymer is an excellent adsorbent and has broad application prospects in the enrichment and separation of trace analytes in complex samples.     

Micelle‐Directing Synthesis of Ag‐Doped WO3 and MoO3 Composites for Photocatalytic Water Oxidation and Organic‐Dye Adsorption

In this paper, an Ag‐doped WO₃ (and MoO₃) composite has been prepared by following a simple micelle‐directed method and high‐temperature sintering route. The as‐prepared samples were characterized by X‐ray diffraction, inductively coupled plasma, transmission electron microscopy, X‐ray photoelectron spectroscopy, UV/Vis diffuse reflectance spectroscopy, Brunauer–Emmett–Teller, photoluminescence spectroscopy, and electrochemical impedance spectroscopy techniques. The photocatalytic experiments reveal that their oxygen‐production rates are up to 95.43 μmol (75.45 μmol) for Ag‐doped WO₃ (MoO₃), which is 9.5 (7.3) times higher than that of pure WO₃: 9.012 μmol (MoO₃: 9.00 μmol) under visible‐light illumination (λ ≥420 nm), respectively. The improvement of their photocatalytic activity is attributed to the enhancement of their visible‐light absorption and the separation efficiency of photogenerated carriers by Ag doping. Moreover, Ag‐doped WO₃ (MoO₃) also shows excellent adsorption of rhodamine B (RhB) and methylene blue (MB) in aqueous solution, with maximum adsorption capacities towards RhB and MB of 822 and 820 mg g⁻¹ for Ag‐doped WO₃, and 642 and 805 mg g⁻¹ for Ag‐doped MoO₃, respectively.     

Phosphonate‐Modified UiO‐66 Brønsted Acid Catalyst and Its Use in Dehydra‐Decyclization of 2‐Methyltetrahydrofuran to Pentadienes

Phosphorus‐modified all‐silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well‐defined sites, we report the incorporation of Brønsted acidity to metal–organic frameworks with the UiO‐66 topology, achieved by attaching phosphonic acid to the 1,4‐benzenedicarboxylate ligand and using it to form UiO‐66‐PO₃H₂ by post‐synthesis modification. Characterization reveals that UiO‐66‐PO₃H₂ retains stability similar to UiO‐66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra‐decyclization of 2‐methyltetrahydrofuran (2‐MTHF). For the later reaction, the reported catalyst exhibits site‐time yields and selectivity approaching that of phosphoric acid on all‐silica zeolites. Using solid‐state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined.     

Catalytic synthesis of cyclic carbonates from epoxides and carbon dioxide by magnetic UiO‐66 under mild conditions

The catalytic activity of UiO‐66@Fe₃O₄@SiO₂ catalyst was investigated in the fixation of carbon dioxide with epoxides under mild conditions. In this manner, a facile magnetization of UiO‐66 was achieved simultaneously by simply mixing this metal–organic framework and silica‐coated Fe₃O₄ nanoparticles in solution under sonication. The prepared catalyst was characterized using Fourier transform infrared and UV–visible spectroscopies, X‐ray diffraction, transmission and field emission scanning electron microscopies, N₂ adsorption and inductively coupled plasma atomic emission spectroscopy. This new heterogeneous catalyst was applied as a highly efficient catalyst in the coupling of carbon dioxide with epoxides at mild temperatures and pressures. Furthermore, it could be easily recovered with the assistance of an external magnetic field and reused three consecutive times without significant loss of activity and mass.     

Pseudopeptide‐Based Hydrogels Trapping Methylene Blue and Eosin Y

We present herein the preparation of four different hydrogels based on the pseudopeptide gelator Fmoc‐l ‐Phe‐d ‐Oxd‐OH (Fmoc=fluorenylmethyloxycarbonyl), either by changing the gelator concentration or adding graphene oxide (GO) to the water solution. The hydrogels have been analysed by rheological studies that demonstrated that pure hydrogels are slightly stronger compared to GO‐loaded hydrogels. Then the hydrogels efficiency to trap the cationic methylene blue (MB) and anionic eosin Y (EY) dyes has been analyzed. MB is efficiently trapped by both the pure hydrogel and the GO‐loaded hydrogel through π–π interactions and electrostatic interactions. In contrast, the removal of the anionic EY is achieved in less satisfactory yields, due to the unfavourable electrostatic interactions between the dye, the gelator and GO.     

Cooperative Multifunctional Catalysts for Nitrone Synthesis: Platinum Nanoclusters in Amine‐Functionalized Metal–Organic Frameworks

Nitrones are key intermediates in organic synthesis and the pharmaceutical industry. The heterogeneous synthesis of nitrones with multifunctional catalysts is extremely attractive but rarely explored. Herein, we report ultrasmall platinum nanoclusters (PtNCs) encapsulated in amine‐functionalized Zr metal–organic framework (MOF), UiO‐66‐NH₂ (Pt@UiO‐66‐NH₂) as a multifunctional catalyst in the one‐pot tandem synthesis of nitrones. By virtue of the cooperative interplay among the selective hydrogenation activity provided by the ultrasmall PtNCs and Lewis acidity/basicity/nanoconfinement endowed by UiO‐66‐NH₂, Pt@UiO‐66‐NH₂ exhibits remarkable activity and selectivity, in comparison to Pt/carbon, Pt@UiO‐66, and Pd@UiO‐66‐NH₂. Pt@UiO‐66‐NH₂ also outperforms Pt nanoparticles supported on the external surface of the same MOF (Pt/UiO‐66‐NH₂). To our knowledge, this work demonstrates the first examples of one‐pot synthesis of nitrones using recyclable multifunctional heterogeneous catalysts.     

A Bio‐inspired Nano‐pocket Spatial Structure for Targeting Uranyl Capture

Biology has evolved excellent spatial structures for high‐selectivity and high‐affinity capture of heavy metals. Inspired by the spatial structure of the superb‐uranyl binding protein SUP, we mimic the spatial structure of SUP in metal–organic frameworks (MOFs). The MOF UiO‐66‐3C4N fabricated by introducing 4‐aminoisophthalic acid into UiO‐66 shows high uranyl adsorption capacity both in simulated seawater and in natural seawater. In natural seawater, UiO‐66‐3C4N exhibits 17.03 times higher uranium extraction capacity than that of vanadium, indicating the high selectivity of the adsorbent. The EXAFS analysis and DFT calculation reveal that UiO‐66‐3C4N forms smaller nano‐pocket for uranyl capture than that of SUP protein, which can both restrict the entrance of the other interfering ions with larger size and reinforce the binding by increasing the coordination interaction, and therefore qualify the nano‐pocket with high affinity and high selectivity to uranyl.     

Self‐Assembly of Metal–Organic Frameworks into Monolithic Materials with Highly Controlled Trimodal Pore Structures

We present a two‐step template‐free approach toward monolithic materials with controlled trimodal porous structures with macro‐, meso‐, and micropores. Our method relies on two ordering processes in discrete length scales: 1) Spontaneous formation of macroporous structures in monolithic materials by the sol–gel process through the short‐range ordered self‐assembly of metal–organic frameworks (MOFs), and 2) reorganization of the framework structures in a mediator solution. The Zr‐terephthalate‐based MOF (UiO‐66‐NH₂) was adopted as a proof of concept. The self‐assembly‐induced phase separation process offered interconnected macropores with diameters ranging from 0.9 to 1.8 μm. The subsequent reorganization process converted the microporous structure from low crystalline framework to crystalline UiO‐66. The resultant mesopore size within the skeletons was controlled in the range from 9 to 21 nm. This approach provides a novel way of designing spaces from nano‐ to micrometer scale in network‐forming materials.