Sulfamic acid incorporated HKUST-1: a highly active catalyst and efficient adsorbent

Herein we introduce an effective approach for incorporating sulfamic acid (SA) into HKUST-1. The synthesized materials have been characterized using XRD, XPS, BET, FT-IR, SEM, EDX and TEM. The X-ray diffraction pattern of SA@HKUST-1 is analogous to that of parent HKUST-1 in line shape and d-spacing, proving that chemical modification could be obtained without damage to structural solidity. The XPS spectra confirmed successful sulfonation, due to the single S 2p peak being attributable to SO₃H groups at 168 eV. Catalytic efficiency was studied for 7-hydroxy-4-methyl coumarin and 3,4-dihydropyrimidinone synthesis and it was found to be highly dependent on the amount of SA loaded over HKUST-1. Moreover, the adsorptive removal activity of some common organic and inorganic pollutants from water has been studied. To fully understand the adsorption process, the effects of initial dye concentration, pH of solution, adsorbent dosage, contact time and temperature on the adsorption process were successfully studied. Under the optimum conditions 10 wt% SA@HKUST-1 was able to reach the maximum adsorption capacity for Pb²⁺ (298 mg g⁻¹) and Malachite green (290 mg g⁻¹). Hopefully, this will facilitate research on improving the prospective use of MOFs for future applications.

Herein we introduce an effective approach for incorporating sulfamic acid (SA) into HKUST-1.     

An efficient Nozaki–Hiyama allenylation promoted by the acid derived MIL-101 MOF

A concise synthesis of the sulfonic acid-containing MIL-101 MOF catalyst was reported using commercially available materials. A series of characterization of as-synthesized MIL-101-SO₃H including SEM, XRD, FTIR, BET and TGA was also demonstrated. Using MIL-101-SO₃H as a catalyst, an efficient Nozaki–Hiyama allenylation reaction was achieved to generate various polyfunctionalized α-allenic alcohols in high yield and good selectivity. Taking advantage of the high acidity of the MIL-101-SO₃H MOF structure, such transformations were also achieved under mild reaction conditions and short reaction times. Based on our observed evidence during this study, a mechanism was proposed involving a substrate activation/γ-nucleophilic addition reaction sequence. In addition, the MIL-101-SO₃H catalyst can be recycled ten times during the Nozaki–Hiyama allenylation reaction without compromising the yield and selectivity.

A concise synthesis of the sulfonic acid-containing MIL-101 MOF catalyst was reported using commercially available materials.     

Anhydrous proton conductivity of electrospun phosphoric acid-doped PVP-PVDF nanofibers and composite membranes containing MOF fillers

A high-temperature proton exchange membrane was fabricated based on polyvinylidene fluoride (PVDF) and polyvinylpyrrolidone (PVP) blend polymer nanofibers. Using electrospinning method, abundant small ionic clusters can be formed and agglomerated on membrane surface, which would facilitate the proton conductivity. To further enhance the conductivity, phosphoric acid (PA) retention as well as mechanical strength, sulfamic acid (SA)-doped metal–organic framework MIL-101 was incorporated into PVP-PVDF blend nanofiber membranes. As a result, the anhydrous proton conductivity of the composite SA/MIL101@PVP-PVDF membrane reached 0.237 S cm⁻¹ at 160 °C at a moderate acid doping level (ADL) of 12.7. The construction of long-range conducting network by electrospinning method combined with hot-pressing and the synergistic effect between PVP-PVDF, SA/MIL-101 and PA all contribute to the proton conducting behaviors of this composite membrane.

A composite SA/MIL101@PVP-PVDF membrane was fabricated via electrospinning and reached a conductivity of 0.237 S cm⁻¹ at 160 °C with a moderate acid doping level (12.7).     

Adsorption characteristics of metal–organic framework MIL-101(Cr) towards sulfamethoxazole and its persulfate oxidation regeneration

A metal–organic framework, MIL-101(Cr), was used to adsorb sulfamethoxazole (SMZ) in water and activated persulfate (PS) oxidation was investigated to regenerate SMZ-saturated MIL-101(Cr). Adsorption and oxidation were combined in this study. MIL-101(Cr) was characterized by SEM, BET, XPS and FT-IR analyses. Effects of various operating parameters on adsorption efficiency were studied. The dosages of persulfate for SMZ desorption and oxidation were investigated. The results showed that the recommended pH was 6–8 for SMZ adsorption and optimum MIL-101(Cr) dosage was 0.1 g L⁻¹. SMZ adsorption by MIL-101(Cr) was a spontaneous process and nearly exothermic. Saturation adsorption capacity was achieved in 180 s and the adsorption followed the pseudo-second-order model. The maximum adsorption amount of MIL-101(Cr) to SMZ was 181.82 mg g⁻¹ (Langmuir). MIL-101(Cr) also showed good adsorption capacities for sulfachloropyridazine (SCP), sulfamonomethoxine (SMM), and sulfadimethoxine (SDM). Persulfate was helpful for SMZ desorption from the surface of saturated MIL-101(Cr) and sufficient persulfate could simultaneously oxidize the SMZ. XPS analysis showed that the structure of MIL-101(Cr) was stable after the persulfate oxidation process. Regenerated MIL-101(Cr) had the same level of adsorption capacity as fresh MIL-101(Cr). An adsorption–oxidation combined process may be set up based on the results. This study provides basic data for the deep treatment of organic micropollutants in urban water bodies.

A metal–organic framework, MIL-101(Cr), was used to adsorb sulfamethoxazole (SMZ) in water and activated persulfate (PS) oxidation was investigated to regenerate SMZ-saturated MIL-101(Cr).     

In situ Raman and FTIR spectroscopic study on the formation of the isomers MIL-68(Al) and MIL-53(Al)

The topological metal–organic framework isomers MIL-53 and MIL-68 form from similar educts but differ in their pore geometries. They have been known for several years, but their synthesis is always reported separately. In consequence, the underlying mechanism and decisive synthesis parameters leading to the formation of either MIL-53 or MIL-68 are not understood. The present study shows how to induce the formation of MIL-68(Al) rather than MIL-53(Al) at low synthesis temperatures in N,N-dimethylformamide (DMF) using a modulated synthesis approach. MIL-68(Al) is identified as the intermediate product of formic acid modulated synthesis, which converts into the thermodynamically stable MIL-53(Al) product at longer synthesis times. The interactions of formic acid with the synthesis precursors responsible for inducing MIL-68(Al) formation are investigated with in situ Raman and FTIR spectroscopy. In contrast to the commonly assumed modulation mechanism of competitive coordination of linker and modulator with the metal node, formic acid is shown to form hydrogen bonds via the carboxylic group of the terephthalic acid (H₂BDC) linker, slowing prenucleation building unit and subsequent crystal growth. MIL-68(Al) formation is favored by the combination of a deficiency of terephthalic acid in solution and a slow MOF growth rate. Dissolved H₂BDC in solution is proposed to hinder MIL-68(Al) formation by serving as a molecular template for the rhombic MIL-53(Al) pore channels.

The paper describes a method to induce the formation of MIL-68(Al) rather than MIL-53(Al) using a formic acid modulated synthesis approach.     

The role of PMA in enhancing the surface acidity and catalytic activity of a bimetallic Cr–Mg-MOF and its applications for synthesis of coumarin and dihydropyrimidinone derivatives

In the present study, a bimetallic Cr–Mg-MOF was successfully synthesized by the solvothermal method and then modified by loading different amounts of phosphomolybdic acid (PMA) using a simple wet impregnation technique. The morphological and structural properties of the prepared samples were investigated using X-ray diffraction, TEM, SEM, BET and FTIR spectroscopy. Importantly, Mg doping not only caused the Cr–Mg-MOF to have a higher surface area than MIL-101 (Cr) or MOF-74 (Mg), but the strategy of doping metal ions can be an effective way to improve the adsorption performance of MOFs. The surface acidity and the acid strength of the samples were determined using potentiometric titration and the FTIR of pyridine adsorption. The incorporation of PMA crystals gradually enhances both the surface acidity and the acid strength of the PMA/Cr–Mg-MOF catalysts up to 75 wt%. The catalytic performances of the prepared catalysts were tested in two acid-catalyzed organic transformations, namely, 7-hydroxy-4-methyl coumarin and 3,4-dihydropyrimidinone. In the two reactions, the catalytic activity attains the maximum value at 75 wt% PMA loading. The PMA catalysts supported on Cr–Mg-MOF are potentially promising heterogeneous catalysts for acid-catalyzed organic transformations in environmentally friendly processes, to replace the use of conventional homogeneous PMA catalysts.

PMA supported on Cr–Mg-MOF has been successfully synthesized. All catalysts exhibits distinct catalytic activity in the synthesis of 3,4-dihydropyrimidinones and 7-hydroxy-4-methyl coumarin and showed excellent % yield and recycling efficiency.     

An organic–inorganic hybrid nanomaterial composed of a Dowson-type (NH4)6P2Mo18O62 heteropolyanion and a metal–organic framework: synthesis,characterization, and application as an effective adsorbent for the removal of organic dyes

In this work, an inorganic–organic hybrid nanomaterial, P₂Mo₁₈/MIL-101(Cr), based on Wells–Dawson-type (NH₄)₆P₂Mo₁₈O₆₂ polyoxometalate (abbreviated as P₂Mo₁₈) and the MIL-101(Cr) metal–organic framework was fabricated by the reaction of (NH₄)₆P₂Mo₁₈O₆₂, Cr(NO₃)₃·9H₂O and terephthalic acid under hydrothermal conditions. The as-prepared recyclable nanohybrid was fully characterized using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR) equipped with energy dispersive X-ray microanalysis (EDX), field emission scanning electron microscopy (FE-SEM), Raman spectroscopy and Brunauer–Emmett–Teller (BET) specific surface area studies. All the analyses confirmed the successful insertion of P₂Mo₁₈O₆₂⁶⁻ heteropolyanion within the cavities of MIL-101(Cr). The encapsulated MIL-101(Cr) showed a considerable decrease in both pore volume and surface area compared with MIL-101(Cr) due to incorporation of the very large Dowson-type polyoxometalate into the three-dimensional porous MIL-101(Cr). The nanohybrid had a specific surface area of 800.42 m² g⁻¹. The adsorption efficiency of this nanohybrid for removal of methylene blue (MB), rhodamine B (RhB), and methyl orange (MO) from aqueous solutions was evaluated. Surprisingly, the composite not only presented a high adsorption capacity of 312.5 mg g⁻¹ for MB, but also has the ability to rapidly remove 100% MB from a dye solution of 50 mg L⁻¹ within 3 min. These results confirmed that this adsorbent is applicable in a wide pH range of 2–10. The nanohybrid showed rapid and selective adsorption for cationic MB and RhB dyes from MB/MO, MB/RhB, MO/RhB and MB/MO/RhB mixed dye solutions. The equilibrium adsorption data were better fitted by the Langmuir isotherm. Kinetics data indicate that the adsorption of the dye follows a pseudo-second order kinetics model. Also, this material could be effortlessly separated and recycled without any structural modification. Accordingly, it is an efficient adsorbent for removing cationic dyes.

An MIL-101(Cr) metal–organic framework nanocomposite containing P₂Mo₁₈O₆₂⁶⁻ polyanions was prepared and applied as an ultrafast adsorbent to remove organic dyes from water.     

Preparation and characterization of novel polyoxometalate/CoFe2O4/metal–organic framework magnetic core–shell nanocomposites for the rapid removal of organic dyes from water

In this study, the MIL-101(Cr) metal–organic framework was functionalized with a Dowson-type polyoxometalate (P₂W₁₈O₆₂⁶⁻; POM) and magnetic spinel cobalt ferrite (CoFe₂O₄; CFO) through a hydrothermal route and was characterized by means of FT-IR, XRD, FE-SEM, EDX, BET, and VSM measurements. All analyses confirmed the successful encapsulation of POM (∼32.2 wt%) into the magnetic MIL-101(Cr) framework. Compared to the pristine MIL-101(Cr) MOF, the as-prepared magnetic ternary nanocomposite (abbreviated as POM/CFO/MIL-101(Cr)) demonstrated a notable decrease in both the surface area and pore volume because of the incorporation of CoFe₂O₄ nanoparticles and huge P₂W₁₈O₆₂⁶⁻ polyanions into the cages of the MIL-101(Cr) framework. The POM/CFO/MIL-101(Cr) was then applied as a magnetically separable adsorbent for the rapid elimination of rhodamine B (RhB), methyl orange (MO), and methylene blue (MB) dye pollutants from aqueous solutions. For achieving the optimized conditions, the effects of initial pH, initial dye concentration, temperature, salt effect, and adsorbent dose on MB and RhB elimination were investigated. The dye adsorption isotherms followed the Langmuir model and pseudo-second-order kinetic model. The POM/CFO/MIL-101(Cr) composite material not only exhibited a fast adsorption rate towards dye molecules, but also demonstrated the selective adsorption of the cationic dyes in wastewater. The recycling experiments also demonstrated that the POM/CFO/MIL-101(Cr) adsorbent was highly stable and could be quickly recovered under a magnetic field without any alteration in the structure. The high adsorption capacity, simple fabrication method, rapid separation by a magnet and supreme reusability of the POM/CFO/MIL-101(Cr) nanocomposite make it an attractive adsorbent for the elimination of cationic dyes from wastewater.

The magnetic CoFe₂O₄/MIL-101 (Cr) metal–organic framework nanocomposite containing P₂W₁₈O₆₂⁶⁻ polyoxometalate was fabricated and applied as an ultrafast adsorbent to remove organic dyes from water.     

MIL-101(Cr)–cobalt ferrite magnetic nanocomposite: synthesis,characterization and applications for the sonocatalytic degradation of organic dye pollutants

In this study, for the first time, a novel magnetically recyclable MIL-101(Cr)/CoFe₂O₄ nanocomposite was prepared via a facile solvothermal method. The morphology, structural, magnetic and optical properties of the nanocomposite were characterized via field emission scanning electron microscopy (FE-SEM), transmission electron microscope (TEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometer (VSM), UV-visible spectroscopy (UV-visible) and BET surface area analysis. Furthermore, the sonocatalytic activity of the MIL-101(Cr)-based magnetic nanocomposite was explored for the degradation of organic dye pollutants such as Rhodamine B (RhB) and methyl orange (MO) under ultrasound irradiation in the presence of H₂O₂. Under optimized conditions, the degradation efficiency reached 96% for RhB and 88% for MO. The sonocatalytic activity of MIL-101(Cr)/CoFe₂O₄ was almost 12 and 4 times higher than that of the raw MIL-101(Cr) and pure CoFe₂O₄, respectively. The improved sonocatalytic performance of the as-prepared binary nanocomposite can be attributed to the relatively high specific surface area of MIL-101(Cr) and magnetic property of CoFe₂O₄, as well as the fast generation and separation of charge carriers (electrons and holes) in MIL-101(Cr) and CoFe₂O₄. In addition, the trapping tests demonstrated that ·OH radicals are the main active species in the dye degradation process. Moreover, the most influencing factors on the sonocatalytic activity such as the H₂O₂ amount, initial dye concentration and catalyst dosage were investigated. Finally, the nanocomposite was magnetically separated and reused without any observable change in its structure and performance even after four consecutive runs.

A magnetically separable MIL-101(Cr)/CoFe₂O₄ binary nanocomposite was prepared via a hydrothermal route and applied as a sonocatalyst for the efficient degradation of organic dyes.     

Efficient conversion of glucosamine to levulinic acid in a sulfamic acid-catalyzed hydrothermal reaction

Glucosamine is a monomer of chitosan, which is a biopolymer derived from the exoskeletons of crustaceans. This work investigated the conversion of glucosamine into the platform chemical levulinic acid (LA), in a sulfamic acid-catalyzed hydrothermal reaction. The optimized results of LA production showed that the conditions of 200 °C, 125 g L⁻¹ glucosamine, 0.3 M sulfamic acid, and 15 min produced a 33.76 ± 0.19 mol% LA yield. The same conditions produced only 0.14 mol% 5-HMF yield. These results show that glucosamine is a potential bioresource to produce platform chemicals. Also, in the field of biofuels and chemical synthesis processes, the catalytic system using sulfamic acid is significant.

Glucosamine, which is a monomer of chitosan, and sulfamic acid, which has dual active sites, were employed as substrate and catalyst, respectively, to produce the bio-based platform chemicals LA and 5-HMF.     

Immobilization of Lewis acidic ionic liquid on perlite nanoparticle surfaces as a highly efficient solid acid catalyst for the solvent-free synthesis of xanthene derivatives

In this study, perlite nanoparticles were prepared through a simple method and then modified with Lewis acidic ionic liquid (perlite NP@IL/ZrCl₄) through a two step procedure. The prepared solid acid catalyst was characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX) and thermo gravimetric analysis (TGA). Perlite NP@IL/ZrCl₄ was used as a new solid acid, reusable and green heterogeneous nanocatalyst for the one-pot synthesis of xanthene derivatives. Synthesis of xanthenes was performed under solvent free conditions using a catalytic amount (0.005 g, 0.4 mol%) of the prepared catalyst with simple work-up and high to excellent yield of products. The reusability and high efficiency of this catalyst makes this method attractive for large scale environment-friendly operations.

Perlite nanoparticles were prepared, modified with Lewis acidic ionic liquid, and used as a highly efficient catalyst for the eco-friendly, solvent free and high yield synthesis of xanthenes via a multicomponent reaction.     

High removal of thiophene from model gasoline by porous MIL-101(Cr)/SA hybrid membrane

Membrane separation technologies have great promising potential for applications in several industries. Metal–organic frameworks (MOFs), for their large surface areas, low framework densities, transition-metal ions in the skeleton and high pore volumes relative to other porous matrices, have great potential for the removal of sulfur from gasoline with high efficiency. In the present study, a novel porous membrane adsorbent MIL-101(Cr)/SA was prepared by immobilizing MIL-101(Cr) onto sodium alginate (SA) matrix, which can combine the size/shape selectivity of MIL-101(Cr) with the processability and mechanical stability of SA polymer. The physico-chemical properties of MIL-101(Cr)/SA were investigated by FT-IR, SEM, BET, XRD and EDX methods. To investigate the effects of some important factors on the adsorption behavior for thiophene, a batch of experiments were performed by changing the concentration of porogen polyethylene glycol in the MIL-101(Cr)/SA, solution temperature, initial thiophene concentration and contact time. Meanwhile, benzothiophene, thiophene and 3-methyl thiophene were used to test the selectivity of MIL-101(Cr)/SA. The MIL-101(Cr)/SA showed an excellent uptake capacity of 671 mg g⁻¹ under the optimal adsorption conditions. Selectivity testing indicated that the uptake capacity of MIL-101(Cr)/SA follows the order of benzothiophene > thiophene > 3-methyl thiophene. Kinetics experiments indicated the pseudo-second-order model displayed good correlation with adsorption kinetics data. The Crank model showed that the intraparticle solute diffusion is the rate-controlling adsorption step. Regeneration experiment result shows that the prepared MIL-101(Cr)/SA has excellent adsorption and desorption efficiencies.

Membrane separation technologies have great promising potential for applications in several industries.     

Fabrication of salicylic acid nanosphere for long-term induced immunity performance

We synthesised a silicon dioxide nanosphere with a novel nanostructure by loading salicylic acid (SA) as a plant disease resistance inductor to prolong plant life. The SA nanosphere was evaluated by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, N₂ adsorption method, enzyme activity test and pot experiments. The results demonstrated that the SA nanosphere induced the activities of polyphenol oxidase, phenylalanine ammonia-lyase, peroxidase, and chitinase to enhance plant immunity to inhibit Phytophthora nicotianae. Its SA loading capacity reached approximately 80%. The SA nanospheres exhibited a sustained release and maintained its resistance effect at 84.79% after 15 days. Thus, the SA nanospheres could gradually release SA to enhance inhibitive enzyme activity in diseased plants. Furthermore, finite element method was used to establish different nanosphere models and analyse the SA releasing process. SA concentration sharply increased near the nanospheres, and SA was slowly released to the solution. This SA nanosphere will have a great potential in future environmental-friendly practical application.

We synthesised a silicon dioxide nanosphere with a novel nanostructure by loading salicylic acid (SA) as a plant disease resistance inductor to prolong plant life.     

High acidity cellulose sulfuric acid from sulfur trioxide: a highly efficient catalyst for the one step synthesis of xanthene and dihydroquinazolinone derivatives

A cellulose sulfonate catalyst (HS-cellulose sulfonate) with high stability, excellent catalytic activity and high acidity value (about 1.55 mmol g⁻¹) was successfully prepared by SO₃ gas phase sulfonation. The basic morphology and nanostructure of the catalyst were determined by HRTEM, XRD, IR, TG, etc. In addition, the catalyst was applied to the catalytic reaction of a dihydroquinazolinone derivative and a xanthene compound, and very valuable results were obtained. The development and preparation of cellulose sulfonate catalysts provide a good approach for the development and application of cellulose, and also an important application of green organic catalytic synthesis methodology.

The HS-cellulose sulfonate catalysed green and efficient one-step synthesis of xanthene and dihydroquinazolinone derivatives.     

Comparative research on three types of MIL-101(Cr)-SO3H for esterification of cyclohexene with formic acid

MIL-101(Cr)-SO₃H was prepared by a one-pot synthesis method using CrO₃ or Cr(NO₃)₃^·9H₂O as a Cr source and 2-sulfoterephthalic acid monosodium salt as a ligand with three different mineralizers, HCl, HF and NaAC, respectively. Among the prepared catalysts, MIL-101(Cr)-SO₃H, which uses HCl as a mineralizer, has a high specific surface area and the strongest acidity compared with the other two mineralizers. When these catalysts were used to catalyze the esterification of cyclohexene with formic acid, MIL-101(Cr)-SO₃H prepared using HCl as a mineralizer possessed the highest catalytic activity in the esterification, because the conversion rate of cyclohexene is 63.97%, whereas MIL-101(Cr)-SO₃H prepared using NaAC and HF as a mineralizer shows cyclohexene conversion rates of 38.40% and 32.46%, while their selectivity to cyclohexyl formate is about 97.50%. MIL-101(Cr)-SO₃H with HCl as a mineralizer can be reused three times in succession without any loss of catalytic activity.

MIL-101(Cr)-SO₃H was prepared with three different mineralizers, namely HCl, HF and NaAC, respectively. And catalytic performance and stability of three samples catalyzing the esterification of cyclohexene with formic acid were compared.     

K6P2W18O62 encapsulated into magnetic Fe3O4/MIL-101 (Cr) metal–organic framework: a novel magnetically recoverable nanoporous adsorbent for ultrafast treatment of aqueous organic pollutants solutions

In this study, a Wells–Dawson type K₆P₂W₁₈O₆₂ polyoxometalate was encapsulated into the magnetic Fe₃O₄/MIL-101 (Cr) metal–organic framework and applied as a new magnetically recoverable ternary adsorbent to remove organic dyes from aqueous solutions. The as-prepared ternary magnetically recyclable hybrid (denoted as P₂W₁₈O₆₂@Fe₃O₄/MIL-101 (Cr)) was characterized by FT-IR spectroscopy, powder X-ray diffraction (XRD), Raman spectroscopy, EDX, SEM, BET surface area, and magnetic measurements. The results showed the successful encapsulation of K₆P₂W₁₈O₆₂ (∼26.5 wt%) into the magnetic Fe₃O₄/MIL-101 (Cr) framework. The magnetic hybrid had a high specific surface area of 934.89 m² g⁻¹. The adsorption efficiency of this nanohybrid for the removal of methylene blue (MB), rhodamine B (RhB), and methyl orange (MO) from aqueous solutions was evaluated. The magnetic nanohybrid demonstrated the fast and selective adsorption of cationic dyes from mixed dye solutions. The adsorption rate and capacity of P₂W₁₈O₆₂@Fe₃O₄/MIL-101 (Cr) were increased as compared with MIL-101 (Cr), P₂W₁₈O₆₂, and Fe₃O₄/MIL-101 samples due to the increased electrostatic attraction. The effects of parameters such as the adsorbent dosage, temperature, dye concentration, and pH were investigated on the adsorption process. The adsorption kinetics was analyzed by the Freundlich, Langmuir, and Temkin isotherm models and pseudo-second-order and pseudo-first-order kinetics models, with the Langmuir isotherm and pseudo-second-order kinetic model found to be suitable to describe the equilibrium data. Also, the thermodynamic results of the nanohybrid indicated that the adsorption was an endothermic and spontaneous process. After the adsorption reaction, the magnetic nanohybrid could be easily separated and reused without any change in structure. Based on the results of this study, the nanohybrid was an efficient adsorbent for eliminating cationic dyes.

A Wells–Dawson-type K₆P₂W₁₈O₆₂ polyoxometalate was encapsulated into the magnetic Fe₃O₄/MIL-101 (Cr) metal–organic framework and applied as a new magnetically recoverable ternary adsorbent to remove organic dyes from aqueous solutions.     

Preparation of aminated porous polyacrylonitrile nanofibers as adsorbent for methyl orange removal

In this study, porous electrospinning polyacrylonitrile nanofiber (PPAN) surface functionalization with amine groups is studied for methyl orange (MO) dye removal from aqueous solution. A series of adsorption experiments were carried out to investigate the influence of initial solution pH value, contact time, initial solution concentration, and adsorption temperature on the adsorption performance. The experimental results showed that the removal of MO on these PPAN-PEI and PPAN-TEPA nanofibrous mats was a pH-dependent process with the maximum adsorption capacity at the initial solution pH of 3, and that the PPAN-PEI and PPAN-TEPA nanofibrous mats could be regenerated successfully after 4 recycling processes. The adsorption equilibrium data were all fitted well to the Langmuir isotherm equation, with maximum adsorption capacity of 1414.52 mg g⁻¹ and 1221.09 mg g⁻¹ for PPAN-PEI and PPAN-TEPA, respectively. The kinetic study indicated that the adsorption of MO could be well fitted by the pseudo-second-order equation and Weber–Morris model. Thermodynamic parameters such as free energy, enthalpy, and entropy of adsorption of the MO were also evaluated, and the results showed that the adsorption was a spontaneous exothermic adsorption process.

Amino functionalized porous polyacrylonitrile electrospun nanofibers were fabricated, which have good adsorption performance for MO in an acidic environment.     

Fabrication of UiO-66/MIL-101(Fe) binary MOF/carboxylated-GO composite for adsorptive removal of methylene blue dye from aqueous solutions

This study provides a novel composite as an efficient adsorbent of cationic methylene blue dye. UiO-66/MIL-101(Fe) binary metal organic framework (MOF) was fabricated using a solvothermal technique. Additionally, the developed binary MOF was modified with carboxylated graphene oxide (GOCOOH) using a post-synthetic technique. The as-fabricated UiO-66/MIL-101(Fe)-GOCOOH composite was analyzed by FTIR, XRD, SEM, BET, TGA, XPS and zeta potential analysis. The adsorption performance of UiO-66/MIL-101(Fe)-GOCOOH composite was examined for its aptitude to adsorb cationic MB dye using a batch technique. The obtained data revealed that, the developed UiO-66/MIL-101(Fe)-GOCOOH composite exhibited higher adsorption capacity compared to UiO-66/MIL-101(Fe) binary MOF. Adsorption isotherms and kinetic studies revealed that MB dye adsorption onto UiO-66/MIL-101(Fe)-GOCOOH composite fitted a Langmuir isotherm model (q_m = 448.71 mg g⁻¹) and both pseudo 1^st order and pseudo 2^nd order kinetic models. An intra-particle diffusion model showed that the adsorption process occurs through three steps. Besides, thermodynamic data reflected that the adsorption of MB onto UiO-66/MIL-101(Fe)-GOCOOH composite is an endothermic and spontaneous process and the adsorption involves both physisorption and chemisorption interactions. The as-fabricated UiO-66/MIL-101(Fe)-GOCOOH composite exhibited good reusability and can be considered as a promising reusable adsorbent for the treatment of dye-containing industrial effluents with high efficiency.

This study provides a novel composite as an efficient adsorbent of cationic methylene blue dye.     

Highly efficient catalyst-free domino conjugate addition,decarboxylation and esterification/amidation of coumarin carboxylic acid/esters with pyrazolones: a green chemistry approach

Tandem conjugate addition, decarboxylation and esterification/amidation of coumarin 3-carboxylic acid derivatives with pyrazolones have been developed. The reactions were performed with coumarin 3-carboxylic acid/esters and pyrazolone in alcohol as a solvent to afford the corresponding pyrazolyl 2-hydroxy phenylpropionate derivatives. Amines and green solvents were employed for amidation in the addition reaction. The methodology has advantages such as excellent yields, a broad substrate scope, catalyst-free, easy purification by simple filtration without any workup, mild conditions and does not require any organic solvents, ligands, base or any additives. This is a green and general synthetic protocol, which could be applicable for the synthesis of substituted pyrazolyl phenyl propionate/amide derivatives. This approach demonstrates the importance of the coumarin 3-carboxylic acid/ester core structure for Michael addition.

Tandem conjugate addition, decarboxylation and esterification/amidation of coumarin 3-carboxylic acid derivatives with pyrazolones have been developed.     

Layer-by-layer coating of MIL-100(Fe) on a cotton fabric for purification of water-soluble dyes by the combined effect of adsorption and photocatalytic degradation

Efforts have been made for sustainable development of adsorbents to purify organic contaminants from wastewater. In this study, a MIL-100(Fe) based textile that acts as a reusable adsorbent and photocatalytic agent was developed by synthesizing MIL-100(Fe) onto a cotton fabric by the layer-by-layer (LBL) process using water-based solutions. As the number of LBL cycles increased, the add-on''s of MIL-100(Fe) showed a drastic increase up to 8 cycles, then showed gradual increases with further treatments. The overall adsorption performance was enhanced with the increased MIL-100(Fe) add-on''s, but the specific adsorption efficiency per unit mass of MIL-100(Fe) was reduced as the LBL cycles increased, implying the reduced average adsorption efficiency with a thicker coating. To examine the reusability of the adsorbent, desorption efficiency of RhB was measured. The desorption after the first-time adsorption was not efficient due to the strong binding inside the pores. For the later cycles of adsorption–desorption, desorption occurred more efficiently, probably because RhB molecules were adhered mostly at the outer surface of the MOF layer. Simultaneously, MIL-100(Fe)@cotton demonstrated the photocatalytic degradation performance against RhB in the presence of H₂O₂ by the Fenton reaction. With the combined effect of adsorption and photodegradation, the developed fabric attained 96% removal efficiency for RhB dissolved in water. This study demonstrates an environmentally responsible process of developing a MIL-100(Fe) coated fabric that is readily available for effective removal of organic foulants in water. This fabrication method can be applied as a scalable manufacturing of metal–organic framework-based photocatalytic adsorbent textiles.

A MIL-100(Fe)-based water purifying textile that functions by dual action of adsorption and photocatalytic activity is designed via a layer-by-layer process without using toxic organic solvents.