Sulfonic acid-functionalized k-carrageenan/Cr-based metal-organic framework: An efficient and recyclable catalyst for fructose conversion to 5-hydroxymethylfurfural.

A novel bio-based catalyst was developed by in-situ forming Chromium(III) (Cr)-based metal-organic framework, MIL-101(Cr), in the presence of k-carrageenan (k-Car) and followed by a post-synthetic modification to introduce additional -SO3H functional groups into the composite structure of k-Car/MIL-101(Cr). Different analyses were conducted to confirm the successful catalyst formation. The catalyst performance was evaluated in the solid acid catalyzed dehydration of fructose to 5-hydroxymethylfurfural. The Response Surface Method (RSM) optimization determined that employing 33 wt% of the catalyst at 105 °C for 40 min resulted in a remarkable 97.8 % yield. The catalyst demonstrated suitable recyclability, maintaining its catalytic efficiency over four cycles. Comparative studies with k-Car and the non-sulfonated composite highlighted the superior activity of the catalyst, emphasizing the synergy between the k-Car, MIL-101(Cr) and the influence of -SO3H post-functionalizing on the catalytic performance.

Sulfonic acid-functionalized chitosan-metal-organic framework composite for efficient and rapid conversion of fructose to 5-hydroxymethylfurfural.

In pursuit of designing a bio-based catalyst for the dehydration of biomass (i.e., fructose) to 5-hydroxymethylfurfural, a novel catalytic composite was prepared by in-situ formation of an Al-based metal-organic framework in the presence of chitosan. To enhance the acidity of the as-prepared catalyst, it was sulfonated with chlorosulfonic acid. Various characterization techniques, including XRD, XPS, FTIR, SEM/EDX, TGA, and elemental mapping analysis were applied to validate the formation of the acidic composite. Fructose dehydration conditions were also optimized using Response Surface Method (RSM) and it was found that reaction in the presence of catalyst (23 wt%) in DMSO, at 110 °C for 40 min led to the formation of HMF in 97.1%. Noteworthy, the catalyst was recyclable and stable up to five runs with a minor reduction in its activity.

Clay-supported bio-based Lewis acid ionic liquid as a potent catalyst for the dehydration of fructose to 5-hydroxymthylfurfural.

Caffeine and halloysite nanoclay mineral that are bio-based compounds were utilized to synthesize a novel Lewis acid heterogeneous catalyst. To this aim, halloysite was functionalized with 2,4,6-trichloro-1,3,5-triazine and reacted with caffeine, which was then converted to ionic liquid via a reaction with ZnCl2. The catalyst was applied for promoting the dehydration of fructose to 5-hydroxymethylfurfural. To investigate the effects of the reaction variables, response surface methodology was used. The product was achieved in 98.5% in 100 min using a catalyst loading of 30 wt% at 100 °C. Moreover, the catalyst was recyclable up to six runs with slight zinc leaching. Comparison of the catalytic activity of the catalyst with that of halloysite and a control catalyst with one caffeine-based Lewis acid ionic liquid confirmed the superior activity of the former and the important role of 2,4,6-trichloro-1,3,5-triazine for increasing the number of the grafted caffeine and thus the acidic sites of the catalyst. A plausible reaction mechanism was proposed, and the activity of the catalyst for other carbohydrates was also studied. According to the results, this catalyst catalyzed the reaction of other substrates to furnish 5-hydroxymethylfurfural in low to moderate yields. According to the kinetic studies, the activation energy was estimated to be 22.85 kJ/mol.

3D-Printed Cyclodextrin Polymer Encapsulated Wells-Dawson: A Novel Catalyst for Knoevenagel Condensation Reactions.

In the pursuit of enhancing the catalytic potential of the Wells-Dawson (WD) polyoxometalate (POM) while addressing its solubility challenges, this study focuses on devising a sustainable catalyst that operates effectively in aqueous environments. Leveraging cyclodextrin (CD) polymer chemistry in conjunction with 3D printing technology, a CD nanosponge, recognized for its interaction with POMs and molecular shuttle attributes, is synthesized as a scaffold for WD immobilization. Through integration into a 3D-printed monolith framework, the supported WD species becomes embedded within the catalyst structure, facilitating its application. Extensive characterization encompassing X-ray diffraction, thermogravimetric analysis, Fourier transform infrared, scanning electron microscopy/energy-dispersive system, elemental mapping analysis, and compression testing confirms the structural integrity and viability of the resulting catalyst. The catalytic assessment of the developed catalyst in the Knoevenagel condensation reaction within aqueous settings demonstrates enhanced reusability attributed to the encapsulation within the 3D matrix. Notably, a hot filtration test provides empirical evidence of heterogeneous catalysis mode, further underpinning the catalyst's performance and potential for sustainable applications.

Heteropolyacid supported on ionic liquid decorated hierarchical faujasite zeolite as an efficient catalyst for glycerol acetalization to solketal.

To handle huge amount of glycerol produced in biodiesel industry, glycerol is transformed to value-added products. In this regard, glycerol acetalization to solketal is industrially attractive. As in this process various by-products can be formed, designing highly selective catalysts is of great importance. In this line, we wish to report a novel catalyst that benefits from strong acidity, high specific surface area and thermal stability, which can selectively form solketal in glycerol acetalization. To prepare the catalyst, hierarchical zeolite was prepared via a novel method, in which partially dealuminated NaY was treated with PluronicF-127 and then reacted with NH4NO3 to furnish the H-form zeolite. Hierarchical faujasite was then achieved through calcination and template removal. Subsequently, it was functionalized with ionic liquid and used for the immobilization of heteropolyacid. The results indicated the importance of the mesoprosity of zeolite and the presense of ionic liquid functionality for achiveing high solketal yield. Moreover, among three investigated heteropolyacids, phosphomolybdic acid exhibited the highest catalytic activity. In fact, using 10 wt% catalyst at 55 °C and glycerol to acetone molar ratio of 1:20, solketal with yield of 98% was furnished under solvent-less condition. Besides, the catalyst was recyclable with low leaching of heteropolyacid.

Palladated Cyclodextrin Nanosponge-Alginate Dual Bead as an Efficient Catalyst for Hydrogenation of Nitroarenes in Aqueous Solution.

In this study, we present a novel composite material consisting of ß-cyclodextrin nanosponge and sodium alginate, used as a support for the immobilization of palladium (Pd) nanoparticles. The composite alginate-cyclodextrin nanosponge beads were prepared, taking advantage of the 3D polymeric network and ß-cyclodextrin cavity of the nanosponge. These beads exhibited excellent encapsulation capabilities for hydrophobic substrates, allowing their transfer in aqueous media. The cyclodextrin nanosponge served as a stabilizer for Pd nanoparticles and facilitated phase transfer. Additionally, the sodium alginate bead contributed to the robustness of the structure and improved the recovery and recyclability of the composite material. Comparative studies with control catalysts confirmed the beneficial effect of incorporating cyclodextrin nanosponge within alginate beads, particularly for more hydrophobic substrates. Optimization of reaction conditions revealed that employing 0.03 g of catalyst per mmol of nitroarene at 45 °C resulted in the maximum yield within 90 min. Evaluation of the substrate scope demonstrated the hydrogenation capability of various substrates with different electronic properties under the developed protocol. Notably, the nitro group was selectively reduced in substrates featuring competing functionalities. Furthermore, the recyclability and stability of the composite catalyst were confirmed, making it a promising candidate for sustainable catalysis.

Tuning the acidity of halloysite by polyionic liquid to develop an efficient catalyst for the conversion of fructose to 5-hydroxymethylfurfural.

In an attempt to prepare a low-cost and efficient acidic heterogeneous catalyst for the conversion of fructose to 5-hydroxymethylfurfural under mild reaction conditions, the acidity of halloysite was improved by covalent grafting of an acidic polyionic liquid. More precisely, halloysite was first vinyl functionalized and then polymerized with vinyl imidazole and 2-acrylamido-2-methylpropanesulfonic acid. The tangling imidazole rings were further converted to acidic ionic liquids by treating them with chlorosulfuric acid. UV-Vis spectroscopy and Hammett equation confirmed that conjugation of acid polyionic liquid resulted in the increase of the acidity of halloysite. Investigation of the efficiency of the catalyst for the synthesis of 5-hydroxymethylfurfural and optimization of reaction variables showed that 5-hydroxymethylfurfural was yielded in 97.8% after 30 min under the optimum conditions, i.e. catalyst loading of 20 wt% at 70 °C. Notably, the catalyst was highly reusable and it could be reused for at least seven reaction runs with insignificant loss of its activity. Furthermore, this catalyst could also promote the conversion of sucrose and maltose to give moderate yields of 5-hydroxymethylfurfural.

Thermoplastic starch/bentonite clay nanocomposite reinforced with vitamin B2: Physicochemical characteristics and release behavior.

This study presents the development and characterization of a nanocomposite material, consisting of thermoplastic starch (TPS) reinforced with bentonite clay (BC) and encapsulated with vitamin B2 (VB). The research is motivated by the potential of TPS as a renewable and biodegradable substitute for petroleum-based materials in the biopolymer industry. The effects of VB on the physicochemical properties of TPS/BC films, including mechanical and thermal properties, water uptake, and weight loss in water, were investigated. In addition, the surface morphology and chemical composition of the TPS samples were analyzed using high-resolution SEM microscopy and EDS, providing insight into the structure-property relationship of the nanocomposites. The results showed that the addition of VB significantly increased the tensile strength and Young's modulus of TPS/BC films, with the highest values observed for nanocomposites containing 5 php of VB and 3 php of BC. Furthermore, the release of VB was controlled by the BC content, with higher BC content leading to lower VB release. These findings demonstrate the potential of TPS/BC/VB nanocomposites as environmentally friendly materials with improved mechanical properties and controlled release of VB, which can have significant applications in the biopolymer industry.

Chitosan bead containing metal-organic framework encapsulated heteropolyacid as an efficient catalyst for cascade condensation reaction.

Using cyclodextrin and chitosan that are bio-based compounds, a novel bi-functional catalytic composite is designed, in which metal-organic framework encapsulated phosphomolybdic acid was incorporated in a dual chitosan-cyclodextrin nanosponge bead. The composite was characterized via XRD, TGA, ICP, BET, NH3-TPD, FTIR, FE-SEM/EDS, elemental mapping analysis and its catalytic activity was examined in alcohol oxidation and cascade alcohol oxidation-Knoevenagel condensation reaction. It was found that the designed catalyst that possess both acidic feature and redox potential could promote both reactions in aqueous media at 55 °C and various substrates with different electronic features could tolerate the aforementioned reactions to furnish the products in 75-95% yield. Furthermore, the catalyst could be readily recovered and recycled for five runs with slight loss of the catalytic activity. Notably, in this composite the synergism between the components led to high catalytic activity, which was superior to each component. In fact, the amino groups on the chitosan served as catalysts, while cyclodextrin nanosponge mainly acted as a phase transfer agent. Moreover, measurement of phosphomolybdic acid leaching showed that its incorporation in metal-organic framework and bead structure could suppress its leaching, which is considered a drawback for this compound. Other merits of this bi-functional catalyst were its simplicity, use of bio-based compounds and true catalysis, which was proved via hot filtration.

Synthesis and physicochemical evaluations of a novel MIL-101(Fe)-PMA-Biochar triple composite photocatalyst activated through visible-light and utilized toward degradation of organic pollutants: optimal operations and kinetics investigations.

A triple photocatalytic composite of biochar, metal-organic framework, and phosphomolybdic acid was prepared through hydrothermal treatment of iron (III) chloride hexahydrate, terephthalic acid, lavandulifolia-derived biochar, and phosphomolybdic acid. It was characterized and utilized for photodegradation of Rhodamine-B (RhB) dye under visible-light irradiation. Investigations of reaction variables confirmed that, the highest yield of 96.2% was achieved at ambient temperature using 0.07 g of catalyst at pH of 7, and a dye concentration of 10 ppm. Under these optimum conditions, Methyl Orange (MO) dye was also degraded to yield 93% removal. In addition, the kinetic and thermodynamic parameters for RhB were determined. It was revealed that the photodegradation of RhB followed a pseudo-first-order kinetics with no mass transfer limitations. A corresponding chemical mechanism for this process was also suggested. Adsorption isotherms were investigated for rate of adsorption as well as adsorption capacity of the catalyst under dark conditions. Notably, the catalyst could have been reused for five cycles with a loss of around 20% activity.

Influence of the Ethanol Content of Adduct on the Comonomer Incorporation of Related Ziegler-Natta Catalysts in Propylene (Co)polymerizations.

The aim of this work is to investigate the influence of the ethanol content of adducts on the catalytic behavior of related Ziegler-Natta (ZN) catalysts in propylene homo- and copolymerizations (with 1-hexene comonomer) in terms of activity, isotacticity, H2 response, and comonomer incorporation. For this purpose, three MgCl2.nEtOH adducts with n values of 0.7, 1.2, and 2.8 were synthesized and used in the synthesis of related ZN catalysts. The catalysts were thoroughly characterized using XRD, BET, SEM, EDX, N2 adsorption-desorption, and DFT techniques. Additionally, the microstructure of the synthesized (co)polymers was distinguished via DSC, SSA, and TREF techniques. Their activity was found to enhance with the adduct's ethanol content in both homo- and copolymerization experiments, and the increase was more pronounced in homopolymerization reactions in the absence of H2. Furthermore, the catalyst with the highest ethanol content provided a copolymer with a lower isotacticity index, a shorter meso sequence length, and a more uniform distribution of comonomer within the chains. These results were attributed to the higher total surface area and Ti content of the corresponding catalyst, as well as its lower average pore diameter, a larger proportion of large pores compared to the other two catalysts, and its spherical open bud morphology. It affirms the importance of catalyst/support ethanol-content control during the preparation process. Then, molecular simulation was employed to shed light on the iso-specificity of the polypropylene produced via synthesized catalysts.

Heteroployacid on the composite of boehmite and polyionic liquid as a catalyst for alcohol oxidation and tandem alcohol oxidation Knoevenagel condensation reactions.

Using boehmite as an available and low-cost natural compound, a bi-functional catalytic composite is prepared through vinyl-functionalization of boehmite, followed by polymerization with the as-prepared bis-vinylimidazolium bromide ionic liquid and supporting of phosphotungstic acid. The catalyst was characterized via ICP, XRD, TGA, FTIR, SEM/EDS and elemental mapping analysis and applied for promoting alcohol oxidation reaction and one-pot tandem alcohol oxidation/Knoevenagel condensation reaction in aqueous media under mild reaction condition. The results indicated high catalytic activity of the catalyst for both reactions. This protocol showed high generality and aliphatic, aromatic and heterocyclic alcohols could be applied as substrates to furnish the corresponding products in high to excellent yields. Furthermore, hot filtration test confirmed true heterogeneous nature of the catalysis. The catalyst could also be recovered readily and reused for at least five runs of the reaction with low loss of the activity and phosphotungstic acid leaching upon each run.

Pd on cyclotriphosphazen-hexa imine decorated boehmite as an efficient catalyst for hydrogenation of nitro arenes under mild reaction condition.

Cyclotriphosphazen-hexa imine ligand was prepared through successive reactions of phosphonitrilchloride trimer with 4-hydroxybenzaldehyde and (3-aminopropyl) triethoxy silane. The as-prepared ligand was then covalently grafted on boehmite to furnish an efficient support for the immobilization of Pd nanoparticles and synthesis of a novel heterogeneous catalyst for hydrogenation of nitro arenes. The catalytic tests revealed that the catalyst had excellent catalytic activity for hydrogenation of various nitro arenes with different steric and electronic features under mild reaction condition in aqueous media. Noteworthy, the catalyst was highly selective and in the substrates with ketone or aldehyde functionalities, reduction of nitro group was only observed. The catalyst was also recyclable and only slight loss of activity was detected after each recycling run. Hot filtration test also approved true heterogeneous nature of catalysis.

Pd on thermo-responsive composite of silica-coated carbon nanotube and 1-vinyl-3-butylimidazolium-based ionic liquid copolymers as an efficient catalyst for hydrogenation of nitro compounds.

In this work, an ionic liquid-containing thermo-responsive heterogeneous catalyst with utility for promoting hydrogenation of nitro-compounds in aqueous media is developed. To prepare the catalyst, silica-coated carbon nanotubes were synthesized and vinyl-functionalized. The resulted compound was then polymerized with 1-viny-3-butylimidazolium bromide and N-isopropylacrylamide. The obtained ionic liquid-containing thermo-responsive composite was palladated via wet-impregnation method to give the final catalyst. Study of the performance of the catalyst confirmed high catalytic activity of the catalyst at temperature above the lower critical solution temperature. Furthermore, the catalyst was highly recyclable and showed negligible Pd leaching upon recycling. Broad substrate scope and selectivity of the catalyst towards reduction of nitro functionality were also confirmed. Furthermore, hot filtration test implied the heterogeneous nature of the catalysis. The comparison of the activity of Pd/CNT-P with some control catalysts approved the importance of hybridization of P and CNT and the presence of ionic liquid for the catalytic activity.

A novel composite of ionic liquid-containing polymer and metal-organic framework as an efficient catalyst for ultrasonic-assisted Knoevenagel condensation.

1-Butyl-3-vinylimidazolium chloride was synthesized and polymerized with acrylamide to furnish an ionic liquid-containing polymer, which was then used for the formation of a composite with iron-based metal-organic framework. The resultant composite was characterized with XRD, TGA, FE-SEM, FTIR, EDS and elemental mapping analyses and its catalytic activity was appraised for ultrasonic-assisted Knoevenagel condensation. The results confirmed that the prepared composite could promote the reaction efficiently to furnish the corresponding products in high yields in very short reaction times. Moreover, the composite exhibited high recyclability up to six runs. It was also established that the activity of the composite was higher compared to pristine metal-organic framework or polymer.

Composite of MOF and chitin as an efficient catalyst for photodegradation of organic dyes.

A novel composite has been fabricated by using MOF and chitin as a natural and biocompatible compound. To this purpose, MOF was synthesized by using 2-aminoterephthalic acid and iron (III) chloride hexahydrate and then reacted with Cl-functionalized chitin. The resulting composite was characterized and utilized as a catalyst for degradation of methylene blue both in dark condition and under visible light irradiation. The results indicated superior catalytic activity under visible light irradiation. Furthermore, study of the reaction variables, including basicity, dye concentration and catalyst loading showed that the highest catalytic activity was achieved at basic condition. It was also found that both initial dye concentration and catalyst loading can affect the catalytic activity. To disclose the merits of the composite compared to its individual components, kinetic studies of the photo-degradation process in the presence of the composite, chitin and MOF have been performed. The results confirmed superior activity the composite compared to its components. The study of the mechanism of the reaction using scavengers confirmed that the created holes (h+) are the most effective species in the process of photocatalytic degradation of MB. Notably, the catalyst was recyclable and could be used for degradation of other dyes.

Composite of bentonite and cyclodextrin as an efficient catalyst for promoting chemical transformations in aqueous media.

Combining the encapsulating capability of cyclodextrin and instinctive features of bentonite clay, a versatile metal free catalyst has been developed that could promote various chemical reactions such as Knoevenagel condensation, synthesis of xanthan and octahydroquinazolinones in aqueous media under ultrasonic irradiation. To prepare the catalyst, bentonite was Cl-functionalized and then reacted with isatin and guanidine successively to furnish amino functionalized bentonite. The latter then reacted with tosylated cyclodextrin. The resultant catalytic composite was characterized via XRD, SEM, EDS, BET, elemental mapping analysis, TGA and FTIR. The catalytic activity tests approved excellent activity of the catalyst as well as broad substrate scope. Notably, the catalyst could be simply recovered and reused for several reaction runs. Moreover, the activity of the composite was superior to that of its components.

Efficient hydro-finishing of polyalfaolefin based lubricants under mild reaction condition using Pd on ligands decorated halloysite.

To achieve efficient hydrofinishing of polyalfaolefin based lubricants under mild reaction condition, a novel catalyst is designed and fabricated through supporting Pd nanoparticles on ligand functionalized halloysite clay. In this line, first, using DFT calculations a scan of a library of 36 diamines was performed to find the most proper ligand that can provide the best interactions with Pd nanoparticles, improve Pd anchoring and supress Pd leaching. Characterization of the rather strong covalent and ionic interactions by a Mayer Bond Order analysis, and the non-covalent interactions by NCI plots as well, unveiled the preference for a particular system. The perfect in silico candidate was then studied on an experimental level, and also by studying its reaction profile for the hydrogenation of ethylene by calculations. In the experimental section, halloysite was functionalized with the selected ligand in simulation part and employed for the hydrofinishing of polyalfaolefin type lubricants. Characterization results revealed successful synthesis of the nano catalyst containing tiny Pd nanoparticles with a mean diameter in the range of 2.37 ± 0.5 nm, which homogeneously dispersed on the functionalized halloysite. The synthesized catalyst exhibited excellent activity (98% hydrogenation yield after 6 h) under mild reaction condition (T = 130 °C and PH2 = 6 bar). Furthermore, the catalyst can be recycled for several times with insignificant Pd leaching and loss of its activity.

Biochar-Based Graphitic Carbon Nitride Adorned with Ionic Liquid Containing Acidic Polymer: A Versatile, Non-Metallic Catalyst for Acid Catalyzed Reaction.

A novel biochar-based graphitic carbon nitride was prepared through calcination of Zinnia grandiflora petals and urea. To provide acidic and ionic-liquid functionalities on the prepared carbon, the resultant biochar-based graphitic carbon nitride was vinyl functionalized and polymerized with 2-acrylamido-2-methyl-1-propanesulfonic acid, acrylic acid and the as-prepared 1-vinyl-3-butylimidazolium chloride. The final catalytic system that benefits from both acidic (-COOH and -SO3H) and ionic-liquid functionalities was applied as a versatile, metal-free catalyst for promoting some model acid catalyzed reactions such as Knoevenagel condensation and Biginelli reaction in aqueous media under a very mild reaction condition. The results confirmed high activity of the catalyst. Broad substrate scope and recyclability and stability of the catalyst were other merits of the developed protocols. Comparative experiments also indicated that both acidic and ionic-liquid functionalities on the catalyst participated in the catalysis.

Fabrication of a metal free catalyst for chemical reactions through decoration of chitosan with ionic liquid terminated dendritic moiety.

In attempt to develop a biocompatible metal-free catalyst, a dendritic moiety was grown on chitosan through successive reactions with 2,4,6-trichloro-1,3,5-triazine and ethylenediamine. Subsequently, the terminal functional groups of the dendron were decorated with 1-methylimidazolium chloride. The catalyst was characterized with SEM, EDS, TGA, FTIR, XRD and mapping analysis. Then, the catalytic activity of the resultant composite was scrutinized for catalyzing Knoevenagel condensation and synthesis of xanthene derivatives in aqueous media under mild reaction condition. The results confirmed high activity of the catalyst, superior to ionic liquid free counterpart and bare chitosan. This observation was ascribed to the instinct catalytic activity of ionic liquid. Moreover, using control catalysts, it was confirmed that the presence of the dendritic moiety that could increase the content of ionic liquid on the backbone of the catalyst enhanced the catalytic activity.