ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
