Elsevier

Materials Chemistry and Physics

Volume 222, 15 January 2019, Pages 63-74
Materials Chemistry and Physics

Novel rice husk ash - reduced graphene oxide nanocomposite catalysts for solvent free Biginelli reaction with a statistical approach for the optimization of reaction parameters

https://doi.org/10.1016/j.matchemphys.2018.09.078Get rights and content

Highlights

  • A highly efficient novel heterogeneous catalyst for the multicomponent Biginelli reaction is prepared from rice husk ash and graphene oxide.

  • Present study exploited the use of experimental design, Box-Behnken to optimize the effect of reaction parameters with restricted number of experiments.

  • Novel catalyst prepared using 10 wt% GO sheets were found to be highly reusable while retaining the structure even after 7 repeated runs.

Abstract

Here we report the preparation of novel rice husk ash – reduced graphene oxide nanocomposites and their catalytic application in Biginelli reaction. Hydrothermal treatment is given to a mixture of rice husk ash and graphene oxide for the formation of a uniform composite. XRD and FTIR spectral analyses confirmed the partial reduction of graphene oxide in the nanocomposites during hydrothermal treatment. The binding between rice husk silica particles and graphene sheets through Sisingle bondOsingle bondC bonding is revealed from XPS analysis. Graphene is found to be less defective in nature in the composite as evident from the reduced ID/IG value in the Raman spectrum. SEM and TEM images showed the effective dispersion of rice husk SiO2 particles on the wrinkled graphene layers. Present study also exploited the use of a statistical model, response surface methodology, for the optimization of reaction parameters on the catalytic synthesis of dihydropyrimidinones via multicomponent solvent free Biginelli reaction. The cost effective highly efficient rice husk ash - reduced graphene oxide catalyst is found to be reusable till 7 repeated cycles with only about 4% reduction of its initial activity.

Graphical abstract

A facile synthesis of novel rice husk ash – reduced graphene oxide nanocomposite is achieved and its catalytic activity is evaluated in the multicomponent Biginelli reaction with statistical optimization for the optimization of reaction parameters.

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Introduction

“Wealth from Waste” is pertinent with the effective utilization of agricultural waste products in various industries as well as in the field of research, which were intensified in past two decades. Rice husk (RH), one of the widely studied agricultural waste products, is regarded as the most prevalent crop residue around the worldwide and is usually left aside in landfills or burnt. The effective utilization of RH is a major challenge in front of the people since its improper disposal may leads to environmental problems [1]. The high calorific value of about 16720 kJ/kg had made RH as an excellent fuel in Kilns leading to the mass production of rice husk ash (RHA) [2]. RH contains about 20% of silica and its pyrolysis leads to the removal of volatile carbonaceous organic materials with the formation of RHA which is mainly composed of silica (about 90%) [3].

Extensive research has been carried out on the application of RHA derived catalysts in various chemical transformations [[4], [5], [6], [7], [8], [9]]. First study on the catalytic action of RHA derived material was reported by Chang et al. [4]. They successfully supported Ni particles on RHA and performed the gas phase hydrogenation of CO2 over the prepared catalyst. In 2006, Adam et al. reported the preparation of silica supported iron catalysts from RHA, which was used for the benzylation reaction of toluene with benzyl chloride [5]. Krisnandi et al. reported the catalytic activity studies of ZSM-5 zeolite prepared from RHA for the partial oxidation of methane to methanol [6]. Radhika and Sugunan successively employed rice husk silica as a promoter for vanadia supported ceria catalysts and studied the catalytic action of the prepared systems towards liquid phase oxidation of benzene as well as high temperature cyclohexanol decomposition reaction [7,8]. Recently Hindryawati et al. prepared sulphonated RHA and effectively used it for the synthesis of biodiesel from palm oil adsorbed on palm decanter cake [9].

Multicomponent reactions (MCRs), that involve the combination of three or more reagent partners with the formation of one complex molecule incorporating most of the atoms of the starting adducts, are getting high relevance in this era of green chemistry due to its competence with ideal synthesis [[10], [11], [12]]. Catalysts derived from RH also found immense application in various MCRs. The work of Shirini is regarded as the first report on the application of cleaned RH in MCR [13]. They used RH for the one pot synthesis of 12-aryl-8, 9, 10, 12-tetrahydro [a] xanthene-11-ones and quinoxaline derivatives under mild conditions. Ramazani and Mahyari in 2010 reported the multicomponent synthesis of isocoumarin using silica nanoparticles prepared from rice hulls [14]. Davarpanahab and Kiasat modified amorphous silica obtained from RH using an acidic ionic liquid containing double-charged diazoniabi-cyclo[2.2.2]octane chloride by a sol gel method and used as a reusable catalyst for the synthesis of 1H-pyrazolo[1,2-b]phthalazine-5,10-diones via three-component reaction between phthalhydrazide, aromatic aldehydes, and malononitrile [15].

Among the various MCRs, one of the most studied MCRs, Biginelli reaction involves the synthesis of 3,4-dihydropyrimidinones (DHPMs) [[16], [17], [18]]. DHPMs are best known for their biological and pharmacological effects [[19], [20], [21]]. There are many reports on the synthesis of these DHPMs using various catalysts such as Au nanorods [22], ZrCl4 [23], Zn(NH2SO3)2 [24], BiONO3 [25], H3PMo12O40 [26], fluoroboric acid [27], CaF2 [28], chloroferrate(III) ionic liquid [29], triethyl ammonium tetrafluoroborate [30], sulphonated carbon [31] etc. The studies embrace any one of the drawbacks such as high cost of production, harsh reaction conditions, low yield of the product, longer reaction time etc. Therefore research works leading to the high yielding, cost effective and eco-friendly synthesis of DHPMs under mild conditions are of prime importance.

Graphene, the two dimensional network of carbon chains, had found paramount application in various fields due to its remarkable electronic, mechanical and optical properties [[32], [33], [34]]. Reduction of graphene oxide (GO) is regarded as the easy and large scale method for the synthesis of graphene. Even though graphene is hydrophobic, the presence of various functional groups such as carboxyl, hydroxyl and carbonyl groups makes GO hydrophilic and a better candidate for graphene based composite preparation [35,36].

As a part of our investigations in the development of environmentally benign catalysts for multicomponent Biginelli reaction [37], herein we report the easy and scalable synthesis of novel rice husk ash – reduced graphene oxide (RHA-G) nanocomposites via hydrothermal method and its catalytic application towards Biginelli reaction. The prepared nanocomposites were characterized using various techniques to investigate the interaction between RHA and graphene and also to analyze the nature of the catalyst. To optimize the reaction conditions in a more economical manner, a statistical model is also applied. Reports regarding statistical optimization for Biginelli reactions [38,39] are only limited in number. Besides the amount of catalyst, Biginelli reaction mainly depends upon the reaction temperature and time of reaction. In order to study the effect of various factors simultaneously, the statistical model Box-Behnken Design using response surface methodology (RSM) is applied.

Section snippets

Experimental

RH was collected from nearby Regional Agricultural Research Station (RARS), Pattambi. All other chemicals were of reagent grade and were procured from Sigma Aldrich Chemicals Pvt. India Ltd., Nice Chemicals Pvt. Ltd. and Loba chemie Pvt. Ltd. Graphite oxide (GrO) was prepared using modified Hummers method [40]. Details of GrO preparation is given in the supplementary data.

Results and discussion

In the present study, highly efficient novel RHA-G hybrid nanostructures were successfully synthesized via hydrothermal method. The schematic representation of RHA-G hybrid nanostructure formation is shown in Scheme 1. Hydrothermal treatment (HT) leads to the partial reduction of GO into reduced graphene oxide (rGO) in the nanocomposites as evident from the material characterization studies. Different weight percentages of GO has been used in the composite preparation. Hydrothermal treatment of

Conclusions

A highly efficient novel heterogeneous catalyst for the multicomponent Biginelli reaction is prepared from rice husk ash and graphene oxide. The material characterization studies indicated the effective binding and dispersion of RHA silica nanoparticles on the graphene sheets. Partial reduction occurred to GO upon hydrothermal treatment with RHA as evident from the FTIR and Raman spectral analysis. Present study exploited the use of experimental design, Box-Behnken with RSM to optimize the

Acknowledgement

Authors acknowledge Sree Neelakanta Govt. Sanskrit College Pattambi and University of Calicut for providing the facilities for carrying out the research work. Binitha N. Narayanan is grateful to the University Grants Commission, New Delhi, India, for UGC Research Award (2012–2014). Panichikkal Abdul Faisal, Enzyme Technology Laboratory, Biotechnology Division, Department of Botany, University of Calicut is acknowledged for help in the statistical optimization studies. SAIF, STIC, CUSAT, Kochi,

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