Journal of Nanomedicine & Nanotechnology

The Uses of Various Nanoparticles in Organic Synthesis: A Review

Khaturia S¹, Chahar M^2*, Sachdeva H³, Sangeeta¹ and Mahto CB^{2 1}Department of Chemistry, School of Sciences, Mody University of Science and Technology, Laxmangarh (Sikar), Rajasthan, India
²Department of Chemistry, Nalanda College of Engineering, Chandi, Nalanda, Bihar, India
³Department of Chemistry, University of Rajasthan, Jaipur, India
^*Correspondence: Chahar M, Department of Chemistry, Nalanda College of Engineering, Chandi, Nalanda, Bihar, India, Tel: 7737075718, Email:

Received: 10-Feb-2020 Published: 24-Apr-2020, DOI: 10.35248/2157-7439.19.11.543

Introduction

The last decade has witnessed enormous development in the field of nanoscience and nanotechnology. Several reports show the amazing level of the performance of nanoparticles as catalysts in terms of selectivity, reactivity and improved yields of products. In addition, the high surface-to-volume ratio of nanoparticles provides a larger number of active sites per unit area, in comparison with their heterogeneous counter sites [1,2]. In this review, we focus on green nanocatalysts as well as industrially important green reactions. This article has two parts. The first part involves green nanocatalysts and the second part involves green reactions.

Synthesis of Various Nanoparticles

Various nanoparticles are shown in Figure 1 and Schemes 1-53 in Tables 1-15.

Figure 1: Various Green Nanocatalysts.

Table 1: Reduction Reactions.

Table 2: Oxidation reactions.

Table 3: Conversion of organosilanes to silanols.

Table 4: Suzuki cross-coupling Reactions and Sonagashira Reaction.

Table 5: Hydrogenations.

Table 6: Ullmann Reaction.

Table 7: Heck cross-coupling Reaction.

Table 8: Deoxygenation Reaction.

Table 9: Alkynylation of Aryl Halides.

Table 10: Arylations and Diarylations.

Table 11: Deoxygenation of Epoxides.

Table 12: Oxidative Coupling of Alcohols.

Table 13: Esterification of Alcohols.

Table 14: Hydration of Nitriles.

Table 15: Additional Organic Synthesis Reactions.

Calcium oxide nanoparticles

Among various nanoparticles, calcium oxide nanoparticles have received considerable attention because of their unusual properties and potential applications in diverse fields [3]. Calcium oxide (CaO) itself as cost effective, highly basic, non-corrosive, environment friendly, and economically benign, that can be regenerate and reused. Also, they require only mild reaction conditions to produce high yields of products in short reaction times, in comparison with traditional catalysts [4-6]. Many researchers reported that calcium oxide nanoparticles as an active catalyst in many chemical transformations such as adsorption of Cr (VI) from aqueous solutions [7], biodiesel trans-esterification [8-19], removal of toxic heavy metal ions in water [20] and artificial photosynthesis [21] and the degradation of bromocresol green [22], purification of vehicle gas exhaust [23]. In accordance with the above mentioned consequence of nanoparticles in catalysis, and the significance of highly substituted pyridines as privileged medicinal scaffolds.[24] Calcium oxide nanoparticles, as an efficient, non-explosive, ecofriendly, non-volatile, recyclable and easy to handle catalyst, can be used in the catalysis of many organic transformations.

Preparation of CaO nanoparticles

NaOH (1 g) was added to a mixture of ethylene glycol (12 ml) and Ca(NO₃)₂. 4H₂O (6 g) and the solution stirred vigorously at room temperature for 10 min; the gel solution was kept about 5 h at static state. Afterwards, it was washed using water and dried under vacuum drying. Finally, the prepared CaO nanoparticles were calcinated at 700°C for 3 h [23].

Iron nanoparticles

Iron nanoparticles have been synthesized using polymers as capping agents in water as green solvent as well as other types of green methods. A green synthesis of iron nanoparticles has been prepared by using tea polyphenols without the use of additional polymers and surfactants [24]. The iron nanoparticles are used to catalyze the hydrogen peroxide for treatment of organic contamination. Iron nanoparticles have been used as environmentally benign catalysts for alkene and alkyne hydrogenations [14]. Iron nanoparticles that have been synthesized used as catalysts for environmentally benign alkene and alkyne hydrogenation reactions [25].

Rhodium nanoparticles

CaO and co-workers have reported the catalytic activity of rhodium nanoparticles deposited on modified SiO₂ for hydrogenation of nitrile butadiene rubber (NBR) [26]. Kang et al. investigated the morphology control synthesis of Rh nanostructures for cancer treatment [27]. Rhodium nanoparticles were used in Suzuki-Miyamuri reaction and hydrogenation of Benzene by Gniewek and coworkers [28]. Rh nanoparticles can be synthesized using a variety of green methods such as the hydrogen reduction method in water as solvent, ethanol reduction method in an ethanol water mixture in which the ethanol can be rotovaped, and several other green methods. Rhodium nanoparticles adsorbed onto titanium dioxide supports are synthesized using water as the solvent [29].

Zinc oxide nanoparticles

Zinc oxide nanoparticles (ZnO NPs) are cost effective and relatively less toxicity, significant biocompatibility reveal their remarkable biomedical applications, such as anticancer, drug delivery, antibacterial, diabetes treatment and anti-inflammation [30-35].

Due to the strong UV absorption properties of Zinc Oxide, they are used in cosmetics and sunscreen [36-38]. In addition, these particles also show excellent luminescent properties and used for bioimaging [39,40].

Zinc is the most important component of various enzyme systems, it takes part in body’s metabolism and plays essential roles in proteins and nucleic acid synthesis, hematopoiesis, and neurogenesis [41,42].

Johnson et al. developed a new method for the green synthesis of ZnO nanoparticles. In this method, a new leucine-based diamine amphiphile was synthesized and self-assembled. In the presence of Zn²⁺ ions, the leucine-based diamine amphiphile assembled into nanofibers that efficiently formed ZnO nanoparticles on heating with Zn(CH₃COO)₂ [43].

Platinum nanoparticles

Platinum nanoparticles (PtNs) possess a wide range of properties that can be used for various applications such as catalysts in organic catalysis, fuel cells, hydrogen storage, electrical conductivity, optics and nonlinear optics, coating, plastics, textile, biosensors and biomedicine [44-50]. Engelbrekt and co-workers demonstrated the synthesis of PtNPs using a variety of green methods such as the hydrogen reduction method in water as solvent, ethanol reduction method in an ethanol- water mixture. Monodisperse green Pt nanoparticles were synthesized by using glucose as the reducing agent and starch as the protective agent [51,52]. This synthesis method is environmentally friendly, highly reproducible, and easy to scale up. These nanocatalysts were tested for reduction and oxidation reactions and were found to have high catalytic activity. Moreover, these Pt nanoparticles are stabilized with ionic liquids and used as catalysts for four-electron reduction of dioxygen to water [53].

Gold nanoparticles

In recent years, AuNPs had attracted an immense interests in different fields of science, due to their unique features such as high X-ray absorption coefficient, ease of synthetic strategy, enabling precise control over the particle's physico-chemical properties, strong binding affinity to thiols, disulfides and amines, unique tunable optical and distinct electronic properties [54-60]. The optical-electronics properties of gold nanoparticles are being explored extensively for high technology applications such as sensory probes, electronic conductors, therapeutic agents, organic photovoltaics, Fuel cells, drug delivery in biological and medical applications, and catalysis [61-65].

Itoh et al. investigated the synthesis and functions of gold nanoparticles with ionic liquids based on the imidazolium cation.

At room temperature green imidazolium-based ionic liquids such as 1-butyl-3-methylimidazolium hexafluorophosphate are used as liquid media for the synthesis of gold nanoparticles which can be used in dyes [66].

The gold nanoparticles were prepared by the addition of HAuCl₄ to green tea leaves extract at room temperature. The synthesis of the Au nanoparticles does not involve any toxic chemicals/ organic solvents so it is a green synthetic process. The gold nanoparticles are used as catalysts for the reduction of methylene blue dye [67]. Au nanoparticles have been synthesized by a green photo catalytic method in which the synthesis is conducted in water [68]. Calcium-alginate stabilized gold nanoparticles are prepared using a photochemical green synthetic method [69]. Zhan and coworkers used Au nanoparticles as catalysts for the 4-nitrophenol reduction reaction. They have prepared Gold/TS-1 nanoparticles using two green routes which are sol-immobilization method and adsorption reduction method [70]. This gold nanoparticle catalyst show excellent performance for the propylene oxidation reaction.

Silver nanoparticles

Silver nanoparticles have commercialization applications for instance, sterilizing nanomaterials in consuming and medical products, textiles, food storage bags, refrigerator surfaces, and personal care products [71-74]. Additionally, they show optical, thermal, and catalytic properties and antimicrobial ability [75-79]. Silver nanoparticles have been synthesized using several green methods such as the seed-mediated growth method, in the presence of ionic liquids, and other reduction methods such as hydrazine reduction method, and sodium borohydride reduction method. Ag nanoparticles have been synthesized by a green photocatalytic method in which reaction is conducted in water [68]. Calciumalginate stabilized silver nanoparticles are prepared using a photochemical green synthetic method [69]. These nanoparticles are used as catalysts for the 4-nitrophenol reduction reaction.

Aluminium nanoparticles

Solvent-free methods as well as methods involving the use of water as solvent have been used to synthesize aluminum oxide nanoparticles. Aluminum oxide nanoparticles are synthesized in water as the solvent which makes it a green nanocatalyst [80].

Bimetallic nanoparticles

Bimetallic nanoparticles (Figure 2) have been prepared by the ethanol reduction method, hydrogen reduction method, and other green methods. These nanoparticles have been used as catalysts in several organic chemistry, including, oxidation of carbon monoxide in aqueous solutions, hydrogenation of alkenes in organic or biphasic solutions and hydrosilylation of olefins in organic solutions [81,82].

Figure 2: Bimetallic Nanoparticles.

Nickel platinum nanoparticles

Nickel encapsulated by Pt (NiPt) has been synthesized using a green colloidal method [83]. Pt NPs are very expensive as electrocatalysts so the remedy for this is to diminish the cost by the synthesis of Ni-Pt bimetallic nanoparticles.

Gold-palladium nanoparticles

Au-Pd nanoparticles are preared in the absence of organic ligands and adsorbed onto TiO₂ supports and is found to be stable in oxidative catalysis conditions [84]. It was investigated that 70% gold, 30% Pd composition of the bimetallic nanoparticles show the highest catalytic activity for the oxidative catalysis.

Application of various nanoparticles in green reactions Applications of different nanoparticles in green reactions are brief in Figure 3 and summarized in Tables 1-15 [85-145].

Figure 3: Varoius nanoparticles green reactions.

Conclusion

There been many different types of metal nanoparticles that have been used as catalysts for many reactions. In many cases, the metal nanoparticles are synthesized in aqueous solution in which water is the solvent, or is conducted in the presence of ionic liquids. There have also been cases where the nanoparticles are used as catalysts for different types of green reactions. Green reaction conditions include using water as the solvent, using solvent that is organicfree, conducting the reaction using ionic liquids, and running the reaction at atmospheric pressure. While there has been a lot of progress in applying the use of green chemistry to catalysis with nanoparticles, there is lot more room to further expand this field. In this review article, we have focused on the synthesis of various nanoparticles and their use in organic synthesis. Still there is need to explore and to synthesize new nanocatalysts with more properties. This review provides a comprehensive understanding on organic reactions which are catalyzed using environmentally friendly nanoparticles and nanocatalysts.

Acknowledgements

We would like to thank to NPIU-TEQIP, AICTE, MHRD for research fund in CRS Project (CRS ID: 1-5724887263).

Conflict of Interest

No authors have stated any conflicts of interest.

Contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

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