Microwave Synthesis of Trimesic acid capped silver nanofluids: Characterization and Catalytic Applications

doi:10.21203/rs.3.rs-2098197/v1

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Microwave Synthesis of Trimesic acid capped silver nanofluids: Characterization and Catalytic Applications

https://doi.org/10.21203/rs.3.rs-2098197/v1

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A simple, fast, efficient and cost-effective synthetic strategy based on microwave irradiation is described for the preparation of silver encapsulated in trimesic acid nanofluid (Ag-TMA NF). The was confirmed by The surface plasmon resonance peak at 440 nm was indicative of formation of Ag NF and was further characterized by Transmission electron microscopy, Selected Area Electron Diffraction and Raman spectroscopic techniques. The resultant Ag-TMA NF consisted of pseudo spherical and ellipsoidal particles of size ~3.64 nm oriented in fcc plane (111). The trimesic acid capped silver nanoparticles were investigated for pseudo homogeneous catalytic reduction of nitro aromatic compounds.

nanofluid

silver

pseudocatalysis

nitro deriivatives

trimesic acid

The use of non-supported metal colloids has attracted attention as green catalysts at the frontier between homogeneous and heterogeneous catalysis. This is due to the ease of their preparation and high catalytic performances resulting from facile access of reactants to the nanoparticle surfaces [1].

Nanofluid (NF) is a form of stable colloidal pseudo-homogeneous phase system comprising of metal nanoparticles in some base fluid [2] which have received attention due to their satisfactory dispersion stability with increased surface area resulting in improved mass transfer and increased adsorption and viscosity properties and applications in heat transfer and catalysis.

Noble metal colloids are usually synthesised in high boiling solvents with such as ethylene glycol or oleylamine. Alkaline ethylene glycol functions both as a solvent and reducing agent, with the reaction products stabilizing the NPs [3] while water as the solvent requires surfactants, such as glucose based, to stabilize the NPs [4]. DTPA capped silver nanofluids in water have been used as sensors for detection of chromium species [5]. Nanofluids supported on Al₂O₃ have been used as catalysts for the removal of 4 nitrophenol [6]. Cu –Ag and Au-Ag based bimetallic nanoparticle nanofluids have been used for heat transfer and catalytic reduction of 4 nitrophenol [7].

In the present work we have prepared stable AgNF using trimesic acid (TMA) as stabilizer with the help of microwave energy. The potential of Ag-TMA NF has been investigated for catalytic reduction of model aromatic nitro compounds.

Silver nitrate (Spectrochem; 99.9%), Trimesic acid (Sigma aldrich), were used in this study without further purification. Microwave make ONIDA (1200W, 2450 MHz) used here for nanoparticle synthesis.

Microwave synthesis of Ag-TMA NF

AgNF synthesis was carried out by mixing 0.5 mL each of 0.03 M AgNO₃ solution and 0.03 M Trimesic acid (prepared in 0.2 M NaOH) in 50 mL conductivity water. The solution was then irradiated under 100 W power in microwave oven for 120 seconds. The yellowish-brown colored solution indicated the formation of Ag-TMA NF. The resultant solution is diluted to 50 mL and used for experiments and characterization.

Characterization of silver nanofluid

The synthesized AgNF was characterized by UV visible spectral analysis using UV visible spectrophotometer make JASCO V-630 at wavelength of 200–800 nm. Size, shape and crystallinity of AgNF were examined using Transmission electron microscope make Philips CM 200. The surface charge and distribution of particle size were measured by particle size analyser model ZetaPlus 90Plus/BI-MAS BrookHaven. Raman spectroscopy analysis was used to confirm the functional groups present using Micro raman model STR 500 (Atrix corporation with) Nd-YAG laser (785 nm wavelength).

Catalytic experiments

The catalytic activity of trimesic acid capped AgNF was examined by reduction of Nitro derivatives (p-Nitroaniline, m-Nitroaniline, p-Nitrophenol) and Nitroso derivative, 1-Nitroso-2-naphthol (Fig. 1) into their respective amino derivatives using NaBH₄ and AgNF. In a typical experiment, 0.2 mL of 100 ppm of the nitro compound was diluted to 2 ml and transferred into cuvette followed by addition of 0.2 mL of 0.1 M NaBH₄. Thereafter 0.2 mL of AgNF solution was added to evaluate its catalytic reduction potential towards nitro compounds. The progress of the reactions was monitored at 1 minute intervals using UV–visible spectrophotometer.

Characterization of AgNF

The Surface Plasmon Resonance of AgNF resulted in absorption in the visible region [8]. On addition of trimesic acid to silver nitrate solution, a yellowish-brown color, indicative of formation of AgNF was observed. Ag-TMA NF exhibited an SPR peak (Fig. 2a) at 440 nm characteristic of silver nanoparticles and at 900 nm in the near IR region which is attributed to SPR of non-spherical particles [9].

The average hydrodynamic size of silver nanoparticles in AgNF was observed to be 128.6 nm (Fig. S1).

TEM images of Ag nanofluid and the SAED pattern depicted in Fig. 2c indicated the particles to be pseudospherical and ellipsoidal with a particle size of about 3.64 nm. The SAED pattern indicated cluster of minute crystals of Ag with face centred cubic geometry predominantly oriented in the (111) plane.

Raman spectral analysis of Ag_TMA NF (Fig. 2b) exhibited a strong peak at 152.60 cm^− 1 that was assigned to Ag-O stretching vibrations [10] indicating that the nature of bond between silver and carboxylate group of trimesic acid is ionic in nature. The absorption band at 1407.81 cm^− 1 was assigned to the symmetric stretch of carboxylate groups [11] while the peak at 1609.89 cm^− 1 was assigned to asymmetric stretch mode. The peaks observed at 932.81 cm^− 1, 1095.31cm^− 1 and 1258.33 cm^− 1 may be ascribed to C-C stretching, CH in-plane bending and deformation modes respectively.

Catalytic activity of Ag nanofluid

The catalytic reduction potential of Ag-TMA NF was monitored by UV- visible spectroscopy. The UV–Vis spectra and kinetic plots for gradual reduction of p-nitroaniline, m-nitroaniline, p-nitrophenol and 1- nitroso 2 napthol with time are shown in Fig. 3.

The conversion from nitro to amino compound occurs through formation of phenolate ion in case of p-Nitrophenol and 1-Nitroso-2-napthol. The characteristic absorption peak of PNP at ∼317 nm, exhibited a red shift to 400 nm indicating the formation of 4-nitrophenolate ion in alkaline medium on addition of NaBH₄. Addition of NaBH₄, resulted in decrease in absorbance of the peak at 400 nm and appearance of an additional peak with increasing absorbance at 298 nm indicating the formation of reduction product, para amino phenol. A similar observation was made in case of 1-Nitroso-2-napthol where the absorbance maxima at 375 nm was observed to red shift to 290 nm confirming the formation of m-Phenylenediamine while a redshift from 374 to 315 nm and 375 to 290 nm was observed in case of p-Nitroaniline and m-Nitroaniline respectively.

To check the effect of Ag-TMA content on reduction kinetics, the time for reduction was measured by UV spectroscopy taking 0.0225 mM, 0.03 mM and 0.0375 mM of the catalyst solution (Fig. 3e). From the spectra it was observed that the time for reduction decreased as the catalyst dose increased.

The catalytic reduction of aromatic nitro compounds are reported to follow pseudo-first-order kinetics [12].

The reduction rate for the reactants under study has been observed to follow the sequence p-nitrophenol, m-Nitroaniline, p-Nitroaniline, 1-Nitroso-2-napthol with rate constants 8.41×10^− 3, 8.91×10^− 4, 9.54×10^− 4, 5.59×10^− 4 sec^− 1 as seen from Fig. 4. The rate constants were comparable to literature reported silver-based catalysts as seen from Table 1.

Table 1

Rate constants of literature reported catalysts for degradation of various nitro pollutants:
Reactant	Catalyst	Rate constant		Reference
p-Nitrophenol	Ag-SiO₂ NP	6.02×10^− 3		[13]
	Au–Ag bimetallic NP	47.88		[14]
	Silver nanoparticles from the Psidium guajava leaf extract.	9.54		[15]
	Ag–γ-Fe₂O₃	1.44×10^− 3		[16]
	Ag-TMA nanofluid	8.41×10^− 3		This work
m-Nitroaniline	Ag-NP synthesized using Tamarindus indica seed coat extract	2.43×10^− 3	[17]
	Ag–γ-Fe₂O₃	0.904×10^− 3	[16]
	Ag-TMA nanofluid	8.91×10^− 4	This work
p-Nitroaniline	Ag-NP synthesized using Tamarindus indica seed coat extract	6.22× 10 − 3	[17]
	Ag-TMA nanofluid	9.54×10^− 4	This work
1-Nitroso-2-napthol	Ag-TMA nanofluid	5.59×10^− 4	This work

In this work, Ag-TMA NF was successfully prepared by microwave irradiation. The carboxylate anions of trimesic acid coordinated to the metal surface and aided in stabilization of silver and reduction under microwave energy. The duration of irradiation and power of microwaves influenced the formation of silver nanoparticles. Ag-TMA NF exhibited characteristic absorbance peaks at 440nm and 900 nm. TEM studies revealed their pseudo-spherical and ellipsoidal nature with fcc geometry (111). The Ag-TMA NF has ability to act as pseudo homogeneous catalyst for various organic transformations where it acts as reducing agent. The rate constants of reduction for p-nitrophenol, m-Nitroaniline, p-Nitroaniline, 1-Nitroso-2-napthol were calculated to be 8.41×10^− 3, 8.91×10^− 4, 9.54×10^− 4, 5.59×10^− 4 sec^− 1 respectively and were found to be comparable to literature reported silver-based catalysts Work is in progress for the preparation of magnetic Ag-TMA to achieve recyclability of the catalyst.

Acknowledgement: One of the authors Mohini Sadhu, would like to acknowledge DST-WTI and UGC-RFSMS, New Delhi for financial assistance and Department of Chemistry. The Maharaja Sayajirao University of Baroda for laboratory facilities. The authors would like to thank the ONGC for SEM facility, IIT Bombay for TEM analysis.

Ethical Approval

Not Applicable

Competing interests

The authors declare no conflict of interest

Authors' contributions

Padmaja Sudhakar and Mohini have equally contributed to the work

Funding

DST-WTI and UGC RFMS have funded the project

Availability of data and materials

The data obtained and utilized in this research has been shown in the figures and graphics and as supporting data

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No competing interests reported.

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Microwave Synthesis of Trimesic acid capped silver nanofluids: Characterization and Catalytic Applications

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1. Introduction

2. Materials And Methods

2. Results And Discussion

4. Conclusions And Further Work

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