Immobilization of Cr (III) on the surface of natural asphalt sulfonic acid (NASA): novel and efficient nanocatalyst for the oxidation of sulfides

doi:10.21203/rs.3.rs-2239330/v1

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Immobilization of Cr (III) on the surface of natural asphalt sulfonic acid (NASA): novel and efficient nanocatalyst for the oxidation of sulfides

https://doi.org/10.21203/rs.3.rs-2239330/v1

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In this research, we reported synthesis of NASA@Cr(III) nanoparticles using natural asphalt. Characterization of this heterogeneous nanocatalyst was performed using various analysis including FT-IR, SEM, EDX, XRD, TGA and BET techniques. Then activity of the NASA@Cr(III) nanoparticles in the chemoselective oxidation of sulfides, was investigated. Use of this nanocatalyst for the oxidation of sulfides have features such as green condition, high yield, low time and reusability of the catalyst for the several times.

Nanoparticles

Oxidation

Sulfides

Reusability

Catalysis has a specific role in academic and industrial researches. Todays, some of organic reactions is moving towards procedures that comply with the principal of green chemistry, especially use of green solvents and catalysts. Nanocatalysts open a new path for the chemists in order to achieve their goals. In the nanocatalytic systems, the surface area is especially increased due to the decrease size of the nanoparticles to the nanometer scale. Therefore, these catalysts have high catalytic activity, selectivity and stability [1-6].

Among the various nanomaterials, carbon nanostructures and their derivatives extracted high attention due to their extraordinary applications in the various fields. Carbon substrates have received a great attention in compare to other non-carbon substrates such as Al₂O₃ and silica. Silica has the lower thermal stability than carbon substrates and Al₂O₃ although has good thermal and mechanical stability but in recycling it cannot compete with carbon. Carbon substrates in catalytic applications have advantages such as high surface area, stability in acidic and alkaline environments, appropriate pore size distribution for specific reactions, stable structure at high temperatures and lower cost in compare to alumina and silica substrates [7-15].

In this research, we introduce natural asphalt as a new natural carbon support for preparation of nano catalyst. Natural asphalt often found in underground mines as a hard and black material which contain approximately 70-80 wt.% of carbon. The average molecular weight of natural asphalt is higher than other asphalt products and synthetic resins. Natural asphalt is ideal choice for the development of heterogeneous catalysts awning to reusability nature and green chemistry content. Therefore, we employed a new and selective catalyst for oxidation of sulfides.

The oxidation of sulfides into sulfoxides is a useful reaction because of the applications of sulfoxides in the various biological, medical and nanotechnological fields. Some sulfoxides have biological activities such as antibacterial, antifungal, antihypertensive, anti-ulcer and anti-atherosclerotic agents as well as psychotropics and vasodilators [16-18].

Herein, we reported selective oxidation of sulfides to sulfoxides by NASA@Cr(III) nanoparticles.

Chemicals and instrumentation

Natural asphalt was purchased from the Kimia Bitumen Zagros Cooperative Iran, and the chemicals from Fluka and Merck Chemical Companies. The reactions were monitored with TLC on silica-gel Polygram SILG/UV254 plates. Fourier-transform infrared spectroscopy (FTIR) was performed using FTIR-8300 spectrometer made by Shimadzu. Proton nuclear magnetic resonance (¹H NMR) spectroscopy was also performed on Bruker AVANCE DPX-400 and DPX-500 spectrometers. Chemical shifts were reported in ppm relative to TMS as the internal standard. The morphology of the catalyst was examined by performing scanning electron microscopy (SEM) using Mira 3-XMU. The elemental composition was determined using EDS and Mira 3-XMU. X-ray diffraction (XRD) was investigated using a Holland Philips X, and the thermogravimetric analysis (TGA) curve is recorded using a PL-STA 1500 device manufactured by Thermal Sciences.

Synthesis of NASA@Cr (III) NPs

Synthesis of NASA NPs

In order to synthesis of NASA, a mixture of (1 g) of natural asphalt and (10 mL) of concentrated of sulfuric acid stirred at 220 ^oC for the 2 h. Next, the reaction mixture cooled to room temperature and poured with to (20 mL) of distilled water. Finally, for the extraction of the product, used of filtration, the product washed with water and dried at 100 ^oC in oven [39].

Synthesis of NASA@Cr(III) NPs

In this step, Cr(NO₃)₃ (0.2 g) was added to NASA (0.5 g) in (15 mL) DMF and the reaction mixture stirred at room temperature for 21 h. After completion, the product was separated using filtration, and dried at 60 ^oC in oven.

Synthesis of sulfoxide

A mixture of sulfide (1 mmol), H₂O₂ (0.4 mL) and NASA@Cr(III) (30 mg) in H₂O (2 mL) stirred at room temperature. After completion, the product extracted using H₂O and EtOAc. For the characterization of the product, used of NMR analysis.

In Scheme 1, General procedure for the synthesis of NASA@Cr(III) is shown. This nanocatalyst characterized by FT-IR, SEM, EDX, XRD, TGA and BET techniques.

FT-IR analysis

The FT-IR spectrum for the NASA@Cr(III) is shown in Figure 1. According to this Figure, the peak at near 3400 cm^-1 is belong to the surface hydroxyl and amine groups and the stretching vibrations at 1450-1640 cm^-1 are related to the aromatic rings (Fig.1a).

The stretching vibrations at 616 cm^-1 and 1126 cm^-1 attributed to the symmetric and asymmetric O=S=O bands (Fig.1b). In (Fig.1c) shifting some stretching vibrations to lower frequencies confirmed existence of Cr on the surface of the nanocatalyst.

SEM analysis

For the study the morphology and the size of NASA@Cr(III), used of Scanning electron microscopy (SEM) analysis. Figure 2 shows the SEM image of the catalyst. According to this image, morphology of NASA@Cr(III) sample consists of uniform spherical particles and the size of the nanoparticles is between 91 nm 191 nm.

EDX analysis

One of the suitable analyses for the elemental study of the catalyst, is the energy dispersive spectrum (EDS). Figure 3 shows the present of C, Cr, N and S species in the structure of NASA@Cr(III) nanocatalyst and approves successful synthesis of the nanoparticles. Also, the EDS mapping (Figure 4) confirmed existence of C, Cr, N and S in the NASA@Cr(III) structure.

XRD analysis

The crystalline structures of the NASA@Cr(III) was investigated by powder X-ray diffractometer (XRD). The XRD spectrum (Figure 5) shows peaks at 2θ= 24.65, 33.70, 36.25, 41.60, 50.30, 54.90, 63.50, 65.15 and 73.05 that are quite match with standard patterns and confirmed structure of the catalyst.

TGA analysis

Figure 6 shows the TGA curve of NASA@Cr(III) NPs from room temperature to 600 ^oC. This curve shows two weight losses. The first mass loss (4.06%) was happened in the below of 200 °C is related to the removal of physically adsorbed water and the solvent present inside the pores channels and the next weight loss (32.76%) was happened between 250-500 ^oC belong to the thermal decomposition of the organic groups on the surface of the catalyst.

BET analysis

The nitrogen adsorption and desorption isotherms of NASA@Cr(III) is shown in Figure 7. Based on the IUPAC classification, the samples displayed the isotherm type of IV. The BET specific surface areas and the average pore diameters of NASA@Cr(III) are 10.57 m²/g and 14.44 nm respectively. Moreover, the pore volumes of NASA@Cr(III) is 0.038 cm³g⁻¹.

Catalytic activity

After synthesis and characterization of NASA@Cr(III), its catalytic activity in oxidation of sulfides to sulfoxides was studied. For the gain to optimum conditions, oxidation of diphenyl sulfide using H₂O₂ and in the presence of various amounts of catalyst was investigated at room temperature that the best yield was obtained at water solvent using 30 mg of the nanocatalyst (Table 1). After reach to optimum conditions some derivatives of sulfoxides were synthesized that results are shown in Table 2.

3.8. Possible Mechanism

The possible mechanism for the oxidation of sulfides has been reported in the literature as shown in (Scheme 2) [24]. According to this mechanism, initial NASA@Cr(III) reacts with H₂O₂ and intermediate (A) is produced that convert to the intermediate (B). Next, sulfide reacted with intermediate (B) to produce compound (C). In the following by separation of the catalyst, sulfoxide is produced.

3.9. Recovery of the catalyst

One main aspect for the any catalyst, is the capability of the recovery and reusability. For this purpose, after completion of the reaction, the NASA@Cr(III) NPs was recovered and its catalytic activity in the model reaction was studied that results shown this nanocatalyst can be recovered and reused for the five times with maintaining its catalytic activity in the synthesis of product 2c (Figure 8). Also, the FT-IR, SEM and XRD analysis after recovery, confirmed stability of the catalyst (Figure 9, 10, 11).

3.10. Comparison of catalytic activity

In order to comparison the activity of NASA@Cr(III) NPs in the synthesis of sulfoxides with known other catalysts in the literature, the results obtained from the synthesis of methyl phenyl sulfoxide 2j by NASA@Cr(III) nanoparticles compared with the previous researches that outlined in the Table 3. The results that obtained from this Table shown use of NASA@Cr(III) for the oxidation of sulfides have benefits such as higher yield and lower time in compare with other catalytic systems.

In this research, NASA@Cr(III) synthesized in two steps. Initial, NASANPs were synthesized using sulfonation of natural asphalt. Then, NASAfunctionalized withCr(NO₃)₃. For the characterization of the nanocatalyst used of various techniques such as FT-IR, SEM, EDX, XRD, TGA and BET techniques. This catalyst shown high efficiency in the oxidation of sulfides to sulfoxide derivatives. Also, this catalyst can be separated from the reaction medium using filtration and reused for several times without significant loss in its activity. In addition, the synthesis of sulfoxides in the presence this nanocatalyst was performed in water under green conditions with good to excellent yields.

Acknowledgements

We thank the Ilam University for their financial support.

Ethical Approval

not applicable

Competing interests

The authors declare no conflict of interests, financial or otherwise in the manuscript.

Authors' contributions

M.S.-B. supervised the research project, made interpretation of data and corrections to the text and is the corresponding author of the manuscript. M.A and H.K. made the experiments, collected the data, and wrote the main manuscript text.

Funding

This research received no specific grant from any funding agency.

Availability of data and materials

All data generated or analyzed during this study are included in this published article [and its supplementary information files].

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Table 1 and 2 are available in the Supplementary Files section.

Table 3. Comparison of activity NASA@Cr(III) NPs with other catalysts for the synthesis of compound 2j

Entry	Catalyst	Time (h)	Yield (%)	Reference
1	Zr6-Irphen	6	98	[25]
2	TsOH	4	88	[26]
3	VO₂F(dmpz)₂	5	95	[27]
4	Copper–Schiff base complex	9	82	[28]
5	IL(R = t -Bu)-V(IV)	4	85	[29]
6	IL(R = NO₂ )-V(IV)	4	76	[29]
7	VO 2 F(dmpz) ₂	5	95	[30]
8	V(IV)O-MCM-41	8	95	[31]
9	Fe ₃O₄@SiO₂@VO(salen)	6	83	[32]
10	Fe₃O₄/salen of Cu(II)	3	83	[33]
11	NASA@Cr(III)	2.5	93	This work

Scheme 1 and 2 are available in the Supplementary Files section.

No competing interests reported.

SupportingInformation.docx
Table1to2.docx
Scheme1.png
Scheme 1. General procedure for the synthesis of NASA@Cr(III) NPs
Scheme2.png
Scheme 2. Possible mechanism for the oxidation of sulfides to sulfoxides using NASA@Cr(III)

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Immobilization of Cr (III) on the surface of natural asphalt sulfonic acid (NASA): novel and efficient nanocatalyst for the oxidation of sulfides

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Version 1

Abstract

Figures

Introduction

Experimental Section

Results And Discussion

FT-IR analysis

SEM analysis

EDX analysis

XRD analysis

TGA analysis

BET analysis

Catalytic activity

3.8. Possible Mechanism

3.9. Recovery of the catalyst

3.10. Comparison of catalytic activity

Conclusion

Declarations

References

Table 3

Schemes

Additional Declarations

Supplementary Files

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