Synthesis of Vanadium Pentoxide Nanoparticles as

Ozone: Science & Engineering The Journal of the International Ozone Association

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Synthesis of Vanadium Pentoxide Nanoparticles as Catalysts for the Ozonation of Palm Oil Bilal Wasmi, Ahmed A. Al-Amiery, Abdul Amir H. Kadhum, Mohd S. Takriff & Abu Bakar Mohamad To cite this article: Bilal Wasmi, Ahmed A. Al-Amiery, Abdul Amir H. Kadhum, Mohd S. Takriff & Abu Bakar Mohamad (2016) Synthesis of Vanadium Pentoxide Nanoparticles as Catalysts for the Ozonation of Palm Oil, Ozone: Science & Engineering, 38:1, 36-41, DOI: 10.1080/01919512.2015.1074536 To link to this article: http://dx.doi.org/10.1080/01919512.2015.1074536

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Date: 07 May 2017, At: 00:21

OZONE: SCIENCE & ENGINEERING 2016, VOL. 38, NO. 1, 36–41 http://dx.doi.org/10.1080/01919512.2015.1074536

Synthesis of Vanadium Pentoxide Nanoparticles as Catalysts for the Ozonation of Palm Oil Bilal Wasmi

a

, Ahmed A. Al-Amiery

ab

, Abdul Amir H. Kadhuma, Mohd S. Takriffa and Abu Bakar Mohamada

a Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia (UKM), Bangi, Selangor 43000, Malaysia; bEnvironmental Research Center, University of Technology (UOT), Baghdad 10001, Iraq

ABSTRACT

ARTICLE HISTORY

Vanadium pentoxide nanoparticles were synthesized using a solvo-thermal method and were characterized via X-ray powder diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). The ozonation of palm oil was performed by using vanadium pentoxide nanoparticles as catalysts to synthesize ethyl malonate. This procedure presented several advantages, such as simple operation for a precise ozonation, excellent yield, short reaction times and reusability because of the recyclability of palm oil. Ethyl malonate was synthesized via the one-step ozonolysis of palm oil and was spectroscopically characterized using gas chromatography-mass spectroscopy (GC-MS).

Received 8 May 2015 Accepted 24 June 2015

Introduction The widely available global applications for nanomaterials, which include their use in catalysis, energy production, medicine, environmental remediation, and the automotive industry, represent novel opportunities to create better materials and products, including automotive parts, defense applications, drug delivery devices, coatings, computers, clothing, cosmetics, sports equipment, and medical devices (Kumar et al. 2014; Mishra et al. 2014; Nadagouda et al. 2013). The easily changed oxidation state of vanadium leads to a wealth of oxides; hence, vanadium shows 20 oxides with many different crystal structures in the phase diagram of the vanadiumoxygen system (Bezerra et al. 2012). In biological media, it is very difficult to interpret the data obtained for vanadium oxides. Vanadium pentoxide (V2O5) has the ability to reversibly change its optical and electronic behavior in response to a variety of stimuli, including externally applied electric field (Xiong et al. 2008), ultraviolet light irradiation (Cheremisin et al. 2009), and thermal treatment (Cui et al. 2008). Because of its ability to change its electrical resistance, vanadium pentoxide is a promising candidate for gas sensing applications. Adopting vanadium oxide with metal oxides led to its use in resistive sensors. A reduction of the crystal size of V2O5, when processed as nanotubes, nanowires, and nanobelts, to maximize its surface area has been successfully used to detect ethanol (Raj et al. 2010), ammonia

KEYWORDS

Ozone; Ethyl Malonate; Palm Oil; Synthesis; Vanadium Pentoxide Nanoparticles

(Shimizu et al. 2009), and amines (Raible et al. 2005). Of great interest to synthetic organic chemistry is ozonolysis due to oxidatively cleaving carbon-carbon double bonds. Ozonolysis as an oxidation method is generally used to prepare biologically active molecules because the oxidation of organic compounds (Bailey 1978) continues to be a subject of significant interest from mechanistic, synthetic and environmental perspectives (Johnson and Marston 2008). The importance of ozone for the oxidation of olefins both in the troposphere and in solution has led to many experimental and theoretical studies of their kinetics and mechanism (Reichardt 2004). The present work addresses vanadium pentoxide nanoparticle synthesis for use as a catalyst in the novel one-step synthesis of ethyl malonic acid. Ethyl malonic acid was directly synthesized and esterified via the ozonolysis of palm oil. In continuation of previous studies on ozonation (Kadhum et al. 2012; Wasmi et al. 2014), we have focused on synthesis of malonic acid via ozonation catalyzed by vanadium pentoxide nanoparticles. The main advantage of using vanadium pentoxide nanoparticles as the catalyst for this esterification is to shorten the reaction time. Using vanadium pentoxide nanoparticles also has minor advantages, such as simple synthetic operation, excellent yields and recyclability. The structures and sizes of the vanadium nanoparticles were investigated via field emission scanning electron microscopy (FE-SEM) and X-ray powder diffraction (XRD). The ethyl malonic acid was

CONTACT Ahmed A. Al-Amiery [email protected] Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia (UKM), Bangi, Selangor 43000, Malaysia. Color versions of one or more of the figures in the article can be found online at www.tandfonline.com/BOSE © 2016 International Ozone Association

OZONE: SCIENCE & ENGINEERING

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spectroscopically characterized via gas chromatographymass spectroscopy (GC-MS).

subsequently subjected to a liquid-liquid extraction using hexane (Al-Amiery et al. 2015).

Experimental

Catalysis synthesis

Materials

A solvothermal technique was used for the synthesis of vanadium pentoxide nanoparticles. This technique involve stirring of 6 mM of ammonium m-vanadate in 40 ml ethane-1,2-diol for 30 min. After the solution become yellow, it was transferred to an autoclave at 180 °C for 24 h. The blue color precipitate was separated out, centrifuged with ethanol, and then calcinated at 600 °C for 1 h to form V2O5 nanorods.

The starting material, palm oil, was purchased from LAM SOON Company, and all of the chemicals were purchased from Sigma Aldrich. Thin-layer chromatography (TLC) was used to check purities of the compounds on silica gel G plates with different system solvents as the mobile phase (toluene-acetone 75:25 (v/v)), and the spots were visualized under UV light at 254 and 365 nm. The GC/MS analyses were performed using an Agilent 7890A gas chromatograph (GC) directly coupled to an Agilent 5975C inert MSD mass spectrometer (MS) system with a triple-axis detector. The column was a DB-5 MS UI model with a 5% phenyl methyl polysiloxane stationary phase.

Methods The size, content and shape of the vanadium pentoxide and ruthenium-doped vanadium oxide were confirmed using X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM). The product was purified, separated and characterized via gas chromatography-mass spectrometry (GC-MS).

Ozonolysis Oxygen gas was fed into the electric ozone generator at a flow rate of 500 ml/min and a pressure of 0.03 MPa to generate the ozone gas that was directed into the reactor containing palm olein as fine bubbles. The reaction temperature was maintained at 150 °C for 2 h with vigorous stirring. The unreacted ozone was decomposed before emission into the atmosphere. The ozonation products were further oxidized for 30 min using a 10:90 (w/w) ratio of hydrogen peroxide to ozonolysis products, as shown in Figure 1. The products were

Figure 1. Synthesis of propanedioic acid.

Results and discussion Chemical characterization and chemistry of ozonolysis The synthetic reaction sequence for ethyl propanedioic ester through high-pressure ozonolysis with vanadium pentoxide nanoparticles used as the catalyst in ethanol is outlined in Figure 1. Palm oil was the initiator material and was financially accessible. Palm oil is made of unsaturated fats, specifically, tetradecanoic acid, palmitic acid, stearic acid, oleic acid and octadeca-9,12-dienoic acid. Unsaturated oils can be ozonized with a catalyst. The oxidation of octadeca-9,12-dienoic yields nonanedioic acid, propanedioic acid and hexanoic acid. To characterize the products, we used mass spectroscopy techniques. The mass spectroscopy techniques provided great confirmation of the propanedioic ester formation. The ozonolysis mechanism hypothesized by Criegee is the cleavage of olefin double bonds through their response with ozone (Supothina et al. 2007). The profoundly exothermic 1,3-dipolar cycloaddition of ozone to octadeca-9,12-dienoic acid gave the Criegee intermediate product, which could break down into carbonyls. The carbonyls responded through a 1,3-dipolar cycloaddition to a relatively stable ozonide intermediate. Characterization of ethyl propanedioic ester by mass spectroscopy was utilized for the identification of ethyl

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B. WASMI ET AL.

Figure 2. Mass spectrum of propanedioic ester.

propanedioic ester (Figure 2). The spectrum of the researched ethyl propanedioic ester showed molecular ion peaks (with m/z qualities relating to the molecular weight) for ethyl propanedioic ester. The abundant ethyl propanedioic ester fragment was at (m/z 160). As indicated by the fragmentation top at (m/z 145), the sections were caused by the breaking of the bond between the carbon-carbon atoms in the ethyl ester group. The fracture peaks at (m/z 133 and 115) were between the oxygen-hydrogen bond and the carbon-oxygen bond, respectively, in the ester group cleavage. The fragmentation peaks at (m/z 88, m/z 70, and m/z 60) were due to the loss of hydroxyl, carbonyl, and ethyl groups, separately. Finally, the fragmentation peak at (m/z 43) was due to the cleavage of the hydroxyl group and the intermediate cyclization to give an epoxy compound that decomposed to formyl aldehyde (m/z 29) (Figure 3).

FE-SEM (field emission scanning electron microscopy) morphologies of the synthesized vanadium pentoxide nanoparticles The morphology of the vanadium pentoxide nanoparticles was inspected through FE-SEM. Figure 4(a-e) demonstrates the SEM images for the vanadium pentoxide nanoparticles, with the nanorod structures unmistakably noticeable. The FE-SEM images affirmed that the vanadium pentoxide nanoparticles were almost perfect rods and had a normal grain size of approximately 60–90 nm. Figure 4(a-e) shows different types of vanadium pentoxide nanoparticle nanostructures that were acquired by the reaction of ammonium m-vanadate salt with ethane-1,2-diol for 30 min. Figure 4(a) demonstrates the morphology of the nanorod particles. The nanoparticles were altogether spherical rods and had diameters of 75 nm, as observed in Figure 4(a,b). Figure 4(c) shows the


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Figure 3. Fragmentation of propanedioic ester.

Figure 4 (a-e). Field emission scanning electron microscopy morphologies of the synthesized vanadium pentoxide nanoparticles.

prepared vanadium pentoxide nanoparticles at the resolution of 50.00 KX. Figure 4(d) demonstrates the prepared nanoparticles at a resolution of 25.00 KX, and Figure 4(e) demonstrates the prepared vanadium pentoxide nanoparticles at a resolution of 10.00 KX. These nanoparticles were similar to those reported in reference (Ng et al. 2009), however, our prepared nanoparticles had diverse

shapes. Similarly, in contrast with the particular case published in reference (Asim et al. 2009), our prepared nanoparticles were smaller in diameter. The impact of reaction time assumes a prominent role in the morphology of the nanoparticles. The impact of reaction conditions on the physical properties of the prepared nanoparticles and the mechanism are yet to be examined.

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Structural investigation of vanadium pentoxide nanoparticles by XRD The molecule size was ascertained utilizing the Scherrer mathematical statement, considering the XRD information, as in Equation [1]: D ¼ Kλ=βcosθ

½1

where I is the particle size, K is a dimensionless shape variable with a value near solidarity, λ is the X-beam wavelength, β is the line width at half maximum intensity (FWHM), θ is the Bragg plot, » is equal to 0.92 nm, β is FWHM(30) = 0.136, and θ is equal to 30. Therefore, D is equal to a 63.72 nm molecule size, and the ISCD/JCPDS card number for the blended oxide particles is 01–072-0433. The XRD pattern for the maximum intensity is indicated in Figure 5(a) and

demonstrated a single-phase with a monoclinic structure. The peak intensities and positions agreed well with the Euclid library information in Figure 5(b). Catalytic oxidation of palm oil using ozone Figure 6 demonstrates the impact of oxidation at different catalyst on the palm oil conversion utilizing ozone. The catalytic activities of V2O5 at the higher percentage were much higher than that of the low percentage. Figure 6 also demonstrates that the ozone conversion extremely decently coordinated to that of palm oil, with higher ozone change additionally indicating higher palm oil change. Conclusions This study utilized another method to prepare ethyl propanedioic ester through the direct ozonolysis of

Figure 5(a,b). The structural investigation of vanadium pentoxide nanoparticles by XRD.

100 Reaction conversion (%)

98 96 94 92 90 88

Vanadium pentoxide

86 84 82 80

0

0.05 0.1 0.15 0.2 0.25 0.3 Loaded vanadium pentoxide amount (gm)

Figure 6. Catalytic oxidation of palm oil at varying catalyst amounts.

0.35


palm olein, in which the bubbles of ozone assumed a dynamic role to cleave the double bonds. This technique was surprisingly utilized with vanadium pentoxide nanoparticles as the catalyst for the esterification of propanedioic acid and had the favorable advantages of simplicity in preparation, a good 30% yield, shorter reaction time and recyclability. Ethyl propanedioic ester was identified utilizing mass spectroscopy. The synthesized vanadium pentoxide nanoparticles had a rod shape and a diameter of 75 nm, and they were examined by FE-SEM and XRD, separately.

ORCID Bilal Wasmi http://orcid.org/0000-0002-0987-9803 http://orcid.org/0000-0003Ahmed A. Al-Amiery 1033-4904

Funding This study was supported by the University of Technology, Baghdad, Iraq, and Universiti Kebangsaan Malaysia under the DIP-2012-02 Grant.

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