Green Synthesis by Microwave Irradiation of TiO<sub>2</sub> Using <i>Cinnamomum verum</i> and the Application in Photocatalysis

González-Anota, Dante E.; Paredes-Carrera, Silvia P.; Pérez-Gutierrez, Rosa M.; Arciniega-Caballero, Brandon; Borja-Urby, Raul; Sánchez-Ochoa, Jesús C.; Rojas-García, Elizabeth

doi:https://doi.org/10.1155/2023/2245685

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Metal and Metal Oxide Nanomaterials for the Environment and Engineering Applications

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Research Article | Open Access

Volume 2023 | Article ID 2245685 | https://doi.org/10.1155/2023/2245685

Green Synthesis by Microwave Irradiation of TiO₂ Using Cinnamomum verum and the Application in Photocatalysis

Dante E. González-Anota,¹Silvia P. Paredes-Carrera,¹Rosa M. Pérez-Gutierrez,²Brandon Arciniega-Caballero,¹Raul Borja-Urby,³Jesús C. Sánchez-Ochoa,¹and Elizabeth Rojas-García⁴

Academic Editor: B. R. Ramesh Bapu

Received14 Oct 2022

Revised21 Nov 2022

Accepted03 Apr 2023

Published12 May 2023

Abstract

The extraction process of bioactives from the aqueous extract of cinnamon (Cinnamomum verum) was optimized using the Design Expert 11 program and analysis of variance (ANOVA) by considering the following parameters: cinnamon weight (g), power (W), and time (s) of microwave irradiation. The optimal conditions are cinnamon weight of 4.5 grams, time of 600 seconds, and power of 150 watts of microwave irradiation. With Cinnamomum verum extract under optimal conditions and titanium (IV) tetrachloride as a precursor, TiO₂ nanostructures were synthesized using the sol-gel method assisted by microwave irradiation in the crystallization stage with a power and irradiation time of 150 W and 600 sec, respectively. Similarly, a sample without extract was synthesized under the same conditions. The following techniques characterized the materials: X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, UV-vis diffuse reflectance, Raman spectrometry, and high-resolution transmission electron microscopy (HRTEM). It was feasible to obtain nanocrystalline solids of TiO₂ anatase phase with and without cinnamon extract; the particle size and the crystallinity were influenced by the bioactive agents during the synthesis (aqueous extract of Cinnamomum verum) and the synthesis method (microwave irradiation); a smaller crystal size, a smaller particle size, a higher crystalline order, and a lower band gap were achieved for the material synthesized with cinnamon extract compared to the material synthesized without extract and other methods. The synthesized materials were evaluated in the photodegradation of methyl orange (as a model of photodegradation), employing as reference parameters the commercial TiO₂ brand Sigma-Aldrich phase anatase and the photolysis of the system. The amount of dye adsorbed in the tested materials was quantified, finding an equilibrium time of 15 min, where the TiO₂ synthesized with Cinnamomum verum extract was the material that most adsorbed methyl orange at 7.5%. In the case of photodegradation, the TiO₂ synthesized with cinnamon extract apparently promoted the total mineralization of methyl orange in 40 minutes of reaction, making it the best material of those evaluated in the photodegradation. In all cases, the degradation models were adjusted to a first-order kinetic model, where it was confirmed that the highest reaction rate corresponded to TiO₂ synthesized with Cinnamomum verum.

1. Introduction

The generation of nanomaterials through green synthesis uses low-cost sustainable methodologies with low or zero emission of waste and toxic by-products [1, 2] as an alternative to existing synthesis methods such as coprecipitation, solvothermal, and the sol-gel method, among others, that require a high energy expenditure and purification and generate toxic by-products and waste for the environment [3].

In green synthesis, natural sources such as microorganisms (bacteria, fungi, and yeasts), extracts of plants (flowers, stems, and leaves), or products of metabolism or parts of them (enzymes) are used [4, 5]. Natural extracts contain bioactive compounds present in plants, such as alkaloids, polyphenols, terpenoids, antioxidants, sugars, flavonoids, organic acids, and quinones, together with low molecular weight proteins [6] which can be used in the reduction of precursor agents for the synthesis of nanomaterials [4, 7] because they act as electron donors [8], stabilizers, and capping agents [9–11]. Coating agents prevent coagulation and spontaneous flocculation of the precursors and intermediate products during the synthesis processes through electrostatic interaction [12].

A viable biological material for the green synthesis of nanomaterials is cinnamon (Cinnamomum verum) due to its high content of bioactive compounds such as aldehydes, alcohols, esters, acids, monoterpenes, diterpenes, sesquiterpenes, benzopyrenes, hydrocarbons, flavonoids (procyanidin dimers type A and B), and phenolic compounds (eugenol and pyrogallol). Previous studies have shown that the aqueous extract of Cinnamomum verum has high antioxidant activity [13, 14], which suggests its application in the synthesis of nanomaterials as an effective reducing agent for metallic particles and promoting chemical processes such as hydrolysis [15]; in addition, no reported applications for the synthesis of nanomaterials were found for this compound.

The nanomaterial employed in this work was titanium dioxide (TiO₂), with high photocatalytic activity (>50–80% in 2 H) [16, 17] and can be found in three crystalline structures: anatase, rutile, and brookite [18]. The anatase phase is the one with the highest photoactivity [19]. However, although TiO₂ is an excellent photocatalytic material, it also has some drawbacks since it has a limited absorption in the visible spectrum with a band gap of 3.2 eV [20], mainly absorbing UV radiation, with a high recombination rate of electron-hole pairs and presenting photo corrosion which decreases its photocatalytic efficiency. For this reason, various works [21–23] have sought to generate a change in the band pap, morphology, texture, and/or particle size [20, 24]. This is through doping (with noble metals such as silver and gold), coupling it to other semiconductors and/or materials such as graphene (composites and hybrid materials), with morphosynthesis (polymeric templates), and/or obtaining with different synthesis methodologies and precursors [25, 26]. This is where microwave-assisted green synthesis provides a viable and novel technology.

Microwave irradiation has been implemented in the search for methodologies that represent a lower energy expenditure and allows the manipulation of properties such as the texture and morphology of nanoparticles [27]. Microwaves are a type of electromagnetic radiation between 0.3 and 300 GHz; the heating mechanism involves two main processes: dipolar polarization and ionic conduction. Irradiation of a sample with microwaves results in the alignment of the dipoles or ions in the electric field. Because electromagnetic radiation produces an oscillating field, the dipoles or ions continually try to realign themselves in the electric field. Depending on the oscillation phenomena in relation to the frequency of the irradiation, different amounts of heat are produced through molecular friction and dielectric loss [28, 29]; this superheat allows a fast reaction speed, reproducibility, and control of the morphology and texture depending on the parameters of power and irradiation time [28, 30], which makes it a suitable irradiation source both for the extraction of bioactive compounds and for the synthesis of nanomaterials [30–32].

Methyl orange was used as a photodegradation model for the synthesized materials [33, 34], belonging to the azo dyes, and these constitute between 60 and 70% of the dyes used in the industry, being one of the most important contaminants that reproduce in the environment [35–37]. It is worth mentioning that the objective of this research is focused on the properties of TiO₂ synthesized by green synthesis by microwave irradiation of TiO₂ using Cinnamomum verum and its potential application, constituting a starting point for future work. The quantification of the percentage of methyl orange degradation was evaluated by UV-vis spectroscopy (467 nm).

On the other hand, the optimization of the aqueous extract of Cinnamomun verum was carried out using the Box–Behnken Design (BBD) model, which is one of the methods for predicting response surface methodologies (RSMs). This model has its origin from the graphic perspective and an adjustment through empirical models. The response surface methodology (RSM), introduced by George E. P. Box and K. B. Wilson in the early 1950s, consists of the collection of statistical and mathematical techniques useful for modeling and analyzing experimental data, which determine the effects and response of quantitative variables to identify the optimal point. The advantage is the decrease in the number of experiments to evaluate their independent variables, and the disadvantage is the inability to provide a global optimal point. The RSM largely uses the BBD response surface, which is suitable for fitting quadratic and cubic models and is feasible to investigate and optimize variables in the experimental space with the fewest number of experiments without being an expert in statistics. The central composite design (CCD) is based on the same criteria as BBD; however, the main difference between them is the number of star points or center points in the experimental space, which gives CCD more points and, therefore, more experiments. Compared to the “one-variable-at-a-time” approach and the full factorial design, the BBD has more advantages due to the reduced number of experiments [38–46].

In this work, we sought to obtain photocatalytic nanomaterials such as TiO₂ via green synthesis by the sol-gel method assisted with microwave irradiation of the TiO₂ type through the use of bioactive compounds from the aqueous extract of Cinnamomum verum, which were optimized using the RSM statistical technique, with the premise of obtaining efficient and economically sustainable nanomaterials that improve the photocatalytic processes.

2. Experimental

2.1. Chemicals

The reagents used for the preparation of the precursor solutions for the extraction of bioactives from cinnamon and TiO₂ synthesis were as follows: TiCl₄Sigma-Aldrich 99.9%, C₁₄H₁₄N₃O₃SNa Sigma-Aldrich 99.9%, C₂H₅OH Sigma-Aldrich 98%, TiO₂Sigma-Aldrich 99.5%, and Caledon brand bidistilled, tridistilled, and deionized water.

2.2. Cinnamomum verum Aqueous Extract Optimization

Cinnamomum verum aqueous extract optimization by microwave irradiation was performed with the use of Design Expert software (Version 8.0.6, Stat-Ease Inc., Minneapolis, MN, USA). It employs the BBD as an algorithm, which is one of the methods for predicting response surface methodologies (RSMs) to examine the relationship between one or more response variables and a set of quantitative experimental parameters. The optimization was made using three independent variables and one response variable, with 17 runs to optimize the extraction conditions of bioactive (Table 1). Aqueous extracts of Cinnamomum verum were obtained in an SBL CW-2000A microwave reactor. The three independent variables were as follows: the weight of Cinnamomum verum (1.5, 3.0, and 4.5 g) with deionized water, microwave irradiation time (300, 600, and 900 s), and microwave irradiation power (150, 250, and 350 W); the response variable was the weight of the Cinnamomum verum extract. Regression analysis was made according to the experimental data, and the second-order polynomial model (equation (1)) was fitted to express the amount of extract obtained through the ANalysis Of VAriance (ANOVA) [47].where Y is the amount of Cinnamomum verum extract, a₀ is the intersection (constant), 𝑎₁X₁ to 𝑎₃X₃ are linear coefficients, to are quadratic coefficients and interaction coefficients, X₁ is the weight of the Cinnamomum verum (g), X₂ is microwave irradiation power (W) y, and X₃ is the microwave irradiation time (s).

2.3. Green Synthesis of TiO₂ Nanoparticles by the Sol-Gel Method Assisted by Microwave Irradiation and Cinnamomum verum Extract as Reductant

In the synthesis of TiO₂ nanoparticles (a code C-TiO₂ was assigned) using the sol-gel method assisted by microwave irradiation, 100 ml of Cinnamomum verum extract (prepared according to optimal results) was added to a flanged reactor, and the equivalent of 5% TiCl₄ was added dropwise, keeping the system under constant agitation for 40 minutes in a cryogenic bath at 4°C. Finally, the mixture was introduced into the SBL CW-2000A microwave reactor and irradiated for 10 minutes at 150 W. Washes were performed by centrifugation with a 1: 1 ethanol-water mixture at 15 000 rpm at room temperature for 15 minutes. The precipitate was dried in a convection oven for 5 hours at 70°C, and the resulting material was calcined for 4 hours at 450°C with a heating ramp of 30 minutes at 10°C·min⁻¹. The procedure was repeated without extract, and the code CO-TiO₂ was assigned to this sample. It is worth mentioning that in the evaluation, Sigma-Aldrich brand TiO₂ was used as a reference, which was identified as A-TiO₂.

2.4. Characterization of the Samples

The synthesized compounds were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), UV-vis diffuse reflectance spectroscopy (UV-vis), Raman spectroscopy, and High-resolution transmission electron microscopy (HRTEM). The XRD spectra were obtained on a PANalytical model X’Pert PRO diffractometer for thin films or crystalline coatings (λ = 1541 Å), and the infrared spectra were obtained on a Nicolet Magna-IR 550 spectrometer in a range of 4000 − 650 cm. UV-vis spectra were obtained via a Cary 100 UV-vis spectrophotometer, with an integrating sphere (Labsphere DRA-CA-30) and was operated over a wavelength interval between 200 and 800 nm. Raman spectra were recorded at ambient temperature on a Raman Thermo Nicolet Almaga between 100 cm⁻¹ and 1000 cm⁻¹ with an exposure time of 1 s; the emission wavelength was 532 nm, and a nominal power of 25 mW was applied with a Nd: YVO4 laser. HRTEM and BFTEM micrograms were obtained in a transmission electron microscope JEOL brand JEM-ARM200CF model at 200 kV.

2.5. Evaluation of the Adsorption-Photodegradation of Methyl Orange

2.5.1. Adsorption of Methyl Orange

The materials were left in the dark in contact with the 3 ppm solution of methyl orange and found that the equilibrium time was 15 min. The adsorption of methyl orange was quantified in a Perkin Elmer brand UV-vis Lambda XLS spectrophotometer at a wavelength of 467 nm. After the adsorption, the materials were subjected to the photodegradation process.

2.5.2. Photodegradation of Methyl Orange

The process was carried out in 15 ml vials in triplicate for each point. 10 ml of methyl orange at 3 ppm and 0.1 g of C-TiO₂ were added to each vial; the resulting suspensions were subjected to UV light irradiation in a Luz Chem brand photoreactor equipped with 2 Philips 125 W UV lamps and an agitation system. Every 10 minutes, 5 ml aliquots were taken in triplicate until reaching equilibrium (100 minutes of reaction), and each aliquot was filtered with a 45 μ hydrophobic membrane. The concentration of degraded methyl orange was quantified in a Perkin Elmer brand UV-vis Lambda XLS spectrophotometer at a wavelength of 467 nm. The above procedure was repeated for the CO-TiO₂ and A-TiO₂ photocatalysts and the photolysis.

3. Results and Discussion

3.1. Cinnamomum verum Aqueous Extract Optimization

According to Table 1, the highest amount of extracts was obtained for run number 3 with 0.0902 g of bioactive, with 4.5 g of ground cinnamon, power of 150 W, and microwave irradiation time of 600 s, followed by runs 9 and 13, and the one that obtained the least amount of cinnamon extract was run 5. ANOVA results considering the second-order polynomial model of the 17 runs are shown in Tables 2 and 3.

ANOVA results predicted a quadratic model (equation (2)) for the three independent variables (weight of Cinnamomum verum, microwave irradiation time, and microwave irradiation power). The results in Table 2 suggested that the generated model had a high value of the coefficient of determination R squared (0.8283). The results in Table 3 indicate that the model had a high F value (3.75) and a low value (0.0476) for the response indicating that the quadratic model is significant. This suggests that the model could predict 82% of the variations in the experimental data. In this sense, the quadratic model is significant during microwave extraction.

The analysis of variance (ANOVA) determined the following second-order polynomial model:

The analysis of the response surface and contour is shown in Figure 1. 3D dimensional graphs were obtained by the ANOVA for the 17 runs, and the relationship of the independent and dependent variables was studied for getting the Cinnamomum verum extract.

(a)

(b)

(c)

The analysis of the response surface and contour of the weight of the Cinnamomum verum extract shows the effect of these independent variables. It can be seen in the response surface graphs that the best results for the weight of the Cinnamomum verum extract tend to be red color, that is, lower microwave irradiation powers produce higher cinnamon extract weights, and the lowest value on the blue scale with higher irradiation power and lower Cinnamomum verum weights produces the lowest cinnamon extract weights (Figures 1(a)–1(c)).

When comparing the same weight of cinnamon and microwave irradiation power at different irradiation times at (A) 300 sec, it can be seen that the best results in terms of the greater amount of extract obtained tend to have higher cinnamon weights (4.5 g) and low microwave irradiation powers (150 W). In the case of (B) 600 sec and (C) 900 sec, the same trend can be observed. In general, the increase of the microwave irradiation time during the extraction of the bioactives promotes a decrease in the amount of extract obtained due to the degradation effect.

Preferably, when comparing the same weight of cinnamon and microwave irradiation power, the degradation of the resulting bioactives is promoted as the irradiation time increases.

Figure 2 shows the Pareto diagram, prepared with the variables X₁, X₂, and X₃ and the frequency of the response variable (amount of the Cinnamomum verum extract) for the 17 experiments proposed by the Design Expert program.

Based on the 80/20 Pareto principle to establish priorities in obtaining the greatest amount of the Cinnamomum verum extract, it corroborates the trend of the ARS graphs; that is, the greatest amount of the extract is obtained towards greater weights of cinnamon (4.5 g), at low microwave irradiation powers (150 W) and an irradiation time of 600 sec [48–51].

3.2. X-Ray Diffraction (XRD)

Figure 3 shows the normalized X-ray diffraction patterns of the C-TiO₂ and CO-TiO₂ samples.

Based on the JCPDS (Joint Committee on Powder Diffraction Standards) library, it can be seen that in all cases, the characteristic reflections of the anatase phase were obtained at 2θ = 25.3, 38.5, 48.03, 55.0, 62.11, 68.76, 75.05, and 82.16° (JCPD letter 00-021-1272) corresponding to a tetragonal unit cell. The CO-TiO₂ sample synthesized without the extract has a reflection attributed to the brookite phase (JCPD letter 01-075-2548) at 2θ = 31° (B), and for the C-TiO₂ sample, two reflections are observed at 2θ = 28 and 42° (R) identified for the rutile crystallographic phase (JCPD letter 00-021-1276), where the commercial sample A-TiO₂ is the lowest crystallinity. Comparing the intensity of the reflections (1 0 1), (1 0 3), (2 0 0), and (1 0 5) shows that the CO-TiO₂ sample is more ordered than the C-TiO₂ sample. The crystal size was determined by the Debye–Scherrer equation. The sample synthesized by microwave and the aqueous extract of Cinnamomum verum (C-TiO₂) presented a smaller crystal size (1.96 nm) than the one synthesized without extract CO-TiO₂ (2.35 nm), which indicates that the phenolic and flavonoid compounds contained in the cinnamon extract promote a smaller crystal size and improve the crystallinity since both samples were synthesized under the same microwave irradiation conditions [52]. Also, the reaction time is reduced from hours to minutes (10 minutes) during the synthesis of materials with the use of microwaves.

3.3. Fourier Transform Infrared (FTIR) Spectroscopy

Figure 4 shows the absorption bands of the functional groups present in TiO₂, obtained by Fourier transform infrared (FTIR) spectroscopy for samples A-TiO₂, C-TiO₂, CO-TiO₂, and the aqueous extract of cinnamon.

In the cinnamon extract, it is possible to observe the signal corresponding to the ⁻OH bonds of the phenolic compounds of the extract at 3244 cm⁻¹. At 2922 cm⁻¹, the signal for the C-H bond of the methylene group corresponds to terpenes. The phenolic compounds appear with the absorption bands for ⁻COOH bonds at 1350 cm⁻¹, for C-O at 1230 and 1055 cm⁻¹, and for the flavonoids, the signals for aromatic C=O bonds are presented at 1600 cm⁻¹ with its harmonics at 1500 and 1435 cm⁻¹. This indicates that the extract of Cinnamomum verum is composed of phenolic compounds, terpenes, and flavonoids, which have been reported to be able to promote the synthesis of TiO₂ [53].

In the case of the C-TiO₂ and CO-TiO₂ samples, the signal at 1104 cm⁻¹ indicates the distribution of TiO₂ nanoparticles in the anatase phase; this has already been reported by Raghunandan et al. [54]. The additional signals that appear in the C-TiO₂ sample at 1633, 1387, and 1250 cm⁻¹ could correspond to remnants of the extract.

3.4. High-Resolution Transmission Electron Microscopy

Figure 5 shows the images by bright-field micrographs (BFTEM) at different magnifications for the commercial samples A-TiO₂ (A and D) and the samples synthesized by microwave irradiation in 10 min: CO-TiO₂ (B and E) and C-TiO₂ (C and F).

At 20 and 10 nm scales, it can be seen that the sample synthesized with the Cinnamomum verum extract C-TiO₂ (C and F) is the one with the smallest particle size and with regular hemispherical shapes with an approximate size of 15 nm, followed by the synthesized sample without the extract CO-TiO₂ (B and E) with semielliptical irregular shapes and sizes from 20 to 40 nm and the commercial A-TiO₂ (A and D) with the least uniform shape and particle size ranging from 20 to 50 nm. At magnifications of 10 nm, it can be seen that the samples synthesized with microwaves CO-TiO₂ (E) and C-TiO₂ (F) planes of atoms with preferential orientation are observed.

Figure 6 shows the images by high-resolution transmission electron microscopy (HRTEM) at different magnifications of the C-TiO₂ sample: (A) 5 nm, (B) 1.5x, and (C) 5x. Additionally, the diffraction pattern obtained by TEM is shown in (D).

The digital enlargement of the microgram of a C-TiO₂ nanoparticle is shown (Figure 5(b)), in which the crystal lattice of this material can be observed, and the top view of the unit cell can be seen (Figure 5(c)), which corresponds to the tetragonal crystal system (marked in yellow) corresponding to the anatase phase for TiO₂, according to what was found by XRD. Therefore, the use of the aqueous extract of Cinnamomum verum during the synthesis assisted by microwave irradiation with titanium precursor (TiCl₄) promoted nanoparticles of uniform nanometric size (approximately 15 nm in diameter) with a high degree of crystallinity and preferential anatase phase. The diffraction pattern of the C-TiO₂ sample (Figure 5(d)) indicates that a polycrystalline sample of TiO₂ nanoparticles was obtained, confirming the polycrystalline nature of the material as shown in the HRTEM images (Figure (A)) [55–57].

3.5. UV-Vis Diffuse Reflectance Spectroscopy

Based on the diffuse reflectance data, it is possible to determine the optical band gap (Eg) of the A-TiO₂, C-TiO₂, and CO-TiO₂ samples using the Kubelka–Munk equation and the Tauc graphs following the formula: αhν = A (hν − Eg)^n/2 for semiconductors [58–60]; these values are represented in Figure 7.

The samples synthesized by microwave irradiation with C-TiO₂ and without the CO-TiO₂ extract have a band-gap value of 3.42 and 3.67 eV, respectively, both being higher than the commercial sample A-TiO₂ brand Sigma-Aldrich (3.19 eV), which would indicate in the theory that to photoactivate the C-TiO₂ and CO-TiO₂ samples with UV light, more energy will be required, whereas the commercial sample (A-TiO₂) needs less energy to be photoactivated by UV light.

The TEM images show that the CO-TiO₂ sample has sizes between 20 and 40 nm (Figures 5(b) and 5(e)) with a band gap equal to 3.67 eV. In the case of the sample synthesized by cinnamon C-TiO₂ of 15 nm (Figures 5(c) and 5(f)), its band-gap value decreases to 3.42 eV, which indicates that there is a correspondence between the particle size and the band-gap value. This is attributed to the effect of quantum confinement of the material promoted by miniaturization, having a greater uptake of UV light absorption for the sample synthesized with the Cinnamomum verum extract.

3.6. Raman Spectroscopy

In Figure 8, the Raman spectra of the C-TiO₂ and CO-TiO₂ samples are presented.

In all cases, the vibrations that characterize the typical tetragonal structure of the anatase phase can be seen; the signal that appears at 450 cm⁻¹ can be attributed to traces of the rutile crystallographic phase with a face-centered cubic structure, according to what is indicated in the X-ray diffraction spectra in the reflections at 28 and 42° (Figure 1) [61, 62]. The vibrations at 144 and 639 cm⁻¹ are generated by the symmetric stretching of the O-Ti-O bond; the vibration at 399 cm⁻¹ is caused by the symmetric bending of the O-Ti-O bonds; the vibration at 519 cm⁻¹ was generated by the asymmetric bending in the O-Ti-O bond, sending signals that confirm the anatase phase as predominant in all cases [63, 64].

In Figure 9, we present a reaction proposal for the synthesis of TiO₂ using the Cinnamomum verum extract, based on what was proposed for the sol-gel method by Rojas et al. [65].

The synthesis of TiO₂ needs an abundance of ⁻OH ions; on the other hand [66], the bioactives contained in the Cinnamomum verum extract (mainly flavonoids and phenolic compounds) contain numerous ⁻OH groups in their structure [67–69], which efficiently promote a nonstable polymeric structure by hydrolysis generating Ti(OH)₄ and HCl, where the use of the aqueous extract of cinnamon contributes to the nucleation and growth of the polymeric phase. The resulting mixture was washed to remove HCl and calcined (450°C for 4 h); after calcination, the tetragonal crystallographic structure was generated, and that corresponds to the anatase phase for the nanometric TiO₂ (Figure 7), which has a smaller particle size, more uniform size, and crystallinity than the rest of the materials evaluated (CO-TiO₂ and A-TiO₂).

3.7. Evaluation of the Adsorption-Photodegradation of Methyl Orange

Figure 10 shows the profile with the adsorption-photodegraded percentages of methyl orange at the optimal conditions for the samples C-TiO₂, CO-TiO₂, and A-TiO₂ and the photolysis (without catalyst) of the system at 3 ppm of contaminant with adsorption (15 min (a)) and degradation (100 min (b)) time of equilibrium, respectively, using a ratio of 1 g of catalyst per liter of methyl orange.

(a)

(b)

According to Figure 10(a), the sample synthesized with the Cinnamomum verum extract (C-TiO₂) is the one with the highest percentage of adsorption (7.5%), reaching equilibrium time experimentally in 15 min, followed by the C-TiO₂ sample (4.7%) and A-TiO₂ (1.76%). 10(b) The percentages of photodegradation for photolysis and samples A-TiO₂, CO-TiO₂, and C-TiO₂ with 100 min of UV irradiation resulted in 34.22, 81.42, 95.56, and 100%, respectively. The C-TiO₂ sample, synthesized with an aqueous extract of cinnamon (Cinnamomum verum), completely photodegraded methyl orange (100%) in just 40 minutes, reaching equilibrium at this time, unlike the rest of the experiments.

Figure 11 shows a comparison of the percentages of adsorption-photodegradation with all the materials evaluated with an exposure of 40 min.

The photolysis after 40 minutes only reaches up to photodegradation of 12.95%, followed by the A-TiO₂ sample (commercial) with 36.97%. For the samples synthesized with TiCl₄, with the aqueous extract of Cinnamomun verum and microwave irradiation (C-TiO₂), there is an improvement of 52.22% of methyl orange photodegradation when compared with CO-TiO₂. This can be attributed primarily to the fact that the band gap for the C-TiO₂ sample (Eg = 3.42 eV) is lower than that for the CO-TiO₂ sample (Eg = 3.67 eV), indicating that less energy is required to pass electrons from the valence band to the conduction band. In addition, the particle size was smaller, and the crystallinity was higher than the synthesized sample without extract; therefore, the active sites of the catalyst were better exposed than the sample synthesized without the extract. Other authors have found that there could be traces of the bioactives used as precursors (corroborated by FTIR, Figure 3), which could additionally have a photochromic effect and facilitate the photoreaction [66]. Additionally, when quantifying the adsorption of the dye, it can be seen that the resulting morphology for the C-TiO₂ sample allowed a better interaction of the catalyst with the reaction medium, contributing to the photodegradation (Figure 5(f)).

In the comparison of the C-TiO₂ (15 nm) and A-TiO₂ (50 nm) samples, the smaller particle size of the sample prepared with extract allowed for the exposure of a greater number of active sites in photodegradation, in addition to the already mentioned photochromic effect. Therefore, the sample synthesized with the aqueous cinnamon extract, despite having a higher band gap (Eg = 3.42 eV), was more photoactive than the commercial sample (Eg = 3.19 eV).

Figure 12, (A) shows the values obtained for the constant rate (k (min⁻¹)) and the order (n) of the reaction calculated for the adsorption-degradation of methyl orange. Sections (B) to (C) present the speed profiles (-r_{methyl orange adsorption-degradation}) for the evaluated samples.

(a)

(b)

(c)

In all cases, the adjustment of the speed model (ppm methyl orange/min) corresponds to order one (n = 1), where the speed constants (k) resulted in values of k = 0.89, 0.021, 0.012, and 0.003 min⁻¹ for the samples C-TiO₂, CO-TiO₂, A-TiO₂, and the photolysis of the system, respectively, with R² settings between 0.89 and 0.99 (Figure 12(a)). These values can be corroborated in the speed profiles (Figures 12(b) and 12(c)), where the sample synthesized with the Cinnamomum verum extract is the one with the highest speed according to the highest value of k of the tested materials, which shows the excellent interaction of TiO₂ with the reaction medium, attributable to the higher adsorption of methyl orange in the C-TiO₂ sample; therefore, the C-TiO₂ sample has smaller crystal size, smaller particle size, higher crystallinity, and smaller band gap than the one synthesized without cinnamon.

Figure 13 shows the UV-vis spectra obtained for the remnants of the sorption photodegradation of methyl orange to identify intermediate products, using the semiconductor CO-TiO₂ (%MOD = 95.56), that did not reach total mineralization after 40 and 100 min of photodegradation.

In the spectrum at the beginning of the reaction (0 min), two signals are presented. The first is located at λ = 466 nm, which is indicative of the chromophore group -N=N- (azo); the second signal at λ = 269 nm is associated with the benzene rings in the methyl orange structure. After 40 min of irradiation with UV light, the signal at 466 nm reduces its intensity, and after 100 min of irradiation, it disappears; this indicates the breaking of the -N=N group bond [70, 71]. In the case of the signal at 269 nm, it can be observed that after 40 min of irradiation it decreased, and at 100 min, a displacement of the signal is observed at approximately 253 nm, which indicates that the aromatic group was not fractionated, generating by-products derived from the aromatic ring which can be attributed to N,N-dimethyl-p-phenylenediamine, as reported by Lide and Col. [72] and sulfanilic acid in [73]. It is worth mentioning that the C-TiO₂ sample does not show any signal after photodegradation, and it is likely that it has reached mineralization.

Table 4 shows a comparison of studies where TiO₂ was used for the degradation of methyl orange compared to TiO₂ synthesized with the Cinnamomum verum extract.

Fortunately, the C-TiO₂ sample being a pristine material shows a very good percentage of degradation in a short time compared to binary and ternary materials (Table 4). So, the green synthesis of nanostructures such as C-TiO₂ represents an area of opportunity for the synthesis of more efficient materials since it can be coupled with other semiconductors and graphitic materials and decorated or doped with metals.

4. Conclusions

The optimization of the aqueous extract of Cinnamomum verum predicts a significant quadratic model, with an 82% prediction to the experimental variations.

It was feasible to synthesize nanocrystalline solids of the TiO₂ anatase phase by microwave irradiation for 10 minutes at 150 watts of power, with and without the aqueous extract of Cinnamomum verum, where the size of the particle is influenced by the bioactive during the synthesis (the aqueous extract of Cinnamomum verum) and the synthesis method (microwave irradiation), resulting in smaller size and crystallinity when synthesized with the aqueous extract of cinnamon.

The signals obtained in the FTIR spectrogram for the aqueous extract of Cinnamomum verum suggest the presence of terpenes, phenolic compounds, and flavonoids. For the samples A-TiO₂, C-TiO₂, and CO-TiO₂, the vibration modes of the Ti-O and Ti-O-Ti bonds are confirmed with the signal at 625 cm⁻¹. For the C-TiO₂ and CO-TiO₂ samples, the signal at 1104 cm⁻¹ confirms the formation of TiO₂ nanoparticles in the anatase phase since this signal does not appear in the A-TiO₂ sample.

The use of the aqueous extract of Cinnamomum verum FIGURAS FIONALES promotes during the synthesis of TiO₂ that the value of the band gap decreases, affects the crystallinity, and decreases the size of the crystal, compared to the sample synthesized without the extract (CO-TiO₂) since both were prepared under the same synthesis conditions.

Raman spectroscopy confirms that the C-TiO₂ and CO-TiO₂ samples mostly contain the tetragonal crystallographic structure corresponding to the anatase phase. In both cases, the presence of traces of the face-centered cubic crystallographic structure of the rutile phase is also confirmed.

The commercial sample A-TiO₂ does not have a good particle size uniformity, where larger size particles predominate (50 nm). The sample synthesized by microwave irradiation without the extract promoted the formation of elliptical nanoparticles with good uniformity and sizes of approximately 20 nm in diameter. When using an aqueous extract of Cinnamomum verum during the synthesis, it generated a material with a uniform particle size (less than 15 nm in diameter), with a higher degree of crystallinity.

The use of the aqueous extract of cinnamon (Cinnamomum verum) during the synthesis of TiO₂ generated a semiconductor with a smaller crystal size, smaller particle size, higher crystallinity, smaller band gap, and greater adsorption capacity for the dye tested as a reaction model (methyl orange) than the one synthesized without cinnamon, which apparently promotes the total mineralization of methyl orange in 40 minutes of reaction, making it the best material of those evaluated in the adsorption-photodegradation.

Data Availability

The experimental data used to support the findings of this study are available from the corresponding author upon request.

Conflicts of Interest

The authors declare that they have no conflicts of interest.

Acknowledgments

The authors wish to thank the “Instituto Politécnico Nacional” for funding this research through the SIP 2022 1522, SIP 2022 0908, and SIP2022 1671 projects.

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Journal of Chemistry

Metal and Metal Oxide Nanomaterials for the Environment and Engineering Applications

Green Synthesis by Microwave Irradiation of TiO2 Using Cinnamomum verum and the Application in Photocatalysis

Abstract

1. Introduction

2. Experimental

2.1. Chemicals

2.2. Cinnamomum verum Aqueous Extract Optimization

2.3. Green Synthesis of TiO2 Nanoparticles by the Sol-Gel Method Assisted by Microwave Irradiation and Cinnamomum verum Extract as Reductant

2.4. Characterization of the Samples

2.5. Evaluation of the Adsorption-Photodegradation of Methyl Orange

2.5.1. Adsorption of Methyl Orange

2.5.2. Photodegradation of Methyl Orange

3. Results and Discussion

3.1. Cinnamomum verum Aqueous Extract Optimization

3.2. X-Ray Diffraction (XRD)

3.3. Fourier Transform Infrared (FTIR) Spectroscopy

3.4. High-Resolution Transmission Electron Microscopy

3.5. UV-Vis Diffuse Reflectance Spectroscopy

3.6. Raman Spectroscopy

3.7. Evaluation of the Adsorption-Photodegradation of Methyl Orange

4. Conclusions

Data Availability

Conflicts of Interest

Acknowledgments

References

Copyright

Green Synthesis by Microwave Irradiation of TiO₂ Using Cinnamomum verum and the Application in Photocatalysis

2.3. Green Synthesis of TiO₂ Nanoparticles by the Sol-Gel Method Assisted by Microwave Irradiation and Cinnamomum verum Extract as Reductant