Quasi-Spherical Brookite TiO2 Nanostructures Synthesized Using Solvothermal Method in the Presence of Oxalic Acid
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Brookite TiO2, the latest TiO2 photocatalyst, promises to be an interesting candidate for photocatalytic applications because of its unique physical and chemical properties. In this study, pure-phase brookite TiO2 with a quasi-spherical nanostructure was successfully synthesized via a solvothermal method using tetrabutyl titanate (Ti(OC4H9)4, TBOT) as the Ti source in the presence of oxalic acid. NaOH was used to regulate the pH of solution. The structure and morphology of the samples were then analyzed using multiple methods, such as X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Brunauer–Emmett–Teller (BET) measurements and ultraviolet–visible diffuse spectroscopy (UV–Vis). Photocatalytic activities of the as-synthesized brookite TiO2 were evaluated by degrading aqueous methylene blue solution under UV light irradiation. The effect of thermal treatment temperature on photocatalytic activity of the samples was also investigated. The produced brookite TiO2 nanopowders calcined at 500 °C for 2 h showed the highest photocatalytic activity, and the corresponding degradation rate of methylene blue (10 mg/L) reached 96.7% after 90 min of illumination. In addition, the formation mechanism of pure-phase brookite TiO2 was investigated. It was found that the formation of pure-phase brookite TiO2 in this study was ascribed to the combined action of oxalic acid and sodium hydroxide.
KeywordsTiO2 Brookite Oxalic acid Photocatalytic properties
It is known that TiO2 shows three types of crystalline polymorphs: rutile (tetragonal, space group: P42/mnm), anatase (tetragonal, space group: I41/amd), and brookite (orthorhombic, space group: Pbca) . Of these polymorphs, anatase and rutile TiO2 have been widely studied over the past decades. However, few reports have focused on the preparation and properties of brookite TiO2, due to the difficulty involved in preparing its pure form [2, 3, 4]. Nevertheless, theoretical studies have demonstrated that brookite TiO2 exhibits superior photocatalytic performance compared to anatase and rutile TiO2 because of its unique orthorhombic crystalline structure [5, 6, 7]. Thus, brookite TiO2 has generated significant interest due to its physicochemical properties and possible applications.
To date, various methods have been developed to synthesize pure brookite TiO2, such as hydrothermal [8, 9, 10, 11, 12], sol–gel [13, 14], thermal decomposition  and solvothermal  methods. For example, Brookite TiO2 derived from hydrothermal/solvothermal treatment of titanium complexes has been widely reported, and this is known to be an effective strategy for synthesizing pure-phase brookite TiO2 [9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21]. Additionally, brookite TiO2 nanoparticles have been prepared via hydrolysis of titanium (IV) isopropoxide at room temperature using isopropanol as both the solvent and the ligand . The Koji group synthesized brookite TiO2 via the hydrothermal treatment of different water-soluble titanium complexes using hydroxyacetic acid, glycolic acid, citric acid, or ethylenediaminetetraacetic acid (EDTA) as complexing agents [9, 10, 11, 12]; they concluded that the structures of titanium complexes were important for forming brookite TiO2.
It is worth mentioning that oxalic acid is a rigid bidentate ligand that can link two metallic centers, and is a good chelating agent that effectively chelates with metal ions, including a titanium ion [17, 22, 23]. The decomposition of oxalate groups is primarily bi-coordinated or mono-coordinated to titanium atoms via a reaction with Ti–OH groups, which results in the evolution of CO, CO2 and a minor amount of H2O . In addition, the titanium oxalate complex, which has a specific octahedral arrangement that is similar to the titanium glycolate complex, facilitates the growth of brookite TiO2 polymorph with a high pH value [12, 19, 21]. Dambournet et al.  reported that mesoporous brookite TiO2 with a high specific surface area and controllable morphology could be synthesized using titanium oxalate hydrate as a precursor in the presence of alkali ions (Li+, Na+). It is thus known that oxalic acid can be used to prepare brookite TiO2 nanostructures with excellent properties. However, due to the strong dependence of brookite TiO2 formation on the synthesis method and experimental conditions involved, more research is required to understand brookite TiO2 formation under different conditions.
In this study, brookite TiO2 was synthesized via the solvothermal method using tetrabutyl titanate (TBOT) as a Ti source and oxalic acid as a complexing agent. N,N-dimethylformamide (DMF) was used as a solvent, and the pH value of the solution was maintained at 10 by adding 2 mol/L NaOH. X-ray diffraction (XRD), Raman spectroscopy, field emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), and ultraviolet–visible diffuse spectroscopy (UV–Vis) were employed to characterize the structure and morphology of the products. The photocatalytic activity of the produced brookite TiO2 was evaluated by photodegrading methylene blue (MB) solution under UV light irradiation. In addition, this work investigated the formation mechanism of brookite TiO2 in the presence of oxalic acid during the solvothermal process.
Tetrabutyl titanate (Ti(OC4H9)4, TBOT) of analytical grade was purchased from Sinopharm Chemical Reagent Co., Ltd., China. Analytical-grade sodium hydroxide (NaOH), oxalic acid (H2C2O4·2H2O), N,N–dimethylformamide (DMF), sodium sulfate (Na2SO4), absolute ethanol, 2-propanol (IPA), and EDTA disodium salt (EDTA-2Na) were purchased from Kewei Company of Tianjin University, China. All chemicals were directly used without further purification.
Synthesis of Brookite TiO2 Nanostructures
In total, 1.27 g of oxalic acid was first dissolved in 50 mL of DMF solution via vigorous stirring, and 1.0 mL of TBOT was then slowly dropped into the mixture. Vigorous stirring was applied until a transparent yellow solution was formed. The pH value of the resulting solution was adjusted to 10 using 2.0 mol/L NaOH during this process. The solution was then stirred for another 1 h, and the slurry formed was transferred to a 100 mL Teflon-lined autoclave and placed in an oven at 180 °C for 8 h. It was then slowly cooled to room temperature, and the white precipitate was subsequently collected using centrifugation. The precipitate was washed several times with distilled water and absolute ethanol and then dried at 80 °C overnight in a drying cabinet.
The crystalline phase, phase composition, and crystallite size of the product were characterized using powder XRD via a DX-2000 X-ray diffractometer with CuKα radiation at a scan rate of 0.06°/s. The accelerating voltage and applied current were 35 kV and 25 mA, respectively. The average TiO2 sample crystallite size (D) was calculated from X-ray line broadening of reflections of the three main peaks using the Scherrer equation.
The morphologies and particle sizes of prepared TiO2 powders were examined using an FESEM (Hitachi, S-4800), and the detailed microscopic nanostructure was observed using a HRTEM (JEOL, JEM 2100F operated at 200 kV). Raman spectra were recorded using a DXR Microscope Raman spectrometer system with an excitation wavelength of 532 nm at room temperature. Nitrogen adsorption–desorption measurements were taken at 77 K using a Micromeritics TriStar nitrogen adsorption apparatus (Micromeritics Instrument Corporation, USA). The samples were degassed at 300 °C for 4 h prior to Brunauer–Emmett–Teller (BET) measurements, and the BET surface areas, S BET, were calculated within the relative pressure range of 0.05 to 0.20. Desorption isotherms were used to determine the pore-size distribution via the Barrett–Joyner–Halenda (BJH) method. UV–Vis diffuse reflectance spectra were recorded using a UV–visible spectrophotometer (UV-2600, Shimadzu, Japan) and then converted into absorption spectra via Kubelka–Munk transformation.
The electrochemical performance of brookite TiO2 was evaluated at a CHI660E electrochemical workstation (Shanghai Chenhua Instrument Co., China). Electrochemical measurements were taken using a conventional three-electrode configuration with an as-prepared brookite TiO2/FTO employed as the working electrode (1 cm × 1 cm), a Pt wire as the counter electrode, and a Ag/AgCl electrode as the reference. The working electrode of TiO2/FTO was prepared according to the method reported in our previous work . The electrodes were placed 3 cm apart, and the supporting electrolyte was 0.1 mol/L Na2SO4 solution. Electrochemical impedance spectroscopy (EIS) measurements were taken in the frequency range of 100–0.01 Hz using amplitude of 5 mV and an open-circuit potential without illumination. The flat band potential (E FB) of the samples was determined from Mott–Schottky (M–S) analysis at an alternating-current potential frequency of 1 kHz under dark conditions.
Photocatalytic Performance Test
The photocatalytic performance of brookite TiO2 powders was evaluated using the photodegradation of an aqueous solution of MB. A Xenon lamp (HXS-F/UV 300, Beijing NBET Technology Co., Ltd) with a 365-nm band filter served as the light source and was placed 10 cm away from the liquid surface, where the light density was approximately 10 MW/cm. An appropriate amount of photocatalyst (15 mg) was added into 75 mL of MB solution (10 mg/L). To equilibrate the adsorption and desorption, the suspension was stirred in the dark for 30 min prior to UV illumination. Samples were periodically collected and centrifuged, and the concentration of the MB solution was analyzed using a UV–Vis spectrophotometer (T6, China).
To determine the effect of active species generated by the photocatalytic system on the photocatalytic activity of samples, various scavengers, including 2-propanol (IPA, 20 mmol/L) and EDTA-2Na (6 mmol/L), were introduced into the MB solution.
Results and Discussion
XRD, Raman, and FTIR Analyses
All peaks of the sample synthesized in the presence of oxalic acid were confirmed to show the orthorhombic crystal structure of brookite TiO2 (PDF# 29-1360). There were no other characteristic peaks observed belonging to impurities or other TiO2 polymorphs (anatase and rutile), which indicated that the sample was pure-phase brookite TiO2. To investigate the effect of oxalic acid on brookite phase formation, another sample was synthesized under the same solvothermal conditions in the absence of oxalic acid and was found to be titanic acid (H2Ti2O5·H2O; PDF# 47-0124) instead of brookite TiO2 (as shown in Fig. 1a) . This result indicates that oxalic acid plays an important role in the crystallization and phase formation of brookite TiO2. However, oxalic acid is not the sole factor influencing the phase formation of pure brookite; a different crystal phase (pure anatase, pure rutile, or anatase–brookite biphase) TiO2 was synthesized at a different pH value when oxalic acid was used as a chelating agent [17, 19]. It is thus concluded that brookite formation in this study is primarily attributed to the synergistic effect between oxalic acid and sodium hydroxide. In addition, the pure brookite phase is only obtained under mild alkaline conditions, and titanate is formed when the pH value of the solution is higher than 10 .
The thermal phase stability of synthesized brookite TiO2 was investigated by annealing the sample at different temperatures for 2 h, as shown in Fig. 1b. No phase transition was observed in the XRD patterns, even at a calcination temperature of 700 °C, which indicates that brookite TiO2 synthesized under the present conditions possesses good thermal stability. The average crystallite sizes of samples without calcination and those calcined at 300, 500, 600 and 700 °C were calculated using Scherrer equation, and the (121) peaks were found to be 27.65, 28.32, 31.86, 33.02, and 35.93 nm, respectively. This result reveals that the thermal treatment temperature has no influence on the phase structure or composition of the samples and it only affects crystal size.
SEM and TEM Analyses
To further investigate the crystal morphology, TEM and HRTEM analyses were conducted to confirm the quasi-spherical TiO2 structures, as shown in Fig. 3f–i. Figure 3f shows the TEM image of brookite TiO2 without calcination, which confirms the existence of abundant quasi-spherical nanoparticles with an average particle size of approximately 20–40 nm. It is in good agreement with results from the SEM image (Fig. 3a) and the crystallite size calculated using Scherrer equation. With an increase in the calcination temperature, the diameters of the quasi-spherical structures increase (Fig. 3g, h); this is attributed to agglomeration of the nanoparticles during the thermal treatment process. Moreover, a large number of white dots are observed on the surface of the quasi-spherical structures, as shown in Fig. 3h, which indicates that the sample calcined at 500 °C exhibits a porous structure resulting from an improvement in crystallinity and the accumulation of small particles, and it is consistent with results from the SEM image shown in Fig. 3c. The HRTEM image of a typical quasi-spherical structure is shown in Fig. 3i, and the distinct lattice spacing of 0.289 nm between the adjacent lattice planes is attributed to the (121) crystal plane.
BET surface area and pore-size distribution of samples
Calcination temperature (°C)
Crystal size (nm)
S BET (m2/g)
Average pore size (nm)
Pore volume (cm3/g)
BJH desorption (nm)
Possible Mechanism for Growth of Brookite TiO2 in the Presence of Oxalic Acid
In recent years, brookite TiO2 nanostructures (synthesized via thermal treatment of titanium complexes derived from different Ti sources and complexing agents) have been widely reported, and their corresponding growth mechanisms have been investigated [15, 16, 17, 18, 19, 20]. Some researchers have suggested that a ligand type is crucial to TiO2 phase formation during the hydrothermal treatment process, because ligand may coordinate to titanium in an octahedral environment and be assembled into the initial structure of anatase, brookite, or rutile crystallites [9, 10, 11, 12, 21, 29, 30, 31, 32]. In general, in an aqueous medium, titanium cations are solvated and form 6-coordinate charged complexes [TiL6]z+, in which the nature of the ligand (L) is indicated by the solution pH and the presence of species that act as complexing agents .
Oxalic acid is a rigid bidentate ligand; it is a good chelating agent that has been used to synthesize TiO2. However, no consensus currently exists about the effect of oxalic acid on TiO2 phase formation. For example, Dambournet et al.  reported that the [C2O4 2−]/[Ti4+] molar ratio (denoted as R) was the key factor in TiO2 phase formation and that the oxalate anion either acts as a ligand to stabilize the oxalate hydrate phase Ti2O3(H2O)2(C2O4)·H2O (R = 1) before the formation of brookite TiO2 after thermal treatment, or acts as a chelating agent (R = 2) to stabilize the rutile phase. However, Kanna and Wongnawa  suggested that oxalic acid inhibited the formation of rutile because the bi-bonds of C2O4 2− on the TiO6 octahedra occupy one full octahedral face and inhibit the growing chain along opposite edges. Truong et al.  proposed that the presence of oxalic acid in solution prevented anatase formation through its chelation to the TiO6 octahedron at the bridging oxo group, which benefited the growth of rutile crystallites. However, the results obtained in this study differed from the reported results when using oxalic acid as a complexing agent. Specifically, pure-phase brookite TiO2 instead of rutile was obtained under solvothermal conditions with R > 2, which indicated that brookite TiO2 derived from the titanium oxalate phase could be obtained with higher oxalate content by tuning other synthesis conditions. It can thus be inferred that the formation of brookite TiO2 is related to the existence of NaOH, which is introduced to maintain the pH value at approximately 10. Dambournet et al.  reported that the titanium oxalate phase played an important role in the morphology and crystallization of TiO2 due to the type of preferentially adsorbed alkali ions (Li+, Na+) on its crystal facets. The three crystal forms of TiO2, including anatase, rutile, and brookite, are composed of a [TiO6] octahedron that has oxygen ions at its vertices and titanium atoms at its center; these have different spatial arrangements that share edges and corners in different manners. The [TiO6] octahedral structure prefers corner sharing to edge sharing to maintain its thermodynamic stability, because the repulsive Coulomb forces that result from the shared edges lead to a decrease in stability . Therefore, it is here considered that the addition of oxalic acid and NaOH changes the spatial arrangement of the [TiO6] octahedron, which results in the formation of brookite TiO2. Na+ ions have been reported to favor the brookite transition because they retard the collapse of layers due to stronger electrostatic interactions with titanate layers and induce the phase transition of titanate into brookite TiO2 . In addition, it has been reported that the pH value of solution significantly influences the TiO2 crystalline structure ; a high pH supports edge-shared bonding (anatase crystallization), while a low pH favors corner-shared bonding (rutile crystallization). Brookite has both shared edges and corners and is midway between anatase and rutile in terms of edge-shared bonding, and at a low NaOH concentration, OH− deficiency leads to the formation of [TiO6] octahedra with brookite rather than anatase.
To further investigate the effects of oxalic acid and NaOH on brookite TiO2 formation, a sample was synthesized using the same solvothermal conditions in the absence of oxalic acid. The XRD result in Fig. 1a demonstrates that titanic acid instead of brookite TiO2 was obtained. Therefore, we conclude that the formation of brookite TiO2 is a result of the combined action of oxalic acid and NaOH, and the possible mechanism involved in this process can be deduced. Specifically, the bond between ligands and the Ti precursor is fragile in a high pH solution and is readily cleaved because of the frequent nucleophilic attack on Ti atoms from abundant hydroxide ions. Thus, hydrolysis and condensation occur primarily along the edge-sharing bonds, which results in the formation of anatase and brookite crystallites. Therefore, the action of oxalic acid and the adjustment of pH value with sodium hydroxide are the main factors involved in forming pure brookite TiO2.
It is known that the photocatalytic activity of TiO2 depends on its structure and physical properties . Examination of electrochemical impedance spectroscopy (EIS) and flat band potential (E FB) of the brookite TiO2/FTO electrodes may be helpful in understanding the relationship between the photocatalytic activity of brookite TiO2 and its physical properties.
Flat band potentials (E FB) and donor density (N D) of brookite TiO2 calcined at different temperatures
Calcination temperature ( °C)
E FB (V vs. Ag/AgCl)
E FB (V vs. NHE)
N D (cm−3)
5.30 × 1020
2.97 × 1019
2.83 × 1022
2.34 × 1022
1.22 × 1022
Photocatalytic Performance Evaluation
The photocatalytic activity of TiO2 catalysts strongly depends on two factors: the adsorption behavior and the separation efficiency of electron-hole pairs [40, 41, 42, 43]. Active oxygen species (such as hydroxyl radicals (OH), superoxide radicals (O2 −), and H2O2 derived from the photogenerated electrons and holes) are considered to be the major active species responsible for the photocatalytic activity of TiO2 [40, 41, 42]. To further understand the photocatalytic mechanism of the as-synthesized brookite TiO2, hydroxyl radicals and hole trapping experiments were designed using 2-propanol as the radical scavenger and EDTA-2Na as the holes scavenger. Results are shown in Fig. 9c, where it can be observed that the decolorization efficiency of MB with addition of EDTA-2Na is slightly smaller than that of MB with no additive. However, the decolorization efficiency of MB with addition of 2-propanol sharply decreases (65% after illumination for 90 min). This result demonstrates that ·OH is one of the major active species in this experiment and that it possesses a strong oxidation ability (its oxidation–reduction potential is + 2.27 V, vs. NHE, pH 7). It is known that ·OH radicals are generated via two pathways: (1) photoelectrons are captured by adsorbed O2 on the surface of TiO2 to form intermediate species, such as superoxide radicals (O2 −) and H2O2, and ·OH radicals are then generated after the series reaction; (2) the holes oxidize adsorbed water or the surface hydroxyl groups to form OH radicals . Therefore, based on the result of our hole trapping experiment, we infer that superoxide radicals (O2 −) and H2O2 play important roles.
The absorption behavior is also another important factor contributing to the photocatalytic activity of TiO2 catalysts [42, 43, 44]; the absorption behavior of organic species on the catalyst surface influences the photoinduced electron transfer, which reduces the rate of the compound cavity electronic structure and increases the photocatalytic activity. However, absorption behavior is significantly influenced by crystallinity, specific surface area, particle size, and morphology [29, 30, 31, 32, 33, 45, 46, 47, 48, 49, 50]. Samples calcined at different temperatures had similar particle sizes and morphologies according to the XRD and SEM analyses. However, the specific surface areas and pore sizes were significantly different. Brookite TiO2 calcined at 500 °C for 2 h had the largest specific surface area (shown in Fig. 4 and Table 1), which explains the highest photocatalytic activity. It is evident that the crystallinity of samples, which is improved after calcination at a relatively high temperature (below 500 °C), is beneficial in reducing the recombination rate of photogenerated electrons and holes (due to a decrease in the number of defects) .
In the current study, we have synthesized quasi-spherical brookite TiO2 nanostructures via a solvothermal method in the presence of oxalic acid; a NaOH solution was introduced to maintain the pH value at approximately 10. Experimental results indicated that pure-phase brookite TiO2 with a quasi-spherical structure was successfully synthesized under solvothermal conditions of 180 °C for 8 h. Oxalic acid played an important role in the morphology of products, and the formation of pure-phase brookite TiO2 was attributed to the combined action of oxalic acid and the pH value, which was adjusted with sodium hydroxide. Photocatalytic activity and photoelectrochemical performance tests indicated that the resulting brookite TiO2 nanopowders calcined at 500 °C for 2 h exhibited high photocatalytic activity for methylene blue (MB) solution, and the degradation rate of methylene blue (10 mg/L) reached 96.7% after UV light illumination for 90 min at 10 mW/cm2.
This work was supported by the National Key Basic Research and Development Program of China (“973” Program, No. 2012CB720100 and No. 2014CB239300), the National Natural Science Foundation of China (No. 21406164, No. 21466035 and No. 21501196) and the Science and Technology Innovation Guide Funds of Civil Aviation Administration of China (MHRD20140209). We are also grateful to the Fundamental Research Funds for the Central Universities (No. 3122016L016) and University’s Training Programs of Innovation and Entrepreneurship for Undergraduates from Civil Aviation University of China (2017).
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