Investigation of novel material for effective photodegradation of bezafibrate in aqueous samples
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A novel composite with an enhanced photocatalytic activity was prepared and applied to study the removal of bezafibrate (BZF), a hypolypemic pharmaceutical, from an aqueous environment. For the enhancement of titanium dioxide photoactivity a fullerene derivative, 2-(ferrocenyl) fulleropyrrolidine (FcC60), was synthesized and applied. Obtained composite was found to show a higher catalytic activity than pristine TiO2. Therefore, high hopes are set in composites that are based on carbonaceous nanomaterials and TiO2 as a new efficient photocatalysts.
KeywordsBezafibrate Fullerene Heterogeneous photocatalysis Nanocomposite Titanium dioxide
Hence, it is important to estimate efficient methods of BZF removal from a natural aqueous environment. Kinetic studies and identification of degradation products are also of a great concern. Accordingly, those issues were a matter of investigations presented in this paper.
A series of attempts were made in order to adequately remove BZF from natural aqueous samples. They included utilization of flocculation (Ternes et al. 2002), ozonation (Dantasa et al. 2007), filtration with granular activated carbon (Ternes et al. 2002), biodegradation (Kunkel and Radke 2008) and photolysis (Razavi et al. 2009). However, none of them seemed to be sufficiently efficient. Therefore, a huge potential lies in the application of heterogeneous photocatalysis (Lambropoulou et al. 2008). This process has a huge potential as a new route of destruction of organic as well as inorganic hazardous materials (Kabra et al. 2004). Photocatalytic degradation involves a photocatalyst presence. This role is mostly fulfilled by transition metal oxide semiconductors, among which titanium dioxide (TiO2) is one of the most widely used. Apart from the removal of pharmaceuticals (Deegan et al. 2011), dyes (Regulska and Karpińska 2012; Regulska et al. 2013; Shang et al. 2011; Fan et al. 2011; Fischer et al. 2011), cyanides (Kabra et al. 2004), malodorous compounds (Kabra et al. 2004), fungicides (Topalov et al. 1999), herbicides (Topalov et al. 2000) and pesticides (Assalin et al. 2010), TiO2 was also satisfactorily applied in a destruction of bacteria, viruses (Henderson 2011) and cancer cells (Rozhkova et al. 2009). What is more, due to its photocatalytic activity, TiO2 was deeply researched in the field of self-cleaning (Sökmen et al. 2011), self-sterilizing (Hashimoto et al. 2005), highly hydrophilic and anti-fogging surfaces (Hashimoto et al. 2005). Another areas concerning the application of TiO2 include dye sensitized solar cells (Jiang et al. 2009), water splitting, CO2 photoreduction and the so-called ‘synthesis by photons’ (Arora et al. 2010).
So far, no attempts have been made to prepare and examine the above mentioned photocatalyst as a way of enhancing TiO2 photocatalytic activity. Therefore, it was described in the present paper. Moreover, the photodegradation process of BZF was studied with the aim of accessing the potential application of prepared photocatalyst in the pharmaceutical removal from the aquatic environment.
Materials and methods
TiO2 (anatase), bezafibrate, ferrocenaldehyd, sarcosin and anhydrous toluene were purchased from Sigma-Aldrich. 4-Chlorophenol (CP), 4-chlorobenzoic acid (CBA), 4-hydroxybenzaldehyde (HBD) (all Merck), absolute methanol, dipotassium hydrogen phosphate, orthophosphoric acid (all POCh, Gliwice, Poland) and ammonium reineckate (BDH Chemicals) were used. All above mentioned chemicals were of analytical grade reagents and used without further treatment. HPLC-grade acetonitrile was purchased from J.T. Baker. All solutions were prepared using deionized water, which was obtained by Polwater apparatus.
Scanning electron microscopy was applied to investigate the morphology of the FcC60/TiO2 composite. Composite was imaged by secondary electron SEM with the use of an Inspect S50 scanning electron microscope from FEI. The accelerating voltage of the electron beam was 30 keV and the working distance was 10 mm. Differential scanning calorimetry (DSC) analyses were performed by a thermal analyzer DSC 1 (Mettler Toledo) with a heating rate of 10 °C/min under air environment with flow rate = 200 mL/min. All runs were carried out from 0 to 500 °C and reverse cycles from 500 to 0 °C were registered too. The measurements were made in open aluminium crucibles, nitrogen was used as the purge gas in ambient mode, and calibration was performed using an indium standard. Attenuated total reflection infrared (ATR-IR) spectra were recorded from 4,000 to 500 cm−1 using a Thermo Scientific Nicolet™ 6700 spectrometer with 32 accumulations at a resolution of 4 cm−1. This instrument was equipped with a KBr beamsplitter, an ETC source and a DTGS detector. Photolytic as well as photocatalytic degradation experiments were carried out in a solar simulator apparatus, namely SUNTEST CPS+ (Atlas, USA). The photon flux of solar simulated radiation was measured by chemical method—Reinecke’s salt actinometer (Kuhn et al. 2004). The photon flux of solar simulated light of 250 W/m2 was 2.18 × 10−6 Einstein/s. The chromatographic experiments with HPLC–UV system were carried out on a Varian 920 liquid chromatograph using a quaternary solvent pump and an autosampler. The chromatographic column used Lichrospher®100 RP-18 125 × 4.6 mm packed with 5 μm particle size. Separation was achieved using a linear gradient method. The mobile phase consisted of two solutions namely A and B. Solution A was prepared from 10 mmol/L disodium hydrogen phosphate, pH adjusted to 7.4 with orthophosphoric acid, whereas solution B was acetonitrile. The initial ratio of A:B was 70:30 (v/v). The gradient was as follows: 0 min, 70 % A; 15 min, 70 % A; 25 min, 20 % A; 30 min, 20 % A; and 35 min, 70 % A. The column was equilibrated for 10 min before performing the next injection. The flow rate of the mobile phase was 1 mL/min and the injection volume was 100 μL. The column was maintained at a room temperature. The eluent was monitored at 226 nm. UV spectrophotometric analyses were performed in a Hitachi U-2800A UV–Vis spectrophotometer equipped with a double monochromator and double beam optical system (190–700 nm). UV studies were done using a 1-cm quartz cell. Absorbance was recorded in the range of 190–400 nm, and the maximum absorption wavelength experimentally registered at λ = 226 nm was used for the calibration curve and further concentration measurements.
FcC60 was synthesized according to the following procedure. A solution of 100 mg of C60, 60 mg of ferrocene aldehyde and 25 mg of N-methyl glycine in 100 mL of toluene was stirred at reflux temperature overnight. The solvent was removed in vacuum. The solid residue was purified by flash chromatography using toluene as an eluent affording 81 mg (21 %). 1H NMR (400 MHz, CDCl3:CS2 = 1:1 v/v) δ 3.05 (s, 3H), 4.20 (m, 1H), 4.21 (m, 1H), 4.26 (m, 1H), 4.28 (s, 1H), 4.30 (s, 4H), 4.48 (m, 1H), 4.49 (s, 1H), 4.58 (m, 1H), 4.84 (m, 1H), 4.88 (s, 1H), and 4.91 (s, 1H); 13C NMR (100 MHz, CDCl3:CS2 = 1:1 v/v) 41.76, 67.02, 67.12, 67.56, 68.21, 69.31, 70.95, 77.00, 141.82, 142.37, and 145.67.
FcC60/TiO2 nanocomposite was prepared by evaporation–drying method (Yao et al. 2008), previously applied to prepare carbon nanotubes–TiO2 nanocomposites. FcC60/TiO2 composite was made at 1:20 mass ratio of FcC60 to TiO2.
Photocatalytic degradation experiment
The photocatalytic degradation experiments were performed in a 50-mL glass cell. The reaction mixture consisted of 20 mL of BZF sample (5 × 10−5 mol/L) and the photocatalyst (1.6 g/L). The pharmaceutical-catalyst suspension was kept in the dark with stirring for 1 h to ensure an adsorption–desorption equilibrium prior to the irradiation experiment. Such prepared mixture was subjected to irradiation by simulated sunlight for 120 min. To determine the BZF degradation, the samples were collected at regular intervals (10 min) and centrifuged to remove the photocatalyst and the spectra of the obtained solution were recorded.
Results and discussion
The characterization of synthesized composite was done before photocatalysis experiments. For this purpose scanning electron microscopy, DSC and ATR-IR spectrometry were used.
Identified compounds by HPLC analysis
Retention time [min]
Photolysis (120 min)
Photocatalysis (TiO2) (120 min)
Photocatalysis (FcC60/TiO2) (120 min)
The efficiency of photocatalytic activity of newly synthesized composite was proved. BZF was found to undergo complete decomposition with the application of both TiO2 and FcC60/TiO2. It was noticed that in the presence of FcC60/TiO2 bezafibrate is quickly transformed into 4-CP instead of three (4-HBD, 4-CP, 4-CBA) in case of photolytic and photocatalytic degradation with the application of bare TiO2.
Conducted experiments confirmed photocatalytic ability of FcC60/TiO2 composite. What is more, prepared photocatalyst showed higher catalytic activity than sole TiO2. Therefore, we believe that huge potential lies in composites that are based on carbonaceous nanomaterials and TiO2 as new efficient photocatalysts. Prepared composite could potentially be used in the decontamination of other organic pollutants from water. Heterogeneous catalysis was proved to have a huge potential as a new route of a destruction of undesired compounds present in the environment. However, the photocatalyst application should be preceded by preliminary studies concerning an identification of degradation products and an assessment of their toxicity.
This work was financially supported by the National Science Centre, Poland (project 2012/05/N/ST5/01479).
The authors thank Dr. Marta E. Plonska-Brzezinska for SEM measurements. DSC, IR spectrometer and SEM were funded by EU, as part of the Operational Programme Development of Eastern Poland 2007–2013, project Nr POPW.01.03.00-20-034/09-00.
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