1. Introduction
In industrial wastewater, the main parameters treatment are high loads of dissolved organic compounds. These pollutants are difficult to remove with the processes commonly used to treat domestic wastewater [
1,
2]. The Political Constitution of the United States of Mexico confers inalienable rights of ownership over all national waters to the nation [
3], providing the foundation for water protection and management laws for hydraulic resources to be exploited [
3]. The current legal framework governing water pollution control is set forth in two laws: the General Law of Ecological Balance and Environmental Protection, which establishes general criteria pertaining to water pollution prevention and control; and the National Waters Law, which provides a comprehensive legal regime that supports the broader provisions set out in the Ecology Law [
3].
Phenolic compounds exist in water bodies due to the discharge of polluted wastewater from industrial, agricultural, and domestic activities into water bodies [
4]. These compounds are known for being toxic and inflict severe and long-lasting effects on humans and animals, acting as carcinogens and causing damage to the red blood cells and the liver even in low concentrations [
4]. The interaction of phenolic compounds with organic material in water can produce substituted compounds or other moieties, which may be as toxic as the original phenolic compounds [
4]. Specific emphasis is placed on the techniques of their removal from water with attention paid to conventional and advanced methods. Among these methods are ozonation, adsorption, extraction, photocatalytic degradation, biological, electro-Fenton, adsorption and ion exchange and membrane-based separation [
4]. In this regard, emerging technologies are based on efficiently degrading the dissolved solids present in wastewater, some of the most used technologies are advanced oxidation processes (AOP).
AOP is a highly effective novel method speeding up the oxidation process. AOP can combine with ozone (O
3), catalyst, or ultraviolet (UV) irradiation to offer a powerful treatment of wastewater [
5]. Several AOP’s such as O
3, O
3/H
2O
2, UV, UV/O
3, UV/H
2O
2, O
3/UV/H
2O
2, Fe
2+/H
2O
2 and photocatalysis processes had been investigated for the oxidation of phenol in an aqueous medium [
6]. Among all, the Fenton process showed the fastest removal rate for phenol in wastewater; the lower costs were observed for ozonation, and single ozonation provides the best results for phenol degradation in ozone combinations [
5].
One of the techniques that has gained a lot of attention due to its potential for scale-up is heterogeneous photocatalysis [
7]; this technique consists of a semiconductor material, which is irradiated with photons of appropriate energy, undergoing excitation of the electrons located in its valence band to its conduction band [
8]. This allows for the formation of a redox couple that interacts with the adsorbed species and can lead to the oxidation of pollutants (phenol) [
8]. The main sub-products related to photocatalytic phenol degradation include hydroquinone, used in the treatment of ephelides (freckles), melasma, post-inflammatory hyperpigmentation and actinic lentigo; benzoquinone, used as a fungicide, a photographic reagent and in the manufacture of dyes and other chemicals; catechol, used as an astringent and as an antiseptic in photography and in the electroplating and processing of other chemicals; and oxalic acid, used as a deoxidising agent to clean radiators and to remove ink stains. These high-value-added sub-products make photocatalytic degradation a profitable technique for phenol treatment. The photocatalytic properties of metal oxide catalysts are due to the fact that excitation of electrons from the valence to the conduction band of the catalyst occurs upon its irradiation with light of the appropriate wavelength [
4]. The promotion of the electrons (e-) creates positive charges or holes (h
+) on the valence band, and an accumulation of electrons on the conduction band of the catalyst the generation of these charge carriers (e- and h
+) initiates the photocatalytic degradation process [
9]. The valence band holes attack and the oxidized surface absorbs water molecules to form hydroxyl radicals (OH *) [
10]. Conduction band electrons reduce oxygen molecules and produce oxygen radicals or superoxide radicals (O
2 *) [
10]. Highly reactive radicals attack and convert the pollutants to harmless products such as carbon dioxide and water [
10,
11]. The photocatalytic degradation of phenolic compounds from wastewater has been demonstrated by many researchers using various catalysts including TiO
2/reduced graphene [
12,
13], ZnO [
14], Fe
2O
3 decorated on carbon nanotubes [
15] and CuO [
16].
Several reports have shown that photocatalytic degradation techniques have been utilized effectively to degrade phenol from the water [
13]. The results confirmed that using zeolite as support for FeO enhancement promotes efficient photocatalytic degradation [
17]. The improved photocatalytic activity of the FeO–zeolite composite was attributed to the fact that the zeolite prevented agglomeration of the FeO nanoparticles and minimized the charge carrier recombination rate [
17]. F. Shahrezaei, A. Akhbari, and A. Rostami. [
18] explored the photocatalytic degradation ability of TiO
2 in the degradation of phenolic compounds present in wastewater from a refinery [
18]. The highest degradation efficiency of the phenol and its derivatives was identified at an optimum temperature of 318 K, pH 3 and 100 mg/L catalyst concentration [
18]. A 90% degradation efficiency of phenol was achieved within 2 h at these optimum conditions. Guangping Zeng, Qiaoling Zhang, Youzhi Liu, Shaochuang Zhang, and Jing Guo [
19] explored the photocatalytic degradation of Toluene with FeO–TiO
2, showing an improvement of 58% in the degradation rates compared to TiO
2 P25 [
19]. Increasing the concentration from 0.5% to 5.0% of Fe
3+ results in a reduction in the band gap energy from 3.06 eV in undoped Fe to 2.86 eV and 2.26 eV. Fe
3+ not only broadens the photo response range but also effectively suppresses the recombination of the electron and hole [
19]. As a result, the catalytic activity was enhanced. The degradation rate of 1.0% Fe–TiO
2 to toluene of 105 ppm reached 95.7% after 4 h under UV light [
19]. The chlorine doping effect was explored by Zhen Cao, Tingting Zhang, Pin Ren, Ding Cao, Yanjun Lin, Liren Wang, Bing Zhang, and Xu Xiang [
20]. The investigation reported that chloride ions adsorbed onto the TiO
2 surface, introducing a negative surface charge that enhances the electrostatic adsorption of cationic dyes, and greatly improves the self-sensitizing degradation performance of the dyes [
20]. Chloride ions replace lattice oxygen atoms in TiO
2, inducing lattice oxygen vacancies that reduce the apparent bandgap of the TiO
2 particles, enhancing its absorption of visible light and further increasing the photocatalytic activity of the composite-coated fabric [
20]. Y. Niu, M. Xing, J. Zhang, and B. Tian [
21] reported the beneficial co-effects between S doping and Fe(III) on phenol photodegradation; doping decreased the bandgap energy due to the formation of impurity levels and suppressed the recombination of electrons and holes by trapping electrons, leading to higher the photoactivity of Fe single-bond S-co doped TiO
2 compared to that of undoped and S-doped TiO
2.
Within this scenario, the purpose of the present investigation was to study the influence of chlorine and sulphur on an FeO–TiO2 catalyst prepared by incipient impregnation. In this regard, the chlorine will modify the iron sphere coordination in order to form FeCl species complexes in the impregnation solution. The FeCl species complexes could improve the formation of the FeS phase in the FeO–TiO2 catalysts after sulfurization activation. The aqueous impregnation solutions of the FeCl species complexes, dried solids and sulphated catalysts were characterized by different physicochemical techniques such as DRS UV–Vis, TPR, Raman and XPS. The oxide and sulphated catalyst activity were evaluated by UV–Vis and TOC techniques on a visible-light reactor.
3. Discussion
Table 7 shows HYDRA-Medusa diagrams that presented the chemical equilibrium diagrams for the solution impregnation ratio iron/chlorine. In this sense, the catalysts Fe–0.25Cl, Fe–0.5Cl and Fe–1.0Cl presented 0.21, 0.41 and 0.70 FeCl fractions species, respectively. Additionally, the Fe–0.25Cl, Fe–0.5Cl and Fe–1.0Cl catalysts exhibited lower degradation. The Fe–2.0Cl and Fe–3.0Cl showed 0.85 FeCl fraction. Besides, the Fe–2.0Cl and Fe–3.0Cl catalysts displayed a higher photocatalytic activity than Fe–0.25Cl, Fe–0.5Cl and Fe–1.0Cl materials. At these ratios, 2.0 and 3.0, the area chemical equilibrium between FeCl species located in the interface region and OH groups of the titania support. K. Bourikas, C. Kordulis, and A. Lycourghiotis [
45] extensively discussed the adsorption between supports and positive species complexes such as FeCl
+, so it will be not considered in this paper.
DRS UV–Vis spectra showed a relation between the bandgap for oxide catalysts and the chlorine concentration presented on
Figure 15. On the one hand, the bandgap of Fe–0.25Cl catalyst was 3.01 and the percentage degradation was about 29.0%. On the other hand, the addition of chlorine species increases the bandgap making suitable for visible-light activation. In this regard, the Fe–2Cl catalyst showed a bandgap value of 3.10 with higher degradation and mineralization percentage than Fe–0.25Cl. However, the excess concentrations of chlorine (Fe–3.0Cl) reduced the bandgap and decreased the degradation–mineralization ratio. According to above, the results suggested that chlorine addition increases the absorbance spectrum for visible-light activation increasing the photocatalytic activity. However, chlorine in the excess condition reduced the bandgap and mineralization.
Table 8 presents the Fe
2+/Fe
3+ ratio observed in TPR. The Fe
2+/Fe
3+ ratio showed that the degradation and mineralization incremented simultaneously until Fe
2+/Fe
3+ ratio at 0.77 (
Figure 16). The Fe
2+/Fe
3+ at 0.84 exhibited a decrement of phenol degradation and mineralization. In this regard, the TPR results suggested that the addition of chlorine in the Fe photocatalyst increased the Fe
2+ species and decreased redox temperature. In addition, the Fe
2+ species promotes photoactivity and mineralization ratios.
Figure 17 shows Fe
2+ reduction temperature vs. degradation and mineralization activity. The Fe
2+ reduction temperature at 670 °C presented 40% and 50% of phenol mineralization and degradation, respectively. The Fe
2+ reduction temperature at 710 C presented 10% and 20% of phenol mineralization and degradation, respectively. This result suggests that the temperature reduction in Fe
2+ influenced on photocatalytic activity. The reduction in Fe
2+ at a lower temperature is related to the moderate-strength metal–support interaction. The temperature shift in Fe
2+ reduction could be related to an increment of sulfurization degree.
The diagrams HYDRA-MEDUSA and Raman results suggested that the formation of Fe–Cl species was replaced by sulphide species after the sulfurization process [
46]. This behaviour could possibly br attributed to the formation of chlorine–sulphur bonds. In addition, chlorine–sulphur bounds are known to be unstable at ambient conditions [
46]. The sulphide–oxide ratio is seen in
Table 9 and
Figure 18. The sulphide–oxide ratio results showed that the sulphurisation degree was similar for all catalysts.
In addition, the difference in photoactivity could be attributed to the formation of FeS species. In this sense, X-ray photoelectron spectra (XPS) at a low resolution were used to calculate the S and Fe ratios (
Table 10 and
Figure 19). The S/Fe ratio results indicated that species S promotes photoreactions and mineralization rates. Fe–Sy species presented higher activity than Fe–Ox species.
XPS diagrams were used to calculate bandgap after sulphurisation (
Table 11 and
Figure 20). The presence of S in the catalysts showed a 3% decrease in the bandgap. However, this slight decrease in bandgap was not attributed to photoactivity. An increase in activity can be attributed to the formation of FeS that provides reducing properties, promoting electron exchange. The bandgap of (3.05 eV) at equilibrium conditions (FeS–2Cl) achieved the highest degradation and mineralization rates.
The results suggested that the addition of chlorine on catalysts promotes the creation of Fe2+ species. In addition, Fe2+ species increase FeS formation rising phenol degradation and mineralization.
According to Dehua Xia, Yan Li, Guocheng Huang, Chi Ching Fong, Taicheng An, Guiying Li, Ho Yin Yip, Hunjun Zhao, Anhuai Lu, and Po Keung Wong, the conduction band (CB) of Fe
2O
3 is more favourable than that of FeS
2. Moreover, this has a more negative valence band (VB) than FeS
2. These suggestions led to the discovery that photogenerated electrons transfer from the CB of FeS
2 to the CB of Fe
2O
3 and, finally, to the VB of the FeS
2 [
47]. The energy band configuration of the photocatalyst system could significantly promote the separation efficiency of photogenerated electron-hole pairs [
42,
48]. Additionally, some reports suggested that calcination at high temperatures and with a fast-heating rate could produce oxygen or sulphur vacancies in the mineral structure [
49,
50].
Figure 21 shows a proposed schematic diagram of the energy band configuration, obtained from conduction band and valence band values from XPS diagrams. Potential OH * and O * values were presented by Dehua Xia, Yan Li, Guocheng Huang, Chi Ching Fong, Taicheng An, Guiying Li, Ho Yin Yip, Hunjun Zhao, Anhuai Lu, and Po Keung Wong. 2015 [
47].
Figure 21 shows the position of the valence and conduction band of FeS–Cl catalysts. The conduction band was obtained throughout XPS diagrams using the position of the Fermi level [
44]. The valence band position was estimated by adding the band gap energy obtained from XPS O1s diagram. The Eg is the minimum energy required to excite an electron from the valence band to the conduction band. On the other hand, FeOx and FeSy phases are present in the sulfided materials. However, only one valence band and conduction band are shown for each one. In this regard, the FeSy–FeOx composite is a new material chemically linked with novelty physical and chemical properties. The band gap, the valence band and the conduction band can be tuned by modifying S/Fe composition. The reduction potential of the photogenerated electrons for the most active composite FeS–2Cl is more negative. Therefore, there was a larger energy available to perform the O
2/*O
2− production. The proposed results suggested that the potential formation of superoxide and peroxide ions produced a higher photocatalytic and mineralization ratio. Additionally, the possible formation of hydroxide and peroxide ions reduced the degradation–mineralization ratio.
4. Materials and Methods
HYDRA program was used to calculate the fraction Fe and Cl species in solution. The iron and chlorine solutions were obtained from the salts FeN3O9 and NaCl, respectively. The iron solution at 5.68 M was modified with chlorine solution at different molar ratio Fe/Cl: 0.25, 0.5, 1.0, 2.0, 3.0. The synthesis of the catalysts was carried out by incipient impregnation. FeN3O9 salt was fixed at 0.82 gr corresponding to 10.0% w per 1.0 gr of catalyst. NaCl salt weight was modified according with the concentration desired. The ionized water volume was added in FeN3O9 and NaCl salts according to support total volume (0.35 mL per gram of support). This mixed solution was calcinated on a VULCAN 3-1750 furnace. Furnace conditions were:
Ramp 1, drying: 5 °C per minute until reaching 120 °C and remained at that temperature for 3 h.
Ramp 2, calcination: 10 °C per minute until reaching 300 °C and remained at that temperature for 5 h.
Ramp 3, cooling: 5 °C per minute until reaching 50 °C and remained at that temperature for 3 h.
These catalysts were sulphated at 300 °C for 1 h and named by the acronyms: TiO2S, FeS–0.25Cl/TiO2, FeS–0.5Cl/TiO2, FeS–Cl/TiO2, FeS–2Cl/TiO2, FeS–3Cl/TiO2.
Characterization of the Synthesized Photocatalysts
Raman spectrometry characterizations were performed with a Thermo Scientific DXR2 equipment with microscope. The sample was placed in the sampler of the equipment where it was analysed with the OMNIC program from 0 to 3500 Raman length, a general sweep was performed and a sweep to the bands of interest. Repetitions per catalyst were performed and an average of analysis was worked on for the appropriate study.
Diffuse reflectance technique (DRS UV–Vis) was obtained with a Cary-100 spectrophotometer using an optical length of 0.2 cm and a diffuse reflectance integrating sphere in the range of 190 to 400 nm, using barium sulphate (BaSO4) as a reference.
Temperature-programmed reduction (TPR) experiments for solids were carried out on an AMI-90 apparatus (Altamira) equipped with a thermal conductivity detector (TCD). About 50 mg of a sample was placed in a quartz sample cell (U-shaped) for each analysis. The samples were pre-treated in situ at 373 K for 1 h under Air flow to remove fissured impurities. The reduction step was performed under a stream of (10 vol.%) H2/Ar (50 cm3 min−1), with a heating rate of 10 K min−1 up to 1073 K. A thermal conductivity detector was used to determine variations in the hydrogen composition of the output stream. A moisture trap was used to avoid interferences in the measurements.
X-ray photoelectron spectrometry (XPS) equipment was used for the determination of oxidation states of components. Abundance and semi-quantitative analysis of components: Fe, S, Cl, Ti, O. Level binding energy: 2p3/2, 2p1/2 of Fe; 2p3/2, 2p1/2 of S; 2p3/2, 2p1/2 of Cl; 2p3/2, 2p1/2 of Ti; 1s of O. High resolution determination of Fe 2p in the region 730 to 700 eV; S 2p in the region 170 to 150 eV; Cl 2p in the region 204 to 194 eV; Ti 2p in the region 470 to 450 eV; O 1s in the region 540 to 520 eV. High resolution determination of C1s as a reference.
The photocatalytic visible-light reactions were carried out in a 0.75 L double jacketed Pyrex® batch reactor with a white LED lamp (λ = 450 nm and 550 nm, 78.5 W m−2). The lamp was placed vertically at the top of the reactor, and airflow was added throughout the reaction. The phenolic solution was kept for 30 min under stirring (600 rpm) and in the dark for adequate dissolution of the contaminant. Subsequently, the catalyst was injected and kept for another 30 min under the same conditions to establish the adsorption pre-equilibrium; then, the lamp was switched on for six h. The samples were analysed in a UV–Vis Lambda 20 spectrometer and a Shimadzu TOC-Lcph/n total organic carbon (TOC) instrument for degradation, and mineralization rates, respectively. The amounts of catalyst and phenol were 1 g L−1 and 40 mg L−1, respectively.