Functionalized mesoporous silicas SBA-15 for heterogeneous photocatalysis towards CECs removal from secondary urban wastewater

Functionalized mesoporous silicas SBA-15 for heterogeneous photocatalysis towards CECs removal from secondary urban wastewater Bruna Castanheiraa, Larissa Otubob, Cristiano L. P. Oliveirac, Rosa Montesd, José Benito Quintanad, Rosario Rodild, Sergio Brochsztaine, Vítor J. P. Vilarf, Antonio Carlos S. C. Teixeiraa,* aResearch Group in Advanced Oxidation Processes (AdOx), Chemical Systems Engineering Center, Department of Chemical Engineering, University of São Paulo, Av. Prof. Luciano Gualberto, tr. 3, 380, São Paulo, SP, Brazil bNuclear and Energy Research Institute (IPEN), Av. Prof. Lineu Prestes, 2242, 05508000, São Paulo, SP, Brazil. cInstitute of Physics, University of São Paulo, Rua do Matão 1371, 05508-090, São Paulo, SP, Brazil dDepartment of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Constantino Candeira S/N, 15782 Santiago de Compostela, Spain. eFederal University of ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil. fLaboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials (LSRE-LCM), Department of Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. Corresponding author: Antonio Carlos S. C. Teixeira ([email protected]). This is the postprint (accepted manuscript) version of the article published in Chemosphere https://doi.org/10.1016/j.chemosphere.2021.132023 © 2021, Elsevier This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/ Highlights  First study using TiO2/SBA-15 for CECs oxidation in an annular FluHelik photoreactor.  Removal of sulfadiazine (SDZ) from pure water and urban waste water (UWW) spiked with SDZ.  The activity of TiO2/SBA-15 in UWW was higher than that of standard TiO2P25 for SDZ degradation.  Adsorption and/or photocatalysis were able to remove other 65 CECs detected in the UWW matrix. Highlights (3 to 5 bullet points (maximum 85 characters including spaces per bullet point) 1 Functionalized mesoporous silicas SBA-15 for heterogeneous photocatalysis 1 towards CECs removal from secondary urban wastewater 2 3 Bruna Castanheiraa, Larissa Otubob, Cristiano L. P. Oliveirac, Rosa Montesd, José 4 Benito Quintanad, Rosario Rodild, Sergio Brochsztaine, Vítor J. P. Vilarf, Antonio 5 Carlos S. C. Teixeiraa,* 6 7 aResearch Group in Advanced Oxidation Processes (AdOx), Chemical Systems 8 Engineering Center, Department of Chemical Engineering, Escola Politécnica, University 9 of São Paulo, Av. Prof. Luciano Gualberto, tr. 3, 380, São Paulo, SP, Brazil 10 bNuclear and Energy Research Institute (IPEN), Av. Prof. Lineu Prestes, 2242, 0550811 000, São Paulo, SP, Brazil. cInstitute of Physics, University of São Paulo, Rua do Matão 12 1371, 05508-090, São Paulo, SP, Brazil 13 dDepartment of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research 14 on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de 15 Compostela, Constantino Candeira S/N, 15782 Santiago de Compostela, Spain. 16 eFederal University of ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil. 17 fLaboratory of Separation and Reaction Engineering-Laboratory of Catalysis and 18 Materials (LSRE-LCM), Department of Chemical Engineering, Faculty of Engineering, 19 University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. 20 21 Corresponding author: Antonio Carlos S. C. Teixeira ([email protected]). 22 23 24 Abstract 25 Revised manuscript Clean version (double-spaced and continuously LINE and PAGE numbered) Click here to view linked References 2 The photocatalytic activity of TiO2 nanoparticles (NP) supported on mesoporous silica 26 SBA-15 (TiO2/SBA-15) was evaluated for the photodegradation of sulfadiazine (SDZ), 27 as target contaminant of emerging concern (CEC), using either pure water solutions (PW) 28 or a real secondary urban wastewater (UWW) spiked with SDZ. For this purpose, 29 TiO2/SBA-15 samples with 10, 20 and 30% TiO2 (w/w) were prepared by the sol-gel post 30 synthetic method on pre-formed SBA-15, using titanium (IV) isopropoxide as a 31 precursor. The TiO2/SBA-15 materials were characterized by HRTEM, SAXS and XRD, 32 nitrogen adsorption isotherms and UV-vis diffuse reflectance spectroscopy. TiO2 NPs 33 were shown to be attached onto the external surface, decorating the SBA-15 particles. 34 The TiO2/SBA-15 catalysts were active in SDZ photodegradation using the annular 35 FluHelik photoreactor, when irradiated with UVA light. The 30% TiO2/SBA-15 sample 36 presented the best performance in optimization tests performed using PW, and it was 37 further used for the tests with UWW. The photocatalytic activity of 30% TiO2/SBA-15 38 was higher (56% SDZ degradation) than that of standard TiO2-P25 (32% SDZ 39 degradation) in the removal of SDZ spiked in the UWW ([SDZ] = 2 mg L-1). The 40 photodegradation of SDZ with 30% TiO2/SBA-15 reached 90% when a UWW spiked 41 with a lower SDZ concentration ([SDZ] = 40 µg L-1). Aside of SDZ, a suit of 65 other 42 CECs were also identified in the UWW sample using LC-MS spectrometry. A fast43 screening test showed the heterogeneous photocatalytic system was able to remove most 44 of the detected CECs from UWW, by either adsorption and/or photocatalysis. 45 46 47 Keywords: Advanced Oxidation Processes; Photocatalysis; Mesoporous Silicas; 48 FluHelik Photoreactor; Sulfadiazine. 49 1. Introduction 50 3 The shortage of good quality water supplies for the world population has become one of the 51 main challenges of the 21st century. In addition to the pollutants commonly found in water, 52 a new class of contaminants has gained increasing attention in recent years. The so-called 53 contaminants of emerging concern (CECs) are synthetic or natural substances found at low 54 concentrations (ng L-1 to µg L-1) in water bodies, and which are suspect of causing hazardous 55 effects to the ecosystem and to the human health (Krzeminski et al., 2019; Rivera-Utrilla et 56 al., 2013; Rodriguez-Narvaez et al., 2017). Pharmaceutical products, antibiotics, hormones 57 and pesticides are relevant examples of CECs. CECs are not regularly monitored in the 58 environment, as there is no regulation for their control in most countries. They are usually 59 not eliminated by conventional water treatment methods, and are then disposed into the 60 environment, where they may accumulate in living organisms. Moreover, wastewater reuse 61 for agriculture might lead to the introduction of CECs in the food chain. Urban wastewaters 62 treatment plants (WWTPs) are the main sources of CECs released into the environment, 63 which can induce bacterial resistance and cause damage to aquatic ecosystems (Kovalakova 64 et al., 2020; Kümmerer, 2009a, 2009b). 65 Different methods for advanced wastewater treatment have been considered in attempt to 66 remove CECs from WWTPs, including adsorption, membrane filtration, ozonation and 67 advanced oxidation processes (AOPs) (Krzeminski et al., 2019; Mohammad et al., 2017; 68 Rivera-Utrilla et al., 2013; Rodriguez-Narvaez et al., 2017). Among AOPs, TiO2-based 69 photocatalysis has been acknowledged as a promising alternative for CECs removal (Fagan 70 et al., 2016; Miranda-García et al., 2014, 2010). TiO2 NPs are low-cost, nontoxic, chemically 71 and physically stable. However, commercially available TiO2 (e.g. P-25) poses some 72 drawbacks, such as low surface area and a tendency to agglomerate in aqueous media. 73 Moreover, small TiO2 particles are difficult to recover by filtration or centrifugation, leading 74 to a difficult separation and recycle, thus limiting its application in industrial scale (Dong et 75 4 al., 2015). To avoid those problems, in this work it was adopted a strategy reported by several 76 authors, namely the immobilization of TiO2 onto mesoporous silica SBA-15 (Acosta-Silva 77 et al., 2011; Araújo et al., 2016; Besançon et al., 2016; Busuioc et al., 2006; Calzada et al., 78 2019; Conceição et al., 2017; Lachheb et al., 2011; Liou et al., 2018; Liu et al., 2016; López79 Muñoz et al., 2005; Mehta et al., 2016; Salameh et al., 2015; Tseng et al., 2012; Van Grieken 80 et al., 2002; Wei et al., 2018; Yang et al., 2006; Yuan et al., 2020). Different techniques have 81 been employed for the functionalization of SBA-15 with TiO2, including incipient wet 82 impregnation (Calzada et al., 2019), microwave assisted technique (Mehta et al., 2016), 83 direct synthesis (Liou et al., 2018) and sol-gel post-synthetic method, (Conceição et al., 84 2017; Yang et al., 2006) which was the technique employed in the present work. In general, 85 TiO2/SBA-15 materials have shown good efficiency for the degradation of CECs such as 86 dyes (Acosta-Silva et al., 2011; Calzada et al., 2019; Tseng et al., 2012) and other industrial 87 organic contaminants (Conceição et al., 2017; Mehta et al., 2016; Yuan et al., 2020). 88 To our knowledge, however, all those investigations were limited to batch reactors and 89 synthetic solutions of the contaminant, which are hard to scale up to real systems. In this 90 context, a new concept of light-driven scalable reactor, the annular FluHelik reactor 91 (Espíndola et al., 2019; Moreira et al., 2019) (Figure S1), which consists of a cylindrical 92 stainless steel shell with inlet and outlet pipes located perpendicularly to the fluid flow on 93 opposite sites and tangentially to the reactor tube in horizontal plane. The single and 94 cylindrical UV lamp is located in a concentric inner quartz sleeve. This design leads to a 95 helicoidal flow around the quartz sleeve allowing a more intense macromixing dynamics, as 96 well as homogenous UV fluence (Figure S1). Furthermore, the design of the FluHelik 97 photoreactor favors the implementation of several reactors in series, promoting their 98 application on an industrial scale (Espíndola and Vilar, 2020). The FluHelik photoreactor 99 has been successfully employed for homogenous photochemical reactions, such as 100 5 UVC/H2O2, UVC/O3 and photo-Fenton, targeting the treatment of leachates from sanitary 101 landfills (pre-industrial scale) (Gomes, et al., 2018), slaughterhouse wastewater and CECs 102 removal from secondary urban wastewaters (Alfonso-Muniozguren et al., 2021; Gomes, et 103 al., 2021; Barbosa et al., 2020; Espíndola et al., 2019; Espíndola et al.,2021). However, the 104 FluHelik reactor has not yet been tested for AOPs involving heterogeneous catalysis. 105 In the present work, the FluHelik reactor was used to promote heterogeneous photocatalysis, 106 using a functionalized silica consisting of TiO2 nanoparticles (NPs) supported on SBA-15 107 mesoporous silica. The system was tested for the photodegradation of sulfadiazine (SDZ) 108 selected as a model of CEC. An example of sulfonamide antibiotics, SDZ is predominantly 109 eliminated in its original form; due to its high stability, about 30-90% of the ingested dose 110 is not absorbed by the body. As a weak acid, SDZ has high solubility (77 mg L-1) and water 111 mobility and has been found in water bodies and wastewater (Balakrishnan et al., 2006; 112 García-Galán et al., 2011). In addition to being able to induce bacterial resistance, SDZ can 113 also cause toxic effects and act as an endocrine disruptor in several living organisms and 114 possibly in humans (Baran et al., 2011; Paulus et al., 2019). 115 The photocatalytic efficiency of TiO2/SBA-15 in the FluHelik photoreactor was optimized 116 for SDZ oxidation using pure water solutions. Furthermore, the TiO2/SBA-15 photocatalysts 117 were also active in the degradation of SDZ spiked in real urban waste water (UWW), 118 collected after secondary treatment and tested as a real matrix. 119 Recently, new analytical methods employing high-resolution mass spectrometry combined 120 with liquid chromatography-quadrupole-time of flight mass spectrometer (LC-QTOF) have 121 allowed the screening of a large number of CECs in water bodies at the ng L-1 to μg L-1 level 122 in a single run (Paíga et al., 2019; Schymanski et al., 2014; Castro et al., 2021; Wilson et al., 123 2021). Using LC-QTOF, we were able to detect 65 other CECs present in the UWW sample. 124 Remarkably, irradiation of the UWW in the FluHelik reactor with the TiO2/SBA-15 125 6 photocatalysts led to a reduction in the concentration of most of these CECs initially present 126 in the UWW. 127 2. Experimental 128 2.1 Chemicals 129 The following reagents were obtained from Sigma-Aldrich: Pluronic P123 (amphiphilic 130 triblock copolymer, average molecular weight 5,800, 97% purity), tetraethyl orthosilicate 131 (TEOS), sulfadiazine (SDZ, 99% purity) and titanium (IV) isopropoxide (TTIP, 97% purity). 132 Hydrochloric acid and isopropanol were purchased from Baker. Standard TiO2 (Aeroxide® 133 P-25; purity ≥ 99.5%; specific surface area 55 m2 g-1) was obtained from Evonik. The real 134 wastewater sample was collected after the secondary treatment of an urban wastewater 135 (UWW) from Portugal in October 2019. Its physicochemical characteristics are summarized 136 in Table S1. 137 2.2 Catalysts synthesis 138 2.2.1 Synthesis of pristine SBA-15 139 The pure SBA-15 matrix was synthesized according to the standard procedure (Zhao et al., 140 1998), as follows: 4.1 g of Pluronic P123 was dissolved in 30 mL of deionized water under 141 stirring at 35 °C, then 120 g of 2 M HCl aqueous solution was added, and the mixture was 142 stirred for 2 h. In the sequence, 8.5 g (41 mmol) of tetraethylorthosilicate (TEOS) was added 143 and the system was maintained at 35 °C for 24 h under constant stirring. Thereafter, the 144 formed gel was transferred to a mini autoclave, which was sealed and subjected to 145 hydrothermal conditions at 100 °C for 24 h. The sample obtained was washed with 2 L of 146 deionized water, and the precipitated solid was filtrated under vacuum, washed once again 147 with 1 L of deionized water and dried under vacuum for 48 h. Finally, the resulting material 148 was subjected to calcination at 500 °C under N2 atmosphere for 4 h with a heating rate of 10 149 °C min-1 to decompose the triblock copolymer and obtain the SBA-15. 150 7 151 2.2.2 Functionalization of SBA-15 with titanium dioxide 152 The titanium dioxide crystals were deposited onto the SBA-15 surface via sol-gel processing 153 according to the procedure described by Yang et al. (Yang et al., 2006) For this purpose, 154 SBA-15 (1.0 g) was sonicated in 50 mL of isopropanol. Different amounts of TTIP were 155 then added, in order to produce samples with different TiO2 contents, as given in Table 1. 156 Deionized water was slowly added to the resulting mixture (TTIP/water with volumetric 157 ratio of 1/10) to guarantee the hydrolysis of the TTIP. The mixture was stirred for 2 h at 158 room temperature, followed by centrifugation and washing with deionized water. The solid 159 product was dried at 80 °C overnight and then calcined in air at 700 °C for 2 h to obtain the 160 x%TiO2/SBA-15 catalysts, where x% represents the wt% of titania loading (Table 1). 161 162 Table 1. Description of the TiO2/SBA-15 samples prepared. 163 Sample Volume TTIP (mL)a Weight % TiO2 Ti/Sib 10% TiO2/SBA-15 0.37 10% 0.08 20% TiO2/SBA-15 0.74 20% 0.15 30% TiO2/SBA-15 1.11 30% 0.23 a Added to 1 g of SBA-15 (dTTIP = 0.96 g cm-3). b Molar ratio. 164 165 2.3 Catalysts characterization 166 The pristine SBA-15 and TiO2/SBA-15 materials were structurally characterized by N2 167 physisorption at 77 K using the Nova 2200 Surface Area and Pore Size Analyzer 168 (Quantachrome). The surface areas were obtained by the BET method, pore volumes were 169 calculated at P/P0 = 0.97 and average pore diameters were obtained by the BJH method 170 (desorption branch). 171 14 303 Figure 2. HRTEM images of pristine SBA-15 (A, B), 10% TiO2/SBA-15 (C, D), 20% 304 TiO2/SBA-15 (E, F) and 30% TiO2/SBA-15 (G, H). 305 306 The TiO2/SBA-15 samples were further characterized by nitrogen adsorption isotherms 307 (Figure 3A). The corresponding pore size distributions are shown in the insert of Figure 3A. 308 15 Textural parameters are given in Table S2. All the materials presented type IV(a) isotherms 309 with H1 hysteresis loop, which are typical of 2D-hexagonal SBA-15 materials (Zhao et al., 310 1998). The data in Table S2 suggest that the TiO2 NP were mainly attached to the external 311 surface of the SBA-15 particles, as seen in the TEM images (Figure 2), since specific surface 312 areas, pore volumes and pore diameters did not decrease substantially in comparison with 313 SBA-15, as would be expected if the NP were inside the pores. The surface areas and pore 314 volumes actually increased, which is likely due to the extra external area impinged by the 315 presence of the coating NP. The large surface areas are beneficial for contaminant molecules 316 to access the exposed active sites, thus favoring photocatalytic performance. 317 The presence of TiO2 in the samples was further detected in the powder diffuse reflectance 318 spectra of the catalysts (Figure 3B). The spectra show the typical UV absorption band of 319 TiO2, which is not seen in the spectrum of SBA-15. The spectra end at about 415 nm, 320 corresponding to a bandgap energy of 3.0 eV, and are shifted to longer wavelengths 321 compared to the TiO2-P25 spectrum, showing that the absorption of UVA radiation by the 322 synthesized TiO2/SBA-15 materials is favored. 323 0.0 0.2 0.4 0.6 0.8 1.0 0 100 200 300 400 500 600 700 3 4 5 6 7 8 9 10 pore diameter (nm) volume adsorbed (cm3 g-1) A P/P0 300 330 360 390 420 450 480 TiO2-P25 B SBA-15 10% TiO2/SBA-15 20% TiO2/SBA-15 30% TiO2/ SBA-15 absrobance (a.u.) wavelength (nm) 324 Figure 3. (A) Nitrogen adsorption isotherms of the TiO2/SBA-15 catalysts. Inset: Pore size 325 distributions (BJH from adsorption branches). Data for pristine SBA-15 are included for 326 comparison. SBA-15 ( ); 10% TiO2/SBA-15 ( ); 20% TiO2/SBA-15 ( ); 30% 327 16 TiO2/SBA-15 ( ). (B) Absorbance spectra (from diffuse reflectance measurements) of 328 the SBA-15, TiO2-P25 and TiO2/SBA-15 catalysts. 329 3.2 Photocatalytic activity 330 3.2.1 Effect of TiO2 content on SDZ degradation 331 The photocatalytic activity of the TiO2/SBA-15 materials was monitored using SDZ as a 332 model CEC. Figure 4 shows the influence of the TiO2 content on the SDZ degradation 333 kinetics, and the results of the experiments are summarized in Table 2. Note that direct 334 photolysis of SDZ, in homogeneous solution, was almost negligible, reaching only 1.6% of 335 SDZ degradation after 180 min (Table 2). When the non-functionalized SBA-15 was present, 336 ca 14% of the SDZ was removed by adsorption, and only 3% of the SDZ was removed by 337 photodegradation. In the presence of TiO2, however, most of the SDZ was removed by 338 photocatalysis, rather than adsorption; in fact, only 2-6% of the SDZ was adsorbed on the 339 TiO2/SBA-15 materials. The photocatalytic degradation of SDZ, on the other hand, 340 increased with TiO2 content from 32% (10% TiO2/SBA-15) to 65% (20% TiO2/SBA-15) 341 and to 73% (30% TiO2/SBA-15). Reaction rates also increased with increasing TiO2 content. 342 A four-fold increase in the pseudo-first order kinetic constant was observed as going from 343 10% to 30% TiO2 (Table 2). 344 A relevant issue is whether the SDZ is deactivated by the irradiation treatment, forming 345 decomposition products with no capability of inducing bacterial resistance. The 346 photocatalytic degradation of SDZ and other sulfonamides over TiO2 has been studied by 347 several authors (Baran et al., 2009; Batista et al., 2014; Calza et al., 2004; Castanheira et al., 348 2018; Huang et al., 2015; Liu et al., 2018). The main pathway reported begins with the 349 breakdown of the S−N bond, followed by secondary fragmentation reactions. Baran et al 350 (Baran et al., 2006) and Zessel et al (Zessel et al., 2014) have shown that the photolytic 351 products of SDZ degradation were devoid of antibacterial activity, and therefore could not 352 17 cause bacterial resistance. Moreover, those reports suggest that total mineralization is not 353 necessary for SDZ deactivation. The characterization of the degradation products, however, 354 is out of the scope of the present work. 355 030 60 90 120 150 180 0.0 0.2 0.4 0.6 0.8 1.0 [SDZ]/ [SDZ]0 time (min) lamp on 356 Figure 4. Photolysis ( ), and the photocatalytic performance of SBA-15 ( ), 10% 357 TiO2/SBA-15 ( ), 20% TiO2/SBA-15 ( ) and 30% TiO2/SBA-15 ( ) for SDZ 358 photodegradation in the FluHelik photoreactor. Conditions: mphotocat = 150 mg; Vsol = 1.5 L; 359 [SDZ]0 = 1.88 ± 0.11 mg L-1; pH0 = 7.0; T = 25 °C. Time values below zero represent the 360 adsorption time in the dark (prior turning on the lamp) and are out of scale (the actual 361 adsorption time was 24 hours). 362 363 3.2.2 Effect of the mass of catalyst employed 364 Considering that 30% TiO2/SBA-15 showed the best photocatalytic performance among the 365 three samples, this material was selected for further experiments. Figure 5 shows the effect 366 of varying the mass of 30% TiO2/SBA-15 catalyst on SDZ photodegradation. Table 2 shows 367 the corresponding parameters obtained from the experiments. The adsorption of SDZ 368 increased with the increase in the catalyst content, reaching the limiting value of 8% SDZ 369 adsorption. Furthermore, photocatalytic performance was also improved, with the best 370 18 performance obtained for 500 mg of the 30% TiO2/SBA-15 catalyst, resulting in complete 371 SDZ removal after 120 min of irradiation. A further increase in catalyst mass did not result 372 in a better performance (Figure 5), both in terms of removal percentage and removal rate, 373 which can be attributed to the increasing turbidity of the suspensions, partially blocking the 374 penetration of the radiation. 375 030 60 90 120 150 180 0.0 0.2 0.4 0.6 0.8 1.0 lamp on [SDZ]/ [SDZ]0 time (min) 376 Figure 5. Photocatalytic performance of 50 mg ( ), 150 mg ( ), 200 mg ( ), 300 377 mg ( ), 500 mg ( ) and 600 mg ( ) of 30% TiO2/SBA-15 for SDZ 378 photodegradation in the FluHelik photoreactor. Conditions: Vsol = 1.5 L; [SDZ]0 = 1.88 ± 379 0.11 mg L-1; pH0 = 7.0; T = 25 °C. Time values below zero represent the adsorption time in 380 the dark (prior turning on the lamp) and are out of scale (the actual adsorption time was 24 381 hours). 382 383 3.2.3 Photocatalyst reutilization 384 From the previous results, the mass of 500 mg of the 30% TiO2/SBA-15 catalyst was selected 385 for the reutilization studies. Figure 6 shows SDZ photodegradation over three cycles with 386 the selected sample, and Table 2 shows the corresponding parameters. As seen in Table 2, 387 19 the adsorptive capacity of the material decreased after the first cycle. This result may be an 388 indication that the remaining sulfadiazine, or intermediates formed during photodegradation 389 remain on the surface of the photocatalyst material after the end of the first cycle. The 390 photoactivity, however, remained high in the subsequent cycles, regardless of the lower 391 adsorption capacity. More than 90% of freshly added SDZ was photodegraded in the second 392 and third cycles, and with nearly the same rate constant as the first cycle (Table 2). The 393 possibility of reutilization is essential for any practical large-scale application. 394 0100 200 300 400 500 600 0.0 0.2 0.4 0.6 0.8 1.0 cycle #3 cycle #2 [SDZ]/ [SDZ]0 time (min) cycle #1 395 Figure 6. Reuse of 30% TiO2/SBA-15 for SDZ photodegradation in a FluHelik photoreactor. 396 Conditions: mphotocat = 500 mg; Vsol = 1.5 L; [SDZ]0 = 1.88 ± 0.11 mg L-1; pH0 = 7.0; T = 25 397 °C. 398 399 3.2.4 Performance of TiO2/SBA-15 catalysts in urban wastewater matrix 400 The degradation of SDZ was also evaluated using a sample of UWW (Table S1), spiked with 401 2 mg L-1 of SDZ. The best condition from the previous experiments, 30% TiO2/SBA-15 (500 402 mg), was employed here. The photocatalytic performance of this sample was compared to 403 that of commercially available TiO2-P25. As observed in Figure 7, TiO2-P25 was more 404 efficient for SDZ degradation than 30% TiO2/SBA-15 in PW. In the UWW, however, the 405 20 opposite behavior was observed, with TiO2/SBA-15 showing better performance than TiO2406 P25. 56% SDZ degradation was obtained after 180 min, with 30% TiO2/SBA-15 in the 407 UWW, as compared to 32% SDZ degradation with TiO2-P25 (Table 2). Moreover, SDZ 408 degradation was faster with 30% TiO2/SBA-15, as indicated by the rate constants in Table 409 2. These results may be due to the reported agglomeration of TiO2-P25 NPs when suspended 410 in wastewater samples, arising from the combined effect of high ionic strength and dissolved 411 organic matter (Romanello and Cortalezzi, 2013; Zhou et al., 2015; Ren et al., 2017; Xu, 412 2018). Zhou et al. (2015), for example, showed that TiO2 NPs with 21 nm diameter formed 413 aggregates with sizes greater than 200 nm when dispersed in real wastewater samples. Thus, 414 dispersion of the TiO2 NP onto the SBA-15 support helped to avoid catalyst nanoparticles 415 agglomeration, leading to a better performance than the standard TiO2-P25 in the real water 416 studied. 417 030 60 90 120 150 180 0.0 0.2 0.4 0.6 0.8 1.0 A lamp on [SDZ]/[SDZ]0 time (min) 030 60 90 120 150 180 0.0 0.2 0.4 0.6 0.8 1.0 B lamp on [SDZ]/[SDZ]0 time (min) Figure 7. Comparison between 30% TiO2/SBA-15 ( ) and TiO2-P25 ( ) for SDZ 418 photodegradation from (A) PW and (B) UWW matrices in the FluHelik photoreactor. 419 Conditions: mphotocat = 500 mg; Vsol = 1.5 L; [SDZ]0 = 1.88 ± 0.11 mg L-1; pH0 = 7.0 (PW) 420 and 7.5 (UWW); T = 25 °C. Time values below zero represent the adsorption time in the 421 dark (prior turning on the lamp) and are out of scale (the actual adsorption time was 24 422 hours). 423 21 424 The SDZ concentration ([SDZ]0 = 1.88 mg L-1) employed in the optimization experiments 425 reported above is much higher than the [SDZ] expected to be found in real wastewater. 426 Therefore, a new SDZ-spiked UWW sample, with [SDZ] = 40 µg L-1, was prepared and 427 irradiated in the FluHelik, with 500 mg of 30% TiO2/SBA-15 (other conditions as above). 428 For this sample, although the adsorption was null, 90.0% of the SDZ was removed by 429 photodegradation (Table 2, last entry), stressing the high efficiency of the present system in 430 conditions similar to real conditions. 431 432 433 434 435 436 437 438 439 440 22 Table 2. Percentage of adsorption (% SDZads), percentage of photodegradation (% SDZdeg), pseudo-first order reaction rate constant (kSDZ), 441 determination coefficient (R2) of the nonlinear data fit and initial reaction rate (r0,SDZ) values obtained in the degradation experiments of SDZ with 442 TiO2/SBA-15 catalyst in the FluHelik photoreactor. 443 Experimenta Matrixb photocatalyst mphotocat (mg) CTiO2 (mg L-1) pHf %SDZ ads %SDZ deg kSDZ (10-2 min-1)c R2 Homogeneous (photolysis) PW − − − 7.4 − 1.6 − − Heterogeneous (photocatalysis) Influence of TiO2 content PW SBA-15 150 0 7.4 13.8 3.1 0.05 0.97 PW 10% TiO2/SBA-15 150 15 7.4 5.6 31.6 0.20 0.96 PW 20% TiO2/SBA-15 150 30 7.2 2.4 65.2 0.61 0.99 PW 30% TiO2/SBA-15 150 45 7.4 4.9 73.2 0.81 0.99 Effect of the mass of photocatalyst employed PW 30% TiO2/SBA-15 50 15 7.3 1.4 40.7 0.23 0.98 PW 30% TiO2/SBA-15 200 60 7.0 6.2 82.5 1.26 0.99 PW 30% TiO2/SBA-15 300 90 7.1 8.6 87.3 1.86 0.98 PW 30% TiO2/SBA-15 500 150 7.1 8.4 88.8 2.36 0.99 PW 30% TiO2/SBA-15 600 180 7.3 8.7 86.2 1.85 0.99 Photocatalyst reutilization PW 30% TiO2/SBA-15 (1st cycle) 500 150 7.2 9.7 87.3 1.87 0.99 PW 30% TiO2/SBA-15 (2nd cycle) 500 150 7.1 2.7 94.5 1.72 0.99 PW 30% TiO2/SBA-15 (3rd cycle) 500 150 7.3 3.1 94.0 1.66 0.99 23 Matrix influence PW TiO2-P25 150 150 6.6 2.2 95.0 6.09 0.99 UWW TiO2-P25 150 150 7.2 1.6 31.6 0.25 0.97 UWW 30% TiO2/SBA-15 500 150 7.6 0.6 (0)d 56.4 (90.0)d 0.43 0.99 a Conditions: Vsol = 1.5 L; Irradiation range: 0-180 min; Q = 75 L h-1; [SDZ]0 = 2 mg L-1 (nominal value); pH0 = 7.0 (PW), 7.5 (UWW). b PW: Pure water; UWW: Urban wastewater. 444 c Apparent first-order rate constant (kapp) of the photocatalytic SDZ degradation. d Data in parenthesis are for the experiment with [SDZ]0 = 40 µg L-1 in UWW. 445 30 Castanheira, B., Triboni, E.R., Andrade, L.S., Trindade, F.J., Otubo, L., Teixeira, 577 A.C.S.C., Politi, M.J., Queiroz, T.B., Brochsztain, S., 2018. 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Chemosphere 119, 568–576. 747 https://dx.doi.org/10.1016/j.chemosphere.2014.07.037 748 749 750 Declaration of interests ☒ The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. ☐The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Declaration of Interest CREDIT AUTHOR STATEMENTS Bruna Castanheira: Conceptualization, methodology, validation, formal analysis, experimental investigation, data curation, writing – original draft; Larissa Otubo: Formal analysis, data curation, writing – original draft; Cristiano L. P. Oliveira: Formal analysis, data curation, writing – original draft; Rosa Montes: Formal analysis, data curation, writing – original draft; José Benito Quintana: Formal analysis, data curation, writing – original draft; Rosario Rodil: Formal analysis, data curation, writing – original draft; Sergio Brochsztain: Supervision, conceptualization, project administration, writing – original draft; Vítor J. P. Vilar: Supervision, conceptualization, project administration, writing – original draft, resources; Antonio Carlos S. C. Teixeira: Supervision, conceptualization, project administration, writing – original draft, resources, funding acquisition. Credit Author Statement 1 Supplementary Information Functionalized mesoporous silicas SBA-15 for heterogeneous photocatalysis towards CECs removal from secondary urban wastewater Bruna Castanheiraa, Larissa Otubob, Cristiano L. P. Oliveirac, Rosa Montesd, José Benito Quintanad, Rosario Rodild, Sergio Brochsztaine, Vítor J. P. Vilarf,*, Antonio Carlos S. C. Teixeiraa,* aResearch Group in Advanced Oxidation Processes (AdOx), Chemical Systems Engineering Center, Department of Chemical Engineering, Escola Politécnica, University of São Paulo, Av. Prof. Luciano Gualberto, tr. 3, 380, São Paulo, SP, Brazil bNuclear and Energy Research Institute (IPEN), Av. Prof. Lineu Prestes, 2242, 05508000, São Paulo, SP, Brazil. cInstitute of Physics, University of São Paulo, Rua do Matão 1371, 05508-090, São Paulo, SP, Brazil dDepartment of Analytical Chemistry, Nutrition and Food Sciences, Institute of Research on Chemical and Biological Analysis (IAQBUS), Universidade de Santiago de Compostela, Constantino Candeira S/N, 15782 Santiago de Compostela, Spain. eFederal University of ABC, Av. dos Estados, 5001, 09210-580, Santo André, SP, Brazil. fLaboratory of Separation and Reaction Engineering-Laboratory of Catalysis and Materials (LSRE-LCM), Department of Chemical Engineering, Faculty of Engineering, University of Porto, Rua Dr. Roberto Frias, 4200-465 Porto, Portugal. Corresponding authors: Antonio Carlos S. C. Teixeira ([email protected]) 8 Table S2. Textural parameters of pristine SBA-15 and TiO2/SBA-15 materials. Sample S BET a (m2 g-1) V p b (cm3 g-1) d c (nm) a 0 d (nm) wt e (nm) L f (nm) SBA-15 394 0.90 6.3 11.5 5.2 − 10% TiO 2 /SBA-15 460 0.96 6.3 10.8 4.5 7.94 20% TiO 2 /SBA-15 460 0.90 6.3 10.8 4.5 6.62 30% TiO 2 /SBA-15 473 0.94 6.3 10.8 4.5 6.18 a Specific surface area (multipoint BET method). b Total pore volume (calculated at P/P0 = 0.97). c Pore diameter (from BJH method, adsorption branch). d Lattice parameter determined from SAXS (Equation 1). e Wall thickness (wt = a0 − pore diameter). f Average TiO2 (anatase) crystallite size (Equation 2). 9 Table S3. Nomenclature, abbreviation, chemical formula, retention time (Rt) and application of the CECs in the UWW identified with LCMS/MS analyzes. Name Abbreviation Chemical Formula Rt (min) Name Abbreviation Chemical Formula Rt (min) Drugs for nervous system 8-Chlorotheophylline Ctp C7H7ClN4O2 6.204 Memantine MEM C12H21N 8.835 Amantadine AMD C10H17N 4.925 Mirtazapine MTZ C17H19N3 6.040 Amisulpride AMI C17H27N3O4S 5.433 Norcitalopram N-CTA C19H19FN2O 9.309 Amitriptyline AMT C20H23N 11.294 O-Desmethylvenlafaxine (Desvenlafaxine) O-DV C16H25NO2 5.815 Caffeine Caf C8H10N4O2 5.636 O-Desmethyltramadol O-DT C15H23NO2 4.633 Carbamazepine CBZ C15H12N2O 11.502 Riluzole RZ C8H5F3N2OS 11.622 Carbamazepine 10,11epoxide CBZ-E C15H12N2O2 8.985 Sulpiride SUL C15H23N3O4S 3.200 Citalopram CTA C20H21FN2O 9.250 Tapentadol TAP C14H23NO 6.830 Gabapentin GABA C9H17NO2 3.329 Topiramate TPM C12H21NO8S 9.205 Hydroxybupropion HBUP C13H18ClNO2 6.526 Tramadol TD C16H25NO2 6.349 Ketamine KTM C13H16ClNO 5.832 Trazodone TZ C19H22ClN5O 8.003 Melperone Me C16H22FNO 7.269 Venlafaxine VEN C17H27NO2 8.304 Drugs for cardiovascular system 5-Hydroxypropafenone 5-OHPF C21H27NO4 9.593 Losartan LOS C22H23ClN6O 13.279 Acebutolol ACE C18H28N2O4 6.914 Perindopril PRD C19H32N2O5 10.378 Bisoprolol BIS C18H31NO4 8.543 Propranolol PRN C16H21NO2 8.845 Celiprolol CLP C20H33N3O4 8.008 Sotalol STL C12H20N2O3S 2.396 Flecainide FLE C17H20F6N2O3 9.398 Telmisartan TEL C33H30N4O2 13.042 Irbesartan IST C25H28N6O 13.546 Drugs for respiratory system Chlorpheniramine CPMH C16H19ClN2 7.21 Fexofenadine FEX C32H39NO4 11.709 Diphenhydramine DPH C17H21NO 9.146 Lidocaine (Diocaine) LDC C14H22N2O 4.687 Doxylamine DOX C17H22N2O 4.707 Drugs for genito urinary system 10 Alfuzosin ALF C19H27N5O4 8.228 Trospium TSP C25H30NO3 8.437 Antiinfectives and antibacterials drugs Clarithromycin CR C38H69NO13 11.091 Sulfapyridine SPy C11H11N3O2S 4.112 Sulfamethoxazole SMX C10H11N3O3S 6.269 Trimethoprim TMP C14H18N4O3 5.058 Dermatologicals drugs Climbazole CLZ C15H17ClN2O2 11.118 Fluconazole(II) FLC C13H12F2 N6O 7.746 Drugs for musculo-skeletal Flufenamic acid FA C14H10F3NO2 15.783 Nimesulide NIM C13H12N2O5S 12.847 Niflumic acid NIF C13H9F3N2O2 14.212 Other pharmaceutical drugs Bicalutamide BIC C18H14F4N2O4S 13.426 Levorphanol LEV C17H23NO 6.317 Diethyltoluamide DEET C12H17NO 12.259 Sitagliptin SGN C16H15F6N5O 6.869 Denatonium DE C21H29N2O 9.267 Tiemonium TI C18H24NO2S 6.554 Levofloxacin LVX C18H20FN3O4 5.640 Warfarin WAR C19H16O4 13.440 Other substances Fipronil FIP C12H4Cl2F6N4OS 15.769 Sucralose SUC C12H19Cl3O8 6.055 Nitrophenolate NP C6H5NO3 6.144 Terbutryn TB C10H19N5S 12.140 Ritalinic acid RA C13H17NO2 5.993 Toluene-2-sulfonamide TSN C7H9NO2S 5.886