Alapi, Tünde

Náfrádi, Máté

Takács, Erzsébet

Wojnárovits, László

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     PROCEEDINGS OF THE   25th International Symposium on Analytical and Environmental Problems     Szeged, Hungary October 7-8, 2019       University of Szeged   25th International Symposium on Analytical and Environmental Problems 2   Edited by: Tünde Alapi István Ilisz     Publisher: University of Szeged, H-6720 Szeged, Dugonics tér 13, Hungary         ISBN 978-963-306-702-4         2019. Szeged, Hungary   25th International Symposium on Analytical and Environmental Problems 3  The 25th International Symposium on Analytical and Environmental Problems   Organized by: SZAB Kémiai Szakbizottság Analitikai és Környezetvédelmi Munkabizottsága    Supporting Organizations Institute of Pharmaceutical Analysis, University of Szeged Department of Inorganic and Analytical Chemistry, University of Szeged Institute of Environmental Science and Technology, University of Szeged Hungarian Academy of Sciences   Symposium Chairman: István Ilisz, DSc  Honorary Chairman: Zoltán Galbács, PhD  Organizing Committee: István Ilisz, DSc associate professor University of Szeged, Institute of Pharmaceutical Analysis ilisz@pharm.u-szeged.hu  Tünde Alapi, PhD assistant professor University of Szeged, Department of Inorganic and Analytical Chemistry alapi@chem.u-szeged.hu     25th International Symposium on Analytical and Environmental Problems 23 DETERMINATION OF HYDROXYL RADICALS USING COUMARIN AND COUMARIN-3-CARBOXYLIC ACID DURING GAMMA RADIOLYSIS AND HETEROGENEOUS PHOTOCATALYSIS  Máté Náfrádi1, László Wojnárovits2, Erzsébet Takács2, Tünde Alapi1  1Department of Inorganic and Analytical Chemistry, University of Szeged, H-6720 Szeged, Dóm tér 7, Hungary 2Institute for Energy Security and Environmental Safety, Centre for Energy Research, Hungarian Academy of Sciences, Budapest, Hungary e-mail: nafradim@chem.u-szeged.hu  Abstract Coumarin and 3-carboxycoumarinic acid, two fluorescent probes commonly used for HO• detection has been used during gamma radiolysis and heterogeneous photocatalysis. The O2 dependency and the radiation yield of their hydroxylated flurescent products (7-hydroxy-coumarin and 7-hydroxy-3-carboxycoumarinic acid) has been investigated during gamma radiolysis. The radiation yields were found to be 1.2(±0.2) % in O2-free solutions, while it was 2.9 (±0.06) % in the presence of O2, proving the importance of peroxyl radicals in the formation of these products. The results obtained from radiolysis experiments, were employed during heterogeneous photocatalysis performed with commercial TiO2 catalyst. The effect of dissolved O2 was also investigated, as its electron scavanging role during photocatalyis is also important. The formation rate of HO• during photocatalysis was calculated from the formation rate of the fluorescent products, and were found to be 1.8×10-7 mol dm-3 s-1, while the quantum efficiency for its formation is 0.0038.  Introduction Advanced oxidation processes (AOPs) have been investigated in the last few decades for their possible use as an additional wastewater purification method. During AOPs different reactive species form, the most important one is the hydroxyl radical (HO•), due to its high reaction rate with most organic pollutants. However several methods can be employed, like time-resolved spectroscopy, ESR, the determination of HO• formation rates is a complicated task. Fluorescent probes, like terephtalic acid or coumarines, have also been applied during heterogeneous photocatalyis to evaluate the formation rate of HO•. [1-5] In this study coumarin (COU) and coumarin-3-carboxylic acid (3-CCA) have been used as a fluroescent probe for determination of the HO• formation rate. They are reported to form highly fluorescent hydroxylated prodcts in their reaction with HO•, 7-hydroxy-coumarin (7-HO-COU) and 7-hydroxy-3-carboxycoumarinic acid (7-HO-3-CCA), respectively. The formation rate of both hydroxylated products are reported to be dependant on dissolved O2. In the presence of O2 they form via peroxyl type radicals, while in the abscence of O2 they form via dismutation, significantly reducing their formation rate. [1-3] The application of COU and 3-CCA for HO• detection was investigated during two, different AOPs. In the case of gamma radiolysis the formation rate of all reactive species (HO•, eaq-, H•) is well determined, since the values of their radiation yields (G value) are well known. Heterogeneous photocatalysis is also a highly researched field of AOPs, but the reacton mechanisms are often not clear. The transformation of organic compounds is mostly related to the reactions with HO•. In addition, the reactions initiated directly by the photogenerated charges (hvb+ and ecb-) has to be taken into consideration too. The reactions take place on the surface or close to the surface of photocatalyst, and consequently the interactions between the photocatalyst and substrate may have an important role.   25th International Symposium on Analytical and Environmental Problems 24 The aim of this study is to determine the radiation yields of 7-HO-COU and 7HO-3-CCA, and investigate the effect of dissolved O2 during gamma radiolysis. Based on these result, the formation rate of HO• and the quantum yield of the HO• formation (ΦHO•) may be determined during the heterogeneous photocatalysis. By comparing the transformation of the non-adsorbed COU, and the well adsorbed 3-CCA, we may investigate the importance of adsorption on the reactions of these substrates with HO•.   Experimental In the gamma-radiolysis experiments a 60Co gamma source was used in a panoramic type irradiator, the dose rate was 1.48 Gy min-1. The solutions of COU and 3-CCA were irradiated in sealed ampulles, which were saturated with either O2, N2O or N2. All experiments were performed in 10-4 mol dm-3 solutions of COU and 3-CCA in pH = 7.0 (in 0.01 mol dm3 phosphate buffer). Photocatalysis experiments were performed in a glass reactor. 1.0 g dm-3 TiO2 Aeroxide P25 (Acros Organics) was added to the 250 cm3 solutions, and irradiated using a fluorescent UV light source (GCL303T5/UVA, Lighttech) emitting in the 300-400 nm range. The photon flux of the lamp was 1.20×10-5 molphoton min-1, determied by ferrioxalate actinometry. Since 3-CCA adsorbed on the photocatalyst surface (≈30 % adsorbed on TiO2), NaF was added to the samples, for the desorption of the analytes. All samples were centrifuged at 15000 RPM, and filtered using 0.22 µm syringe filters (FilterBio PVDF-L).  The transformation of COU and 3-CCA (λCOUmax = 277 nm, λ3-CCAmax = 291 nm, εCOU=10300 dm3 mol-1 cm-1, ε3-CCA=12170 dm3 mol-1 cm-1) has been followed using UV-Vis spectrophotometry (Agilent 8453). The formation of 7-HO-COU and 7-HO-3-CCA were followed using fluorescence spectroscopy (Hitachi F4500) at 455 and 447 nm, respectively. The initial transformation rates of COU and 3-CCA were determined from linear regression fits to the actual concentration versus the duration of irradiation, up to 15 % conversion. The initial formation rates of 7-HO-COU and 7-HO-3-CCA were obtained from the linear regression fits to the actual concentration versus the duration of irradiation.  Results and discussion First the effect of O2 on the formation of 7-HO-COU and 7-HO-3-CCA was investigated. In the case of radiolysis mainly HO• and eaq- forms from water. In the presence of O2 eaq- transforms into O2•-. Since both O2•- and its protonated form, HO2• have a low reactivity towards organic compounds, mainly HO• is responsible for the transformation of COU in this case. Moreover, from carbon centered radicals peroxyl radicals form immediately. The formation of peroxly radicals opens a new pathway for the formation of hydroxilated products via unimolecular HO2• elimination. In O2-free solutions both the HO• and the eaq- are able to initiate the transformation of COU. Without O2, the formation of 7-HO-COU happens via bimolecilar dismutation. The formation rate of HO• in the presence of O2, air or N2 can be calculated (r0HO• = 6.91×10-9 mol dm-3 s-1). In N2O saturated solutions eaq- transforms into HO•, and doubling the HO• yield (r0HO• = 1.33×10-8 mol dm-3 s-1).           25th International Symposium on Analytical and Environmental Problems 25   Figure 1. Concentration of COU (A) and 3-CCA (B) as a function of dose in O2 (■), N2O (■)) and N2 (■) saturated solutions, and the formation of 7-HO-COU during gamma radiolysis in O2 (◊), N2O (◊) and N2 (◊) saturated solutions.   The effect of the different gases on the transformation rate of COU and 3-CCA were negligible. Despite the similar transformation rates, the formation rate of the hydroxylated products show significant differences. The lowest formation rate can be observed in O2-free solution, due to the lack of the possibility of peroxyl radical formation, and probably because of the significant contribution of eaq- to the transformation of COU/3-CCA, which do not result in hydroxilated products. The formation rates in N2O saturated solutions are greatly increased, due to the increased HO• formation rate. The formation rates are even higher in the presence of O2, despite the lower HO• formation, proving the importance of peroxyl radicals in the formation of the hydroxylated products. (Figure 1. and Table 1) From the formation rates of the hydroxylated products and the formation rate of HO•, the radiation yield for both fluorescent product can be calculated. In N2 saturated solutions 0.94 and 1.35 %, in N2O saturated solutions 1.16 and 1.29 %, while in O2 saturated solutions 2.99 and 2.86% of HO• produces 7-HO-COU from COU and 7-HO-3-CCA from 3-CCA, respectively.    Table 1. Initial transformation rates of COU and 3-CCA and initial formation rates of 7-HO-COU and 7-HO-3-CCA during gamma radiolysis  r0COU  (× 10-9mol dm-3 s-1) r07-HO-COU (× 10-10mol dm-3 s-1) r03-CCA (× 10-9mol dm-3 s-1) r07-HO-3-CCA (× 10-10mol dm-3 s-1) O2 3.35 2.06 3.23 1.98 Air 4.33 1.55 2.40 1.71 N2 3.38 0.64 2.73 0.93   During heterogeneous photocatalysis the main reactive species is the HO•. The photogenerated hvb+ and ecb- pair may also react with organic compounds, especially when there is special interaction between the substrate and the catalyst surface. COU and 3-CCA have different adsorption properties, as COU do not adsorb on the catalyst surface, as opposed to 3-CCA, due to the strong interaction between its carboxyl groups and TiOH surface groups of phtocatalyst.  A B  25th International Symposium on Analytical and Environmental Problems 26    Figure 2. Transformation of COU (A) and 3-CCA (B) as a function of time, in O2 (■), air (■) and N2 (■) saturated suspensions, and the formation of 7-HO-COU during heterogeneus photocatalysis in O2 (◊), air (◊) and N2 (◊) saturated suspensions.   O2 plays a crucial role as an electron scavenger, hindering charge recombination, and helping HO• formation via O2•-. In the case of COU there was no difference in the transformation rates determined in O2 saturated and airated suspensions. At the same time, the formation rate of 7-HO-COU is nearly 1.5 times greater in the case of higher dissolved O2 concentration. In the case of 3-CCA the transformation rate is also higher with 25% in the case of O2 saturated suspension, while the formation rate of 7-HO-3-CCA increased with 33 %. In N2 saturated suspensions the transformation of COU and the formation of 7-HO-COU is negligible. This suggests, that direct charge transfer reactions have a low probability, and HO• formation is negligible. The transformation rate of the well adsorbed 3-CCA is 47 % of the value measured in O2 saturated suspension, and there is no 7-HO-3-CCA formation. This suggest that, 3-CCA transformation can happen via direct charge transfer, but this way does not results in hydroxilated products.   Table 2. Initial transformation rates of COU and 3-CCA and initial formation rates of 7-HO-COU and 7-HO-3-CCA during heterogeneous photocatalysis  r0COU × 10-8 (mol dm-3 s-1) r07-HO COU× 10-9 (mol dm-3 s-1) r03-CCA× 10-8 (mol dm-3 s-1) r07-HO-3-CCA× 10-9 (mol dm-3 s-1) O2 6.15 2.55 8.98 2.77 Air 6.08 1.73 7.10 2.08 N2 0.29 - 4.23 -   Using the results obtained from gamma radiolysis, the formation rate of HO• in the case of O2 saturated TiO2 suspension was found to be 1.78×10-7 and 1.86×10-7 mol dm-3 in the case of COU and 3-CCA respectively. Assuming that, TiO2 absorbs completly the emitted photons from the light source, the quantum yield for the formation of HO• is 0.0037 and 0.0039, respectively.    A B  25th International Symposium on Analytical and Environmental Problems 27 Conclusion  The formation of 7-HO-COU from COU and 7-HO-3-CCA from 3-CCA requires HO•, while dissolved O2 highly enhances their formation rate.  The radiation yield of 7-HO-COU from COU and 7-HO-3-CCA from 3-CCA were determined in the case of gamma-radiolysis  Based on radiation yields of the hydroxylated products, and the photon flux of the light source, the formation rate of HO• and its quantum efficiency has been determined during heterogeneous photocatalysis, using TiO2 as photocatalyst  Acknowledgements This work was financially supported by Industrial Research and development Projects of Hungarian-Indian cooperation (TÉT_15_IN-1-2016-0013). This publication was supported by the János Bolyai Research Scholarship of the Hungarian Academy of Sciences, ÚNKP-19-3-SZTE-207 and UNKP-19-4-SZTE-115, new national excellence programs of the Ministry for Innovation and Technology.  References [1] Louit, G., Foley, S., Cabillic, J., Coffigny, H., Taran, F., Valleix, A., Renault, J.P., Pina, S., Radiation Physics and Chemistry 72 (2005) 119–124. [2] Manevich, Y., Held, K., Biaglow, J.E., Radiation Research 148 (1997) 580–591. [3] Yamashita, S., Baldacchino, G., Maeyama, T., Taguchi, M., Muroya, Y., Lin, M., Kimura, A., Murakami, T., Katsumura, Y., Free Radical Research 46 (2011) 861–871. [4] Zhang, J., Nosaka, J., Applied Catalysis B: Environmental 166–167 (2015) 32–36. [5] Nosaka Y., Nishikawa, M., Nosaka, A.Y., Molecules 19 (2014) 18248–18267.   

Determination of Hydroxyl Radicals Using Coumarin and Coumarin-3-Carboxylic Acid During Gamma Radiolysis and Heterogeneous Photocatalysis

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Determination of Hydroxyl Radicals Using Coumarin and Coumarin-3-Carboxylic Acid During Gamma Radiolysis and Heterogeneous Photocatalysis

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