Keywords
How to Cite
Abstract
In this work, hydrofluoric acid and ammonium hydrofluoride were used as fluorine precursors, and thiourea and sulfuric acid - as sulfur precursors, and the phase composition, morphology, texture, and electronic structure of non-metals doped TiO2 nanostructures compared, the chemical state of dopants in the obtained materials was examined, and the influence of the specified factors on photocatalytic activity in the processes of photodegradation of complex organic compounds, for example on antibiotic of the tetracycline series – doxycycline, was stadied. It is shown that hydrofluoric acid and thiourea lead to the formation of anatase, while at low ratios of ammonium hydrofluoride to titanium butoxide, anatase heterostructures with brukite are formed, and at high ratios of sulfuric acid to titanium butoxide, the formation of the crystalline phase of titanyl sulfate is observed. It was determined that hydrofluoric acid causes the formation Sheet-like morphology, and the presence of sulfuric acid in the sol-gel reaction mixture leads to the formation of spheroidal particles, which at small ratios of sulfuric acid to titanium butoxide form loosely agglomerated particles of spheroidal morphology, which are formed from anatase crystallites. The photocatalytic activity of codoped TiO2 nanostructures in the doxycycline photodegradation process under UV and visible light irradiation was investigated and it was established that under UV light irradiation the activity mainly depends on the phase composition and crystallite sizes, while under visible light irradiation the activity depends from the interstitual dopants content that increase the materials sensitivity to visible light. It was established that nitrogen, carbon and fluorine co-doped TiO2 nanostructures obtained in the presence of ammonium hydrofluoride are characterized by the presence of surface Ti-F groups and interstitual carbon and surface carbonate, while carbon and sulfur co-doped TiO2 nanostructures obtained in the presence of thiourea after hydrothermal treatment contain Ti-SH groups, which are oxidized as a result of calcination at 450 °C are oxidized with the formation of interstitual sulfur (S6+) and surface sulfate.
References
Крюков А.И., Строюк А.Л., Кучмий С.Я., Походенко. В.Д. Нанофотокатализ, Академпериодика: Киев, 2013, с. 618.
Stroyuk O. Solar Light Harvesting with Nanocrystalline Semiconductors, Springer-Science+Business Media, B.V., 2018, V. 99.
Nasirian M., Lin Y.P., Bustillo-Lecompte C.F., Mehrvar M. Enhancement of Photocatalytic Activity of Titanium Dioxide Using Non-Metal Doping Methods under Visible Light: A Review. Int. J. Environ. Sci. Technol., 2018, 15(9), 2009–2032.
Kang X., Liu S., Dai Z., He Y., Song X., Tan Z. Titanium Dioxide: From Engineering to Applications; Catalysts, 2019, 9(191), 1–32.
Etacheri V., Di Valentin C., Schneider J., Bahnemann D. Visible-Light Activation of TiO2 Photocatalysts: Advances in Theory and Experiments. J. Photochem. Photobiol. C Photochem., 2015, 25, 1–29.
Wang K., Janczarek M., Wei Z., Raja-Mogan T., Endo-Kimura M., Khedr T.M., Ohtani B., Kowalska E. Morphology-and Crystalline Composition-Governed Activity of Titania-Based Photocatalysts: Overview and Perspective. Catalysts, 2019, 9, 1054–1084.
Kumar N., Chauhan N.S., Mittal A., Sharma S. TiO2 and Its Composites as Promising Biomaterials: A Review. BioMetals, 2018, 31(2), 147–159.
Pelaez M., Nolan N.T., Pillai S.C., Seery M.K., Falaras P., Kontos A.G., Dunlop P.S.M., Hamilton J.W.J., Byrne J.A., O’Shea K., Entezari M.H., Dionysiou D.D. A Review on the Visible Light Active Titanium Dioxide Photocatalysts for Environmental Applications. Appl. Catal. B Environ., 2012, 125, 331–349.
Seh Z.W., Li W., Cha J.J., Zheng G., Yang Y., Mcdowell M.T., Hsu P., Cui Y. Sulphur–TiO2 Yolk–Shell Nanoarchitecture with Internal Void Space for Long-Cycle Lithium–Sulphur Batteries Batteries. Nat. Commun., 2013, 4, 1331.
Романовская Н.И., Овчаров М.Л., Мишура А.М., Гранчак В.М., Манорик П.А. Фотокаталитическая Активность Наноструктур ТіО2, cформированных золь-гель методом в присутствии плавиковой кислоты, в процессах превращения оксидов углерода. Теор. экспер. химия, 2019, 55(6), 373–380.
Romanovska N.I., Grebennikov V.M., Shulzshenko O.V., Yaremov P.S., Selyshchev O.V., Zahn D.R.T., Manoryk P.A. Influence of Conditions of Preparation of C,N,F-TiO2 Nanostructures on Their Photocatalytic Activity in Doxycycline Photodegradation Process. Theor. Exp. Chem., 2022, 58(1), 40–47.
Романовская Н.И., Манорик П.А., Селищев А.В., Ермохина Н.И., Яремов П.С., Гребенников В.Н., Щербаков С.Н., Цан Д.Р.Т. Влияния модифицирования ТіО2 тиомочевиной на его фотокаталитическую активность в процессах деградации доксициклина. Теор. экспер. химия, 2020, 56(3), 172–180.
Романовская Н.И., Манорик П.А., Ермохина Н.И., Яремов П.С., Гребенников В.Н. Влияние структурно-размерных характеристик ТіО2 и его фотокаталитическая активность в реакции окисления тетрациклина. Теор. экспер. химия, 2019, 55(5), 316–324.
Ren L., Li Y., Hou J., Bai J., Mao M., Zeng M., Zhao X. The Pivotal Effect of the Interaction between Reactant and Anatase TiO2 Nanosheets with Exposed {001} Facets on Photocatalysis for the Photocatalytic Purification of VOCs. Appl. Catal. B, 2016, 181, 625–634.
Wang W., Zhou Y., Lu C., Ni Y., Rao W. The Effect of Hydrothermal Temperature on the Structure and Photocatalytic Activity of { 001 } Faceted Anatase TiO2. Mater. Lett., 2015, 160, 231–234.
Yu J.C., Yu J., Zhang L., Ho W. Effects of F- Doping on the Photocatalytic Activity and Microstructures of Nanocrystalline TiO2 Powders. Chem. Mater., 2002, 148(14), 3808–3816.
Yu J., Yu Ã.J.C., Cheng B., Hark S.K., Iu K. The Effect of F-Doping and Temperature on the Structural and Textural Evolution of Mesoporous TiO2 Powders. J. Solid State Chem., 2003, 174, 372–380.
Yu J., Wang W., Cheng B., Su B. Enhancement of Photocatalytic Activity of Mesporous TiO2 Powders by Hydrothermal Surface Fluorination Treatment. J. Phys. Chem. C, 2009, 113, 6743–6750.
Doeuff S., Henry M., Sanchez C. Hydrolysis of Titanium Alkoxides: Modification of the Molecular Precursor by Acetic Acid. J. Non. Cryst. Solids, 1987, 89, 206–216.
Wu J.C.S., Yeh C. Sol-Gel-Derived Photosensitive TiO2 and Cu/TiO2 Using Homogeneous Hydrolysis Technique. J. Mater. Res., 2001, 16(2), 615–620.
Nishikiori H., Hayashibe M. Visible Light-Photocatalytic Activity of Sulfate-Doped Titanium Dioxide Prepared by the Sol−Gel Method. Catalysts, 2013, 3, 363–377.
Valentin C. Di, Pacchioni G. Trends in Non-Metal Doping of Anatase TiO2: B , C , N and F. Catal. Today, 2013, 206, 12–18.
Ливер Е. Электронная Спектроскопия Неоранических Соединений, Мир. Москва, 1987, c. 445.
Li Y., Jiang Y., Peng S., Jiang F. Nitrogen-Doped TiO2 Modified with NH4F for Efficient Photocatalytic Degradation of Formaldehyde under Blue Light-Emitting Diodes. J. Hazard. Mater., 2010, 182, 90–96.
Cui Y., Du H., Wen L. Doped-TiO2 Photocatalysts and Synthesis Methods to Prepare TiO2 Films. J. Mater. Sci. Technol., 2008, 24(5), 675–689.
Linnik O., Chorna N., Smirnova N. Non-Porous Iron Titanate Thin Films Doped with Nitrogen: Optical, Structural, and Photocatalytic Properties. Nanoscale Res. Lett., 2017, 12(1), 249–259.
Bickley R.I., Gonzalez-Carreno T., Lees J.S., Palmisano L., Tilley R. Structural Investigation of Titanium Dioxide Photocatalysts. J. Solid State Chem., 1991, 92, 178–190.
Lin X., Fu D., Hao L., Ding Z. Synthesis and Enhanced Visible-Light Responsive of C,N,S-Tridoped TiO2 Hollow Spheres. J. Environ. Sci., 2013, 25(10), 2150–2156.
Wang P., Yap P.S., Lim T.T. C-N-S Tridoped TiO2 for Photocatalytic Degradation of Tetracycline under Visible-Light Irradiation. Appl. Catal. A, 2011, 399(1–2), 252–261.
Xiang Q., Yu J., Jaroniec M. Nitrogen and Sulfur Co-Doped TiO2 Nanosheets with Exposed {001} Facets: Synthesis, Characterization and Visible-Light Photocatalytic Activity. Phys. Chem. Chem. Phys., 2011, 13(11), 4853–4861.
Xu J.H., Li J., Dai W.L., Cao Y., Li H., Fan K. Simple Fabrication of Twist-like Helix N,S-Codoped Titania Photocatalyst with Visible-Light Response. Appl. Catal. B, 2008, 79, 72–80.
Periyat P., McCormack D.E., Hinder S.J., Pillai S.C. One-Pot Synthesis of Anionic (Nitrogen) and Cationic (Sulfur) Codoped High-Temperature Stable, Visible Light Active, Anatase Photocatalysts. J. Phys. Chem. C, 2009, 113(8), 3246–3253.
Eslami A., Amini M.M., Yazdanbakhsh A.R., Mohseni-Bandpei A., Safari A.A., Asadi A. N,S Co-Doped TiO2 Nanoparticles and Nanosheets in Simulated Solar Light for Photocatalytic Degradation of Non-Steroidal Anti-Inflammatory Drugs in Water: A Comparative Study. J. Chem. Technol. Biotechnol., 2016, 91(10), 2693–2704.
Lim M., Zhou Y., Wood B., Guo Y., Wang L., Rudolph V., Lu G. Fluorine and Carbon Codoped Macroporous Titania Microspheres: Highly Effective Photocatalyst for the Destruction of Airborne Styrene under Visible Light. J. Phys. Chem. C, 2008, 112, 19655–19661.
Xu P., Xu T., Lu J., Gao S., Hosmane N.S., Huang B., Dai Y., Wang Y. Visible-Light-Driven Photocatalytic S- and C- Codoped Meso/Nanoporous TiO2. Energy Environ. Sci., 2010, 3, 1128–1134.
Naik B., Parida K.M., Gopinath C.S. Facile Synthesis of N- and S-Incorporated Nanocrystalline TiO2 and Direct Solar-Light-Driven Photocatalytic Activity. J. Phys. Chem. C, 2010, 114, 19473–19482.
Di Valentin C., Finazzi E., Pacchioni G., Selloni A., Livraghi S., Paganini M.C., Giamello E. N-Doped TiO2: Theory and Experiment. Chem. Phys., 2007, 339(1–3), 44–56.
Накамото К. ИК-Спектры и Спектры КР Нерганических и Координационных Соединений; Мир: Москва, 1991, c. 455.
Huang D., Liao S., Quan S., Liu L., He Z., Wan J., Zhou W. Preparation and Characterization of Anatase N–F-Codoped TiO2 Sol and Its Photocatalytic Degradation for Formaldehyde. J. Mater. Res., 2007, 22, 2389–2397.
Lv K., Xiang Q., Yu J. Effect of Calcination Temperature on Morphology and Photocatalytic Activity of Anatase TiO2 Nanosheets with Exposed {001} Facets. Appl. Catal. B, 2011, 104, 275–281.
Sadoc A., Body M., Legein C., Biswal M., Fayon F., Rocquefelte X. NMR Parameters in Alkali , Alkaline Earth and Rare Earth Fluorides from First Principle Calculations. Phys. Chem. Chem. Phys., 2011, 13, 18539–18550.
Zeng L., Song W., Li M., Jie X., Zeng D., Xie C. Comparative Study on the Visible Light Driven Photocatalytic Activity between Substitutional Nitrogen Doped and Interstitial Nitrogen Doped TiO2. Appl. Catal. A, 2014, 488, 239–247.
Yu J., Xiang Q., Mann S. One-Step Hydrothermal Fabrication and Photocatalytic Activity of Surface-Fluorinated TiO2 Hollow Microspheres and Tabular Anatase Single Micro-Crystals with High-Energy Facets. CrystEngComm, 2010, 12, 872–879.
Palanivelu K., Im J.-S., Lee Y.-S. Carbon Doping of TiO2 for Visible Light Photo Catalysis - A Review . Carbon Lett., 2007, 8(3), 214–224.
Wu X., Yin S., Dong Q., Guo C., Li H., Kimura T., Sato T. Synthesis of High Visible Light Active Carbon Doped TiO2 Photocatalyst by a Facile Calcination Assisted Solvothermal Method. Appl. Catal. B, 2013, 142–143, 450–457.
Pany S., Naik B., Martha S., Parida K. Plasmon Induced Nano Au Particle Decorated over S,N-Modified TiO2 for Exceptional Photocatalytic Hydrogen Evolution under Visible Light. ACS Appl. Mater. Interfaces, 2014, 6, 839–846.
Манорик П.А., Лампека Я.Д., Ермохина Н.И., Цымбал Л.В., Тельбиз Г.М., Гуртовий Р.И. Функциональные материалы на основе диоксида титана различной морфологии и металл-органических каркасных соединений. Теор. экспер. химия, 2017, 53(5), 326–334.
Chen Y., Jiang Y., Li W., Jin R., Tang S. Adsorption and Interaction of H2S/SO2 on TiO2. Catal. Today, 1999, 50, 39–47.
Ohno T., Akiyoshi M., Umebayashi T., Asai K., Mitsui T., Matsumura M. Preparation of S-Doped TiO2 Photocatalysts and Their Photocatalytic Activities under Visible Light. Appl. Catal. A, 2004, 265, 115–121.
Szatmáry L., Bakardjieva S., Šubrt J., Bezdička P., Jirkovský J., Bastl Z., Brezová V. Korenko M. Sulphur Doped Nanoparticles of TiO2. Catal. Today, 2011, 161(1), 23–28.