[en] Phthalocyanines (Pcs) are often used in photosensitization of titanium(IV) oxide, a commonly employed photocatalyst, as such an approach holds the promise of obtaining highly stable
and efficient visible light-harvesting materials. Herein, we report on the preparation, characterization and photoactivity of a series of composites based on TiO2 and peripherally modified metallophthalocyanines: either tetrasulfonated or 4,4′,4′′,4′′′-tetraazaphthalocyanines, with either copper(II), nickel(II) or zinc(II) as the central metal ion. Physicochemical characterization was performed using UV-Vis diffuse reflectance spectroscopy, hydrodynamic particle-size analysis, surface-area analysis using N2 adsorption-desorption measurements and thermogravimetry combined
with differential scanning calorimetry. The band-gap energy values were lower for the composites
with peripherally modified phthalocyanines than for the commercial TiO2 P25 or the unsubstituted
zinc(II) phthalocyanine-grafted TiO2. TG–DSC results confirmed that the chemical deposition, used
for the preparation of Pc/TiO2 composites, is a simple and efficient method for TiO2 surface modification, as all the Pc load was successfully grafted on TiO2. The photocatalytic potential of the Pc/TiO2
materials was assessed in the photocatalytic removal of sulfamethoxazole—a commonly used antibacterial drug of emerging ecological concern. To compare the activity of the materials in different
conditions, photodegradation tests were conducted both in water and in an organic medium.
Disciplines :
Materials science & engineering
Author, co-author :
Musial, Joanna
Belet, Artium ; Université de Liège - ULiège > Chemical engineering
Dariusz T. Mlynarczyk; Poznan University of Medical Sciences
Michal Kryjewski 4; Poznan University of Medical Sciences
Tomasz Goslinski; Poznan University of Medical Sciences
Lambert, Stéphanie ; Université de Liège - ULiège > Chemical engineering ; Université de Liège - ULiège > Department of Chemical Engineering > Nanomaterials, Catalysis, Electrochemistry
Poelman Dirk; University of Ghent
Beata J. Stanisz; Poznan University of Medical Sciences
Language :
English
Title :
Nanocomposites of titanium dioxide and peripherally modified metallophthalocyanines for the photocatalytic degradation of sulfamethoxazole
Burns E.E. Carter L.J. Kolpin D.W. Thomas-Oates J. Boxall A.B.A. Temporal and Spatial Variation in Pharmaceutical Concentrations in an Urban River System Water Res. 2018 137 72 85 10.1016/j.watres.2018.02.066 29544205
Pereira A. Silva L. Laranjeiro C. Lino C. Pena A. Selected Pharmaceuticals in Different Aquatic Compartments: Part I—Source, Fate and Occurrence Molecules 2020 25 1026 10.3390/molecules25051026 32106570
Kucharski D. Nałęcz-Jawecki G. Drzewicz P. Skowronek A. Mianowicz K. Strzelecka A. Giebułtowicz J. The Assessment of Environmental Risk Related to the Occurrence of Pharmaceuticals in Bottom Sediments of the Odra River Estuary (SW Baltic Sea) Sci. Total Environ. 2022 828 154446 10.1016/j.scitotenv.2022.154446 35283119
Liu Q. Feng X. Chen N. Shen F. Zhang H. Wang S. Sheng Z. Li J. Occurrence and Risk Assessment of Typical PPCPs and Biodegradation Pathway of Ribavirin in Wastewater Treatment Plants Environ. Sci. Ecotechnol. 2022 11 100184 10.1016/j.ese.2022.100184
World Health Organization Pharmaceuticals in Drinking-Water World Health Organization Geneva, Switzerland 2013
Khan S. Naushad M. Govarthanan M. Iqbal J. Alfadul S.M. Emerging Contaminants of High Concern for the Environment: Current Trends and Future Research Environ. Res. 2022 207 112609 10.1016/j.envres.2021.112609 34968428
Houtman C.J. Emerging Contaminants in Surface Waters and Their Relevance for the Production of Drinking Water in Europe J. Integr. Environ. Sci. 2010 7 271 295 10.1080/1943815X.2010.511648
Benitez F.J. Acero J.L. Real F.J. Roldan G. Casas F. Comparison of Different Chemical Oxidation Treatments for the Removal of Selected Pharmaceuticals in Water Matrices Chem. Eng. J. 2011 168 1149 1156 10.1016/j.cej.2011.02.001
Belet A. Wolfs C. Mahy J. Poelman D. Vreuls C. Gillard N. Lambert S. Sol-Gel Syntheses of Photocatalysts for the Removal of Pharmaceutical Products in Water Nanomaterials 2019 9 126 10.3390/nano9010126
Feng Y. Li L. Ge M. Guo C. Wang J. Liu L. Improved Catalytic Capability of Mesoporous TiO2 Microspheres and Photodecomposition of Toluene ACS Appl. Mater. Interfaces 2010 2 3134 3140 10.1021/am100620f
Araña J. Herrera Melián J.A. Doña Rodrı́guez J.M. González Dı́az O. Viera A. Pérez Peña J. Marrero Sosa P.M. Espino Jiménez V. TiO2-Photocatalysis as a Tertiary Treatment of Naturally Treated Wastewater Catal. Today 2002 76 279 289 10.1016/S0920-5861(02)00226-2
Levinson R. Berdahl P. Akbari H. Solar Spectral Optical Properties of Pigments—Part I: Model for Deriving Scattering and Absorption Coefficients from Transmittance and Reflectance Measurements Sol. Energy Mater. Sol. Cells 2005 89 319 349 10.1016/j.solmat.2004.11.012
Zu M. Zhou X. Zhang S. Qian S. Li D.-S. Liu X. Zhang S. Sustainable Engineering of TiO2-Based Advanced Oxidation Technologies: From Photocatalyst to Application Devices J. Mater. Sci. Technol. 2021 78 202 222 10.1016/j.jmst.2020.10.061
Youssef Z. Colombeau L. Yesmurzayeva N. Baros F. Vanderesse R. Hamieh T. Toufaily J. Frochot C. Roques-Carmes T. Acherar S. Dye-Sensitized Nanoparticles for Heterogeneous Photocatalysis: Cases Studies with TiO2, ZnO, Fullerene and Graphene for Water Purification Dyes Pigments 2018 159 49 71 10.1016/j.dyepig.2018.06.002
Shayegan Z. Lee C.-S. Haghighat F. TiO2 Photocatalyst for Removal of Volatile Organic Compounds in Gas Phase—A Review Chem. Eng. J. 2018 334 2408 2439 10.1016/j.cej.2017.09.153
Krakowiak R. Musial J. Bakun P. Spychała M. Czarczynska-Goslinska B. Mlynarczyk D.T. Koczorowski T. Sobotta L. Stanisz B. Goslinski T. Titanium Dioxide-Based Photocatalysts for Degradation of Emerging Contaminants Including Pharmaceutical Pollutants Appl. Sci. 2021 11 8674 10.3390/app11188674
Pereira G.F.M. Tasso T.T. From Cuvette to Cells: How the Central Metal Ion Modulates the Properties of Phthalocyanines and Porphyrazines as Photosensitizers Inorganica Chim. Acta 2021 519 120271 10.1016/j.ica.2021.120271
Jang B.U. Choi J.H. Lee S.J. Lee S.G. Synthesis and Characterization of Cu -Phthalocyanine Hybrid TiO2 Sol J. Porphyr. Phthalocyanines 2009 13 779 786 10.1142/S1088424609001054
Rodríguez-Morgade M.S. Stuzhin P.A. The Chemistry of Porphyrazines: An Overview J. Porphyr. Phthalocyanines 2004 8 1129 1165 10.1142/S1088424604000490
De la Torre G. Claessens C.G. Torres T. Phthalocyanines: Old Dyes, New Materials. Putting Color in Nanotechnology Chem. Commun. 2007 20 2000 2015 10.1039/B614234F
Vignesh K. Rajarajan M. Suganthi A. Photocatalytic Degradation of Erythromycin under Visible Light by Zinc Phthalocyanine-Modified Titania Nanoparticles Mater. Sci. Semicond. Process. 2014 23 98 103 10.1016/j.mssp.2014.02.050
Mapukata S. Nyokong T. Development of Phthalocyanine Functionalised TiO2 and ZnO Nanofibers for Photodegradation of Methyl Orange New J. Chem. 2020 44 16340 16350 10.1039/D0NJ03326J
Fei J. Han Z. Deng Y. Wang T. Zhao J. Wang C. Zhao X. Enhanced Photocatalytic Performance of Iron Phthalocyanine/TiO2 Heterostructure at Joint Fibrous Interfaces Colloids Surf. Physicochem. Eng. Asp. 2021 625 126901 10.1016/j.colsurfa.2021.126901
Colbea C. Oancea P. Puiu M. Galaon T. Raducan A. Reusable Hybrid Nanocomposites for Clean Degradation of Dye Waste under Visible Light Mater. Today Commun. 2022 30 103091 10.1016/j.mtcomm.2021.103091
Szymczak J. Kryjewski M. Porphyrins and Phthalocyanines on Solid-State Mesoporous Matrices as Catalysts in Oxidation Reactions Materials 2022 15 2532 10.3390/ma15072532
Musial J. Krakowiak R. Frankowski R. Spychala M. Dlugaszewska J. Dobosz B. Bendzinska-Berus W. Krzyminiewski R. Tykarska E. Zgoła-Grześkowiak A. et al. Simple Modification of Titanium(IV) Oxide for the Preparation of a Reusable Photocatalyst Mater. Sci. Eng. B 2022 276 115559 10.1016/j.mseb.2021.115559
Krakowiak R. Musial J. Frankowski R. Spychala M. Mielcarek J. Dobosz B. Krzyminiewski R. Sikorski M. Bendzinska-Berus W. Tykarska E. et al. Phthalocyanine-Grafted Titania Nanoparticles for Photodegradation of Ibuprofen Catalysts 2020 10 1328 10.3390/catal10111328
Zhang L. Cole J.M. Anchoring Groups for Dye-Sensitized Solar Cells ACS Appl. Mater. Interfaces 2015 7 3427 3455 10.1021/am507334m 25594514
Genc E. Yüzer A.C. Yanalak G. Harputlu E. Aslan E. Ocakoglu K. Ince M. Patir I.H. The Effect of Central Metal in Phthalocyanine for Photocatalytic Hydrogen Evolution via Artificial Photosynthesis Renew. Energy 2020 162 1340 1346 10.1016/j.renene.2020.08.063
Ramirez C. Antonacci C. Ferreira J. Sheardy R.D. The Facile Synthesis and Characterization of Novel Cationic Metallated and Nonmetallated Tetrapyridino Porphyrazines Having Different Metal Centers Synth. Commun. 2004 34 3373 3379 10.1081/SCC-200030591
Szulbinski W.S. Kincaid J.R. Synthesis and Spectroscopic Characterization of Zinc Tetra(3,4-Pyridine)Porphyrazine Entrapped within the Supercages of Y-Zeolite Inorg. Chem. 1998 37 5014 5020 10.1021/ic971118s
Feofanov A. Grichine A. Karmakova T. Kazachkina N. Pecherskih E. Yakubovskaya R. Luḱyanets E. Derkacheva V. Egret-Charlier M. Vigny P. Chelation with Metal Is Not Essential for Antitumor Photodynamic Activity of Sulfonated Phthalocyanines Photochem. Photobiol. 2007 75 527 533 10.1562/0031-8655(2002)0750527CWMINE2.0.CO2
Kubelka P. New Contributions to the Optics of Intensely Light-Scattering Materials Part I J. Opt. Soc. Am. 1948 38 448 10.1364/JOSA.38.000448 18916891
Tauc J. Optical Properties of Amorphous Semiconductors Amorphous and Liquid Semiconductors Tauc J. Springer Boston, MA, USA 1974 159 220 978-1-4615-8705-7
Jin K. Qin M. Li X. Wang R. Zhao Y. Wang H. Z-Scheme Au@TiO2/Bi2WO6 Heterojunction as Efficient Visible-Light Photocatalyst for Degradation of Antibiotics J. Mol. Liq. 2022 364 120017 10.1016/j.molliq.2022.120017
Noroozi R. Gholami M. Farzadkia M. Rezaei Kalantary R. Synthesis of New Hybrid Composite Based on TiO2 for Photo-Catalytic Degradation of Sulfamethoxazole and Pharmaceutical Wastewater, Optimization, Performance, and Reaction Mechanism Studies Environ. Sci. Pollut. Res. 2022 29 56403 56418 10.1007/s11356-022-19375-9 35334054
Bui V.H. Vu T.K. To H.T. Negishi N. Application of TiO2-Ceramic/UVA Photocatalyst for the Photodegradation of Sulfamethoxazole Sustain. Chem. Pharm. 2022 26 100617 10.1016/j.scp.2022.100617
Zhang J. Zhou P. Liu J. Yu J. New Understanding of the Difference of Photocatalytic Activity among Anatase, Rutile and Brookite TiO2 Phys. Chem. Chem. Phys. 2014 16 20382 20386 10.1039/C4CP02201G
Cui Z.-H. Wu F. Jiang H. First-Principles Study of Relative Stability of Rutile and Anatase TiO2 Using the Random Phase Approximation Phys. Chem. Chem. Phys. 2016 18 29914 29922 10.1039/C6CP04973G
Greenstein K.E. Nagorzanski M.R. Kelsay B. Verdugo E.M. Myung N.V. Parkin G.F. Cwiertny D.M. Carbon–Titanium Dioxide (C/TiO2) Nanofiber Composites for Chemical Oxidation of Emerging Organic Contaminants in Reactive Filtration Applications Environ. Sci. Nano 2021 8 711 722 10.1039/D0EN00975J
Hurum D.C. Agrios A.G. Gray K.A. Rajh T. Thurnauer M.C. Explaining the Enhanced Photocatalytic Activity of Degussa P25 Mixed-Phase TiO2 Using EPR J. Phys. Chem. B 2003 107 4545 4549 10.1021/jp0273934
Scanlon D.O. Dunnill C.W. Buckeridge J. Shevlin S.A. Logsdail A.J. Woodley S.M. Catlow C.R.A. Powell M.J. Palgrave R.G. Parkin I.P. et al. Band Alignment of Rutile and Anatase TiO2 Nat. Mater. 2013 12 798 801 10.1038/nmat3697
Kosmulski M. The Significance of the Difference in the Point of Zero Charge between Rutile and Anatase Adv. Colloid Interface Sci. 2002 99 255 264 10.1016/S0001-8686(02)00080-5
Blakemore J.D. Hull J.F. Crabtree R.H. Brudvig G.W. Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex Dalton Trans. 2012 41 7681 7688 10.1039/c2dt30371j 22585306
De S. Devic T. Fateeva A. Porphyrin and Phthalocyanine-Based Metal Organic Frameworks beyond Metal-Carboxylates Dalton Trans. 2021 50 1166 1188 10.1039/D0DT03903A 33427825
Wang Z. Mao W. Chen H. Zhang F. Fan X. Qian G. Copper(II) Phthalocyanine Tetrasulfonate Sensitized Nanocrystalline Titania Photocatalyst: Synthesis in Situ and Photocatalysis under Visible Light Catal. Commun. 2006 7 518 522 10.1016/j.catcom.2006.01.010
Zhou S. Lai J. Liu X. Huang G. You G. Xu Q. Yin D. Selective Conversion of Biomass-Derived Furfuryl Alcohol into n-Butyl Levulinate over Sulfonic Acid Functionalized TiO2 Nanotubes Green Energy Environ. 2022 7 257 265 10.1016/j.gee.2020.09.009
Ji T. Li Z. Liu C. Lu X. Li L. Zhu J. Niobium-Doped TiO2 Solid Acid Catalysts: Strengthened Interfacial Polarization, Amplified Microwave Heating and Enhanced Energy Efficiency of Hydroxymethylfurfural Production Appl. Catal. B Environ. 2019 243 741 749 10.1016/j.apcatb.2018.11.013
Zhang L. Cole J.M. Dai C. Variation in Optoelectronic Properties of Azo Dye-Sensitized TiO2 Semiconductor Interfaces with Different Adsorption Anchors: Carboxylate, Sulfonate, Hydroxyl and Pyridyl Groups ACS Appl. Mater. Interfaces 2014 6 7535 7546 10.1021/am502186k
Oprea C.I. Panait P. Lungu J. Stamate D. Dumbravă A. Cimpoesu F. Gîrţu M.A. DFT Study of Binding and Electron Transfer from a Metal-Free Dye with Carboxyl, Hydroxyl, and Sulfonic Anchors to a Titanium Dioxide Nanocluster Int. J. Photoenergy 2013 2013 1 15 10.1155/2013/893850
Harima Y. Fujita T. Kano Y. Imae I. Komaguchi K. Ooyama Y. Ohshita J. Lewis-Acid Sites of TiO2 Surface for Adsorption of Organic Dye Having Pyridyl Group as Anchoring Unit J. Phys. Chem. C 2013 117 16364 16370 10.1021/jp405835y
Ooyama Y. Inoue S. Nagano T. Kushimoto K. Ohshita J. Imae I. Komaguchi K. Harima Y. Dye-Sensitized Solar Cells Based On Donor-Acceptor π-Conjugated Fluorescent Dyes with a Pyridine Ring as an Electron-Withdrawing Anchoring Group Angew. Chem. Int. Ed. 2011 50 7429 7433 10.1002/anie.201102552
Mohamed M.M. Bayoumy W.A. Khairy M. Mousa M.A. Synthesis of Micro–Mesoporous TiO2 Materials Assembled via Cationic Surfactants: Morphology, Thermal Stability and Surface Acidity Characteristics Microporous Mesoporous Mater. 2007 103 174 183 10.1016/j.micromeso.2007.01.052
Bezrodna T. Puchkovska G. Shimanovska V. Chashechnikova I. Khalyavka T. Baran J. Pyridine-TiO2 Surface Interaction as a Probe for Surface Active Centers Analysis Appl. Surf. Sci. 2003 214 222 231 10.1016/S0169-4332(03)00346-5
Zaki M.I. Hasan M.A. Al-Sagheer F.A. Pasupulety L. In Situ FTIR Spectra of Pyridine Adsorbed on SiO2–Al2O3, TiO2, ZrO2 and CeO2: General Considerations for the Identification of Acid Sites on Surfaces of Finely Divided Metal Oxides Colloids Surf. Physicochem. Eng. Asp. 2001 190 261 274 10.1016/S0927-7757(01)00690-2
Mathew S. Sebastian A. Kuttassery F. Takagi S. Tachibana H. Inoue H. Acid-Base Equilibria of Axial Ligand and Peripheral Pyridyl Group with Stepwise Formation of Nine Species of Aluminum (III) Tera(4-Pyridyl) Porphyrin Inorganica Chim. Acta 2021 526 120529 10.1016/j.ica.2021.120529
Gutz I.G.R. CurTiPot–PH and Acid–Base Titration Curves: Analysis and Simulation Freeware (Version 4.3.1) 2021 Available online: http://www.iq.usp.br/gutz/Curtipot_.html (accessed on 2 May 2022)
Mesgari Z. Gharagozlou M. Khosravi A. Gharanjig K. Spectrophotometric Studies of Visible Light Induced Photocatalytic Degradation of Methyl Orange Using Phthalocyanine-Modified Fe-Doped TiO2 Nanocrystals Spectrochim. Acta. A Mol. Biomol. Spectrosc. 2012 92 148 153 10.1016/j.saa.2012.02.055 22446761
Vallejo W. Navarro K. Díaz-Uribe C. Schott E. Zarate X. Romero E. Zn(II)-Tetracarboxy-Phthalocyanine-Sensitized TiO2 Thin Films as Antimicrobial Agents under Visible Irradiation: A Combined DFT and Experimental Study ACS Omega 2021 6 13637 13646 10.1021/acsomega.1c00658
Priyanka K.P. Sankararaman S. Balakrishna K.M. Varghese T. Enhanced Visible Light Photocatalysis Using TiO2/Phthalocyanine Nanocomposites for the Degradation of Selected Industrial Dyes J. Alloys Compd. 2017 720 541 549 10.1016/j.jallcom.2017.05.308
Hudec P. Smiešková A. Idek Z. Schneider P. Ŝolcová O. Determination of Microporous Structure of Zeolites by T-Plot Method—State-of-the-Art Studies in Surface Science and Catalysis Aiello R. Giordano G. Testa F. Impact of Zeolites and other Porous Materials on the new Technologies at the Beginning of the New Millennium Elsevier Amsterdam, The Netherlands 2002 142 1587 1594
Thommes M. Kaneko K. Neimark A.V. Olivier J.P. Rodriguez-Reinoso F. Rouquerol J. Sing K.S.W. Physisorption of Gases, with Special Reference to the Evaluation of Surface Area and Pore Size Distribution (IUPAC Technical Report) Pure Appl. Chem. 2015 87 1051 1069 10.1515/pac-2014-1117
Gommes C.J. Ravikovitch P. Neimark A. Positive Curvature Effects and Interparticle Capillary Condensation during Nitrogen Adsorption in Particulate Porous Materials J. Colloid Interface Sci. 2007 314 415 421 10.1016/j.jcis.2007.05.072
Wu L. Yu J.C. Zhang L. Wang X. Ho W. Preparation of a Highly Active Nanocrystalline TiO2 Photocatalyst from Titanium Oxo Cluster Precursor J. Solid State Chem. 2004 177 2584 2590 10.1016/j.jssc.2004.03.033
Islam S. Fast Responsive Anatase Nanoparticles Coated Fiber Optic PH Sensor J. Alloys Compd. 2021 850 156246 10.1016/j.jallcom.2020.156246
Cadman C.J. Pucci A. Cellesi F. Tirelli N. Water-Dispersible, Ligand-Free, and Extra-Small (<10 Nm) Titania Nanoparticles: Control Over Primary, Secondary, and Tertiary Agglomeration Through a Modified “Non-Aqueous” Route Adv. Funct. Mater. 2014 24 993 1003 10.1002/adfm.201301998
Li D. Zhang P. Ge S. Sun G. He Q. Fa W. Li Y. Ma J. A Green Route to Prepare Metal-Free Phthalocyanine Crystals with Controllable Structures by a Simple Solvothermal Method RSC Adv. 2021 11 31226 31234 10.1039/D1RA04064B
Pająk A. Rybiński P. Janowska G. Kucharska-Jastrząbek A. The Thermal Properties and the Flammability of Pigmented Elastomeric Materials J. Therm. Anal. Calorim. 2014 117 789 798 10.1007/s10973-014-3739-x
Rodriguez-Mozaz S. Chamorro S. Marti E. Huerta B. Gros M. Sànchez-Melsió A. Borrego C.M. Barceló D. Balcázar J.L. Occurrence of Antibiotics and Antibiotic Resistance Genes in Hospital and Urban Wastewaters and Their Impact on the Receiving River Water Res. 2015 69 234 242 10.1016/j.watres.2014.11.021 25482914
Chang H. Hu J. Asami M. Kunikane S. Simultaneous Analysis of 16 Sulfonamide and Trimethoprim Antibiotics in Environmental Waters by Liquid Chromatography–Electrospray Tandem Mass Spectrometry J. Chromatogr. A 2008 1190 390 393 10.1016/j.chroma.2008.03.057
Göbel A. McArdell C.S. Suter M.J.-F. Giger W. Trace Determination of Macrolide and Sulfonamide Antimicrobials, a Human Sulfonamide Metabolite, and Trimethoprim in Wastewater Using Liquid Chromatography Coupled to Electrospray Tandem Mass Spectrometry Anal. Chem. 2004 76 4756 4764 10.1021/ac0496603
Dąbrowski J.M. Pucelik B. Regiel-Futyra A. Brindell M. Mazuryk O. Kyzioł A. Stochel G. Macyk W. Arnaut L.G. Engineering of Relevant Photodynamic Processes through Structural Modifications of Metallotetrapyrrolic Photosensitizers Coord. Chem. Rev. 2016 325 67 101 10.1016/j.ccr.2016.06.007
Miller J.S. Cornwell D.G. The Role of Cryoprotective Agents as Hydroxyl Radical Scavengers Cryobiology 1978 15 585 588 10.1016/0011-2240(78)90082-2
Misik V. Riesz P. Free Radical Formation by Ultrasound in Organic Liquids: A Spin Trapping and EPR Study J. Phys. Chem. 1994 98 1634 1640 10.1021/j100057a016
Gupta S. Gomaa H. Ray M.B. A Novel Submerged Photocatalytic Oscillatory Membrane Reactor for Water Polishing J. Environ. Chem. Eng. 2021 9 105562 10.1016/j.jece.2021.105562
European Chemicals Agency Titanium Dioxide—Brief Profile 2022 Available online: https://echa.europa.eu/brief-profile/-/briefprofile/100.033.327 (accessed on 20 April 2022)
