0910 nghiên cứu khả năng hấp phụ một số hợp chất hữu cơ trên các vật liệu tio2 và khoáng sét bằng phương pháp hóa học tính toán luận văn tốt nghiệp

MINISTRYOF EDUCATIONANDTRAINING QUYNHONUNIVERSITY NGUYEN NGOCTRI STUDY ON THE ADSORPTION ABILITY OF ORGANICMOLECULES ON TiO2AND CLAY MINERAL MATERIALS USINGCOMPUTATIONALCHEMISTRYMETHODS DOCTORALTHESISINCHEMISTRY BINHDINH-2021 NguyenNgocTri STUDY ON THE ADSORPTION ABILITY OF ORGANICMOLECULES ON TiO2AND CLAY MINERAL MATERIALS USINGCOMPUTATIONALCHEMISTRYMETHODS Major : PhysicalandTheoreticalChemistry944 CodeNo : 0119 Reviewer1 : Assoc.Prof.PhamTranNguyenNguyenAss Reviewer2 : oc.Prof.TranVanTan Reviewer3 : Assoc.Prof.PhamVuNhat Supervisors: Assoc.Prof.NguyenTienTrung Prof.MinhTho Nguyen BINHDINH-2021 Declaration This thesis was completed at the Department of Chemistry, Faculty of NaturalSciences,QuyNhonUniversity(QNU)underthesupervisionofAssoc.Prof.Ngu yen Tien Trung (QNU, Vietnam) and Prof Minh Tho Nguyen (KU Leuven,Belgium) I hereby declare that the results presented in this thesis are new andoriginal While most of them were published in peer-reviewed journals, the otherparthasnotbeenpublishedelsewhere BinhDinh,2021 Author NguyenNgocTri Acknowledgements First of all, I would like to express my sincerest thanks to the supervisors,Assoc Prof Nguyen Tien Trung and Prof Minh Tho Nguyen, for their patientguidance, genius support, and warm encouragement I would also like to thank themfor their valuable comments, suggestions,and corrections.I n fact, without t h e i r help,thisthesis couldnothavebeenachievable I am grateful to all LCCM members for their help and valuable discussionduring my research time I am very thankful to my friend, Dai Q Ho, for his helpduring my graduate study I would like to thank Prof A.J.P Carvalho, University ofEvora,Portugal,forhisvaluablecomments,revisions,andcomputing facilities Ia m t h a n k f u l t o Q u y N h o n U n i v e r s i t y a n d K U L e u v e n f o r p r o v i d i n g m e withsuchagreatopportunitytopursuemydoctoralprogram.Mythanksareextended toallstaff a t theFacultyofNaturalSc ie nces, QuyNhonU niversity andthe Department of Chemistry, KU Leuven for their help and supports during myPhDt i m e M y a c k n o w l e d g e m e n t s a l s o g o t o m y f r i e n d s a n d c o l l e a g u e s f o r t h e i r timeandfriendship Furthermore, I would also like to thank the VLIR-TEAM project awarded toQuy Nhon University with Grant number ZEIN2016PR431 (2016-2020) and theVINIF scholarship with code number VINIF.2019.TS.73 for the financial supportsduring mydoctoralstudies Lastly and most importantly, I am forever grateful to my family for all theirloveandsupportthrough thenumerousdifficultiesIhavebeenfacing BinhDinh,2021 NguyenNgocTri TABLEOFCONTENTS ListofSymbolsandNotationsList ofFigures ListofTables INTRODUCTION 1 Motivation Research purpose 3 Objectandscopeofthisstudy 4 Research contents Methodology .5 Novelty,scientificandpracticalsignificance PART1 OVERVIEW OFLITERATURE Organicpollutantsandantibioticsresiduesinwastewaters TiO2nanomaterialanditsapplications .8 Claymineralsandtheirapplicationsinthe treatmentofpollutants 10 Investigationson materialssurfacesusingcomputationalchemistry .12 PART 2.T HE ORE TI C A L B A C KGR OU N D ANDCOMPUTATIONAL METHODS 13 Quantumchemicalapproaches .13 1.1 Schrödingerequations 13 1.2 TheBorn-Oppenheimerapproximation andPauli‘sexclusionprinciple .15 1.2.1 Born– Oppenheimerapproximation 15 1.2.2 Pauli’sexclusionprinciple .15 1.3 Thevariational principle 16 1.4 Basis sets 17 1.4.1 SlaterandGaussianorbitals 17 1.4.2 Somepopularbasissets 18 1.5 Hartree-Fockapproximation 19 1.6 Densityfunctionaltheory 20 1.6.1 TheHohenberg-Kohntheorem .21 1.6.2 Kohn-Sham equations 21 1.6.3 Localdensityapproximation 22 1.6.4 Generalgradient approximation 23 1.6.5 Hybridfunctionals 24 1.6.6 VanderWaalsfunctionals 25 1.7 Pseudopotentialandplane-wavemethods 26 1.8 AtomsInMoleculesandNaturalBondOrbitalsapproaches 29 1.8.1 AtomsInMoleculesanalysis 29 1.8.2 NaturalBondOrbitalsanalysis 31 Computationalmethods 33 2.1 TiO2systems 33 2.2 Claymineralsystems 35 2.2.1 Adsorption oforganicmoleculeson kaolinitesurfaces 35 2.2.2 Adsorptionofantibioticsonvermiculite surface 35 2.3 Quantumchemical analyses .36 PART3.RESULTS ANDDISCUSSION 38 CHAPTER1 A D S O R P T I O N O F O R G A N I C M O L E C U L E S O N M A T E R I A L S SURFACES .38 1.1 Adsorptionof organic moleculesonrutile-TiO2(110)surface .38 1.1.1 Optimizedstructures .38 1.1.2 Energeticaspects 40 1.1.3 The quantumchemicalanalysisfor theinteractionsonsurface 42 1.1.4 Summary 44 1.2 Adsorptionofbenzenederivativesonrutile-TiO 2(110)andanataseTiO 2(101)surfaces .44 1.2.1 Geometrical structures 44 1.2.2 Energeticaspectsof theadsorptionprocess .48 1.2.3 Formation androleofintermolecularinteractions 50 1.2.4 Summary 56 1.3 Adsorptionof benzenederivativesonkaolinite(001) surface 57 1.3.1 Optimizedgeometries 57 1.3.2 Energeticaspectsof theadsorptionprocess .59 1.3.3 Formation androleofintermolecularinteractions 61 1.3.4 Summary 65 1.4 Adsorption ofbenzenederivativeson aK+-supportedkaolinite(001)surface.65 1.4.1 Stablecomplexes 65 1.4.2 Adsorption energy 66 1.4.3 AIMandNBOanalyses 68 1.4.4 Summary 70 CHAPTER2 A D S O R P T I O N O F A N T I B I O T I C M O L E C U L E S O N T i O 2A N D VERMICULITESURFACES 72 2.1 Adsorptionof enrofloxacinmoleculeonrutile-TiO2(110)surface .72 2.1.1 Stablestructures 72 2.1.2 Energeticaspectsof theadsorptionprocess .74 2.1.3 Characteristicsofinteractionsonthesurface 75 2.1.4 Summary 77 2.2 Adsorptionofampicillin,amoxicillin, andtetracyclinemoleculesonrutile-TiO2(110)surface 78 2.2.1 Stablecomplexes 78 2.2.2 Energeticaspectsof theadsorptionprocess .81 2.2.3 Characteristicpropertiesof intermolecularinteractions 83 2.2.4 Summary 87 2.3 Adsorptiono f ampicillina n d a m o x i c i l l i n m o l e c u l e s o n a n a t a s e - T i O 2(101)surface 88 2.3.1 Stablestructures 88 2.3.2 Adsorption energy 90 2.3.3 AIMandNBOanalyses 92 2.3.4 Summary 94 2.4 Adsorptionofchloramphenicolmoleculeonavermiculitesurface .95 2.4.1 Geometricalstructures 95 2.4.2 Adsorption,interaction,anddeformationenergies 97 2.4.3 Characteristicsofstableinteractionsuponadsorptionprocess .100 2.4.4 Summary 104 2.5 Adsorptionofβ-lactamantibioticson vermiculitesurface 105 2.5.1 Stablestructures 105 2.5.2 Energeticaspectsoftheadsorptionprocess 109 2.5.3 Existenceandroleofdifferentinteractionsuponcomplexation 113 2.5.4 Summary 118 CONCLUSIONSANDOUTLOOK 120 Conclusions .120 Outlook 122 LISTOFPUBLICATIONSCONTRIBUTES TOTHISTHESIS 123 REFERENCES 124 Appendix LISTOF SYMBOLSAND NOTATIONS Symbol Description 2(ρ(r)) : Laplacianofelectrondensity AIM : AtomsinMoleculestheory AP : Ampicillin a-TiO2 : Anatase-TiO2(101)surface AX : Amoxicillin BCP : Bondcriticalpoint BP : Benzylpenicillin CP : Chloramphenicol d : Distanceofcontact DFT : DensityFunctional Theory DPE : Deprotonationenthalpy Eads : Adsorptionenergy EB : Hydrogenbondenergy Edef-mol : Deformationenergyformolecules Edef-surf : Deformationenergyforsurfaces EDT : Electrondensitytransfer Eint : Interactionenergy ER : Enrofloxacin H(r) : Totalofelectrondensityenergy H-slab : Hydrogen-richfacetofkaolinite(kaolinite(001)surface) K+-slab : K+-supportedkaolinite(001)surface MEP : MolecularElectrostaticPotential NBO : NaturalBondOrbitals O-slab PA : Oxygenrichf a c e t o f k a o l i n i t e ( k a o l i n i t e ( 0 1)s u r f a c e ) : Protonaffinity PBE : Perdew–Burke-Ernzerhof(densityfunctional) q : Netchargeatatom r-TiO2 : Rutile-TiO2(110)surface TC : Tetracycline VASP : ViennaAbinitioSimulationPackage vdW : VanderWaals α : Bondangle Δrr : Changeofbondlength ρ(r) : Electrondensity(atBCP)