Synthesis and Analysis of UV-filters Intercalated in Zeolite L A Major Qualifying Project Submitted to the Faculty of Worcester Polytechnic Institute in partial fulfillment of the requirements for the Degree in Bachelor of Science in Chemical Engineering Chemistry By ____________________________________Fengfan Zhu Date: __________ Project Advisors ___________________________________Marion Emmert _____________________________________Arne Gericke [PRINTED CONFIDENTIAL] This report represents work of WPI undergraduate students submitted to the faculty as evidence of a degree requirement. WPI routinely publishes these reports on its web site without editorial or peer review. For more information about the projects program at WPI, see http://www.wpi.edu/Academics/Projects. 1 | Page Abstract Infrastructure maintenance costs billions of dollars every year. ABSTRACT This project aimed to optimize the intercalation process for non-charged UV-filters in Zeolite L as well as characterize the intercalated products using different analytical technologies. UV-Visible, Fluorescence, Raman and Infrared Spectroscopy have all been tested to characterize the intercalated products. Of these, UV-Visible Spectroscopy of the washing solution provided the best indirect characterization for intercalated products. To optimize the intercalation process, loading rates were improved by varying the experimental conditions: dispersion time, size, temperature, heating time, and humidity. This project will contribute to the future work of the Meso Sun sunscreen project. 1 ACKNOWLEDGEMENT I would like to extend my sincere gratitude to all those who helped me during the project. I could not complete this project without all of your insight, advice and guidance. A special acknowledgement should be shown to our sponsor, Zürich University of Applied Sciences and Professor Achim Ecker for offering me this great opportunity to work in Switzerland. I also want to extend my thanks to Professor Arne Gericke and Professor Marion Emmert in Worcester Polytechnic Institute, who saved me a spot for this MQP project. Finally, I am particularly indebted to Lucie Sägesser, who gave me kind encouragement and useful instructions all through the project. 2 Table&of&Contents& ABSTRACT'...............................................................................................................................................'1! ACKNOWLEDGEMENT'.........................................................................................................................'2! LIST'OF'FIGURES'...................................................................................................................................'4! LIST'OF'TABLES'.....................................................................................................................................'5! CHAPTER'1:'INTRODUCTION:'...........................................................................................................'6! CHAPTER'2:'BACKGROUND'...............................................................................................................'7! 2.1'UVA/UV[3]'.....................................................................................................................................................'7! 2.2'UV@filtErs'.....................................................................................................................................................'7! 2.2.1!No.4!!!!!Benzophenone.3!....................................................................................................................................!8! 2.2.2!No.18!!!Methylbenzylidene!Camphor!...........................................................................................................!9! 2.3'ZeolitE'L'.....................................................................................................................................................'10! 2.4'Host@'GuEst'CoMpound'.........................................................................................................................'12! CHAPTER'3:'METHODOLOGY'.........................................................................................................'14! 3.1'IntErcalation'procEdurE'for'nEutral'chargE'UV@filtEr'................................................................'14! 3.1.1!Preparation!...........................................................................................................................................................!15! 3.1.2!Factor:!dispersion!time!....................................................................................................................................!15! 3.1.3!Factor:!temperature,!heating!time!or!size!...............................................................................................!16! 3.2.3!Factor:!humidity!.................................................................................................................................................!19! 3.2'SaMplE'charactErization'......................................................................................................................'20! 3.2.1!UV.Visible!Spectroscopy!for!washing!solution!......................................................................................!21! 3.2.2!Fluorescence!Spectroscopy!............................................................................................................................!25! 3.2.3!Raman!Spectroscopy!.........................................................................................................................................!26! 3.2.4!Fourier!transform!Infrared!Spectroscopy!...............................................................................................!26! CHAPTER'4:'RESULTS'&'DISCUSSION'..........................................................................................'28! 4.1'IntErcalation'procEss'analYsis'and'optiMization'........................................................................'28! 4.1.2!Fact:!dispersion!time!........................................................................................................................................!28! 4.1.3!Fact:!humidity!......................................................................................................................................................!29! 4.1.4!Fact:!small.scale!or!big.scale!procedure!..................................................................................................!30! 4.1.5!Fact:!temperature!and!heating!time!...........................................................................................................!31! 4.2'OthEr'CharactErization'MEthods'......................................................................................................'34! 4.2.1!Fluorescence!Spectroscopy!............................................................................................................................!34! 4.2.2!Raman!Spectroscopy!.........................................................................................................................................!34! 4.2.3!Infrared!Spectroscopy!......................................................................................................................................!35! CHAPTER'5:'CONCLUSIONS'AND'RECOMMENDATIONS'........................................................'37' BIBLIOGRAPHY'...................................................................................................................................'38' 3 LIST OF FIGURES Figure 1: Structure of Benzophenone-3 Figure 2: Raw UV-Vis spectrum for pure UV-filter 4 (0.00015 mol/L) in solvent ethanol Figure 3: Structure of 4-Methylbenzylidene Camphor Figure 4: Raw UV-Vis spectrum for pure UV-filter 18 (0.00006 mol/L) in solvent ethanol Figure 5: Framework Type Data for Zeolite L (LTL)[ Figure 6: A) Zeolite L framework projected along the c-axis B) side view of the main channel C) its dimensions Figure 7: Dynamic Light Scattering (DLS) results for Zeolites Figure 8: Scanning Electron Microscopy (SEM) image of Tosoh Zeolite L Figure 9: Mechanism of The Intercalation Process for Neutral UV-filters[14] Figure 10: Flowchart of the intercalation process for neutral UV-filters Figure 11: Timetable for small-scale procedure Figure 12: Timetable for big-scale procedure Figure 13: Raw UV-Vis spectrum for pure UV-filter 4 (green) and 18 (red) in solvent ethanol Figure 14: UV-VIS calibration curve for a) UV-filter 4 (y= 8544.2 x +0.1506) b) UV-filter 18 (y= 22937 x -0.0205) in solvent ethanol Figure 15: Flowchart of The washing process for neutral UV-filters Figure 16: Schematic of an Attenuated Total Reflection accessory for Infrared Spectroscopy Figure 17: Adsorption rate VS dispersion time in room temperature range for UV-filter 4 Figure 18: Humidity test: Loading Rate VS Time for 100 degree UV-filter 18 Figure 19: Loading rate vs. time for 100 degree celsius using the small-scale and big-scale procedure Figure 20: Loading rate vs. time for three temperatures from 0.5 hr to 5 hrs -UV-filter 4 Figure 21: Loading rate with first washing only vs. time for three temperatures from 0.5 hr to 5 hr- UV-filter 4 Figure 22: Equilibrium mechanism for the intercalation process of UV-filter 4 Figure 23: Equilibrium mechanism for the intercalation process of UV-filter 18 Figure 24: Loading rate vs. time for three temperatures for the small-scale procedure from 0.5 hr to 5 hrs- UV-filter 18 Figure 25: Loading rate vs. time for three temperatures for the