PHOTOACTIVE PERFLUORINATED IONOMERIC TRANSPARENT COATING IN THE OXIDATIVE ABATEMENT OF HYDROSOLUBLE POLLUTANTS IN TURBID SUSPENTIONS

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Fluoropolymer 2014, October 13-16, San Diego PHOTOACTIVE PERFLUORINATED IONOMERIC TRANSPARENT COATING IN THE OXIDATIVE ABATEMENT OF HYDROSOLUBLE

1 Fluoropolymer 2014, October 13-16, San Diego PHOTOACTIVE PERFLUORINATED IONOMERIC TRANSPARENT COATING IN THE OXIDATIVE ABATEMENT OF HYDROSOLUBLE POLLUTANTS IN TURBID SUSPENTIONS W. Navarrini, Federico Persico, Maurizio Sansotera Dept. CMIC G.Natta, Politecnico di Milano, via Mancinelli 7, Milano, Italy

2 Fluoropolymer 2014, San Diego Presentation Overview Introduction Aim of the Research Conclusion Photocatalysis as Advanced Oxidation Process Experimental Section Experimental Apparatus Photoactive Coating Analytical Techniques Results and Discussion Photodegradation Results Photoactive Coating Characterization

Aim of the Research Production of a chemically stable and resistent coating, able to promote the photooxidation of hydrosoluble organic pollutants [a,b] Organic Compound hν, TiO 2 H 2 O, O 2

3 Aim of the Research Production of a chemically stable and resistent coating, able to promote the photooxidation of hydrosoluble organic pollutants [a,b] Organic Compound hν, TiO 2 H 2 O, O 2 Mineralization Products Flexible water treatment system developed up to industrial scale [a] A. Mills, S. Le Hunte, J. Photochem. Photobiol., A 108 (1997) 1. [b] S. Gatto, M. Sansotera, F. Persico, M. Gola, C. Pirola, W. Panzeri, W. Navarrini, C.L. Bianchi, Catal. Today, in press, doi: /j.cattod Fluoropolymer 2014, San Diego

4 Organic compounds CO 2, H 2 O, N 2 O 2- Photocatalysis as Advanced Oxidation Process {HO 2, HO 2-, H 2 O 2, OH - } O 2 [c,d,e] H 2 O Organic compounds CO 2, H 2 O, N 2 CB Ti IV OH O 2- {HO 2, HO 2-, H 2 O 2, OH - } H 2 O Ti IV OH s CO 2 CO, H 2 O,, H 2 NO, 2 N 2 VB Ti III OH O 2 H 2 O Organic compounds Ti IV OH + Ti IV OH H 2 O OH H 2 O Organic compounds CO 2, H 2 O, N 2 [c] O. Carp, C.L. Huisman, A. Reller, Prog. Solid State Chem. 32 (2004) 33. [d] M. Sansotera, F. Persico, C. Pirola, W. Navarrini, A. Di Michele, C.L. Bianchi, Appl. Catal., B 148 (2014) 29. [e] M. Sansotera, S. Gatto, F. Persico, C. Pirola, W. Navarrini, C.L. Bianchi, Decomposition of perfluorooctanoic acid photocatalyzed by titanium dioxide: chemical modification of the catalyst surface induced by fluoride ions, awarded as Best Poster on Sustainability at the 17 th ESFC, Paris, July Fluoropolymer 2014, San Diego

Ti IV OH O {HO 2, HO 2-, H 2 O 2, OH - 2- } Photocatalysis as Advanced Oxidation Process Ti IV OH Ti III OH O 2 [c,d,e] H 2 O CB Ti IV OH Organic compounds CO 2, H 2 O, N 2 O {HO 2, HO 2-, H 2 O 2,

5 Ti IV OH O {HO 2, HO 2-, H 2 O 2, OH - 2- } Photocatalysis as Advanced Oxidation Process Ti IV OH Ti III OH O 2 [c,d,e] H 2 O CB Ti IV OH Organic compounds CO 2, H 2 O, N 2 O {HO 2, HO 2-, H 2 O 2, OH - 2- } OH H 2 O Ti IV OH rganic compounds CO 2 CO, H 2 O,, H 2 NO, 2 N 2 VB Ti III OH O 2 H 2 O Organic compounds Ti IV OH + Ti IV OH H 2 O OH H 2 O Organic compounds CO 2, H 2 O, N 2 TiO 2 immobilized into a polymeric matrix Chemical stability UV transparency Gas permeability Hydrophilic IONOMERIC AMORPHOUS FLUOROPOLYMERS [c] O. Carp, C.L. Huisman, A. Reller, Prog. Solid State Chem. 32 (2004) 33. [d] M. Sansotera, F. Persico, C. Pirola, W. Navarrini, A. Di Michele, C.L. Bianchi, Appl. Catal., B 148 (2014) 29. [e] M. Sansotera, S. Gatto, F. Persico, C. Pirola, W. Navarrini, C.L. Bianchi, Decomposition of perfluorooctanoic acid photocatalyzed by titanium dioxide: chemical modification of the catalyst surface induced by fluoride ions, awarded as Best Poster on Sustainability at the 17 th ESFC, Paris, July Fluoropolymer 2014, San Diego

6 Ti IV OH O {HO 2, HO 2-, H 2 O 2, OH - 2- } Photocatalysis as Advanced Oxidation Process Ti IV OH Ti III OH O 2 [c,d,e] H 2 O CB Ti IV OH Organic compounds CO 2, H 2 O, N 2 O {HO 2, HO 2-, H 2 O 2, OH - 2- } OH H 2 O Ti IV OH rganic compounds CO 2 CO, H 2 O,, H 2 NO, 2 N 2 VB Ti III OH O 2 H 2 O Organic compounds Ti IV OH + Ti IV OH H 2 O OH H 2 O Organic compounds CO 2, H 2 O, N 2 TiO 2 immobilized into a polymeric matrix Chemical stability UV transparency Gas permeability Hydrophilic IONOMERIC AMORPHOUS FLUOROPOLYMERS Fluoropolymer 2014, San Diego Easy separation of the treated solution Appliable to turbid solutions Fouling prove photocatalytic assembly [c] O. Carp, C.L. Huisman, A. Reller, Prog. Solid State Chem. 32 (2004) 33. [d] M. Sansotera, F. Persico, C. Pirola, W. Navarrini, A. Di Michele, C.L. Bianchi, Appl. Catal., B 148 (2014) 29. [e] M. Sansotera, S. Gatto, F. Persico, C. Pirola, W. Navarrini, C.L. Bianchi, Decomposition of perfluorooctanoic acid photocatalyzed by titanium dioxide: chemical modification of the catalyst surface induced by fluoride ions, awarded as Best Poster on Sustainability at the 17 th ESFC, Paris, July 2013.

7 Fluorinated Ionomers Ionomers: TFE + Vinylethers containing sulphonic or carboxylic functions [f] High chemical stability High UV transparency Strong acid behaviour Hydrophilicity [f] W.G. Grot, Fluorinated Ionomers; W. Andrew, Ed.; PDL Handbook Series; Elsevier: Amsterdam, Fluoropolymer 2014, San Diego

Fluorinated Ionomers Ionomers: TFE + Vinylethers containing sulphonic or carboxylic functions [f] High chemical stability High UV transparency Strong acid behaviour Hydrophilicity Water collects

8 Fluorinated Ionomers Ionomers: TFE + Vinylethers containing sulphonic or carboxylic functions [f] High chemical stability High UV transparency Strong acid behaviour Hydrophilicity Water collects around the clusters of hydrophilic sulphonate side chains [f] High water absorption in which H + can move freely [f] W.G. Grot, Fluorinated Ionomers; W. Andrew, Ed.; PDL Handbook Series; Elsevier: Amsterdam, Fluoropolymer 2014, San Diego

9 Fluorinated Ionomers Ionomers: TFE + Vinylethers containing sulphonic or carboxylic functions [f] High chemical stability High UV transparency Strong acid behaviour Hydrophilicity MW -R F Polymer Name Company 446 -CF 2 -CF-O-CF 2 -CF 2 -SO 2 F Nafion DuPont CF Flemion Asahi Glass 3 Aciplex Asahi Chemicals 306 -CF 2 -CF 2 -CF 2 -CO 2 -CH 3 Flemion Asahi Glass 380 -CF 2 -CF 2 -CF 2 -CF 2 -SO 2 F 3M Polymer 3M 280 -CF 2 -CF 2 -SO 2 F Dow Polymer Aquivion Dow Chemicals SolvaySpecialtyPolymers Water collects around the clusters of hydrophilic sulphonate side chains [f] High water absorption in which H + can move freely [f] W.G. Grot, Fluorinated Ionomers; W. Andrew, Ed.; PDL Handbook Series; Elsevier: Amsterdam, Fluoropolymer 2014, San Diego

10 Experimental apparatus Quartz sheath TiO 2 containing photoactive coating [g] Low P UV Lamp l = 254 nm W av = 5 W Polluted aqueous solution Constant O 2 feed (7 L/h) Quartz surface AD60 10% thermally treated AD60 10% non-thermally treated AQ 6% - TiO 2 10% Magnetic stirrer [g] F. Persico, M. Sansotera, C.L. Bianchi, C. Cavallotti, W. Navarrini, Photocatalytic Activity of TiO 2 -embedded Fluorinated Transparent Coating for Oxidation of Hydrosoluble Pollutants in Turbid Suspensions, Appl. Catal., B, submitted. Fluoropolymer 2014, San Diego

11 Photoactive Coating Low P UV Lamp Polluted aqueous solution O 2 Feed Magnetic stirrer Quartz surface AD60 10% thermally treated AD60 10% non-thermally treated AQ 6% - TiO 2 10% Primer coating Adhesion primer Hyflon AD60 Solvay Specialty Polymers TFE-MDO copolymer High chemical stability [h] High UV transparency [i] High hydrophobicity [i] [h] W. Navarrini, M.V. Diamanti, M. Sansotera, F. Persico, M. Wu, L. Magagnin, S. Radice, Prog. Org. Coat. 74 (2012) 794. [i] F. Persico, M. Sansotera, M.V. Diamanti, L. Magagnin, F. Venturini, W. Navarrini, Thin Solid Films 545 (2013) 210. Fluoropolymer 2014, San Diego

12 Photoactive Coating Low P UV Lamp Polluted aqueous solution O 2 Feed Magnetic stirrer Quartz surface AD60 10% thermally treated AD60 10% non-thermally treated AQ 6% - TiO 2 10% Photoactive layer Aquivion D83-06A Solvay Specialty Polymers TFE-SFVE copolymer High chemical stability [j] High UV transparency Strong acid behaviour [j] Hydrophilicity [j] W. Navarrini, et al., IT L , Fluoropolymer 2014, San Diego

13 Fluoropolymer 2014, San Diego Experimental apparatus Catalyst: TiO 2 Degussa P25 Nanometric TiO 2 (D p = nm) Anatase : Rutile = 3 : 1 Low P UV Lamp Polluted aqueous solution O 2 Feed Magnetic stirrer

14 Fluoropolymer 2014, San Diego Experimental apparatus Catalyst: TiO 2 Degussa P25 Nanometric TiO 2 (D p = nm) Anatase : Rutile = 3 : 1 Low P UV Lamp Polluted aqueous solution Tested organic pollutants: Rhodamine B-base (RhB) Non biodegradable organic dye C 28 H 30 N 2 O 3 - MW = g/mol λ max = 554 nm O 2 Feed Magnetic stirrer

15 Fluoropolymer 2014, San Diego Experimental apparatus Catalyst: TiO 2 Degussa P25 Nanometric TiO 2 (D p = nm) Anatase : Rutile = 3 : 1 Low P UV Lamp Polluted aqueous solution O 2 Feed Magnetic stirrer Tested organic pollutants: Rhodamine B-base (RhB) Non biodegradable organic dye C 28 H 30 N 2 O 3 - MW = g/mol λ max = 554 nm Crystal Violet (CRY) Photodegradation standard C 25 H 31 N 3 O - MW = g/mol λ max = 592 nm

Fluoropolymer 2014, San Diego Experimental apparatus Catalyst: TiO 2 Degussa P25 Nanometric TiO 2 (D p = 25-85 nm) Anatase : Rutile = 3 : 1 Low P UV Lamp Polluted aqueous solution O 2 Feed Magnetic

16 Fluoropolymer 2014, San Diego Experimental apparatus Catalyst: TiO 2 Degussa P25 Nanometric TiO 2 (D p = nm) Anatase : Rutile = 3 : 1 Low P UV Lamp Polluted aqueous solution O 2 Feed Magnetic stirrer Tested organic pollutants: Rhodamine B-base (RhB) Non biodegradable organic dye C 28 H 30 N 2 O 3 - MW = g/mol λ max = 554 nm Crystal Violet (CRY) Photodegradation standard C 25 H 31 N 3 O - MW = g/mol λ max = 592 nm Analytical technique UV-Visible Spectrophotometry Lambert-Beer law: Abs = ε [pollutant] d

17 Experimental apparatus Low P UV Lamp Polluted aqueous solution O 2 Feed Magnetic stirrer Quartz surface AD60 10% thermally treated AD60 10% non-thermally treated AQ 6% - TiO 2 10% Photoactive layer O 2, hν Photoactive layer operating mode Organic Pollutant (R H ) Fluoropolymer 2014, San Diego R F -SO 3 -H/R H abs TiO 2 * R F -SO 3 H CO 2 + H 2 O + organic intermediates

18 Fluoropolymer 2014, San Diego Photodegradation - Rhodamine B-base Tested organic pollutant: Rhodamine B-base (RhB) - [RhB] 0 = mol/l Tested photocatalysts: Photoactive Coating (PC) - Clear solution Photoactive Coating (PC) - Turbid solution (CaSO 4, 8 g/l) TiO 2 slurry (dispersed TiO 2 = TiO 2 content in the coating)

19 Fluoropolymer 2014, San Diego ln C 0 /C Photodegradation - Rhodamine B-base Tested organic pollutant: Rhodamine B-base (RhB) - [RhB] 0 = mol/l Tested photocatalysts: Photoactive Coating (PC) - Clear solution Photoactive Coating (PC) - Turbid solution (CaSO 4, 8 g/l) TiO 2 slurry (dispersed TiO 2 = TiO 2 content in the coating) C/C TiO2 slurry PC - Turbid solution PC - Clear solution Time (min) TiO2 slurry PC - Turbid solution PC - Clear solution Time (min)

20 ln C 0 /C Photodegradation - Rhodamine B-base Tested organic pollutant: Rhodamine B-base (RhB) - [RhB] 0 = mol/l Tested photocatalysts: Photoactive Coating (PC) - Clear solution Photoactive Coating (PC) - Turbid solution (CaSO 4, 8 g/l) TiO 2 slurry (dispersed TiO 2 = TiO 2 content in the coating) TiO2 slurry PC - Turbid solution PC - Clear solution Pseudo-first order degradation kinetics C/C Time (min) TiO2 slurry 0.8 PC - Turbid solution 0.7 PC - Clear solution Time (min) Fluoropolymer 2014, San Diego C C 0 = exp(-k app t) Test k app (min -1 ) a [RhB] 60 (%) b PC - Clear solution PC - Turbid solution TiO 2 slurry a Correlation coefficients R 2 higher than 0.99 for all the tests presented b RhB concentration decrease calculated after 60 min treatment

21 Fluoropolymer 2014, San Diego Photodegradation - Crystal Violet Tested organic pollutant: Crystal Violet (CRY) - [CRY] 0 = mol/l Tested photocatalysts: Photoactive Coating (PC) - Clear solution Photoactive Coating (PC) - Turbid solution (CaSO 4, 8 g/l) TiO 2 slurry (dispersed TiO 2 = TiO 2 content in the coating)

22 ln C 0 /C Fluoropolymer 2014, San Diego ln C 0 /C Photodegradation - Crystal Violet Tested organic pollutant: Crystal Violet (CRY) - [CRY] 0 = mol/l Tested photocatalysts: Photoactive Coating (PC) - Clear solution Photoactive Coating (PC) - Turbid solution (CaSO 4, 8 g/l) TiO 2 slurry (dispersed TiO 2 = TiO 2 content in the coating) TiO2 slurry PC - Turbid solution PC - Clear solution TiO2 slurry PC - Turbid solution PC - Clear solution Time (min) Time (min)

23 ln C 0 /C ln C 0 /C Photodegradation - Crystal Violet Tested organic pollutant: Crystal Violet (CRY) - [CRY] 0 = mol/l Tested photocatalysts: Photoactive Coating (PC) - Clear solution Photoactive Coating (PC) - Turbid solution (CaSO 4, 8 g/l) TiO 2 slurry (dispersed TiO 2 = TiO 2 content in the coating) TiO2 slurry PC - Turbid solution PC - Clear solution Pseudo-first order degradation kinetics Time (min) TiO2 slurry 0.8 PC - Turbid solution 0.7 PC - Clear solution Time (min) Fluoropolymer 2014, San Diego C C 0 = exp(-k app t) Test k app (min -1 ) a [CRY] 60 (%) b PC - Clear solution PC - Turbid solution TiO 2 slurry a Correlation coefficients R 2 higher than 0.99 for all the tests presented b CRY concentration decrease calculated after 60 min treatment

Fluoropolymer 2014, San Diego Photodegradation - RhB, CRY 1.0 Test Pollutant k app (min -1 ) PC - Clear solution RhB 0.0923 PC - Clear solution CRY 0.0918 PC - Turbid suspention RhB 0.

24 Fluoropolymer 2014, San Diego Photodegradation - RhB, CRY 1.0 Test Pollutant k app (min -1 ) PC - Clear solution RhB PC - Clear solution CRY PC - Turbid suspention RhB PC - Turbid suspention CRY C/C RhB absorption CRY absorption Time (min) Apparent independence of the k app values from the pollutant Pollutant absorption into the photoactive coating is the Rate Determining Step hν CB Organic compounds CO 2, H 2 O, N 2 CO Ti IV Ti OH IV 2, H 2 O, N 2 OH O {HO 2, HO 2-, H 2 O 2, OH - 2- } Organic compounds Ti IV OH + VB Ti III OH O 2 H 2 O

25 Fluoropolymer 2014, San Diego Photoactive coating characterization Profilometry Layer Average Thickness (μm) AQ 6% - TiO 2 10% 3.70 ± 0.44 Double AD60 10% 2.11 ± 0.19 Quartz surface Photoactive Coating 5.81 ± 0.63

26 Fluoropolymer 2014, San Diego Photoactive coating characterization Profilometry Layer Average Thickness (μm) AQ 6% - TiO 2 10% 3.70 ± 0.44 Double AD60 10% 2.11 ± 0.19 Quartz surface Photoactive Coating 5.81 ± 0.63 Scanning Electron Microscope - SEM

27 Fluoropolymer 2014, San Diego Photoactive coating characterization Profilometry Layer Average Thickness (μm) AQ 6% - TiO 2 10% 3.70 ± 0.44 Double AD60 10% 2.11 ± 0.19 Quartz surface Photoactive Coating 5.81 ± 0.63 Scanning Electron Microscope - SEM Atomic Force Microscopy - AFM Average Roughness, Sa = nm Root Mean Square, Sq = nm

28 Photoactive coating characterization Profilometry Layer Average Thickness (μm) AQ 6% - TiO 2 10% 3.70 ± 0.44 Double AD60 10% 2.11 ± 0.19 Quartz surface Photoactive Coating 5.81 ± 0.63 Scanning Electron Microscope - SEM Atomic Force Microscopy - AFM Fluoropolymer 2014, San Diego Average Roughness, Sa = nm Root Mean Square, Sq = nm Homogenous dispersion of TiO 2 in the photoactive layer Presence of TiO 2 clusters - Improvable system efficiency

29 Delta Weight (-) Delta Weight (-) Photoactive coating stability Thermogravimetric analysis - TGA 1 0,9 0,8 0,7 Pure AD60 decomposition starts at 450 C 0,6 0,5 0,4 0,3 0,2 Pure Hyflon 0,1 AD60 Pure Aquivion D83-06A Temperature ( C) Pure Aquivion decomposition starts at 300 C, together with cross-link phenomena that delay the complete degradation 1 0,9 Photoactive Coating TGA curves before and after the use are overlapping Used Photoactive Coating appears to be unhaltered Fluoropolymer 2014, San Diego 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 Pristine Photoactive Coating Used Photoactive Coating Temperature ( C)

30 Fluoropolymer 2014, San Diego Achievements and Future Developments Achievements Future developments

31 Fluoropolymer 2014, San Diego Achievements and Future Developments Achievements The coating allows higher photoabatement rates than TiO 2 slurry Future developments

32 Fluoropolymer 2014, San Diego Achievements and Future Developments Achievements The coating allows higher photoabatement rates than TiO 2 slurry The coating can be employed to treat even turbid solutions Future developments

33 Fluoropolymer 2014, San Diego Achievements and Future Developments Achievements The coating allows higher photoabatement rates than TiO 2 slurry The coating can be employed to treat even turbid solutions The coating guarantees the abatement of different kinds of pollutants Future developments

34 Fluoropolymer Federico 2014, Persico San Diego Achievements and Future Developments Achievements The coating allows higher photoabatement rates than TiO 2 slurry The coating can be employed to treat even turbid solutions The coating guarantees the abatement of different kinds of pollutants Preliminary results show that the coating appears unhaltered after continuous use Future developments

35 Fluoropolymer Federico 2014, Persico San Diego Achievements and Future Developments Achievements The coating allows higher photoabatement rates than TiO 2 slurry The coating can be employed to treat even turbid solutions The coating guarantees the abatement of different kinds of pollutants Preliminary results show that the coating appears unhaltered after continuous use Future developments Evaluation of the system efficiency towards different persistent pollutants (PFOA)

36 Fluoropolymer Federico 2014, Persico San Diego Achievements and Future Developments Achievements The coating allows higher photoabatement rates than TiO 2 slurry The coating can be employed to treat even turbid solutions The coating guarantees the abatement of different kinds of pollutants Preliminary results show that the coating appears unhaltered after continuous use Future developments Evaluation of the system efficiency towards different persistent pollutants (PFOA) Evaluation of the system efficiency with different photocatalyst deposition (Sol-Gel)

37 Fluoropolymer 2014, San Diego Achievements and Future Developments Achievements The coating allows higher photoabatement rates than TiO 2 slurry The coating can be employed to treat even turbid solutions The coating guarantees the abatement of different kinds of pollutants Preliminary results show that the coating appears unhaltered after continuous use Future developments Evaluation of the system efficiency towards different persistent pollutants (PFOA) Evaluation of the system efficiency with different photocatalyst deposition (Sol-Gel) Evaluation of the system efficiency working with different ph conditions

38 Fluoropolymer 2014, San Diego Achievements and Future Developments Achievements The coating allows higher photoabatement rates than TiO 2 slurry The coating can be employed to treat even turbid solutions The coating guarantees the abatement of different kinds of pollutants Preliminary results show that the coating appears unhaltered after continuous use Future developments Evaluation of the system efficiency towards different persistent pollutants (PFOA) Evaluation of the system efficiency with different photocatalyst deposition (Sol-Gel) Evaluation of the system efficiency working with different ph conditions Optimization of the ratio TiO 2 / ionomer into the coating

39 Fluoropolymer 2014, San Diego Achievements and Future Developments Achievements The coating allows higher photoabatement rates than TiO 2 slurry The coating can be employed to treat even turbid solutions The coating guarantees the abatement of different kinds of pollutants Preliminary results show that the coating appears unhaltered after continuous use Future developments Evaluation of the system efficiency towards different persistent pollutants (PFOA) Evaluation of the system efficiency with different photocatalyst deposition (Sol-Gel) Evaluation of the system efficiency working with different ph conditions Kinetic modelling of the system (Diffusion phenomena) Evaluation of this metodologie for the preparation useful organic compond

Acknowledgments Politecnico di Milano Dr. Ing. Francesco Venturini Dr. Ing. M. H. Wu Prof. L. Nobili (DLC) Prof. G. Dotelli Prof. L. Magagnin (AFM) Prof. A. Famulari (QMC) Prof. P. Gallo Stampino Dr.

40 Acknowledgments Politecnico di Milano Dr. Ing. Francesco Venturini Dr. Ing. M. H. Wu Prof. L. Nobili (DLC) Prof. G. Dotelli Prof. L. Magagnin (AFM) Prof. A. Famulari (QMC) Prof. P. Gallo Stampino Dr. D. Picenoni (SEM) Mr. M. Ursini Solvay Solexis Dr. V. Tortelli Dr. M. Galimberti Dr. A. Sanguineti Dr. S. Radice (IR) Dr. E. Barchiesi (NMR) Dr. R. Pieri Ing. M. Apostolo Università degli Studi di Milano Prof. C.L.Bianchi Dr. S. Vitali Mr. A. Beretta Fluoropolymer 2014, San Diego 40

41 Fluoropolymer 2014, San Diego Thanks for your kind attention

Detection of intermediates in the TiO 2 -assisted photodegradation of Rhodamine B under visible light irradiation

Journal of Environmental Sciences 19(2007) 892 896 Detection of intermediates in the TiO 2 -assisted photodegradation of Rhodamine B under visible light irradiation LI Jing-yi 1,2,, MA Wan-hong 2, LEI