National I-lan University, Taiwan 1 Photocatalyst Titanium Nanotubes Study Treatment of Volatile Organic Compounds

2 National I-lan University, Taiwan Syllabus IntroductionLiterature ReviewExperimental Methods and EquipmentResults and DiscussionConclusions Equipment Schematic Preparation of Catalyst Characteristic Analysis Reactor System Characteristic Analysis Performance Assessment Langmuir-Hinshelwood Kinetic Model

3 National I-lan University, Taiwan Motivation Volatile Organic Compounds, VOCs Major sources of contamination in the environment (Borisch al., 2004). VOCs lead to secondary pollutants. Suspended particles and ozone are the most important index. The ozone is produced by nitrogen oxides and VOCs. (Doucet et al., 2006) Stimulate the human body. (Jo et al., 2002) Introduction

4 National I-lan University, Taiwan  Inhalation may cause drowsiness, nausea, vomiting, feeling drunk and dizzy.  The liquid with a severe irritation to the eyes.  Swallowed will cause irritation to the pharynx, esophagus and stomach.  Prolonged or frequent contact may cause skin fat and dermatitis. Acetone Characteristics Motivation Introduction

5 National I-lan University, Taiwan Motivation Treatment Methods Introduction Data Source ：馬志明， 1998 ；陳祐誠， 2009 Processing Technology ShortcomingsAdvantages Adsorption Cumbersome procedures, high equipment costs, water pollution generated. High efficiency Recyclable CondensationLow VOCs removal efficiency.Recyclable Thermal incineration High operating costs, higher risk, Secondary pollution. High efficiency Easy operation Catalytic incineration The high cost of equipment and catalysts Higher level technique High efficiency More difficult to have NOx Absorption Secondary pollution Easily lead to equipment corrosion Recyclable Biological treatment Limited treatment effect, microbial domesticated a long time. Preliminary design and low operating cost

6 National I-lan University, Taiwan Motivation Photocatalysis Energy Preparation is easy Low prices Non-toxic High efficiency Strong physical stability Small operating equipment Simple procedures Titanium dioxide Introduction

7 National I-lan University, Taiwan Large surface areaHigh efficiency Tubular structures Mesoporous High adsorption Motivation Titanium Dioxide Nanotube

8 National I-lan University, Taiwan Objectives  Prepared by hydrothermal system Fe-TNT catalyst.  Doped Fe-TNT photocatalyst of the physical and chemical analysis.  Acetone removal assessment dealing with Fe-TNT.  Evaluation of photocatalytic energy efficiency.  Establishment of the best kinetic model.

9 National I-lan University, Taiwan Literature Review

10 National I-lan University, Taiwan Literature Review Iijima et al. Nishijima et al. Song et al. First published in the journal Nature in the hollow tubular carbon nanotubes. Modification of the TNT iodine doped. At the same time doping metal (Fe) and non-metallic (S) were modified. Seo et al. Photocatalyst used in the TNT sensor.

11 National I-lan University, Taiwan Literature Review Xiao et al.Ho et al. Grandcolas et al. Photocatalyst used in the TNT Dye Sensitized Solar Cell. Photocatalyst used in the TNT photoelectroche mical hydrogen generation. Silver were modified and applied to biological treatment. Doped with nitrogen were modified and applied to wastewater Treatment. Peng et al.

12 National I-lan University, Taiwan Experimental methods and Equipment Equipment Schematic Preparation of Catalyst Characteristic Analysis Reactor System

13 National I-lan University, Taiwan Experimental Structure Photocatalytic degradation / adsorption performance testing Experimental analysis Establishment of kinetic model Metal content Residence time Catalyst Type Concentration Light source RH Experimental analysis, characteristics of catalysts Literature review Experimental design and Planning Research Preparation of the catalyst Establishment of reaction system and stability testing

14 National I-lan University, Taiwan Preparation of Catalyst P25+Fe (NO 3 ) 3 ． 9H 2 O 10 M NaOH 130 ℃ / 72 hr Furnace Autoclave Cleaning

15 National I-lan University, Taiwan Characteristic Analysis Crystal information XRPD analysis. B.E.T. analysis. HR-TEM analysis. Surface morphology SEM Mapping analysis Optical information UV-Vis analysis.

16 National I-lan University, Taiwan Reactor System 1.Air and Acetone 2.Flow meter 3.Humidifier equipment 4. Mixed chamber 5.Two way valve 6.Three way valve 7. Photoreactor 8. Active carbon 9. Gas Chromatography

17 National I-lan University, Taiwan Operating Parameters Experimental parameters Operating conditions Photocatalyst type P25- TiO 2,TNT,Fe-TNT Metal content (%) 0,1.0,3.0,5.0 Relative Humidity (%)0,5,15,35,45 Inlet concentration (ppm)250,500,750,1000 Light source 365nm(UV),365nm(UV-LED),LED- visible Flow (cc / min) (Retention Time, min) 250(4.0),500(2.0),750(1.33),1000(1.0)

18 National I-lan University, Taiwan Results and Discussion Characteristic Analysis Performance Assessment Langmuir-Hinshelwood Kinetic Model

19 National I-lan University, Taiwan Surface Morphology SEM Mapping analysis TiO 2 -P25TNT Fe-TNT Tube length of approximately between 500 nm to several μm Particles Tubular

20 National I-lan University, Taiwan Crystal Information XRPD Analysis (25.3) (37.8) (48.1) (55.1) (62.7)

21 National I-lan University, Taiwan Crystal Information B.E.T Analysis TNT 5wt ％ Fe-TNT

22 National I-lan University, Taiwan Crystal Information TNT 5wt ％ Fe-TNT CatalystSurface areas (m 2 g -1 )Particle sizes (nm) TiO 2 (Degussa P-25) TNT wt.% Fe-TNT wt.% Fe-TNT wt% Fe-TNT

23 National I-lan University, Taiwan Crystal Information 18 nm 5 nm 20 nm HR-TEM analysis TNT 1wt ％ Fe-TNT

24 National I-lan University, Taiwan Optical Information UV-Vis Analysis

25 National I-lan University, Taiwan Optical Information Catalyst Critical wavelength λ (nm) Band gap energy (eV) TiO 2 (Degussa P-25) TNT wt.% Fe-TNT wt.% Fe-TNT wt.% Fe-TNT Kuo et al., (2007)

26 National I-lan University, Taiwan Performance Assessment Blank testConcentration Relative Humidity Retention Time MetalLight source

27 National I-lan University, Taiwan Performace Assessment Blank test In a different light sources for direct photolysis efficiency, its efficiency is about 5%. Light source: LED-365 nm Temperature: 25 ℃ Pressure: 1 atm Retention time: 1 min Relative humidity: 0% Concentration: 1000 ppm Light source: UV-365 nm

28 National I-lan University, Taiwan Performace Assessment Light source: LED-Visible

29 National I-lan University, Taiwan Effect of Concentration Temperature: 25 ℃ Pressure: 1 atm Retention time: 1 min Relative humidity: 0% Light source: UV-365 nm Light source: LED-365 nm

30 National I-lan University, Taiwan Effect of Concentration Light source: LED- visible

31 National I-lan University, Taiwan Effect of Relative Humidity Temperature: 25 ℃ Pressure: 1 atm Retention time: 1 min Concentration: 1000 ppm Light source: UV-365 nm Light source: LED-365 nm

32 National I-lan University, Taiwan Effect of Relative Humidity Light source: LED-visible

33 National I-lan University, Taiwan Effect of Retention Time Temperature: 25 ℃ Pressure: 1 atm Concentration: 1000 ppm Relative humidity: 0% Light source: UV-365 nm Light source: LED-365 nm

34 National I-lan University, Taiwan Effect of Retention Time Light source: LED-visible

35 National I-lan University, Taiwan Effect of Metal 3 wt% Fe-TNT the best efficiency Doped metal modification can improve processing efficiency. Yu et al., 2010

36 National I-lan University, Taiwan Effect of Light source UV light source of traditional and high efficiency as the excitation source. At high concentration (1000ppm) LED light source efficiency of conventional UV light source close to. *L-LED

37 National I-lan University, Taiwan Energy Effectiveness Kinetic Model

38 National I-lan University, Taiwan Energy Effectiveness Shie et al., 2008 P25 TNT

39 National I-lan University, Taiwan Energy Effectiveness 1 wt%Fe-TNT3 wt%Fe-TNT

40 National I-lan University, Taiwan Energy Effectiveness 5 wt%Fe-TNT

41 National I-lan University, Taiwan Kinetic Model Catalyst K LH (ppmv -1 ) k dge (mol min -1 m -2 ) TiO 2 (P25) TNT wt.% Fe-TNT wt.% Fe-TNT wt.% Fe-TNT C ： Concentration (ppm) k deg ： Specific rate constant (mol min -1 m -2 ) K LH ： Adsorption constant (ppm -1 )

42 National I-lan University, Taiwan Conclusions

43 National I-lan University, Taiwan Conclusions XRPD  Fe-TNT does not cause the destruction of crystalline structure.  Fe-TNT does not cause phase transformation of metal and become rutile. UV-vis absorption spectroscopy  Band gap energy increases with the increase in the proportion of Fe doping  Red shift. B.E.T analysis  BET surface area for 390 m 2 g -1.  Fe-TNT surface area for 375, 243, 202 m 2 g -1.

44 National I-lan University, Taiwan Conclusions SEM analysis  Tube length about 500 nm - several μm Degradation efficiency - effect of Concentration  at 250 ppm, TNT catalyst: degradation efficiency of 80-90%.  at 1000 ppm, 3wt% Fe-TNT catalyst: degradation efficiency of 45%. Degradation efficiency - effect of Retention Time  Retention time 4 min is the best degradation efficiency  P25 degradation efficiency of 20%  3 wt% Fe-TNT degradation efficiency of 80%

45 National I-lan University, Taiwan Conclusions Degradation efficiency - effect of Retention Humidity  3 wt% Fe-TNT, relative humidity 35%: 50%.  45% humidity, 3 wt% Fe-TNT: 38%. Degradation efficiency - effect of Light source  Traditional UV light source for the best  LED-365 nm and the LED-visible difference of about 10%. Degradation efficiency - effect of Catalyst  1,3 and 5 wt% Fe-TNT photocatalyst more better than P25  3 wt% Fe-TNT photocatalyst with the highest efficiency

46 National I-lan University, Taiwan Conclusions Kinetic model  Consistent with Langmuir-Hinshelwood kinetic model  The reaction rate constant is mol min -1 m -2. High concentration and low reaction time  New UV-LED light source less than traditional UV light about 1.5 mg kW -1 h -1.  3 wt% Fe-TNT has the highest energy efficiency.

National I-lan University, Taiwan 47