1. PhotoActive tiles: an industrial challenge in the world of photocatalysis

2. Possible alternative to nano-sized TiO2
Final remarks
Only nanocrystallites TiO2 is active from the photocatalytic point of view ? NO
2) Any «chance» for larger-sized TiO2 ????? YES
Possible alternative to nano-sized TiO2
Micro-TiO2 in a construction material: photocatalytic tiles YES
Preservation of the common tiles properties
Good results as a photocatalytic materials
C.L. Bianchi, et al. Advances in Materials Science and Engineering, vol. 2012, Article ID , 8 pages, (2012) doi: /2012/970182
Prof. Claudia L. Bianchi

4. BET (m2/g) XRD Crystallite size (nm) XPS TI2p Band gap (eV)
Pigmentary TiO2
Pure anatase, Uncoated surface,
Commercially available (not sold as photocatalytic materials), Powder form
Sample
BET (m2/g)
XRD
Crystallite size
(nm)
XPS TI2p
Band gap
(eV)
P25 50
75:25
20-25
Ti(IV)
3,21 A 12
100
110
3,15 B 11 95
3,25 C 23 40
3,28 D
Mix
(micro-sized + ultrafine) E
180
3,17
C.L. Bianchi, et al., “Pigmentary TiO2: a challenge for its use as photocatalyst in NOx air purification”, Chemical Eng J, /j.cej

5. I.R. Characterization
IR spectra in the cm-1 spectral region of samples oxidized at 300°C
IR spectra in the cm-1 spectral region of P25, after activation in different conditions

6. Experimental batch set-ups: NOx and VOC degradation
UV lamp ( nm)
1 ppm NOx
T = 30°C
V = 20 l
Relative humidity = 40%
10 W/m2
UV lamp ( nm)
400 ppm VOC
T = 30°C
V = 5 l
Relative humidity = 40%
30 W/m2
Prof. Claudia L. Bianchi

7. Tests on all TiO2 in powder form: the case of sample A
Gas phase
Standard UV-A lamps
30 W/m2 (except for NO/NOx: 10 W/m2)
Pollutant
ppm
Acetaldehyde
400
Micro-GC
my lab
Acetone
Ethanol
Propyl alcohol GC
Milan Polytechnic – Prof. Diamanti
Toluene
NOx 1
chemiluminescence NO
0,4
Univ Venice - Prof. Signoretto
Prof. Claudia L. Bianchi

8. EtOH degradation

9. EtOH degradation: Comparison P25/Kronos 1077 (sample A)

10. Tiles preparation Patent - EP2443076
Industrial porcelain-grés tiles are manufactured under high pressure by dry-pressing fine processed ceramic raw materials and finally fired at high temperatures ( °C) in a kiln.
Photoactive porcelain-grés tiles were subsequently covered at the surface with a mixture of pure anatase micro-TiO2 and a commercial SiO2-based compound.
Tiles were then treated at high temperature (approx. 680°C) for 80 min and hardly brushed to remove the powder present at the sample surface and not completely stuck.
Bianchi, Capucci et al., CCC, 36 (2013) 116

11. 1077 by Kronos (sample A) Tiles name: White Ground ActiveTM
Amount of TiO2 on the tiles = 1.1 g/m2

12. TiO2 + SiO2-based compound
TiO2 + SiO2-based compound: characterization
Sample
BET
surface area
m2/g
XRPD
XPS
Ti 2p eV
pure TiO2
11.0
Pure anatase
458.5
TiO2 + SiO2-based compound
2.6
458.4
Prof. G. Cerrato – Turin University
Prof. Claudia L. Bianchi

13. Mirafiori Motor Village – Torino (Italy)
Final material properties:
hardness
lack of porosity
vitrified surface
durability
Mirafiori Motor Village – Torino (Italy)
Kindergarten «Il bruco» - L’Aquila (Italy)

14. Photocatalytic properties Photocatalytic properties
Self-cleaning performance
De-pollutant
Methylen blue degradation in water
(ISO 10678)
Oleic acid degradation
(ISO )
Photocatalytic properties
Photocatalytic properties
NOx degradation in both batch and plug-flow reactors
Decoloration
of dyes put in contact with the tiles
Antibacterial activity
(ISO 27447)
performed by Artest Modena-Italy

15. PHOTOCATALYSIS: MAKES IT DIFFICULT FOR DIRT TO DEPOSIT
Contact angle measurements
PHOTOCATALYSIS: MAKES IT DIFFICULT FOR DIRT TO DEPOSIT
Modification of Surface Hydrophilic Properties
Common porcelain Photocatalytic porcelain gres tile gres tile
Prof. S. Biella – Milan Polytechnique

16. -----------------------------------
Tiles performance: NOx degradation
NOx: 1000 ppb
Amount of TiO2 on the tiles during the photocatalytic test: 0,004 g
Amount of TiO2 in powder form during the photocatalytic test: 0,04g
Time to reach 80% NOx degradation with the tiles during the photocatalytic test: 360 min
Time to reach 80% NOx degradation with TiO2 in powder form during the photocatalytic test: 36 min
Prof. Claudia L. Bianchi

17. WHO guidelines for NO2
Prof. Claudia L. Bianchi

18. NO2 Hourly limit value NO2 Annual limit value Case History: Hong Kong
Values on the graph in μg/m3
NO2 Hourly
limit value
NO2 Annual
limit value
01/11/2011 – 31/12/2011
Prof. Claudia L. Bianchi

19. Case history: Milano (Italy)
Prof. Claudia L. Bianchi

20. Time to reach the annual mean value
Tiles performance with real pollution levels
Value fixed in
ISO
Time to reach the annual mean value
of 40 μg/m3 h
10 W/m2
20 W/m2
NO2 inlet value
Prof. Claudia L. Bianchi

21. Final remarks
Interesting photocatalytc performance of all microsized samples in gas phase.
Nano-TiO2 shows always the best results towards the photodegradation of both NOx, but with levels of real pollutions, powdered nano and micro-sized TiO2 seems to show similar photodegradation results.
Photocatalytic tiles are now an industrial reality. Photocatalytic tiles, commercially available, combine porcelain-grés material features and photocatalytic properties.
features
Prof. Claudia L. Bianchi