Euroanoforum 2009 Prague, Czeck Republic

June 3rd (Wed.), 2009 9:00-9:30 am Prague Conference Centre

Keynote Lecture

Foundamentals and Applications of TiO2 Photocatalysis Photocatalysis

Akira Fujishima

Chairman of Kanagawa Academy of Science and Technology

Emeritus Professor of the University of Tokyo

Profile of Kanagawa Prefecture

Yamanashi Tokyo
Yokohama

Kawasaki
Kanagawa

Shizuoka

Kanagawa
Capital:

Yokohama City Area: 2,415 km2 Population: 8.6 million (2nd in Japan) Industrial Production: 19,910 billion yen (2nd in Japan Business Establishments: 309,441 (4th in Japan) Researchers and Engineers: 323,008 persons (1st in Japan [2003 Records]

View of Kanagawa Science Park

 Kanagawa Academy of Science and Technology

Three Main Areas of Activities

Research And Development
Members: Revenue:

KAST

Endowments: 5 billion yen

(64% from Prefecture Government)

128 2 billion yen

KAST
Technological Education Analytical Services

Minatomirai Towers in Yokohama

Self-Cleaning Window in Central Japan Airport

Narita Airport

Photocatalysis of TiO2
Air-cleaning Decomposition of aldehyde NOx removal Water-cleaning Decomposition of EDC and organic matter

TiO2
Self-cleaning Decomposition of oily dust Superhydrophilicity

light +
Bactericidal

Kill of bacteria MRSA and virus

Artificial Diamond

Titanium Dioxide Single Crystal

Recent Photo of Mr. Nakazumi

Solar light

A. Fujishima, K. Honda, Nature (1972)

Photosynthesis Photoelectrode
Photosynthesis system

O2

H2

h
TiO2 Pt

Burning of Titanium Metal Plate TiO2

Epoxy resin Burner Cu wire

Firing of Titan plate

Attaching Cu wire to TiO2 plate by use of epoxy resin

Investigation of Hydrogen Evolution under Sunlight Irradiation

Experimental
3 2 1

1. TiO2 electrode 2. Pt electrode 3. Salt bridge

A. Fujishima, K. Kohayakawa, K. Honda, J. Electrochem. Soc. 1975, 122, 1487.

Yearly Citation
300

A. Fujishima, K. Honda, Nature, 1972, 238, 27-28. Total citation till July, 2007: 2184 times

250

200

Citations

150

100

50

0 1974 1977 1980 1983 1986 1989 1992 1995 1998 2001 2004 2007

Year

Perceptional Change
n h

Number of photons needed to decompose 1 mol water (18 g) on 1 cm2 of TiO2 is more than 6x1023

Number of photons in sunlight and even in lamp is much larger than the number of E. coli (106) on 1 cm2 of TiO2

Sun light :1015 photons / cm2

When we think about the energy efficiency, it is more practicable to apply this photocatalytic phenomena to kill bacteria than to generate hydrogen

Bacteria-killing Effect
Bactericidal effect

Hospital

Illumination Lamp for Highway

Photocatalyst Filter

Deodorize, Disinfect, Decompose

Mechanism of Photocatalysis
Reduction O2 O2 R R+ Oxidation 3.0eV 3.2eV 0 V vs NHE

I2 (0.536) 1 Br2 (1.087) H2O/O2 (1.23) Cl2 (1.36) KMnO4 (1.695) H2O2 (1.776) O3 (2.07)

Rutile

Anatase

F2 (2.87) TiO2 (3.0)

Coating on Cars Side Mirror

Side Mirror

 Reports
63(12)515582(2008) TiO2 Photocatalysis

and Related Surface Phenomena

Pages: Number of References: Number of Tables: Number of Figures:

Akira Fujishima, Xintong Zhang, and Donald A. Tryk

Self-cleaning Effect of Photocatalysis

TiO2 Light Light TiO2 Water CO2 CO2

(1) Decomposition of graduallyadsorbed oil spot by strong oxidation

(2) Removal of large amount of oily dust by pouring water (making use of superhydrophilicity effect)


Convent Klongtoey

Torrensville Primary School

: : 550 m2 2007.10

: : 330 m2 2007.08

Teo-Hong chase

Westfield North Rocks

: : 660 m2 2006.11

: : 160 m2 2007.11

m2 18,500

m2

16,500

The Louvre Pyramid

Dives in Misericordia, Rome

U.S.A.
Dallas Cowboys New Stadium Surface area 13,746

Medical Uses

Killing Tumor
UV treated Untreated

Effect of Photocatalysis

Target

lowlarge molecular- molecularweight weight organic Protein, matter DNA

Virus

Bacteria

Cell

Antibacteria

Cytotoxicity reaction (cancer cell) Damage to cell membrane Induce apoptosis

Degradation Denaturize Antivirus ? Effect of TiO2 damage Phage Damage photo to cell catalysis membrane Damage to cell wall

Viral Inactivation Procedures

Influenzavirus A
Orthomyxoviridae Influenzavirus Influenzavirus A Envelope Segmented into eight fragments ssRNA of negative polarity RNA dependent RNA polymerase A diameter of 80120 nm
Hemagglutinin (HA) Bind to the host cell Neuraminidase (NA) Released from the host cell

Influenzavirus A H1N1

Inactivation of Influenzavirus by photocatalyst

Influenzavirus was contacted with TiO2
Compositions of Influenzavirus
Compositions Protein Lipid Carbohydrate RNA 70 75 20 24 58 0.8 1.1

Photocatalysis

Degradation of proteins and RNA comprising virus

Decrease the possibility of infection Degradation of virus

Bacteriophage

Infection of bacteriophage

Methods for bacteriophage

Culture of E. coli
37, 15 h
E. Coli Stock NB agar plate

37, 15 h (Pre-culture)
Liquid NB

37, 15 h (Culture) (OD600>1.0)

(Plating)

Phage preparation and Plaque assay

37, 10 min
E. coli

37, 15 hr (Plating)
Plaque assay: lower concentration Stock preparation: higher concentration

(Infection)

NB agar plate

Count plaque

Phage

Store at -80 and/or Use examination

Plaque assay (Check)

centrifuge filtration (Purification)

Dark place 4, 15 hr (Extraction)

Correct with NB top agar in SM buffer

Methods for bacteriophage

Prepreparation
phage solution

Photo-irradiation UV light
UVA lamp Punching metal

Measurement of number of plaque

Collected Phage Infection E.coli

Light Agar dish Pre UV irradiation phage solution Culture in the incubator (37C) Plaque formation

Test specimen
(reference) 2008

Test specimen

JIS R 1702 2006 ISO

Count plaque and calculation

Photocatalyst antivirus activity value calculation specimen TiO ,

Control UV irradiation 0.1mW/cm2 Time 0h, 4h Virus 0.01mg/ml (1.8E8 TCID50/ml)
2
1.6E+07

Control
1.6E+06

logCt/C0

-1.79 Stabilit y TiO2

TCID50/ml

logNt/N
0

1.6E+05

-4.13 Viral Inactivat ion

logNt/Ct

1.6E+04

-2.33 Antivirus effect

1.6E+03 0 4

Photocatalytic Water Reactor

Final settling basin at sewage treatment plant of Kawasaki City TiO2-modified PTFE mesh sheets
40W Black-light fluorescent lamps

Treatment of Agricultural Waste Water with Photocatalysts ~ Purification

of Nutrient Solution

Tomato Hydroponics

Photocatalytic water reactor

Wastewater Soil Eutrophication

Nutrient solution NO3-, PO33-

400 350 300 250 TOC(mg/L) 200 150 100 50 0 10.4 10.11 10.18

Evolution of TOC (total organic

carbon)

Just after plant

10.25 11.1 11.8 11.15 11.22 11.29 12.6

Production of Tomato

Production

Blank

Treated

2 month later

N700 series Smoking room

For two persons

For four persons

TiO2 nanosheet (TNS)

Ordinary TiO2 coating TiO2 Pollutants

TNS
1m

Substrate SiO2 SiO2

Substrate Flat: difficult to be stained

Rough: easy to be stained

TiO2Nano-sheet on Soda lime Glass

Nb2O5 Nano-sheet on Soda lime Glass

Two coatings Two heating TiO2 SiO2

Na+

One coating One heating Nb2O5NaNbO3

Na+

Na2TiO3 No superhydrophylicity

NaNbO3 Superhydro phylicity

JIS (Japanese Industrial Standards ) for photocatalyst materials

Established so far JIS R701-1 (NOx) JIS R1701-2 (Acetaldehyde) JIS R1701-3 (Toluene) JIS R1702 (Anti-bacteria) JIS R1703-1 (Contact angle) JIS R1703-2 (Degradability) JIS R1704 (Water purification) JIS R1705 (Anti-mold) JIS 1709 (Light source) To be established Test procedure of VOC removal performance Test procedure of deodorizing performance

ISO (International Organization for Standardization) for evaluation of photocatalyst materials

Schedule for establishment of ISOs 2007 2008 2009 2010 2011 Air purification Self-cleaning NOx VOC Odor Contact angle Degradability of MB Anti-bacteria Anti-molds

Anti-bacteria, Anti-molds Light source

Water purification

NEffect of N-Doping on Electronic Structure of TiO2

Low-doping

High-doping

History of the study for photocatalyst 1972 Honda-Fujishima effect has been reported to Nature 1980 Organic substaces and water decomposition (SakataKawai 1990 Anti-fouling, anti-bacteria (Hashimoto, Fujishima 1994 Practical appication of bactericidal tileTOTO) 1996 Superhydrophilic (Hashimoto, Fujishima, TOTO)

The development should be continued to accelerate by Japanese government

2001 Discovery of visible light photocatalyst

Rapid growth of the market

Kanagawa Academy of Science and Technology in KSP

Established in July 1989 Location: Kawasaki

(Southern part of Tokyo)

Chairman: Dr. A. Fujishima

KAST endeavors to form new industries through the creation of R&D ventures and through support for joint projects involving industry, academia and local government.

Organization of Research Laboratories

Hasegawa Nano-Structured Magneto-optical Devices Yokoyama Nano-Medical Polymers Project Hara Solid Acid Ecocatalyst Project Enviroment-Friendly Functional Surface Project Yasuda "On-chip Molecular Cell Phenomics Project Abe Food Safety and Reliability Project Power electronics Project Hashimoto Group Photofunctional Materials Group Suzuki Group Masuda Group Photocatalyst Group Near Field Optics Group Micro Chemistry Group Ohtsu Group Saiki Group Kitamori Group

Research Projects

Special Research Lab

Electrospinning Method
Schematic illustration of experimental setup
Precursor solution / syringe Collector

Nanofiber electrospinning unit

Needle

20

High voltage power supply

Syringe pump

TiO2-SiO2 Fibrous Photocatalyst

Before calcinated

After calcinated

M. Jin, X. Zhang, A. Fujishima et al., Chem. Commun. 2006, 4483

TiO2-SiO2 Fibrous Photocatalyst

300 250
0.05

(a)
0.00 -0.05
light on

(b)

Concentration (ppm)

200 150 100 50 0 -2 -1

CH3CHO

ln C/C0

CO2

-0.10 -0.15 -0.20 -0.25 -0.30

Fiber Film

-5

10

15

20

25

30

35

Time (h)

Time (min)

Photocatalytic oxidation of CH3CHO:

Conditions: 500 mL vessel, Air atmosphere, Humidity 50%, 1.0 mW cm-2 UV light

Fibrous photocatalyst was 15 times more active than film photocatalyst in decomposition of acetaldehyde

The 30,000th Visitor

Date: June 24, 2008

Photocatalyst Museum

Windows in the photocatalyst museum

Uncoated Coated

Outdoor Test on Self-Cleaning Tent Materials in the Photocatalyst Museum

TiO2 -coated not coated

Just after setting

after 2 months

after 6 months

after 1 year

Summer-Holiday Course Held in the Photocatalyst Museum