Commercialisation of Chemistry
Visible light semiconductor photocatalysts
– a novel hygiene solution
Declan McCormack (DIT) and Robert Hickson (Vitra)
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

Nafion
Titania (TiO
2
)
Precipitation of submicron high surface area seconducting titania as a support for metal oxide anodic catalysts, mainly for fuel cells.
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland Annual Congress
Friday, 27th May 2011

Ignatz Semmelweis (1818-1865)
1847- Childbed (Puerperal) Fever in Vienna Hospital Obstetrical Clinic
First clinic Second clinic
Year Births Deaths Rate (%) Births Deaths Rate (%)
1841 3,036 237
1842 3,287 518
7.8
15.8
2,442
2,659
86
202
3.5
7.6
1843 3,060 274
1844 3,157 260
9.0 2,739 164
8.2 2,956 68
6.0
2.3
1845 3,492 241
1846 4,010 459
6.9 3,241 66
11.4 3,754 105
2.0
2.8
“cadaverous particles”
Institute of Chemistry of Ireland Annual Congress
Friday, 27th May 2011
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy

•75% of the total 8,000 cases of hospital acquired infections (HAI) were due to the superbug MRSA
(Methicillin Resistant Staphylococcus Aureus) in
Ireland. Other more virulent strains such as KPC &
NDM-1
•Annual cleaning bills for Irish hospitals are €68 million and the total economic burden of hospital acquired infection is over €150 million every year.
•The proportion of MRSA observed in Ireland is one of the highest in Europe
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland Annual Congress
Friday, 27th May 2011

How the titania coating in Pilkington glass works as a superhydrophilic coating?
Ti
Ti
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland Annual Congress
Friday, 27th May 2011

Visible light active titania
Conventional TiO
2
E
BG
= 3.2eV
Visible light active TiO
2
E
BG
< 3.2eV
Rev. No: C
R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science. 2001, 293, 269.
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011
Issue Date: 08/06/2010 Owner: B. Duffy

First N-doped Titania (TiO
2
)
Asahi (2001)
• TiO
2-x
N x prepared by sputtering with N
2 and annealing in N
2 atmosphere at 550 o C
• Mixture of anatase and rutile
• Yellow transparent films
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland Annual Congress
Friday, 27th May 2011

• Fluorine (In collaboration with JM Kelly and I Gun’ko, TCD)
Chem. Mater ., 19 (18), 2007 , 4474-4481.
• Nitrogen
J. Phys. Chem. C, 111(4), 2007 , 1605 –1611.
• Sulphur
J. Phys. Chem. C, 112 (20), 2008, 44 –7652.
• Nitrogen and Sulphur
J. Phys. Chem. C, 113,(8), 2009 , 3246-3253.
• Nitrogen doped heterojunctions
• Chem. Mater., 22, 2010 , 3843 –3853
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy

Challenge: Anatase to Rutile Transformation
600 to 700 C in pure titania
600- 700 C
Ti
Ti
Ti
Ti Ti
Ti
Anatase
(Edge shared)
Photocatalytic Phase
Rutile
(Corner shared)
Non-Photocatalytic Phase
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

How a delayed phase transition happens
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
J. Phys. Chem. C, 112 (20), 2008, 44
–7652.
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

Sunlight Driven Photocatalysis- 850 O C calcined samples
(a) Control sample
210 minutes
J. Phys. Chem. C, 112 (20), 2008, 44
–7652.
(b) S-doped sample
35 minutes
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

→ O 2•
electron
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

• High temperature stable anatase phase (above 1000 O C)
• Visible light activity by doping
• A stable anatase phase up to the sintering temperature of the ceramic substrates is most desirable for applications on anti-bacterial ceramic materials (e.g. bathroom tile, sanitary ware etc.).
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

• High Sintering temperature
(above 1000 O C).
• Photocatalytic phase anatase change to rutile at 600 O to 700 O C
• High temperature stability and visible light activity are requisite
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

Examples of RADICAL’s anti-bacterials
Photocatalyst products
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

a b
Anti-MRSA test of titania samples (a) control (b) CREST TiO
2
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

External Antimicrobial Testing against E. coli;
Airmid healthgroup , using ISO 27447: 2009
VitrA photocatalytic wall tiles
Conclusion
The presence of visible light killed all the E. coli on VitrA photoactive ceramic tile
(Sample A1)
Institute of Chemistry of Ireland
– Annual Congress
A normal tile showed no change in antibacterial count (Too Numerous To Count, TNTC)
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy

•
A novel industrial viable technology has been developed to prepare visible light active titania.
•
A high temperature stable photo-active titania has been developed
•
Anti-MRSA ceramic tiles have been produced
•
Industrial pilot plant operation has been successfully carried out.
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011

Enterprise Ireland ARE programme
Dr Suresh Pillai
Dr John Colreavy
Dr Hugh Hayden
Mr Darragh Ryan
Dr Pradeepan Periyat
Dr Michael Seery
4/11/2020
Rev. No: C Issue Date: 08/06/2010 Owner: B. Duffy
Institute of Chemistry of Ireland
– Annual Congress
Friday, 27th May 2011