2014/04/10—Advanced Course in Photocatalytic Reaction Chemistry 1
2014/04/10
introduction of Professor Ohtani Laboratory
2014/04/10—Advanced Course in Photocatalytic Reaction Chemistry 2
Advanced Course in Photocatalytic Reaction Chemistry
understanding chemistry by understanding photocatalysisunderstanding photocatalysis by understanding chemistry
Division of Environmental Material Science, Graduate School of Environmental ScienceThe first semester of Fiscal 201408:45─10:15, Thursday at Lecture Room D103
Bunsho Ohtani, Ewa Kowalska and Mai Takase
Catalysis Research Center, Hokkaido University, Sapporo 001-0021, Japan011-706-9132 (dial-in)/011-706-9133 (facsimile)
[email protected]://www.hucc.hokudai.ac.jp/~k15391/
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objectives/goal/keywords
<< objectives >>Understanding the mechanism of decomposition of pollutants, methodsof photocatalysts preparation, design of practical photocatalytic reactionsystems, and strategy for enhancement of photocatalytic activity.
<< goal >>To understand principle of photocatalytic reaction from the standpointof chemistry and strategy for practical applications. To obtain scientificmethod for research on functional solid materials.
<< keywords >>Photocatalyst, Photoinduced oxidative decomposition, Superhydro-philicity, Excited electron-positive hole, Structure-activity correlation,Higher photocatalytic activity, Visible-light response
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schedule
(1) April 10 introduction of photocatalysis(2) April 17 interaction between substances and light(3) April 24 electronic structure and photoabsorption(4) May 1 thermodynamics: electron and positive hole(5) May 8 adsorption(6) May 15 (Professor Ewa Kowalska)(7) May 22 kinetic analysis of photocatalysis (8) May 29 steady-state approximation(9) June 5 kinetics and photocatalytic activity(10) June 12 kinetic analysis(11) June 19 (Professor Mai Takase)(12) June 26 action spectrum analysis (1)(13) July 3 action spectrum analysis (2)(14) July 10 crystal structure of titania(15) July 17 design and development of photocatalysts
July 24 deadline for submission of special report
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comments on this lecture
Please send email in Japanese or English within 48 hours
to: [email protected]: pc2014MMDD-XXXXXXXXbody:
(full name)(nickname)(comments and/or questions on today's lecture)
2014/04/10—Advanced Course in Photocatalytic Reaction Chemistry 6
Hokkaido University: A National University
Hokkaido: A northern island of Japan
Sapporo: A capital city of Hokkaido Prefecture
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Catalysis Research Center, Hokkaido Univ.
Catalysis Research Center
Unique research institute for studies on catalysis, including photocatalysis, in Japan, previously Institute for Catalysis.Twenty faculty members including seven full professors.
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Catalysis Research Center (CRC)
Catalysis Research Center (CRC) originate from Institute for Catalysiswhich was founded in 1943 in Hokkaido University for fundamental studieson catalysis, and started as a national collaborating institution in 1988,followed by scale-up reorganization in 1998 and by reorganization renewalin 2007 for playing a leading role in catalysis studies and a bridging roleamong interdisciplinary research fields.
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Catalysis Research Center
9 Professors (K. Asakura/M. Osawa/B. Ohtani/W. Ueda/A. Fukuoka/T. Takahashi/T. Nakano/J. Hasegawa/M. Nishida)
7 Associate professors 7 Assistant professors29 Research fellows5 Visiting professors19 Collaborative researchers58 Students13 Tentative staff8 Technical staff20 Administrative staff173 Total
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CRC: Divisions and Clusters
Target-Oriented R
esearch Assem
blyTarget-O
riented Research A
ssembly
Professor Associate Professor
触媒理論化学研究部門
触媒理論化学研究部門
Fundamental Research DivisionFundamental Research Division
実用化基盤技術開発部
実用化基盤技術開発部
コーポレートユニット
コーポレートユニット
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2010 Nobel Prize in Chemistry
Professor Akira SUZUKI (Professor Emeritus, Hokkaido University)
Professor Ei-ichi NEGISHI(Purdue University)
These two professors are also Specially Invited Professors in Catalysis Research Center, Hokkaido University
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titania-coated glass of our building
• all glass plates are coated with titania to reduce infrared radiation (with expectation to keep the surfaces clean).
• coated on site; not construction with pre-coated glass plates• expected photocatalytic self-cleaning effect
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to be a world number one labo on photocatalysis
photocatalysis
URL of web page for Professor OhtaniLaboratoryhttp://www.hucc.hokudai.ac.jp/~k15391/
光触媒 研究室 検索
"photocatalysis" and "laboratory"
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critical reviews
critical reviews on, not a compilation of, photocatalytic studies
Open paper: free of charge for downloading the PDF file
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Photocatalysis A to Z [JPPC, 11 (2010) 157-178]
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Ohtani Laboratory for photocatalysis research
collaboration work using advanced instruments designed for photocatalysis
research
collaboration work using advanced instruments designed for photocatalysis
research
evaluation of photocatalytic activitiesevaluation of photocatalytic activities
education for young people education for young people
opened for researchers in academics and industriesopened for researchers in academics and industries
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single-author books
Hikarishokubai no Shikumi ga Wakaru HonHikarishokubai Hyojun Kenkyuho (Scientific Methods in Photocatalysis)
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Professor Ken-ichi Fukui
October 19, 1981: announcement of Nobel Prize in ChemistryJanuary 9, 1998: died
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questions
Q Have you heard or seen a term "photocatalysis" (or "photocatalyst") before attending this class?
Q Do you know the examples of practical applications of photocatalysis? Interpret the mechanism.
Q What is the meaning of "catalyst (or catalysis)" in a term "photocatalyst"?
introduction of photocatalysis
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photocatalysis: two major phenomena
photocatalytic decompositiontarget:
organic compoundssteins (oil)microorganisms
photocatalytic decompositiontarget:
organic compoundssteins (oil)microorganisms
photoinduced (super) hydrophilicitywashable with running wateranti-fogging
photoinduced (super) hydrophilicitywashable with running wateranti-fogging
mechanism
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regular PVC Teflon-coated titania-coated
after exposure outdoor for 5 months
showing change in
color
Taiyo Kogyohttp://www.taiyokogyo.co.jp/
tent material coated with titania photocatalyst
PVC must contain organic additives, which go out to the surface slowly, to be elastic.
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titania-coated glass of our building
• all glass plates are coated with titania to reduce infrared radiation (with expectation to keep the surfaces clean).
• coated on site; not construction with pre-coated glass plates• expected photocatalytic self-cleaning effect
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substrate: steal plates
JFE Building Materialshttp://www.jfe-kenzai.co.jp/index.shtml
exterior materials coated with titania
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with
paints requiring no heating: room-temperature coating
titania photocatalytic painting
painting procedure with brush or roller
painting procedure:spraying
withoutwith
without
with without
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large-scale application of photocatalysts"self-cleaning" window glasses
"Marubiru", a large office building in Tokyo
"Centrea", Chubu International airport, Nagoya
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inside: anti-fogging effect to give water droplet-free surfaceoutside: photocatalytic decomposition and (super) hydrophilicity to
keep the surface clean
photocatalyst coated glass
Japan Hydrotect Coatings
regular glass
titania-coated glass
on-site coating > pre-coating
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Nippon Sodahttp://www.nippon-soda.co.jp/photo/report.html
titania coatings with heating = pre-coating window blinds
titania photocatalyst-including paint
No effect of photo-induced hydrophilicity is expected for indoor use.
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"partition" with photocatalytic coatings
possible effects:cleaning by decomposition of organic matters/deodorization/anti-microorganisms
Mitsubishi Plasticshttp://www.mpi.co.jp/press/pr030501.htm
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titania-coatings for anti-fogging
TOTO
regularpart
titaniacoatedpart
no water droplets due to the (super) hydrophilicity of photocatalytic titania surface
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polycarbonate plates covered withtitania photocatalyst on both sides
Sekisui Plasticshttp://www.sekisuijushi.co.jp/
road-side sound barriers coated with titania
titania1.5 year
regular1.5 year
regular3.5 year
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pavements containing titania photocatalyst
"Photoroad"
Nitrogen oxides (NOx) are oxidized by photocatalystResulting nitrate (NO3
-) ions are captured by calcium ionsCalcium nitrate (Ca(NO3)2) is washed out by rain water
Fujitahttp://www.fujita.co.jp
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Toshiba Lightechttp://www.tlt.co.jp/tlt/new/crean/crean.htm
a covering window glass coated with titania
lights for outdoor use
regularfluorescent lamp
lighting device with titania photocatalyst
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photocatalytic air purifier unit
active air purification: decontamination and deodorization of circulating air
Hitachi Home and Life Solutionhttp://www.hitachi-hl.com/
Daikin Ltd.http://www.daikinaircon.com/
air conditionerair conditioner
air purifierair purifier
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photocatalytic treatment of water
Sumitomo Metal Industrieshttp://www.sumitomometals.co.jp/news/monthly/2001/140.html
polluted gas
drain
aeration unit
water
exhaust
pump
soil
groundwater
air
dryerseparator photocata-lyst
neutra-lizer
decontaminated
polluted gasblack light
flow apparatus
Contaminated ground water is treated to remove volatile organic compounds.
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smoke cleaner/refrigerator
Toshiba/Mitsubishihttp://www.toshiba.co.jp/about/press/2001_09/pr_j0302.htmhttp://www.mitsubishielectric.co.jp/news/2009/0825-a.htm
Toshiba/Mitsubishihttp://www.toshiba.co.jp/about/press/2001_09/pr_j0302.htmhttp://www.mitsubishielectric.co.jp/news/2009/0825-a.htm
deodorization/decomposition of ethylene (CH2=CH2) from vegetables/fruits to keep freshness
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photocatalytic water treatment
photocatalytic fiber cartridge for decomposition of dioxin and sterilization
UBE Industrieshttp://www.ube-ind.co.jp/japanese/japanese/annai/01_05_03.htm
チタニアが有機物を酸化分解する光触媒機能に着目して、接触面積が大きく、丈夫な繊維状にしたのが『光触媒繊維』。既存の光触媒製品と差別化した製品の特色を活かして市場開発を進めています。この新素材はダイオキシンの分解にも期待されています。
チタニアが有機物を酸化分解する光触媒機能に着目して、接触面積が大きく、丈夫な繊維状にしたのが『光触媒繊維』。既存の光触媒製品と差別化した製品の特色を活かして市場開発を進めています。この新素材はダイオキシンの分解にも期待されています。
2014/04/10—Advanced Course in Photocatalytic Reaction Chemistry 38
a TOC analyzer with a photocatalytic reactor
Hiranuma Industrieshttp://www.hiranuma.com/products/envr/toc/Hiranuma Industrieshttp://www.hiranuma.com/products/envr/toc/
• Analyzing TOC (total organic carbon), organic compounds are decomposed by oxidantsinto carbon dioxide (CO2) and the amount of CO2 is measured.
• Conventional analyzers require the use of potassium permanganate as an oxidant or ofa expensive short-wavelength (254 nm) mercury arc lamp.
• Using a titanium(IV) oxide photocatalyst system, any chemicals and their posttreatment are not needed and cheaper long-wavelength mercury arc lamps can beused.
TOC-3000TOC-3000
TOC-2000TOC-2000
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photocatalysis industries in Japanindustries related to photocatalysisalmost 300 million USD after 2005(Photocatalysis Industry Association of Japan)
otherslivingwarecleanuproadinteriorexteriorm
illio
n U
SD
400
300
200
100
02000 2002 2004 2006 2008
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photocatalysis industries in Japan2012 (2011): ca. 400 million USD [370 million USD for 2011]
47(52)%
2(1)%
3(4)%
43(38)%
4(4)%
exteriorexterior
interiorinteriorroad relatedroad related
purifierpurifier
living wareliving ware
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photocatalysis: two major phenomena
superhydrophilicity: the surface of photocatalytic (titania) coatings becomes super hydrophilic, i.e., contact angle to be almost zero.
photocatalytic oxidation: organic and inorganic compounds are oxidized under air to be inorganic materials, i.e, mineralization.
left: photocatalytic/right: ordinaryleft: photocatalytic/right: ordinary
mechanism
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titanium(IV) oxide (titania) as a photocatalyst
no change after reaction = "catalyst"
no reaction in the dark = "safe" and environ-mentally benign
very popular and cheap material
especially strong oxidizing power when irradiated
white or colorless = no effect on appearancebut, requires ultraviolet irradiation
highphoto-
stability
superiorredox ability availability
notpoisonous& natural
titanium(IV) oxideTiO2
titania
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practical applications
Q Which application impressed you the most? What is the reason for that?
Q What is the general chemical reaction(s) included in the practical applications of photocatalysis? Show a reaction formula(s).
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comments on this lecture
Please send email in Japanese or English within 48 hours
to: [email protected]: pc20140410-XXXXXXXXbody:
full namenicknamecomments (questions) on this lectureorder of book(s) if any JPY1,200 (77%) JPY3,500 (79%)
pc20140410-12345678