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Application of Titanium Dioxide Photocatalysis to Create Self-Cleaning Building Materials

Roland Benedix 2 Frank Dehn 3 Jana Quaas, Marko Orgass


SUMMARY To realize self-cleaning material surfaces there are two principal ways: the development of super-hydropho ic or super-hydrophilic materials! "y transferring the microstructure of selected plant surfaces to practical materials li#e tiles and facade paints$ super-hydropho ic surfaces were o tained %&otus effect'! Superhydrophilic materials were developed y coating glass$ ceramic tiles or plastics with the semiconducting photocatalyst titanium dio(ide %Ti)*'! +f Ti)* is illuminated y light$ grease$ dirt and organic contaminants are decomposed and can easily e swept away y water %rain'! Su ,ect of our further research is a detailed study of the interaction etween Ti)* and traditional uilding materials li#e concrete$ mortar and plaster!


In practice, sur ace cleaning o !uilding "aterials like tiles, acades and glass panes causes considera!le trou!le, high consu"ption o energ# and che"ical detergents and, conse$uentl#, high costs% &o reali'e sel (cleaning "aterial sur( aces there are t)o principal )a#s* the de+elop"ent o so(called super( h#dropho!ic or super(h#drophilic sur aces%

,ro % Dr% rer% nat% ha!il%, FB IM-./he"ie, 0&12 3eip'ig 2 Dipl%(Ing%, Institut 4r Massi+!au und Bausto technologie, 5ni+ersit6t 3eip'ig 3 cand%(Ing%, Institut 4r Massi+!au und Bausto technologie, 5ni+ersit6t 3eip'ig


39/:R -o% 7, 2;;; &he )etting o a solid )ith )ater, )here air is the surrounding "ediu", is de( pendent on the relation !et)een the inter acial tensions <)ater.air, )ater.solid and solid.air=% &he ratio !et)een these tensions deter"ines the contact angle !e( o t)een a )ater droplet on a gi+en sur ace% 9 contact angle o ; "eans co"plete o )etting, and a contact angle o 1>; corresponds to co"plete non()etting% 0#dropho!ic sur aces )ith lo) )etta!ilit# and contact angles o a!out 1;; are kno)n or a long ti"e% &he higher this angle the lo)er is the +alue o the adhe( sion )ork% Decreasing o the contact angle leads to enlarged +alues o the adhe( sion )ork <h#drophilic sur aces=% B# trans erring the "icrostructure o selected plant sur aces to practical "aterials, super-hydropho ic sur aces could !e de+eloped% &he )ater repellenc# o plant sur aces has !een kno)n or "an# #ears% &hat )ater(repellent sur aces also indi( cate sel (cleaning properties has !een co"pletel# o+erlooked% Recentl#, Barthlott et al% ?1@ in+estigated and pro+ed the correlation !et)een the "icrostructure, )etta!ilit# and conta"inants in detail using lotus lea+es% &his )as called the &otus -ffect !ecause it can !e de"onstrated !eauti ull# )ith the great lea+es o o the lotus plant% &he "icrorough sur aces sho) contact angles higher than 13; % &hat "eans, the adhesion o )ater, as )ell as particles is extre"el# reduced% 1ater )hich contacts such sur aces )ill !e i""ediatel# contracted to droplets% &he particles o conta"inants adhere to the droplet sur aces and are re"o+ed ro" the rough sur ace )hen the droplets roll o < ig% 1=%

ordinar# Aur ace

h#dropho!ic Aur ace

$ig% 1*

3otus : ect


9pplication o &itaniu" Dioxide ,hotocatal#sis to /reate Ael (/leaning Building Materials /leaning procedures !ased on lo) contact angles are kno)n since the disco+er# o soap <3rd "illenniu" B/=% Benerall#, detergents reduce the sur ace tension o )ater and the contact angle )ill lo)ered% 9nother +er# interesting possi!ilit# to cause lo) contact angles )ithout detergents is the use o acti+e thin il"s on the "aterial sur ace% For the preparation o this thin la#ers "ainl# photocatal#tic acti+e "etal oxides or sul ides ha+e !een applied% In the last #ears &iO2 coated "aterials are o increasing interest ?2@% I &iO2 o the anatase t#pe is exposed to o 5C light +er# lo) contact angles are o!tained << 1 =% &hese "aterials ha+e the uni$ue propert# o DattractingE rather than repelling )ater %super-hydrophilicity'! &he )ater lies lat on the sur ace in sheets instead o or"ing droplets% I the illu"ination is stopped, the super(h#drophilic !eha+iour o the &iO2 sur ace is retained or approxi"atel# t)o da#s% Further"ore, 5C illu"ination o titaniu" dioxide leads to the or"ation o po)er ul agents )ith the a!ilit# to oxidi'e and deco"pose "an# t#pes o !acteria, organic and inorganic "aterials% In the ol( lo)ing, the principles and potential applications o &iO2 photocatal#sis are dis( cussed%



CIP'(S "$ )(T(!"*( ("#S P)"T"CATA'+SIS

In a!sence o a catal#tic acti+e su!stance, the oxidation o the "ost h#drocar!ons proceeds rather slo)l#, )hich can !e explained !# kinetic argu"ents% 9 photo( catal#st decreases the acti+ation energ# o a gi+en reaction% In the result o photoinduced processes o ten particles )ith strong oxidation and reduction a!ilit# occur% 9 heterogeneous photocatal#tic s#ste" consists o se"iconductor particles <photocatal#st= )hich are in close contact )ith a li$uid or gaseous reaction "e( diu"% :xposing the catal#st to light excited states are generated )hich are a!le to initiate su!se$uent processes like redox reactions and "olecular trans or"ations% In ig% 2 a si"pli ied reaction sche"e o photocatal#sis is sho)n% Due to their electronic structure, )hich is characteri'ed !# a illed +alence !and <CB= and an e"pt# conduction !and </B=, se"iconductors <"etal oxides or sul ides as FnO, /dA, &iO2, Fe2O3, and FnA= can act as sensiti'ers or light(induced redox proc( esses% &he energ# di erence !et)een the lo)est energ# le+el o the /B and the highest energ# le+el o the CB is the so(called !and gap energ# :g% It corresponds to the "ini"u" energ# o light re$uired to "ake the "aterial electricall# conduc( ti+e%


39/:R -o% 7, 2;;;


/onduction !and

9 Reduction 9 He 9 9 D
Calence !and
( (


Oxidation D Hh D

$ig% &* particle

Operation o

a photoche"ical excited &iO2

1hen a photon )ith an energ# o h exceeds the energ# o the !and gap an elec( ( tron <e = is pro"oted ro" the +alence !and to the conduction !and lea+ing a hole H <h = !ehind% In electricall# conducting "aterials, i%e% "etals, the produced charge( carriers are i""ediatel# reco"!ined% In se"iconductors a portion o this photo( excited electron(hole pairs di use to the sur ace o the catal#tic particle <electron( hole pairs are trapped at the sur ace= and take part in the che"ical reaction )ith the adsor!ed donor <D= or acceptor <9= "olecules% &he holes can oxidi'e donor "olecules <1= )hereas the conduction !and electrons can reduce appropriate electron acceptor "olecules <2=% D H h D H 9 H e 9(
( H

<1= <2=

9 characteristic eature o se"iconducting "etal oxides is the strong oxidation H po)er o their holes h % &he# can react in an one(electron oxidation step )ith )ater <3= to produce the highl# reacti+e h#drox#l radical < O0=% Both the holes and the h#drox#l radicals are +er# po)er ul oxidants, )hich can !e used to oxi( di'e "ost organic conta"inants% 02O H h O0 H 0
+ +



9pplication o &itaniu" Dioxide ,hotocatal#sis to /reate Ael (/leaning Building Materials In general, air ox#gen acts as electron acceptor <J= !# or"ing the super(oxide ion O2% O2 H e O2


Auper(oxide ions are also highl# reacti+e particles, )hich are a!le to oxidi'e organic "aterials%


&itaniu" dioxide is one o the !asic "aterials in e+er#da# li e% It has !een )idel# used as )hite pig"ent in paints, cos"etics and oodstu s% &iO2 exists in three cr#stalline "odi ications* rutile, anatase, and !rookite% Benerall#, titaniu" diox( ide is a se"iconducting "aterial )hich can !e che"icall# acti+ated !# light% &he photoacti+it# o &iO2 )hich is kno)n or approx% I; #ears is in+estigated exten( si+el#% For a long ti"e there )as a considera!le pro!le" especiall# )hat its ap( plication as pig"ent concerns% 5nder the in luence o light the "aterial tends to deco"pose organic "aterials% &his e ect leads to the )ell(kno)n pheno"enon o Epaint chalkingE, )here the organic co"ponents o the paint are deco"posed as result o photocatal#tic processes% /o"pared )ith rutile and !rookite, anatase sho)s the highest photoacti+it#% &here ore, the &iO2 used in industrial products is al"ost exclusi+el# ro" the rutile t#pe% In the ollo)ing, &iO2 al)a#s denotes the anatase "odi ication% In 1G82, FuKishi"a and 0onda disco+ered the photocatal#tic splitting o )ater on &iO2 electrodes ?3@% &his e+ent "arked the !eginning o a ne) era in heterogene( ous photocatal#sis% 9lthough &iO2 a!sor!s onl# approx% 7 L o the solar light reaching the sur ace o the earth, it is the !est in+estigated se"iconductor in the ield o che"ical con+ersion and storage o solar energ#% In recent #ears se"i( conductor photocatal#sis using &iO2 has !een applied to i"portant pro!le"s o en+iron"ental interest like detoxi ication o )ater and o air% &iO2 is a se"iconductor )ith a !and gap energ# :g M 3,2 eC% I this "aterial is irradiated )ith photons o the energ# > 3,2 eC <)a+elength < 3>> n"=, the !and gap is exceeded and an electron is pro"oted ro" the +alence to the conduction !and% /onse$uentl#, the pri"ar# process is the charge(carrier generation <7=% 1I1

39/:R -o% 7, 2;;;

&iO2 H h h H e


&he a!ilit# o a se"iconductor to undergo photoinduced electron trans er to ad( sor!ed particles is go+erned !# the !and energ# positions o the se"iconductor and the redox potentials o the adsor!ates% &he rele+ant potential le+el o the acceptor species is ther"od#na"icall# re$uired to !e !elo) the conduction !and o the se"iconductor% Other)ise, the potential le+el o the donor is re$uired to !e a!o+e the +alence !and position o the se"iconductor in order to donate an elec( tron to the e"pt# hole% &he !and(edge positions o se+eral se"iconductors are presented in ig% 3%

$ig% ,*

Band(edge energies o t#pical se"iconductors


9pplication o &itaniu" Dioxide ,hotocatal#sis to /reate Ael (/leaning Building Materials &he heterogeneous photocatal#tic oxidation )ith &iO2 "eets the ollo)ing re( $uire"ents )hat could "ake it co"petiti+e )ith respect to other processes oxi( di'ing conta"inants* 9 lo)(cost "aterial is used as photocatal#st% &he reaction is $uite ast at "ild operating conditions <roo" te"perature, at"ospheric pressure=% 9 )ide spectru" o organic conta"inants can !e con+erted to )ater and /O2% -o che"ical reactants "ust !e used and no side reactions are produced% P!ACTICA' APP'ICATI"
S "$ TI"& P)"T"CATA'+SIS

In ig% J the "ain areas o acti+it# in titaniu" dioxide photocatal#sis are sho)n% 9s alread# "entioned, in the last 1; #ears photocatal#sis has !eco"e "ore and "ore attracti+e or the industr# regarding the de+elop"ent o technologies or puri ication o )ater and air% /o"pared )ith traditional ad+anced oxidation proc( esses the technolog# o photocatal#sis is kno)n to ha+e so"e ad+antages, such as ease o setup and operation at a"!ient te"peratures, no need or postprocesses, lo) consu"ption o energ# and conse$uentl# lo) costs%

9nt i( ogging e ect

3ight H &iO2
1at er t reat "ent

Ael ( cleaning e ect

9ir( cleaning e ect 9nt i( !act erial e ect

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MaKor areas o acti+it# in titaniu" dioxide photocatal#sis


39/:R -o% 7, 2;;; In the ield o )aste )ater detoxi ication nu"erous concepts )ere created ?JN 7@% In pre+ious studies, s#ste"s are considered in )hich the ine &iO2 photocatal#st po)der )as dispersed in li$uid suspension% 0o)e+er, these s#ste"s )ere hardl# to handle% 9 ter the degradation process under irradiation )ith 5C light the po)( der re"ains suspended in )ater% &he use o ilters or other "ethods to re"o+e &iO2 has !een pro+ed to !e ine icient and cost(e ecti+e% In the ollo)ing ti"e, reactors )ere designed )here the titaniu" dioxide is ixed on a glass, cera"ics or "etal sur ace% ,resentl# there is high interest in de+elop"ent and i"pro+e"ent o thin( il"( ixed(!ed reactors, )hich is sho)n in ig% 7% In this reactor t#pe indus( trial )aste )ater is passing a &iO2 coated "aterial <glass, pol#st#rene, "ethacr#( late=%


&iO2 coated catal#st sheet

$ig% .* &hin( il"( ixed(!ed reactor ?7@


,hotocatal#tic oxidation has !een applied or re"o+ing and deco"posing pollut( ants in indoor air% &he used reactors trap and che"icall# oxidi'e organic co"( pounds, con+erting the" pri"aril# to /O2 and )ater% &hese reactors operate at roo" te"perature and )ith negligi!le pressure% &here ore, the# "a# !e readil# integrated into ne) and existing heating, +entilation, and air conditioning s#s( te"s% &iO2 coated cera"ic tiles are considered to !e +er# e ecti+e against organic and inorganic "aterials, as )ell as against !acteria% In ig% I 0#drotect tiles are sho)n )hich kill !acteria at an extre"el# high rate o speed ?I@% 1ith other )ords, the !acteria are killed aster than the# can gro)% &he application o these tiles in hospitals and care acilities to reduce the spread o in ections and the 1IJ

9pplication o &itaniu" Dioxide ,hotocatal#sis to /reate Ael (/leaning Building Materials threat to patients )hose i""une s#ste" ha+e !een )eakened, in pu!lic and co""ercial acilities and schools to i"pro+e the h#gienic conditions and in resi( dential kitchens, !aths and loors to pro"ote a"il# h#giene and to reduce house)ork is o general interest% Further"ore, these tiles sho) super(h#drophilic !eha+iour% 1ater or"s a uni or" sheet o+er the sur ace at a contact angle o 8 <exterior= and 27 <interior= degrees% Brease, dirt and other staining "aterials can easil# !e s)ept a)a# )ith a strea" o )ater% Auperh#drophilicit#, co"!ined )ith the strong photocatal#tic oxidi'ing properties "akes this tile sel (cleaning in exterior applications%

ordinar# uncoated tile

$ig% /* Auper(h#drophilicit#

h#drophilic tile coated !# &iO2

$#!T)(! I


9lthough there are outdoor applications o &iO2 photocatal#sis, in the literature no in or"ation on the interaction !et)een titaniu" dioxide and traditional !uild( ing "aterials like concrete, "ortar, and plaster is a+aila!le as #et% For exa"ple, "ost o the external !uilding )alls !eco"e spoiled ro" auto"o!ile exhaust gases, )hich contain oil# co"ponents% B# coating the original !uilding "aterials )ith a super(h#drophilic photocatal#st, the dirt o the )alls can easil# !e )ashed a)a# !# rain, keeping the !uilding external )all clean or long ti"es% &)o e ects should !e considered* Firstl#, a super(h#drophilic sur ace has a higher a init# to )ater than to oil% Aecondl#, ultra+iolet illu"ination o &iO2 leads to the or"ation 1I7

39/:R -o% 7, 2;;; o a photogenerated hole(electron pair that reacts )ith ox#gen and )ater in the en+iron"ent to generate potential cleaning agents on the sur ace o the coated "aterial% &he agents <O0, OO0= deco"pose large organic "olecules to s"aller rag"ents% &he co"!ination o photocatal#sis and super(h#drophilicit# allo)s grease and dirt to !e s)ept a)a# )ith )ater% Au!Kect o our research is the detailed in+estigation o the dependence o the photocatal#tic acti+it# o &iO2 on di erent !uilding "aterials% &he ollo)ing ite"s should !e in+estigated* ,ossi!ilities o ixing &iO2 on !uilding "aterials (

9pplication o the spra#(coating technolog# &he a$ueous or "ethanolic &iO2 suspension is spra#ed on the sur ace o the considered !uilding "aterial% &his "ethod has the ad+antage that the a"ount o &iO2 )hich shall co+er a speci ic area o the sa"ple can !e regulated in a si"ple )a#% 9 ter spra#ing, the sol+ent can !e re"o+ed !# heating the sa"ple to approx% 1;;O /% ( 9pplication o the sedi"entation technolog# &he sa"ple is kept or a de ined ti"e in a &iO2 suspension% &hen the sus( pension slo)l# is drained ro" the !eaker% 9gain, the sol+ent can !e re( "o+ed !# heating the sa"ple to approx% 1;;O /% &he photocatal#tic deco"position o organic d#es <"eth#lene !lue, rhoda( "ine B, and others= as "odel su!stances or organic conta"inants &he photocatal#tic deco"position o grease and +arnish &i"e(dependent "easure"ents o the deco"position reactions


9pplication o &itaniu" Dioxide ,hotocatal#sis to /reate Ael (/leaning Building Materials

/ ?1@ ?2@ ?3@ ?J@



1% Barthlott, /%-eihuis* P,urit# o the sacred lotus, or escape ro" con( ta"ination in !iological sur acesDN ,lanta *.* <1GG8= 1 9% FuKishi"a, 2% 0ashi"oto, &% 1atana!e* P&iO2 ,hotocatal#sis* Funda( "entals and 9pplicationsDN B2/ &ok#oN 1GGG 9% FuKishi"a, 2% 0onda* P:lectroche"ical ,hotol#sis o 1ater at a Ae"i( conductor :lectrodeDN -ature */0 <1G82= 38 D% Bahne"ann* PAolare 9!)asserentgi tungDN -achr% /he"% &ech% 3a!% 1* <1GGJ= 38> Dirk Bockel"ann* PAolare Reinigung +ersch"ut'ter 16sser "ittels ,ho( tokatal#seDN /u+illier CerlagN BQttingen 1GGJ 5R3* )))%h#drotect%co"




39/:R -o% 7, 2;;;