Nano Titania PowerPoint Presentationد رضوي

7/24/2019 Nano Titania PowerPoint Presentation

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Application of nano-titania in water treatment

Dr. Radwa A. Elsalamony

Egyptian Petroleum Research Institute

EPRI


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Titanium dioxide, TiO2

Dr. Radwa A. Elsalamony EPRI1

Titanium dioxide, also known as titanium(I! oxideor titania,is the naturally occurrin oxide o! titanium, chemical !ormulaTiO2."hen used as a #iment, it is called titanium white, Pigment

"hite # (P"#!, or $I %%&'.

$enerally it is sourced !rom Ilmenite ore, Titanium dioxide occursin nature as well%known minerals rutile, anatase and &rookite.

It has a wide rane o! a##lications, !rom paint)sunscreen tofood coloring. Photocatalyst, Electronic data storagemedium, It can &e em#loyed !or solar energy con*ersion+ased on dye#olymer.'ynthetic sinle crystals and (lms o! TiO2are used as a

semiconductor)

and also in dielectric mirrors due to the hihre!racti)e index o! TiO2*2.+2.-.


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Photocatalyt

ic acti*ity ofTi,

Dr. Radwa A. Elsalamony EPRI


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Dr. Radwa A. Elsalamony EPRI/

Photocatalysisre!ers to the acceleration o! the rateo! chemical reactions *oxidation0reduction &rouht a&out &y the

acti)ation o! a catalyst, usually a semiconductor oxide, &yultra)iolet (! or *isi+le radiation.istory dates &acks to 1-2, when /u0ishima and 1ondadisco)ered that water can &e s#lit, i.e., simultaneously oxidi2edto oxygen and reduced to hydrogen, when a &ias #otential isa##lied to an 3illuminated4 TiO2 sinle crystal electrode. Thisremarka&le disco)ery marked the onset o! #hoto induced redoxreactions on semiconductor sur!aces. It was soon reali5ed thatsuch redox #rocesses could &e utili5ed !or en*ironmentalcleanup applications, when /ran3 and 4ard) in '%%,

showed the #hotocatalytic oxidation o! $56and 7,-8 usindi6erent semiconductor materials like Ti,) 9n,) $d7) /e,8and ",8.

Thus, a &rilliant start in Ti, #hotocatalysis was !ollowed &y

some nota&le de)elo#ments includin, metal ion doped Ti,*1--7, super-hydrophilic Ti,:lms *1--, anion doped


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;echanism of

Photocatalysis


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Dr. Radwa A. Elsalamony EPRI+

Ti, < hv = h+< e-

The #hoto%induced hole can oxidi5e a donor molecule(D!adsor&ed on the TiO2 sur!ace.

D < h+ = > DA-The stron oxidation #ower o! the holeena&les aone%electron oxidation ste# with water to #roduce ahydroxyl radical *:O.

1, < h

+

= >,1 < 1

,

-!. The

superoxide ion is a highly reactive particle, able tooxidize organic materials.


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Super-hydrophilicity


The su#erhydro#hilic e6ect is also caused to the#roduction o! holes&ecause the electrons tend toreduce the Ti*I;%cations to Ti*III%ions

e- < Ti


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"hy 5ano-si2ed Ti,@@


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The two most im#ortant #ro#erties o! a nano material, whichmakes it su#erior to other microsco#ic or macrosco#ic #articles!or a##lications in catalysis, are*i the high surface to *olume ratio, and*ii the uantum con:nement at the nano scale.The frst property results in catalysts with high sur!ace area andhih #orosity, which ensures enhanced reaction rates due to thehih le)el o! interaction o! the reactants with the acti)e sites.

The second #ro#erty o)erns the trans#ort o! electrons andholes !rom the &ulk to the sur!ace o! the material,whose lenthscale is also o! the order o! a !ew nanometers *called as electron=ohr radius.

>oreo)er, !or #hoto%a##lications, the catalyst should a+sor+)and not +loc3 or scatter, incident radiation, and generatecharge carriers &y &and a# excitation.This is #ossi&le only with nano%si5ed semiconductor materials

with suita&le &and a# enery. There!ore, owin to the enhancedmolecular trans#ort #ro#erties at the sur!ace, it is e)ident that


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Dr. Radwa A. Elsalamony EPRI-

?ano%TiO2#hotocatalysts ha)e &een synthesi5ed indi6erent shapesand morphologies)which include,nanoparticles,. nanorods, nanotubes, nanopillars andnanowire arrays, nanobowls, nanowhiskers, aerogels,nanosheets, opal and inversed opals


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'ynthesis o!

TiO2

$as

#hase

'olution

#hase


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7olutionphase

sol method(non-

hydrolytic

sol-gel!

sol-gelmethod

7ol*o-thermal

synthesis

Precipitation method

1ydrothermal synthesis


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7olutionphase

$om+ustionsynthesis

Electrochemical

synthesis

7ono-chemicalsynthesis

;icrowa*esynthesis

methodologies

;icelle andin*ersemicellemethod


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$hemical*apor

deposition ($D!

Physical

*apordepositio

n

7praypyrolysisdepositio

n

Basphase


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The fnal properties o! the TiO2 nano#articles like

the #hase com#osition *anatase C rutile, particlesi2e) porosity) surface area) +and gap andsurface hydroxyl content can &e tailored &y)aryin the reaction conditions like@the precursor compound (TiCl4, titanium(!"isopropoxide, etc.",hydrolyzing agent (in the case o# sol$gel synthesis",#uel (in the case o# solution combustion synthesis",molar composition o# the reactants,

reaction temperature,reaction time (ageing time",calcination temperatureandpresence o# gas atmosphere (air, %r, &'


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Preparation ofTi,

Precipitation;ethod

Eect ofprecursor

Eect ofcalcinations

temperature)

Degradationof 4lac3-+ dye

4y gamma rayirradiation

Eect ofpreparation

method)Degradation

of

p-nitrophenol

Preparation ofRuFTi,

Eect ofmetal loading)

Degradationof -

chlorophenol


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Photo%catalytic A##aratus

Dr. Radwa A. Elsalamony EPRI%


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Preparation of Ti, +y

Precipitation ;ethod


Titanium tetrachloride *TiBl7, 1+C was used as a #recursor!or #re#arin nanosi5ed TiO2 #owder &y #reci#itation method

usin ammonia solution as #reci#itatin aent and ethanolas dis#ersin aent.

G ml Ti$l? was dissol)ed in H ml distilled water in an ice%water &ath. The titanium solution was then slowly mixed with 8Hml distilled water and Hml ethanol under )iorous stirrin,

then ammonia solution was added dro#wise until p1 '. Durinthe ammonic addition, an intensi)e #reci#itation occurred.

A!ter the sol)ent was e)a#orated at &H$ for 27h, the#reci#itates were dried at 8HH$ !or 2h to remo)e ?7Bl, then

calcinedin an air stream !or 7h.


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Preparation of Ti, +y

J7ol-gelK ;ethod


A second method !or TiO2 nano#articles#re#aration sol%el method3. Ti*O7 sol was

#re#ared &y mixin Gml titaniumtetraisopropoxide *Ti*OB*B/27, --.+C, Aldrichwith GH ml isopropanol*Adwic, A.R. under )iorousstirrin.

The mixture was then allowed to undero #artial

hydrolysis at room tem#erature &y dro#%wiseaddition o! Gml isopropanol and ml 1$l *# /%7with constant stirrin.

Ti*O7 el was dried at 188 oB o)erniht then

calcined in an air stream !or 7h each.


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T l d l i f


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7ampl

es

Phase ratio

a

$rystal si2e a

(nm! 7peci:c

surface

area+

(mFg!

PoreRadiu

s

D* (r!c

*nm

Totalpore

olumec

(ccFg!

A R 4 DA DR D4

A GHH18

88 8

2.

+% % 9-.+ 7.1 8.21

A #HH 'G G H#.

#

%.

8- G?.8 #.' H.8G

A %HH &8 % H 8%.&

?#.?

- ?#.# #.' H.'

4 GHH 97 1- 11.

1

/7.

/-. 91./ /.1 8.1/+

4 #HH +2 7 8

2+.

/2.

1 % 21. /.- 8.891

Textural and structural properties ofTi,samples


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The euent water o! many industries, such as textiles)leather) paper) printing) cosmetics, etc., containslare amount o! ha5ardous dyes.These com#ounds can cause chanes in +iologicalcycles, #articularly in the #hotosynthesis #rocess. Thesedyes can +loc3 +oth sunlight penetration andoxygen dissolution, which are essential !or aFuatic li!e.>oreo)er, some o! these com#ounds can &ecarcinogenic Presence o! color and color%causin

com#ounds has always &een undesira&le in water !or anyuse. Thus there is a considera&le need to treat thesecolored euents &e!ore discharin them to )arious water&odies.

1a2ardous

Eect ofDyes


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4lac3-+ Dye


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Ti*O7el was o&tained at room tem#erature &y the addition o!concentrated ammonia solution */+C ?/ dro#wise to a

)iorously stirred dilute solution o! TiBl7*Gluka 1+C until a # -

was attained. The ammonia solution was added dro#wise to#re)ent #article adhesion and sudden rain rowth o! #articles.

The white hydrous Ti *O7

solution was irradiated under a#H$o source (5$RRT! with 8H 3By and at a dose rate of8.8?%# 3ByFh. The reactant solution was stirred mildly whileirradiatin it, so as not to &ecome alomerated with each other.

The #articles were then washed riorously and re#eatedly with&idistilled water to remo)e any remainin im#urities. A!ter thesol)ent was e)a#orated at HH$ for ? h, the #reci#itateswere dried at 8HH$ for h to remo)e ?

7Bl, and then

calcined at +88HB !or 7 h to et titania TiO2.

Ti,Anatase nano-powder Prepared

+y a Bamma Ray Irradiation

Dr. Radwa A. Elsalamony EPRI2+


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Bu%do#ed TiO2 nano#articles containin 8.+wtC Bu *II iondo#ant were synthesi5ed )ia a co-preceptation.

=riey, # mL ethanol solution o! 8.+ > o! Bu*?O/.9

2O was

added dro#wise to Ti$l?solution under stirrerin. The # )alue

o! the reaction solution was adJusted to ca. ' +y ammonia.

Then the &lue and dense colloid was !ormed. The colloid wasstirred ently !or 8h, and then washed riorously and re#eatedlywith &idistilled water to remo)e any remainin im#urities.

A!ter the sol)ent was e)a#orated at HH$ for ? h, the#reci#itates were dried at 8HH$ !or 2 h to remo)e ?

7Bl, and

then calcined in an air stream o! 788HB !or 7 h.

reparation of $u-doped Ti,


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Dr. Radwa A. Elsalamony

EPRI2


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7amples

$rystal

si2e of

Ti,

)nm(

7peci:c

surface

area

)mFg(

Pore

Radius

D* (r!

(nm!

Total

pore

olum

e)ccFg(

Acidity

MmolFg

m

N-Ti, 22.35 127.1 1.27 0.334 6055

$uFN-Ti, 16.91 115.8 1.13 8./27 9//7

$u-Ti, 18.62 60.8 1.81 0.476 13343

Textural and structural propertiesof Ti, $atalysts

Dr. Radwa A. Elsalamony EPRI2-


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P-5itrophenol

Dr. Radwa A. Elsalamony EPRI/8

Phenolic com#ounds are amon the mostre!ractory #ollutants #resent in industrialwastewater.Their hih sta+ility and solu+ility in waterre#resent the main o&stacles to com#leteremo)al.Puri(cation o! wastewater contaminated withthese #ollutants is )ery diKcult since they

are resistant to con)entional treatmenttechniFues.

The #%nitro #henol which are used in )ariousindustries like textiles) pulp) paper) leather)wool) sil3 etc. ultimately enter into aFuaticsystem as euent and create )ariousen)ironmental #ro&lems.

The #%nitro #henols exert )arious &iochemicaland mor holo ical e6ects on lants and


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?-5P concentration *s. irradiation timeusing dierent photocatalysts under

irradiation



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The apparent :rst-order 3ineticsfor the photocatalysts


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Gor meso#orous TiO2materials, 8.# g of tetra&utyltitanate was dissol)ed in a&solute ethanol with aweiht ratio o! 10 under stirrin. The resultinsus#ension was stirred !or / h at room tem#erature,and then G ml of deioni2ed water was addeddro#wise.

The solution was stirred !or an additional 2 h,

!ollowed &y e)a#oration at 1+8 oB. The o&tained solid#roduct was exhausti)ely washed with deioni5edwater and ethanol, dried at 8 oB o)erniht, and thencalcined at +88 oB !or / h.

reparation of mesoporous Ti,


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Ru0TiO2 sam#les with Ru loadin ranin !rom 8.2 to8. C *w0w usin TiO2was #re#ared &y inci#ient wetim#renation method with an aFueous solution o!ruthenium trichloride trihydrate. An a##ro#riateamount o! the #recursor, so as to o&tain the desiredRu concentration in TiO2, was mixed with TiO2indistilled water.

The resultin slurry was su&Jected to continuous

stirrin at am&ient tem#erature, and su&seFuentlydried in an o)en at 118 oB !or 18 h. The solidresidue was then crushed and calcined in air !or + h.

reparation of RuFTi, samples

Dr. Radwa A. Elsalamony EPRI2-


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Textural and structuralproperties of Ti, and RuFTi,

samples

7amplesAnataseC

Rutile

$rystalsi2e 7peci:c

surfacearea

(cmFg!

PoreRadius D*

(r!(nm!

Total pore*olume(ccFg!DA DR

Ti, 8 @ /8 //.+ +8.9 2. 9.2 8.12/

H. RuF Ti, ## C 888.%

% &.G #.# H.G

H.? RuF Ti, G% C ?8 &.&GH.#

8.? %.' H.H%

H.# RuF Ti, 99 @ /7 1-.7 2/. 27. 9.9 8.12

H.& RuF Ti, 9/ @ / //.9 9.+ 22.- 9.1 8.8-7


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-$lorophenolThey can &e !ound in round waters, waste waters

and e)en low #ollution le)els. They miht #roducedisareea&le taste and odor to drinkin water atconcentrations &elow 8.1 L %1 and ad)erse e6ectson the en)ironment.Bhloro#henols are thus !ound on &oth the .7.En*ironmental Protection Agency list and the

European community red list of priority.B#s are into the en)ironment as a result o! se)eralman%made acti)ities. =ecause o! their &roads#ectrum antimicro&ial #ro#erties, B#s has &eenused as preser*ati*e agents for wood) paints)*egeta+le :+ers and leather and asdisinfectants. In addition, they ha)e &een widelyem#loyed in many industrial #rocesses as synthesisintermediates or as raw materials in themanu!acturin o! her&icides, !unicides, #esticides,insecticides, #harmaceuticals, dyes, and in themanu!acture o! #a#er B#s may &e also eneratedas &y%#roducts durin waste incineration, the


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Eect of Ru doping concentrations on the O$Pphotodegradation using irradiation


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Dr. Radwa A. Elsalamony EPRI/

/ormation of chloride ions during thephotodegradation of O$P using light


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/ormation of acetate ions during thephotodegradation of O$P using light

Dr. Radwa A. Elsalamony EPRI/-


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Dr. Radwa A.Elsalamony

EPRI

T1A5

7

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