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1lC2/Carbon ComposlLes repared from 8lce Pusk and Lhe 8emoval of 8lsphenol A ln

hoLocaLalyLlc Llquld SysLem



!lyeon klm 8yeong Sub kwak and Mlsook kang*

ueparLmenL of ChemlsLry College of Sclence ?eungnam unlverslLy Cyeongsan Cyeongbuk
712749 korea*
Lmall mskang[ynuackr
8ecelved SepLember 29 2009 AccepLed uecember 17 2009


1he lmproved phoLocaLalyLlc performance of a carbon/1lC
2
composlLe was sLudled for Lhe
8lsphenol A (8A) decomposlLlon 1lLanlum LeLralsopropoxlde (11l) and a rlce husk from korea were
heLerogeneously mlxed as Lhe LlLanlum and carbon sources respecLlvely for 3 h aL room LemperaLure
and Lhen Lhermally LreaLed aL 600
o
C for 1 h ln P
2
gas 1he Lransmlsslon elecLron mlcroscopy (1LM)
lmages revealed LhaL Lhe bulk carbon parLlally covered Lhe 1lC
2
parLlcles and Lhe amounL LhaL was
covered lncreased wlLh Lhe addlLlon of Lhe rlce husk 1he acqulred carbon/1lC
2
composlLe exhlblLed an
anaLase sLrucLure and a novel peak aL 20 32
o
whlch was asslgned Lo bulk carbon 1he speclflc surface
area was slgnlflcanLly enhanced Lo 123 164 m
2
/g ln Lhe carbon/1lC
2
composlLe compared Lo 3243
m
2
/g for Lhe pure 1lC
2
1he xray phoLoelecLron specLroscopy (xS) resulLs showed LhaL Lhe 1lC bond
was weaker ln Lhe carbon/1lC
2
composlLe Lhan ln Lhe pure 1lC
2
resulLlng ln an easler elecLron LranslLlon
from Lhe 1l valence band Lo Lhe conducLlon band 1he carbon/1lC
2
composlLe absorbed over Lhe whole
uvvlslble range whereas Lhe absorpLlon band ln Lhe pure 1lC
2
was only observed ln Lhe uv range
1hese resulLs agreed well wlLh an elecLrosLaLlc force mlcroscopy (LlM) sLudy LhaL showed LhaL Lhe
elecLrons were rapldly Lransferred Lo Lhe surface of Lhe carbon/1lC
2
composlLe compared Lo Lhe pure
1lC
2
1he phoLocaLalyLlc performance of Lhe 8A removal was opLlmlzed aL a 1lC raLlo of 9303 and
Lhls phoLocaLalyLlc composlLe compleLely decomposed 100 ppm 8A afLer 210 mln whereas Lhe pure
1lC
2
achleved no more Lhan 30 decomposlLlon under any condlLlons

key Words Carbon/1lC2 composlLes 8lce husk ln korea 8emoval of 8lsphenol A hoLocaLalysls


lnLroducLlon
8lsphenol A (8A) ls manufacLured ln hlgh quanLlLles and 90 of 8A LhaL ls produced ls used as a
monomer for Lhe producLlon of polycarbonaLe and epoxy reslns unsaLuraLed polyesLersLyrene reslns
and flame reLardanLs 1hese flnal producLs are used as can coaLlngs powdered palnLs Lhermal paper
addlLlves denLal fllllngs and anLloxldanLs ln plasLlcs






8A exhlblLs an esLrogenlc acLlvlLy and ls consldered an envlronmenLal endocrlne dlsrupLer
1

Moreover 8A has been reporLed Lo leach from polycarbonaLe baby boLLles
2
reusable conLalners
3
and
drlnklng waLer Lanks
4
8A has also been deLecLed ln plasLlc wasLe
3
plasma sLored ln polycarbonaLe
Lubes
6
and ln aquaLlc envlronmenLs
7
Plgh concenLraLlons of 8A can also be presenL ln wasLewaLer
from 8A producLlon facLorles because 8A ls only parLlally removed durlng Lhe wasLewaLer LreaLmenL
and Lhe wasLewaLer conLalnlng 8A ls a source of conLamlnaLlon ln aquaLlc envlronmenLs
8
AlLhough
8A ls readlly degraded by mlcroorganlsms Lhe blologlcal meLhods LhaL are used Lo LreaL wasLewaLer
conLalnlng hlgh concenLraLlons of 8A commonly requlre long LreaLmenL Llmes 1herefore a rapld and
slmple wasLewaLer LreaLmenL meLhod for 8A ls urgenLly requlred varlous Lechnlques lnvolvlng
chemlcal
9
blologlcal
610
phoLochemlcal
11
and elecLrochemlcal
7
procedures have been sLudled for Lhe
LreaLmenL of wasLewaLer LhaL conLalns phenollc compounds 8ecenLly several researchers have
examlned Lhe phoLocaLalyLlc LreaLmenL of 8AconLalnlng wasLewaLer Lhrough Lhe degradaLlon of 8A
ln Lhe presence of 1lC
2
as a phoLocaLalysL Lee eL al
12
used lmmoblllzed 1lC
2
parLlcles for Lhe
phoLodegradaLlon 8A where Lhe LlLanlum sol soluLlon LhaL synLheslzed uslng a solgel meLhod was
used as a blnder 1hey also lnvesLlgaLed Lhe effecLs of varlous parameLers such as Lhe fllm Lhlckness Lhe
uv radlaLlon lnLenslLy and Lhe pP on Lhe phoLodegradaLlon kang eL al
13
also reporLed LhaL alkall
meLal1lC
2
parLlcles have an anaLase sLrucLure and were ca 30 100 nm ln slze wlLh a surface area of ca
1424 m
2
/g k1lC
2
phoLocaLalysls was used Lo compleLely degrade 100 ppm 8A afLer 30 h Serpone eL
al
14
examlned Lhe mlcrowaveasslsLed phoLodegradaLlon of 8A ln Lhe presence of 1lC
2
1he phoLo
acLlvlLy of Lhe LlLanlum dloxlde parLlcles was somehow promoLed by Lhe mlcrowave radlaLlon 1sal eL al
13
suggesLed LhaL Lhe phoLocaLalyLlc degradaLlon of 8A ln Lhe 1lC
2
suspenslon process ls an efflclenL
meLhod for qulckly lowerlng Lhe concenLraLlon of Lhe endocrlne dlsrupLlng compound ln waLer
AddlLlonally many groups have recenLly Lrled oLher meLal semlconducLors ln Lhe phoLocaLalysls
1617

uesplLe Lhese research efforLs Lhe phoLodecomposlLlon of macro molecules conLalnlng an aromaLlc rlng
such as 8A ls sLlll dlfflculL 1herefore furLher research on Lhese lmproved maLerlals ls necessary
arLlcularly Lhe developmenL of a phoLocaLalysL LhaL slmulLaneously possesses hlgh adsorpLlon and
decomposlLlon ablllLles would greaLly lmprove Lhe decomposlLlon performance ln Lhls sLudy bulk
carbon was selecLed as Lhe hlgh surface area maLerlal ln order Lo achleve a hlgh adsorpLlon ablllLy was
achleved for macro organlc molecules slmllar Lo 8A 8lce husk LhaL was harvesLed ln SouLh korea was
used as Lhe carbon source because of lLs low cosL and wasLe recycllng capablllLyln Lhls sLudy Lhe 1lC
2

phoLocaLalysLs were prepared uslng a heLerogeneous mlxLure of LlLanlum LeLralsopropoxlde (11l) and
rlce husk for korea as Lhe LlLanlum and carbon sources respecLlvely wlLh Lhermal LreaLmenL aL 600
o
C ln
P
2
gases and bulk carbon parLlally covered Lhese phoLocaLalysLs 1hen Lhe 1lC
2
phoLocaLalysLs were
used Lo phoLodecompose 8A (100 ppm)1he adsorpLlon effecLs sLrucLural varlaLlons surface sLaLe
and elemenLal composlLlons were lnvesLlgaLed four dlfferenL carbon/1lC
2
composlLes 1he chemlcal and
morphologlcal sLrucLure of Lhe carbon/1lC
2
composlLes was sLudled uslng Lhe 8runauerLmmeLL and
1eller (8L1) surface area xray dlffracLlon (x8u)Lransmlsslon elecLron mlcroscopy (1LM) elecLrosLaLlc
force mlcroscopy (LlM) and energy dlsperslve xray (Lux) analyslsllnally Lhe 8A soluLlons LhaL were
obLalned from Lhe phoLolysls and elecLrolysls wlLh Lhe carbon/1lC
2
sysLem were characLerlzed uslng a
uv/vls specLrophoLomeLer

LxperlmenLal
Carbon/1lC
2
caLalysL preparaLlon A convenLlonal lmpregnaLlon meLhod was used Lo prepare Lhe
carbon/1lC
2
phoLocaLalysL 11l (9993 !unsel Chemlcal !apan) and a rlce husk (!e[u korea) were used
as Lhe LlLanlum dloxlde and carbon precursors respecLlvely 1he rlce husk was flnely graLed Lo abouL 23
30 mesh before Lhe mlxlng sLep 1he concenLraLlons of 1l and carbon varled ln Lhe range of 9303
9010 8313 and 7030 for 10 mol per 11l ln Lhe lnlLlal soluLlon ulsLllled waLer was used as Lhe
solvenL for Lhe hydrolysls A mlxed soluLlon of Lhe 11l and rlce husk precursors aceLlc acld (!unsel
Chemlcal Co LLd !apan) and dlsLllled waLer was sLlrred for 3 h unLll a homogeneous gel formed 1he
waLer was evaporaLed ouL aL 80
o
C for 3 h 1he damped preclplLaLe was drled and calclned aL 100
o
C for
24 h and aL 600
o
C for 2 h ln a 90 n2/10 P2 mlxed gasCarbon/1lC
2
caLalysLs characLerlzaLlon 1he
synLheslzed carbon/1lC
2
powders were examlned uslng x8u (xray dlffracLomeLer Mu AnalyLlcal
?eungnam unlverslLy korea) wlLh nlckelfllLered Cuk radlaLlon (30 kv 30 mA) aL 20 angles ranglng
from 10 Lo 73
o
a scan speed of 10
o
mln1 and a Llme consLanL of 1 s 1he slzes and shapes of Lhe
carbon/1lC
2
parLlcles were measured uslng 1LM (1ransmlLLance LlecLron Mlcroscopy P7600 PlLachl
?eungnam unlverslLy korea) LhaL was operaLed aL 120 kv1he 8L1 surface areas and Lhe pore volume of
Lhe powders were measured Lhrough nlLrogen gas adsorpLlon uslng a conLlnuous flow meLhod uslng a
chromaLograph (MeLrlcs Cemlnl 2373 Londonderry ?eungnam unlverslLy korea) LhaL was equlpped
wlLh a Lhermal conducLlvlLy deLecLor (1Cu) aL a llquldnlLrogen LemperaLure A mlxLure of nlLrogen and
hellum was used as Lhe carrler gas and Lhe sample was LreaLed aL 330
o
C for 1 h before Lhe nlLrogen
adsorpLlon 1he xray phoLoelecLron specLroscopy (xS CooperaLlve CenLer Lo 8esearch laclllLles
Sungkyunkwan unlverslLy lnsLrumenLal Analysls CenLer korea) measuremenLs of 1l
2
p C1s Sl
2
p and C1s
were recorded uslng an LSCA 2000 (vZ Mlcro1ech Cxford uk) sysLem LhaL was equlpped wlLh a non
monochromaLlc Alk (14866 ev) xray source 1he base pressure of Lhe LSCA sysLem was below 1
10
3
9
a 1he reflecLance uv vlslble specLra were obLalned uslng a Cary 300 specLromeLer wlLh a
reflecLance sphere over Lhe speclal range of 200 Lo 800 nm 1he surface sLaLes and elecLrlc properLles of
Lhe carbon/1lC
2
fllm were deLermlned uslng LlM (resoluLlon 01 nm (x ?) 001 nm (Z) ulmenslon3100
veeco Co naLlonal CenLer for nanomaLerlals 1echnology ohang korea)hoLodecomposlLlon of
8lsphenol A 8A (97 Slgma Aldrlch korea L1u) was decomposed uslng a general sLaLlonary
apparaLus 1he lnlLlal 8A concenLraLlon was flxed aL 100 ppm llrsL 8A was dlssolved aL a
concenLraLlon of 100 ppm ln waLer and Lhen dlluLed wlLh a 10llLer aqueous soluLlon 1he carbon/1lC2
powders were dlrecLly used for Lhe 8A phoLodecomposlLlon reacLlon 1he uv lamps (model uvA 363
nm 6 W 3 ea 20 cm lengLh 13 cm dlameLer Shlnan Co korea) were equlpped wlLh a phoLocaLalyLlc
llquld sysLem and Lhe phoLocaLalysL concenLraLlon was 03g/10 L 1he 8A concenLraLlon was analyzed
before and afLer Lhe reacLlon uslng uvvlslble specLroscopy (Shlmadzu MS2000 specLromeLer)

8esulLs and ulscusslon
hyslcal characLerlzaLlons of Lhe pure 1lC2 and carbon/1lC2 phoLocaLalysLs llgure 1 shows Lhe x8u
paLLerns of Lhe pure 1lC2 and carbon/1lC2 phoLocaLalysLs wlLh 1lC raLlos of 9303 9010 8313 and
7030 All of Lhe samples exhlblLed a perfecLly anaLase sLrucLure and Lhe peaks aL 233 380 482 34
63 and 68
o
20 were asslgned Lo Lhe (d101) (d004) (d200) (d103) (d211) and (d204) planes
respecLlvely
18
1he llne broadenlng of he 101 peak was relaLed Lo Lhe slze of Lhe hexagonal crysLallne
phase of LlLanla 1he crysLalllne domaln slze was uslng Lhe Scherrer's equaLlon (crysLalllne domaln
slze) 09 / cos0

















llgure 1 x8u paLLerns of Lhe pure 1lC2 and carbon/1lC2 phoLocaLalysLs wlLh varlous 1lC raLlos (a)
pure 1lC2 (solgel meLhod) (b) 03C931l (c) 10C901l (d) 13C831l and (e) 30C701l









llgure 2 1LM lmages of Lhe parLlcle shapes of Lhe pure 1lC2 and carbon/1lC2 phoLocaLalysLs wlLh
varlous 1lC raLlos (a) pure 1lC2 (solgel meLhod) (b) 03C931l (c) 10C901l (d) 13C831l and (e)
30C701l

1able 1 Speclflc surface area and real aLomlc composlLlon of Lhe carbon/1lC2 powders (a) pure
1lC2 (solgel meLhod) (b) 03C931l (c) 10C901l (d) 13C831l and (e) 30C701l

(A) ALomlc composlLlons















(8) Surface areas and pore volumes









where ls Lhe wavelengLh of Lhe lncldenL xrays ls Lhe full wldLh aL Lhe half maxlmum helghL ln
radlans and 0 ls Lhe dlffracLlon angle 1he esLlmaLed crysLalllne domaln slzes were 263 261 292
307 and 407 nm for Lhe 1lC concenLraLlon raLlos of 10000 9303 9010 8313 and 7030
respecLlvely AddlLlonally all of Lhe peaks shlfLed Lo hlgh values of 20 because of Lhe parLlal
lncorporaLlon of carbon lnLo Lhe 1lC
2
anaLase framework 1hls Lendency was dlsLlngulshable
Lhrough Lhe lncrease ln Lhe carbon concenLraLlon A peak LhaL was asslgned Lo bulk carbon (eg aL
31 of 20) appeared when carbon was mlxed lnLo 1lC
2
lndlcaLlng LhaL Lhe bulk carbon covered Lhe
1lC2 surface llgure 2 shows Lhe 1LM lmages of Lhe parLlcle shapes of Lhe pure 1lC
2
and
carbon/1lC
2
phoLocaLalysLs wlLh 1lC raLlos of 9303 9010 8313 and 7030 A relaLlvely
unlform mlxLure of rhomblc and cublc parLlcles was observed ln Lhe pure 1lC2 wlLh an approxlmaLe
slze of 20 nm As carbon was added Lhe bulk carbon more compleLely covered Lhe 1lC
2
parLlcles
excepL for 03 carbon/93 1lC
2
ln Lhe order of pure 03 carbon/93 1lC
2
1lC
2
10 carbon/90 1lC
2

13 carbon/83 1lC2 30 carbon/70 1lC
2
1he surfaces of Lhese composlLes were blacken
ed wlLh lncreaslng carbon conLenL 1hese resulL conflrmed LhaL Lhe bulk carbon LhaL was prepared
from Lhe rlce husk evenly covered Lhe exLernal surface of Lhe 1lC
2
nanoslzed parLlcles raLher Lhan
growlng as separaLe parLlcles 1able 1 summarlzes Lhe speclflc surface area and Lhe real aLomlc
composlLlon of Lhe carbon/1lC
2
powders 1he pure 1lC
2
and Lhe 03 carbon/093 1lC
2
composlLe
were noL porous Powever unlformly pores wlLhouL any 1lC2 lumps were observed when carbon
was added and Lhe pore slze lncreased wlLh lncreaslng carbon amounL
































llgure 3 Comparlson of Lhe (A) absorpLlon ablllLy for 8A on Lhe pure 1lC2 and carbon/1lC2
phoLocaLalysLs and Lhe (8) change of uvvlslble specLrum for 8A over 1l/C(9303) (a) pure 1lC2
(solgel meLhod) (b) 03C931l (c) 10C901l (d) 13C831l and (e) 30C701l 8eacLlon
condlLlons 20 L llquld sysLem room Lemp 8A concenLraLlon 10 ppm caLalysL amounL
03g/10L


1he maxlmum amounL of deposlLed carbon was observed for Lhe 10 carbon/90 1lC2 composlLe
buL Lhe mlnlmum value occurred for Lhe 13 30 carbon / 093 07 1lC2 composlLes because Lhe
carbon evenLually covered Lhe enLlre surface of boLh Lhe SlC2 ln Lhe rlce husk and Lhe 1lC2 and Lhe
amounL of deposlLed carbon was conslderably small 1he amounL SlC2 LhaL was produced lncreased
Lhrough Lhe addlLlon of Lhe rlce husk Cenerally surface area relaLlve Lo Lhe volume ls sLrongly
relaLed Lo Lhe parLlcle slze and Lhe surface area lncreases wlLh decreaslng parLlcle slze Powever
Lhese resulLs showed Lhe opposlLe Lend where Lhe 8L1 surface area of 1644 m2/g was excellenL
for 13 carbon/083 1lC2 compared Lo a value of 3243 m2 /g for 1lC2 1he pore volume exhlblLed
Lhe same Lrend because Lhe blankeL of carbon beLween Lhe neuLrally charged carbon/1lC2 parLlcles
led Lo an lncrease ln Lhe bulk poroslLy CLherwlse Lhe charged 1lC2 parLlcles on Lhe surface
lnduced Lhe parLlcle coagulaLlon Lhereby reduclng Lhe poroslLy






























llgure 4 1he (A) phoLocaLalyLlc performance for Lhe 8A decomposlLlon on Lhe pure 1lC2 and
carbon/1lC2 phoLocaLalysLs and Lhe (8) change of uvvlslble specLrum for 8A over 1l/C(9303)
(a) pure 1lC2 (solgel meLhod) (b) 03C931l (c) 10C901l (d) 13C831land (e) 30C701l
8eacLlon condlLlons 20 L llquld sysLem room Lemp llghL sorce uvA (363 nm 6W 3ea) 8A
concenLraLlon 10 ppm caLalysL amounL 03g/10L



hoLodecomposlLlon of 8A for Lhe pure 1lC2 and carbon/1lC2 phoLocaLalysL llgure 3 shows Lhe
absorpLlon ablllLy of 8A on Lhe pure 1lC2 and carbon/1lC2 phoLocaLalysLs 1he 8A concenLraLlon
was deLermlned uslng a uvvlslble specLromeLer ln Lhe rlghLhand flgure and Lhe Lwo absorpLlon
bands aL 220 and 280 nm were lnduced by Lhe aromaLlc rlng 1he carboncoaLed caLalysLs were
more absorbenL Lo 8A because Lhe carbon had a large speclflc surface area due Lo Lhe bulk pores
Powever over Llme Lhe absorpLlon process sLopped and Lhe concenLraLlon of Lhe 8A ln Lhe
reacLor dld noL change AL Lhls polnL Lhe uvvlslble absorpLlon was consLanL Powever 8A dld noL
adsorb Lo Lhe 1lC2 nanoparLlcles because Lhe pure 1lC2 dld noL conLaln pores and hence had a
very small speclflc surface area MosL noLably 67 of Lhe 8A was absorbed on Lhe 03 carbon/93
1lC2 composlLe afLer 120 mln compared Lo 0 on Lhe pure 1lC2























llgure 3 CuanLlLaLlve xS analysls of Lhe (a) pure 1lC2 and (b) 03 carbon/93 1lC2 parLlcles A)
1l2p 8) C1s C) C1s and u) Sl2p


As predlcLed ln Lhe lnLroducLlon Lhe absorpLlon capablllLy lncreased wlLh lncreaslng carbon conLenL
ln Lhe followlng order 1lC2 03 carbon/93 1lC2 10 carbon/90 1lC2 13 carbon/83 1lC2 30
carbon/70 1lC2 because of Lhe large surface area of carbon llgure 4 shows Lhe phoLocaLalyLlc
performance of Lhe 8A decomposlLlon for Lhe pure 1lC2 and carbon/1lC2 phoLocaLalysLs 1he
phoLodecomposlLlon of 8A lncreased Lhrough Lhe addlLlon of carbon and Lhe lncreased
absorpLlon was parLlcular fasL afLer Lhe lnlLlal carbon addlLlon 8A was perfecLly decomposed
ln Lhe uvA radlaLlon/alr bubbllng/03 carbon/93 1lC2 phoLocaLalyLlc sysLem afLer 210 mln (33 h)
As prevlously reporLed
13
100 ppm 8A was decomposed afLer 32 hours ln pure 1lC2 Powever ln
Lhls presenL sLudy 49 of Lhe 30 ppm 8A was phoLodecomposed ln Lhe pure 1lC2 sysLem afLer 3
hours whlch was an lmprovemenL over Lhe prevlous resulLs ln Lhls sLudy Lhe pure 1lC2 was
reduced by hydrogen gas before Lhe phoLocaLalyLlc reacLlon of 8lsphenol A 1hls process was
expecLed Lo change Lhe oxldaLlon sLaLe of Lhe pure 1lC2 from 4 Lo 3 and Lhls affecLed Lhe band
gap resulLlng ln Lhe change ln Lhe phoLocaLalyLlc acLlvlLy ConsequenLly Lhe reducLlon process
appeared Lo lmprove Lhe acLlve phoLocaLalysL ln parLlcular Lhe presenL daLa resulLs for Lhe
carbon/1lC2 composlLes were very encouraglng AddlLlonally 30 ppm 8A was compleLely
decomposed afLer 30 mln ln Lhe 03 carbon/93 1lC2 phoLocaLalyLlc sysLem buL 130 ppm 8A was
only 73 decomposed even afLer 300 mlnuLes 1he 8A absorpLlon band ln Lhe uvvlslble specLrum
was conslsLenLly small over Lhe phoLo oxldaLlve reacLlon Llme 1herefore Lhe bulk carbon wlLh a
hlgh surface area exerLed a synerglsLlc effecL on Lhe phoLocaLalyLlc performance of Lhe carbon/
1lC2 composlLe for Lhe 8A decomposlLlonComparlson of opLlcal properLy on Lhe pure 1lC2 and
carbon/ 1lC2 phoLocaLalysL 1he quanLlLaLlve xS analysls was performed on Lhe pure 1lC2 and Lhe
03 carbon/93 1lC2 parLlcles whlch was selecLed as Lhe represenLaLlve carbon/1lC2 caLalysL
llgure 3 shows Lhe Lyplcal survey and hlghresoluLlon specLra 1he survey specLra of Lhe pure 1lC2
and carbon/1lC2 parLlcles conLalned 1l2p C1s Sl2p and C1s peaks 1he 1l2p1/2 and 1l2p3/2
splnorblLal spllLLlng phoLoelecLrons of Lhe Lhe Lwo samples were locaLed aL blndlng energles of
4647 ev and 4383 ev respecLlvely 1he blndlng energy was noL expecLed Lo decrease afLer
carbon was added ln general an lncrease ln Lhe blndlng energy corresponds Lo an lncrease ln Lhe
oxldaLlon sLaLe of Lhe meLal

















llgure 6 uvvlslble specLra of Lhe (a) pure 1lC2 and (b) 03 carbon/93 1lC2 parLlcles


19
1he LlLanlum oxldaLlon sLaLe ln Lhe carbon/1lC2 (maybe 1l
3+
)composlLe was hlgher Lhan Lhe 1l
4+

sLaLe ln Lhe pure 1lC2 1he acLlvlLy of Lhe 1l phoLocaLalysLs was closely relaLed Lo Lhe 1l oxldaLlon
sLaLes Cenerally Lhe C1s reglon ls decomposed lnLo several conLrlbuLlons 1he Causslan values
were used ln Lhe curve resoluLlon of Lhe Lwo lndlvldual C1s peaks (flrsL peak C1 330 3310 ev
second peak C2 332 3330 ev) ln Lhe Lwo specLra
and Lhese peaks were asslgned Lo 1lC and 1lCP respecLlvely 1he locaLlon of Lhe blndlng energles
for Lhe second peak agreed well wlLh Lhe reporLed values for Lhe bulk oxlde (C2) and Lhe hydroxyl
(CP) specles Powever Lhe second peak separaLlon ln Lhe pure 1lC2 was noL clear 1hese resulLs
were LenLaLlvely aLLrlbuLed Lo Lhe dlfferenL oxldaLlon sLaLe of Lhe bulk oxygen because oLherwlse
Lhe peak aL 3330 ev would be perfecLly dlvlded from Lhe flrsL peak aL 3300 ev ln Lhe carbon/1lC2
composlLe ln general a large hydroxyl (CP) specles peak lndlcaLes a hlgh hydrophlllclLy
20
and
many CP radlcals are produced ln Lhe holes of Lhe valence band Lhereby lmprovlng Lhe
phoLocaLalyLlc performance 1hese resulLs lndlcaLed LhaL Lhe 1lCP bondlng sLrengLh was weaker
ln Lhe carbon/1lC2 composlLe Lhan ln Lhe pure 1lC2 from Lhe hard sofL acld base (PSA8) rule
resulLlng ln an easler elecLron flow on Lhe exLernal surface of 1lC2 Cn Lhe oLher hand Lhe C1s peak
aL 2846 ev and Lhe Sl2p peak aL 1040 ev were boLh observed ln Lhe carbon/1lC2 sample because
Lhe rlce husk was composed of 20 wL Sl and 80 wL carbon1he uvvlslble specLra of Lhe pure
1lC2 and Lhe 03 carbon/ 93 1lC2 parLlcles whlch was selecLed as Lhe represenLaLlve carbon/1lC2
caLalysL were obLalned ln order Lo deLermlne Lhe relaLlonshlp beLween Lhe phoLocaLalyLlc
performance and Lhe specLroscoplc properLles ln llgure 6 1he absorpLlon band correspondlng Lo
Lhe LeLrahedral symmeLry of 1l
4+
normally appears aL approxlmaLely 330 nm and ls asslgned Lo Lhe
llgand (porblLal oxygen) Lo llgand (s porblLal oxygen) charge Lransfer 1he band gaps of a
semlconducLor maLerlal are closely relaLed Lo Lhe wavelengLh range LhaL ls absorbed and Lhe band
gap decreases wlLh lncreaslng absorpLlon wavelengLh 8emarkably Lhe 03 carbon/93 1lC2
composlLed absorbed Lhe enLlre specLra across Lhe compleLe uv and vlslble range because of Lhe
llgand (porblLal carbon) Lo meLal (dorblLal 1l) charge Lransfer and Lhe dd Lransfer of Lhe meLal
LhaL occurred when an elecLron exlsLed ln Lhe dorblLal of 1l 1herefore Lhe compleLe carbon
coverage of Lhe 1lC2 surface faclllLaLed Lhe elecLron Lransfer desplLe Lhe weak radlaLlon suggesLlng
LhaL Lhe elecLron Lransfer acLlvlLles were eased on Lhe surface of Lhe carbon/1lC2 composlLe
1he analyLlcal LlM meLhod was used ln order Lo deLermlne lf Lhe surface of elecLrode was flaL
because good elecLron flow ls lnduced by a flaL elecLrode surface 1yplcally Lhe presence of a
conducLor and nonconducLor wlLhln a nanomeLerleveled fllm can be dlsLlngulshed uslng aLomlc
force mlcroscopy (AlM) for Lhe modlfled LlM lmage 1he power sLrengLh of Lhe lmage beLween Lhe
samples and Llps was measured whlle Lraverslng Lhe volLage Lo Lhe AlM Llp blas 1he presence of
Lhe conducLlng and nonconducLlng areas ln Lhe sample can be deLermlned from
Lhe responses of Lhe AlM Llp















llgure 7 LlM lmages of Lhe (a) pure 1lC2 and (b) 03 carbon/93 1lC2 parLlcles ln llghL


21
1he phase perlodlcally changed wlLh Lhe Llp vlbraLlng power cycle (charge magneLlc eLc)
ConsequenLly Lhe dlfferences beLween Lhe conducLlng and nonconducLlng surfaces were lndlcaLed
by Lhe ampllLude and phase changes and Lhe change ln Lhe wldLh was expressed by Lhe con
LrasL ln Lhe lmages and Lhe roughness values (8a) 1he 8a value can lndlrecLly be deLermlned by
changlng Lhe LwlLch of Lhe Llp uslng Lhe followlng equaLlon
2223




ln Lhls equaLlon f(x y) ls Lhe surface relaLlve Lo Lhe cenLer plane and Lx and Ly are Lhe dlmenslons
of Lhe surface llgure 7 shows Lhe LlM lmages of Lhe pure 1lC2 and Lhe 03 carbon/93 1lC2
parLlcles whlch was used as Lhe represenLaLlve carbon/1lC2 caLalysL ln llghL A volLage of 30 ev
was Lraversed and 20mLhlck fllm samples were used 1he phase change dld noL exceed 30
degrees ln elLher sample 1he phase dlfference ls Lhe dlfference ln Lhe elecLrosLaLlc force beLween
phases and Lherefore a brlghL lmage generally lndlcaLes Lhe flow of charge
24
As Lhe currenL
passes Lhrough Lhe sample a brlghL phase ls exhlblLed lf Lhe generaLed elecLromagneLlc specLra
undergo relnforclng lnLerference whereas a dark phase ls observed for offseL lnLerference 1he
brlghLness of boLh samples lncreased ln llghL condlLlon compared Lo ln Lhe darkroom 1he
carbon/1lC2 composlLe exhlblLed a beLLer brlghLness ln llghL Lhan Lhe pure 1lC2 1he value aL Lhe
boLLom of Lhe flgure lndlcaLes Lhe averaged 8a values of Lhe Lwo samples ln llghL 1he carbon/1lC2
composlLe was slgnlflcanLly more unlform Lhan Lhe pure 1lC2 and exhlblLed a hlgher 8a value of
093 degrees ln llghL 1herefore Lhe elecLrons flowlng on Lhe surface of Lhe carbon/1lC2 composlLe
exhlblLed a good moblllLy


Concluslons

ln Lhls sLudy carbon/1lC2 composlLes were fabrlcaLed and characLerlzed 1he adsorpLlon ablllLy
Lhe surface properLles and Lhe chemlcal composlLlon of Lhe carbon/1lC2 composlLes were
lnvesLlgaLed 1he surface areas and pore volumes of Lhe carbon/1lC2 samples markedly lncreased
wlLh lncreaslng carbon conLenL 1he 1LM resulLs revealed LhaL Lhe bulk carbon unlformly covered
Lhe nanomeLerslzed sample parLlcles 1he 03 carbon/93 1lC2 composlLe absorbed Lhe enLlre
specLra across Lhe compleLe uv and vlslble range because of Lhe llgand (porblLal carbon) Lo meLal
(dorblLal 1l) charge Lransfer and Lhe dd Lransfer of Lhe meLal LhaL occurred when an elecLron
exlsLed ln Lhe dorblLal of 1l Accordlng Lhe hard and sofL acld and base (PSA8) rule Lhe xS resulLs
lndlcaLed LhaL Lhe 1lCP bondlng sLrengLh was weaker ln Lhe carbon/1lC2 composlLe Lhan ln Lhe
pure 1lC2 resulLlng ln easler elecLron flow on Lhe exLernal surface of 1lC2 1he carbon/1lC2
composlLe was slgnlflcanLly more unlform Lhan Lhe pure 1lC2 and Lhe composlLe exhlblLed
a hlgher 8a value of 093 degrees ln llghL from Lhe LlM lmages 1herefore Lhe elecLrons LhaL
flowed on Lhe surface of Lhe carbon/1lC2 composlLe exhlblLed a good moblllLy 1he phoLoca
LalyLlc resulLs for Lhe uvdecomposlLlon of 8A wlLh Lhe carbon/1lC2 composlLes showed LhaL Lhe
03 carbon/93 1lC2 phoLocaLalyLlc composlLe exhlblLed an excellenL degradaLlon effecL wlLh
respecL Lo Lhe reacLlon Llme because of Lhe lncreased elecLron moblllLy and CP radlcal generaLlon
1he 8A decomposlLlon ln Lhe aqueous soluLlon occurred because of Lhe synerglsLlc effecL beLween
Lhe phoLodecomposlLlon and Lhe absorpLlon efflclency Lhrough carbonphoLocaLalysls
AcknowledgmenLs 1hls research was supporLed by a ?eungnam unlverslLy research granL no209
A380103 and Lhe auLhors are very graLeful for Lhls supporL