中華大學博士論文 -...

Investigation on Photocatalytic Efficiency of TiO2

Photocatalysts under Visible Illumination

D09404009

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I

2007 11


II

()

400700 nm

Kubelka-Munk

(2.98eV)

(2.88eV)(2.63eV) Langmuir-Hinshelwood

/


III

ABSTRACT KeywordsTitania nanoparticle, Hydrothermal treatment, Visible-light

photocatalysis, Methylene blue

In this dissertation, a hydrothermal treatment was employed to doping three types

of metal ions (Fe, Co, and Ni) into commercial TiO2 photocatalysts for improving the

photocatalytic reactivity of methylene blue (MB) under visible light irradiation.

Nitrogen physisorption measurement indicated that surface areas and porosities of

metal-doped titania powders still maintain an identical value, comparing to the starting

material. The diffuse reflection spectra of metal-doped titania reflected a light

absorption edge, shifting to the visible light range of ca. 400700 nm. According to

Kubelka-Munk plot, the optical band gaps were found to have the following order

Fe-doping (2.98 eV) > Co-doping (2.88 eV) > Ni-doping (2.63 eV), based on the fixed

dopant concentration. A Langmuir-Hinshelwood model was used to investigate the

photocatalytic activity for removing MB from liquid phase. It was found that the

decreasing optical band gap is accompanied by increasing photo degradation activity of

MB. This result can be attributed to a fact that metal-doped titania photocatalyst with

the narrowest band gap is capable of generating better redox ability of electronhole

pairs under visible light, thus leading to the greatest photocatalytic activity.

According to the results, the visible-light-derived photocatalysts prepared by the

above hydrothermal synthesis exhibit an excellent photocatalytic capability in

decomposing organic dyes. In practical operation, we employed ceramic tile and toast

as substrates for evaluating the photocatalytic ability under visible illumination.

Experimental results indicated that the metal-doped titania photocatalysts enable to

prevent the growth of E. coli, thus extending the anti-spoiled period of toast. After

coating them onto ceramic tile, the prepared tile leads to keep a cleaner surface than the

tile coated with commercial photocatalysts after two weeks. This fascinating effect

proves that this fabrication technique is an efficient method in preparing

visible-light-derived photocatalysts that can be extensively used in a variety of

applications such as indoor decoration, ceramic tile, glass, house furnishings, and so on.


IV

.......................................................................................1

1.1 ............................................................................1

1.2 ............................................................................2

1.3 ............................................................................3

1.4 ............................................................................4

1.5 ............................................................................5

...................................................................6

2.1 ....................................................6

2.1.1 .............................................................8

2.1.2 ..................................................8

2.1.3 ......................................9

2.2 .........................................................................12

2.2.1 ...............................................................13

2.2.2 ...............................................................13

2.2.3 ........................14

2.3 .....................................................17

2.3.1 ....................................18

2.3.2 ....................................21

.............................................................26

3.1 ..................................................26

3.2 ..............................................31

3.3 TiO2 .........................................32

3.4 TiO2 .............................36


V

3.5 TiO2 .............................41

.................................................................................43

4.1 .........................................................................43

4.2 .................................................................44

4.3 .........................................................................45

4.4 .........................................................................46

4.5 .....................................................47

4.5.1 ................................47

4.5.2 ........................................49

4.5.3 ........................................51

4.5.4 ...................................................54

4.5.5 ........................................55

.................................................................58

5.1 TiO2 .........................................58

5.1.1 TiO2 ..................58

5.1.2 TiO2 ..................................60

5.1.3 TiO2 ..................................62

5.2 TiO2- ................................64

5.3 TiO2 .............................69

5.4 .........................................................................74

TiO2.........................................75

6.1 .........................................................................75

6.2 .........................................................................76

6.3 ..........................................................................77

6.4 ...........................................78


VI

.............................................................................93

7.1 .................................................................................93

7.2 ..............................................................95

................................................................................................97


VII

3.1 ...............................................................35

3.2 ............................................41

4.1 ...................................................................43

4.2 .......................................................................43

4.3 ...................................................................................44

5.1 . .......................59

5.2 . 73

6.1 ...................................................................75


VIII

1.1 .................................................................................5

2.1 .............................................................................9

2.2 ...............................................................10

2.3 ................................................12

3.1 (a)(b) ...............................28

3.2 ...................................................................30

3.3 ...................................................................31

3.4 ........................33

4.1 ....................................46

4.2 FE-SEM ....................................................................48

4.3 ................................................50

4.4 (a)BET (b)

...................................................................................53

4.5 X .......................................................................54

4.6 - ..............................................55

4.7 -(Varian Cary100) .......................57

5.1 .....61

5.2 XRD..........................................63

5.3 . ...................................65

5.4 KM. ..........................................68

5.5 . ........70

6.1 TiO2 ......................77

6.2 (a)(b)................79

6.3 (a)(b) ........80


IX

6.4 TiO2 ..........................82

6.5

..................................................................................................83

6.6 .....85

6.7 TiO2 ...................87

6.8 ............................................89

6.9 ............................90

6.10 .................91

7.1 ....................................96


1

1.1

WTO

(2006~2008 ) 60

( 17%)

(

SARS)

(TiO2)


2

1.2

(TiO2)(ZnO)

(NOx)

[1,2]

N(energy band gap)

3.2 eV 385 nm

[2] 45%

3-4

( 400-700 nm)


3

1.3

(Pt)(V)(Ni)(Mn)(Cr)(Fe)

[3](N)[2]

(TiO2)


4

1.4

(sol-gel method)[3](DC plasma)[4]

(hydrothermal or solvthermal)[5]

110 150 24

(Fe)

(Co) (Ni)

135 1

(pseudo first-order)

(methylene blue, MB)


5

1.5

1.1

1.1

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible

TiO2

TiO2 TiO2 TiO2

BET

XRDTEM

SEM

UV-Visible


6

2.1

(Nanotechnology)

(Richard Feynman) 1959

McKeownNario Taniguchi

1974 Nanotechnology[6]

0.1 nm- 100 nm

(Top-down)1982 (Scanning

Tunneling Microscope, STM)

1989 Foresight Stanford University

1990(Baltimore) STM

2000

National Nanotechnology

Initiative (NNI)

[7]

Research and technology development at the atomic, molecular or

macromolecular levels, in the length scale of approximately 1 - 100

nanometer range, to provide a fundamental understanding of phenomena

and materials at the nanoscale and to create and use structures, devices

and systems that have novel properties and functions because of their small

and/or intermediate size. The novel and differentiating properties and

functions are developed at a critical length scale of matter typically under


7

100 nm. Nanotechnology research and development includes manipulation

under control of the nanoscale structures and their integration into larger

material components, systems and architectures. Within these larger scale

assemblies, the control and construction of their structures and

components remains at the nanometer scale. In some particular cases, the

critical length scale for novel properties and phenomena may be under 1

nm (e.g., manipulation of atoms at ~0.1 nm) or be larger than 100 nm (e.g.,

nanoparticle reinforced polymers have the unique feature at ~ 200-300 nm

as a function of the local bridges or bonds between the nano particles and

the polymer).

1 nm 100 nm

1 nm-100 nm(Mesoscopic)


8

2.1.1

nanometer (nm)1

(nm)=10-3()=10-9(m) 110

[8]

2.1.2

///

[/ (Carbon Nanotube, CNT)]/

(Supermolecule) /

/

(Single Electron Transistors)

(Spintronics) (Magnetic Random Access Memory,

MRAM) Terabyte

//


9

2.1.3

(structure)

(properties) (process)

(top-down) 2.1

2.1

1 nm 10 nm 20 nm 100 nm 1m

Bottom up

(Self-assembly

process)(Supramolecule)

Top Down

1 nm 10 nm 20 nm 100 nm 1m

Bottom up

(Self-assembly

process)(Supramolecule)

Top Down


10

2.2

2.2

1990

1990 1994

1994

nanostructured assembling system

I IIII I1990 1994

:

(nanocrystalline or nanophase)

(0D-0D) (0D-3D)(0D-2D)

(nanostructuredassembling system)

1D2D3Dnano-patterning

STM

I IIII I1990 1994I IIIIIII II I1990 1994

:

(nanocrystalline or nanophase)

(0D-0D) (0D-3D)(0D-2D)

(nanostructuredassembling system)

1D2D3Dnano-patterning

STM


11

(hard

materials)

(soft materials)

(flexibility)

[9]


12

2.2

100

/

2.3

/()-

[10]

2.3

/

/

/

/

/


13

2.2.1

(

)

1 nm""

20 nm 105

[10]

2.2.2

100 nm

(Sphere Equivalent)

6000~9000 nm() 2000~3000 nm

400~760 nm

1~100 nm

103~105()

(1 nm~100 nm)


14

(tunneling

effect)

[10]

2.2.3

(Quantum Size Effect)

(sintering temperature)

(Pb) 600K

20 nm Pb 288K (Ag) 373K

Ag 1173K


15

(Al2O3) 2073~2173K

Al2O3 1423~1773K

99.7%[10]

()

[11]

() ()

[10]


16

(Magnetic Domains)

Hc(Coercive Field)

Hc(Superparamagnetic

Phase)

FeCoNi

Pd

[12]


17

2.3

(Top-Down)

(High Energy Mechanical Milling)

/

60

(Oxide-dispersion Strengthened)

/

(Bottom-up)

(Gas Phase Condensation GPC)

(Liquid Phase Chemical Precipitation) (Sol-Gel)

(Hydrothermal) (Vapor Phase Chemical Reaction)

(Spray Conversion Process SCP)

(Self-assembly)


18

Bottom-up

[12]

2.3.1

0.01~0.05m

1 mm 1~2m


19

1m 20%

2m 90%

0.5m 70

(300~500 m/s)(300~450 )

80

Alpine

1~5m

1m

0.1m


20

5 nm~100

nm

[10]

(Precursor)

(Cluster)

(Cold-trap)

[13]

(1980 )

(1 Pa)102~103 Pa


21

[10]

2.3.2

--

-


22

A () B () + C () (2.1)

Fe(CO)5SiH4Si(NH)2

A () + B ()C () + D () (2.5)

SiH4NH3C2H4 CO2

Fe(CO)5(g) Fe(s) + 5CO(g)

SiH4 Si(s) + 2H2

3[Si(NH)2] Si3N4(s) + 2NH3(g)


SiH4 Si(s) + 2H2

3[Si(NH)2] Si3N4(s) + 2NH3(g)


SiH4 Si(s) + 2H2

3[Si(NH)2] Si3N4(s) + 2NH3(g)


SiH4 Si(s) + 2H2

3[Si(NH)2] Si3N4(s) + 2NH3(g)

(2.2)

(2.3)

(2.4)


SiH4 Si(s) + 2H2

3[Si(NH)2] Si3N4(s) + 2NH3(g)


SiH4 Si(s) + 2H2

3[Si(NH)2] Si3N4(s) + 2NH3(g)

(2.6)

(2.7)

(2.8)


23

(precursor)

1 m

[14]

pH

pH


24

100~350

(dialysis)

(autoclave)

[10,15]

(ZrO2)(Al2O3)

(Fe2O3)

-

-

1 nm


25

-

pH

[10]

Hydrolysis()

Ti-OR+H2O Ti-OH+ROH

Condensation oxolation (dehydration)()

Ti-OH+HO-Ti Ti-O-Ti +HOH

Alcoxolation (dealcoholation)()

Ti-OH+RO-Ti Ti-O-Ti +ROH

Polymerization()

O O

Ti-O-Ti + Ti-O-Ti O-Ti-O-Ti-O

O O

Hydrolysis()

Ti-OR+H2O Ti-OH+ROH

Condensation oxolation (dehydration)()

Ti-OH+HO-Ti Ti-O-Ti +HOH

Alcoxolation (dealcoholation)()

Ti-OH+RO-Ti Ti-O-Ti +ROH

Polymerization()

O O

Ti-O-Ti + Ti-O-Ti O-Ti-O-Ti-O

O O

(2.9)

(2.10)

(2.11)

(2.12)


26

1972Fujishima et al.[16]

(TiO2)

[17]

3.1

(catalyst)

[18]

A+BAB

A B AB

AB


27

A+BAB (3.1)

ABAB (3.2)

A+[Cat.] A[Cat.] (3.3)

A[Cat.]+BAB[Cat.] (3.4)

AB[Cat.] AB+[Cat.] (3.5)

(TiO2ZnONb2O5WO3SnO2ZrO2

KTaO3CdSZnSCdSeGaPCdTeMoSe2WSe2 )

(Semiconductor, SC)(Insulator)(Conductor)

(band gap)

3.1(a)

(Shells) 3.1(a)

(Valence Shell)

(Free Electron)

(

3.1b)


28

3.1(a)

3.1(b)

, Ev

, Ec

, Eg

, Ev

, Ec

, Eg


29

(Conducting Band)

(Valence Band)

(1 eV)(1V)

4 eV

1.1 eV 0.67 eV 3.2[19]

[20]

A P

(B) A N (P)

(As)(Sb)(Carrier)

()

N

(Donor)(Hole)

P

(Acceptor)[20]


30

3.2[19]

V-2.0

-1.0

0

1.0

2.0

3.0

4.0

TiO2 Nb2O5ZnO Fe2O3 WO3SnO2

SrTiO3CdSeCdS KTaO3

KTa0.77Nb0.2303SiGaP ZrO2

2.2

eV

1.1

eV

5.0

eV

2.5

eV 3.2

eV

3.4

eV

3.2

eV

3.0

eV

3.4

eV

1.7

eV

2.5

eV

2.2

eV

3.2

eV

3.5

eV

H2/H2O

O2/H2O

pH=0

(

)

V-2.0

-1.0

0

1.0

2.0

3.0

4.0


SrTiO3CdSeCdS KTaO3


2.2

eV

1.1

eV

5.0

eV

2.5

eV 3.2

eV

3.4

eV

3.2

eV

3.0

eV

3.4

eV

1.7

eV

2.5

eV

2.2

eV

3.2

eV

3.5

eV

H2/H2O

O2/H2O

V-2.0

-1.0

0

1.0

2.0

3.0

4.0


SrTiO3CdSeCdS KTaO3


2.2

eV

1.1

eV

5.0

eV

2.5

eV 3.2

eV

3.4

eV

3.2

eV

3.0

eV

3.4

eV

1.7

eV

2.5

eV

2.2

eV

3.2

eV

3.5

eV

V-2.0

-1.0

0

1.0

2.0

3.0

4.0


SrTiO3CdSeCdS KTaO3


V-2.0

-1.0

0

1.0

2.0

3.0

4.0

V-2.0

-1.0

0

1.0

2.0

3.0

4.0


SrTiO3CdSeCdS KTaO3


2.2

eV

1.1

eV

5.0

eV

2.5

eV 3.2

eV

3.4

eV

3.2

eV

3.0

eV

3.4

eV

1.7

eV

2.5

eV

2.2

eV

3.2

eV

3.5

eV

H2/H2O

O2/H2O

pH=0

(

)


31

3.2

-

3.3[21]

--

O2-OH

[22]

3.3 [21]


32

3.3 TiO2

(Photonic crystal)

(Gas senser)(Wave guide)(Ceramics membrane)

[23,24]

(Anatase)(Rutile)(Brookite)

[23]

600~700

TiO2

edge-sharing

corner-sharing

3.4[25]


33

3.4


34

N

1200

Anatase Anatase

Rutile Rutile

Anatase Rutile

Anatase Anatase

Rutile 3.1 [26]

Anatase(3.79 3.04 )(3.57 2.96 )

(1.949 1.980 )(1.934 1.980

)(mass density, )(band

structure) Anatase 3.9 g/cm3

3.2 eV Rutile 4.23 g/cm3 3.0 eV

[27,28]


35

3.1 [26]

79.9 79.9

(g/cm3) 4.23 3.9

a () 4.58 3.78

c () 2.95 9.49

2.71 2.52

() 6.0 ~ 7.0 5.5 ~ 6.0

(eV) 3.0 3.2

114 31

1858 600

(HCl)

(NaOH)


36

3.4 TiO2

385 nm

OH O2-

TiO2

[29]

1240 / Ebge (3.6)

(nm)

Ebge (band gap energy (eV))

TiO2 3.2 eV

385 nm TiO2

TiO2 UV

TiO2

6[30]

TiO2


37

TiO2

(H2O/O2)

TiO2

O2- OH

OH O2-

TiO2

[31]

TiO2 (anatase) + h TiO2(h+) + TiO2 (e-) (3.7)

TiO2(h+) + H2O H+ + OH (3.8)

TiO2(e-) + O2 O2- (3.9)

e-+ O2 O2- HO2 (3.10)

2HO2 O2 + H2O2 OH +OH- + O2 (3.11)

OH + Ared Aoxd (3.12)

H+

O2-


38

[32]

(Direct photolysis)

A+ hA (3.13)

AD1 + D2 (3.14)

A

h

A

D1, D2

290 nm


39

(Indirect photolysis)

A+ hA (3.13)

A+BA+B (3.15)

BD1 + D2 (3.16)

A

(

)

1.

2.

3.

4.

(Homogeneous Photo- catalysis)

(Hetergeneous Photocatalysis)[33]


40

(TiO2(ZnO)(CdS)


41

3.5 TiO2

3.2

3.2

1994 M. R.

Hoffmann

[34]

1995 N. Serpone CdS

[28]

1995 K.

Vinodgopal

SnO2TiO2

[35]

1999 H. D.

Breuer

CrMo

[36]

2001 R. Asahi N

[37]

2002 T.

Umebayashi

S

[38]

2003 D. W. Park Si Fe

[24]


42

3.2

2003 H. Kisch C

[39]

2004 L. Miao N2/H2 RF

[40]

2004 H. Luo Br Cl

[41]

2004 S.

Sakthivel

N

[42]

2005 J. C. Yu S

[43]


43

4.1

4.1 4.2

4.1

potassium

hydroxide KOH R.D.H. ACS

(P25,

20-40 nm)

Titanium

Dioxide TiO2 Degussa Co. 99%

Nickel nitrate Ni (NO3) 2 R.D.H. ACS

Cobalt nitrate Co (NO3) 2 R.D.H. ACS

Iron nitrate Fe (NO3)3 R.D.H. ACS

4.2

() (g/mol)

(nm)

Methylene Blue (C16H18ClN3S)

319.8 664 280


44

4.2

4.3

4.3

()

Precisa XB220A(4)

Power Sonic 420

DSC158

pH Hanna Instrument pH211

Heldolph MR3001

EYELA VOS-201SD(493K)

DENG YNG DH400(773K)

50 mm () x 100 mm (L)

(1473K)


45

4.3

20-40 nm TiO2(P25,

Degussa Co.)

X-ray [3,5]

(Anatase)(Rutile)

TiO2 0.01 M

() 10 M KOH

TiO2 1g 50 ml

TiO2 1 %

50 mm 100 mm(SUS 306)

135 TiO2

TiO2

pH 6

400

TiO2


46

4.4

4.1

1g 50 ml A

30 min

50 mL 135 1 hr

pH 6

4001 hr

A 10 M 0.01M(Fe(NO3)3 Ni(NO3)2Co(NO3)2)


47

4.5

4.5.1

(field emission scanning electron

microscopy, FE-SEM, LEO 1530)

( 4.2)

FE-SEM(emissive- mode)

CRT(cathode radiation tube)

CRT


48

4.2 FE-SEM


49

4.5.2

(HR-TEM High

resolution transmission electron microscopyJEOL 2010)

( 4.3)

( 1 )

HR-TEM

X

100


50

4.3


51

4.5.3

BET(Brunauer-Emmett-Teller)

Langmuir equationBJH t-plot

BET

77 K Point B P/P0 = 0.05

~ 0.1 isotherm ( 4.4 a) BET Langmuir equation

molecular crossing area

BET equation

V P

Vm

P

P0

C

P

V(P0-P) VmCP0

(C-1)1

VmC= +

P

V(P0-P) VmCP0

(C-1)1

VmC= + (4.1)


52

P/P0( 4.4 b)Kelvin equation

Kelvin equation

Rk Kelvin

R

T

VL

Rk=(-2VL)/RT ln(P/P0)Rk=(-2VL)/RT ln(P/P0) (4.2)


53

(a) (b)

4.4 (a) BET ;

(b)


54

4.5.4

X (X-ray diffraction XRDPhilip PW

1700) X

4.5 X


55

4.5.5

(methylene blue) 664 nm

Beer-Lambert Law

20 mg/L

-(UV-visible spectrometerShimadzu UV-2550)

( 4.6)

-

4.6 -


56

Beer-Lambert Law

Iin

Iout Iin Iout

(Transmittance)T

(4.3)

A(Absorbance)(-1)

(4.4)

Beer-Lambert Law

A=lc (4.5)

l c

A olar absorptivity)

20 mgL-1 0.2

wt.% TiO2 13 W 750

Wcm-2

(Newport FSQ-GG 400)

-( 4.7) (Varian Cary100)

TiO2 /

200 800 nm

T=Iin

IoutT=

Iin

Iout

A=-logT= -logIin

Iout=log

Iin

IoutA=-logT= -log

Iin

Iout=log

Iin

Iout


57

/

-

4.7-(Varian Cary100)

(diffuse reflection)

Kubelka-Munk

S

R

F(R)

F(R)=(1-R)2

2R=

SF(R)=

(1-R)2

2R=

S(4.6)


58

5.1 TiO2

5.1.1 TiO2

-196

TiO2

5.1 TiO2

( TiP) 46 m2/g

TiO2( Fe-TiPCo-TiP Ni-TiP)

TiO2

TiO2 TiO2

5.1 TiO2

79-86%

(mesopore)

TiO2

TiO2

TiO2


59

5.1

Sample SBET a Vt b Pore size distribution Mean pore

type (m2g-1) (cm3g-1) Vmicro c (%) Vmeso d (%) size, D e ().

TiP 46 0.123 0.020 (16) 0.103 (84) 4

Fe-TiP 56 0.141 0.020 (14) 0.121 (86) 42

Co-TiP 55 0.130 0.023 (18) 0.107 (82) 41

Ni-Tip 58 0.151 0.023 (15) 0.128 (79) 43

a SBET BET b Vt 0.98 c Vmicro Dubinin-Radushkevish d Vmeso e D Barrett-Joyner-Halenda


60

5.1.2 TiO2

CoTiO2FE-SEMHR-TEM

5.1(a)(b)TiO2

20-40 nm

5.1(b) TiO2

5.1(b) 4.757

(anatase) TiO2


61

5.1

(a) FE-SEM(b) HR-TEM

(a)

(b)

100 nm


62

5.1.3 TiO2

TiO2

5.2XRD TiO2

400

5.2(a) TiO2(P25)

rutile anatase anatase

(2) 25.28 rutile

(2) 27.44 [14]

TiO2 rutile

anatase TiO2


63

20 30 40 50 60 702

Inte

nsity

(arb

. uni

t)

(a)

(b)

(c)

(d)

: anatase: rutile

(degrees)

5.2 XRD (a)(b)

(c)(d)


64

5.2 TiO2-

TiO2 (diffuse

reflection spectra) 5.3

TiO2 385 nm

TiO2

5.3 400-700 nm

TiO2

TiO2 (band gap)

TiO2


65

5.3 (Diffuse reflection

spectra)

200 300 400 500 600 700 800Wavelength (nm)

0

1

2

3D

iffus

e R

efle

ctan

ce,

Fe-TiPCo-TiP

Ni-TiP

F(R)


66

135

TiO2 Ti-O-Ti Ti-O-K

Ti-OH [14]

Ti-O-M TiO2

TiO2

[5] 0

10% 3.2eV 2.3eV[44]

TiO2

5.3 TiO2

TiO2

Ni TiO2

475 nm 730 nm Fe TiO2

485 nm Co TiO2 605

nm TiO2

Kubelka-Munk(KM)

[45-47] R KM

(5.1)

S

KM

[48][F(R)hv]1/ hv

KM hv

F(R)=(1-R)2

2R=

SF(R)=

(1-R)2

2R=

S


67

[46]

KM ( =2)

( 5.4)

(Co-TiP(2.88 eV)>Ni-TiP(2.63 eV) TiO2(3.2 eV)

(1)

(2)

Ti-O-M

(M=Fe, Co, Ni)


68

5.4 KM

2.0 2.5 3.0 3.5 4.0(eV)

0

1

2

3

4

hv

h

v1/2

Fe-TiP

Ni-TiP

F(R)

Co-TiP

[

]


69

5.3 TiO2

5.5


70

5.5

Langmuir-Hinshelwood

0 20 40 60 80 100 120 140 160 180 200Visible light irradiation (min)

0

10

20

30

40

50

60R

emov

al e

ffic

ienc

y (%

)Ni-TiP

Co-TiP

Fe-TiP


71

(e-)-(h+)[4]

(5.2) TiO2

(OH)(5.3) TiO2

(O2-)(5.4)

(5.5)(5.7)

(MB+)

(5.8)

5.5

Ni-TiP(59.3 %) >Co-TiP(54.6 %)>

Fe-TiP(49.8 %)

TiO2

Ni-TiPNi-TiP

Ni-TiP 2.63 eV

TiO2 -(5.2)

TiO2 + h e + h+ (5.2)

H2O + h+ OH + H+ (5.3)

O2 + e O2 (5.4)

O2 + H+ HO2 (5.5)

2 HO2 H2O2 + O2 (5.6)

H2O2 + O2 OH + O2 + OH (5.7)

OH + MB+ colorless compound (5.8)


72

Langmuir-Hinshelwood(LH)

[49,50]

-(OH)

LH

ra C

k ()

K Ci

(Ci=20 mgL-1=6.2510-5 molL-1) KC

tka(pseudo first-order)

(5.10)

Ct t

ra=k=kKC

1+KCra=k=

kKC

1+KC(5.9)

ra= -dC

dt=kKC=kaCra= -

dC

dt=kKC=kaC (5.10)

lnCi

Ct

=katlnCi

Ct

=kat(5.11)


73

ln(Ci/Ct)(t)

ka TiO2 ka 5.2

Ni-TiP

Ni TiO2

-

( OH)

[50] 5.1

TiO2

TiO2

5.2

Sample type ka102 (min-1)

Fe-TiP 1.37

Co-TiP 1.61

Ni-TiP 1.92


74

5.4

TiO2

(Fe, Co Ni) TiO2

TiO2

KM

Fe-TiP(2.98 eV)>Co-TiP(2.88 eV)>Ni-TiP(2.63 eV)

NiTiO2

Ni-TiP(59.3 %) >Co-TiP(54.6 %)> Fe-TiP(49.8 %)

TiO2

Ni

-


75

TiO2

6.1

6.1

6.1

Ni-TiP(20-40

nm)

Nickel-doped Titanium Dioxide

Ni-TiO2 99%

Titanium Dioxide TiO2

99%

Acetone C3H6O Echo

37%

Alcohol C2H5OH

95%


76

6.2

Ni-TiP

TiO2

0.5 g 50 ml 10

ml 20

2 ml

(Escherichia coli E. Coli) 0.5

ml


77

6.3

6.1

6.1 TiO2

2ml

0.5 ml E. Coli


78

6.4

(O2)

(O2-)(H2O)

( OH)

/ 6.2 6.3

/


79

6.2 (a)(b)

(a)

(b)


80

6.3 (a)(b)

(a)

(b)

(a)

(b)


81

6.4

E. Coli/E. Coli

Ni-TiP

Ni-TiP

6.5

Ni-TiP E. Coli


82

6.4 TiO2(a)(b)

(c)

(d)(e)(f)

(a)

(b)

(c)

(d)

(e)

(f)


83

6.5

Aspergillus niger BCRC31512


84

6.6

(

) TiO2

/

Ni-TiP


85

6.6 (a)

(b)(c) TiO2

(d)(e)(f)

(a)

(b)

(c)

(d)

(e)

(f)


86

Ni-TiP

Ni-TiP 6.7


87

6.7 TiO2(a)(b)

(a)

(b)

(a)

(b)


88

6.8

Ni-TiP

6.9

6.10


89

6.8 (a)

(b)

(a)

(b)


90

6.9 (a)

(b)

(a)

(b)


91

6.10


92

/


93

7.1

/

P25

() XRD anatase

rutile

UVVisible

() TiO2

KM

Fe-TiP (2.98 eV) > Co-TiP (2.88 eV) > Ni-TiP

(2.63 eV)NiTiO2


94

()

Ni-TiP (59.3 %) >

Co-TiP (54.6 %) > Fe-TiP (49.8 %)

TiO2

Ni

-

/


95

7.2

(Dye sensitized

solar cellDSSC) 7.1

(1)( FTO

TiO2)(2) I/I3

(3) (Counter Electrode)

DSSC

DSSC


96

7.1

Light

Electrolyte( S+ / S )

( S+ / S* )

( A / A- )

Load

Anchored dye

Counter electrode

TCO

h V e-

e-

e-

e-

e-

e-

cb

vb

n-SC( TiO2 )

-0.9

2.5

0.8

0.2

-0.7

V, vs SCE

Pt-loaded CNT arrays


97

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