2

AgI/TiO

AgI/TiO2

2011 5
I

UDC

10497

Study on Thermochromic Reversibility and

Photostability of AgI/TiO2 Nanocomposite

AgI/TiO2

2011 5

2011 5

2011 5
II

()

III

AgI 150 oC
AgI
AgI TiO2

AgI/TiO2
1. AgI/ TiO2(P25), AgI/TiO2R AgI/Anatase-TiO2(A)
TEM X
AgI/ TiO2
TiO2 AgI
AgI 150 oC
150 oC AgI/ TiO2(P25)
-
AgI

2.
AgI/TiO2(P25) AgI
IAg+-I-V-Ag+-I-V-Ag+
AgI TiO2 AgI
I- AgI/TiO2 Ag+-O2--Ti4+
AgI Agn AgI/ TiO2

Abstract
Pure AgI particles experience a color evolution at the to phase transition
temperature.

However,

the

photoinstability

of

AgI

due

to

its

labile

photodecomposition to metallic Ag under light illumination greatly hinders its

diverse applications. Herein, it was found for the first time that the formation of
AgI/TiO2 nanocomposite not only result in a considerable reduction of
thermochromic transition temperature of AgI as well as excellent thermochromic
reversibility, but also leads to excellent photostability under the illumination of
indoor fluorescent lamp.
AgI/TiO2(P25), AgI/Rutile-TiO2 and AgI/Anatase-TiO2 nanocomposite was
prepared and characterized by transmission electron microscopy (TEM), X-ray
diffraction (XRD) and diffusive reflectance UV-vis (DRUV-vis) absorption spectra
at different temperatures. All the three AgI/TiO2 samples exhibit thermochromic
switching phenomena at the phase - transition temperature of AgI with the
evolution of its color from light yellow at ambient temperature to dark khaki at 150
o

C. Besides, the AgI/TiO2(P25) nanocomposite exhibits a hysteresis loop on the

heating/cooling cycle, which is attributed to the suppression of to phase

transition due to the higher surface energy of AgI nano particles.
Based on the characterization results by photoluminescence, transient
photocurrent decay and positron annihilation spectra, it is concluded that large size
surface defects, such as I- vacancy clusters (e.g. Ag+-I-V-Ag+-I-V-Ag+) on the surface
of AgI as deep electron traps, are responsible to photodecomposition of pure AgI.
The excellent photostability for the AgI/TiO2 nanocomposite is due to the following
reason: the surface I- vacancy clusters as deep electron traps in pure AgI are replaced
by Ag+-O2--Ti4+ bonds on the interface of AgI/TiO2, thus Agn cluster formation
through the surface migration of photogenerated Ag atoms is completely inhibited,
resulting in the inhibition of photodecomposition of AgI.
Keywords: AgI, Nanocomposite, Thermochromism, Photostability, Positron
annihilation.

II

................................................................................................................................ I
Abstract ......................................................................................................................... II
..............................................................................................................................III
..................................................................................................................1
1.1 ......................................................................................1
1.1.1 ....................................................................2
1.1.2 ............................................................2
1.1.3 ....................................................................................3
1.2 ..............................................3
1.2.1 ....................................................................................3
1.2.2 ....................................................................................4
1.3 ......................................................................................6
1.3.1 ........................................................6
1.3.2 ............................................................................7
1.3.3 ............................................................................9
1.4 AgI ..................................................................................10
1.4.1 ......................................................................10
1.4.2 AgI ....................................................................................12
1.5 ....................................................................13
.AgI/TiO2 .........................................14
2.1 ................................................................................................................14
2.2 ............................................................................................14
2.2.1 ..............................................................................................14
2.2.2............................................................................................15
2.3 ....................................................................................................15
2.3.1 TiO2 ........................................................................15
2.3.2 TiO2 ........................................................................15
2.3.3 TiO2(P25) AgI ....................16
2.4 AgI/TiO2 .....................................16
2.4.1 ..........................................................................................16
2.4.2................................................17
2.5 .....................................................................................................17
2.5.1 ...................................................................................17
2.5.2 XRD ................................................................................19
2.5.3 TEM HRTEM ........................................................22
2.5.4 ...........................................................................23
2.6 ................................................................................................................27
AgI-TiO2 ............................................................................29
3.1 .................................................................................................................29
3.2 ........................................................................................................29
3.2.1 ..............................................................................29
3.2.2 ......................................................................30
III

3.2 AgI/TiO2 AgI .............................................31

3.3 .................................................................................................33
3.4 ........................................................................................35
3.5 ............................................................................39
3.6 ................................................................................................................42
................................................................................................................43
.....................................................................................................................44

........................................................................................................................48
..............................................................................................49

IV

Feyneman 20 60
[1]

Feyneman

1nm-100nm

[2-9]

[10]

[11]

1.1
1

1.1.1
nanocomposites Roy Kormanrneni
[12] 1984
1-100nm[13]

1.1.2
1.1.2.1

[14]
1.1.2.2

1.1.2.3

[15]
1.1.2.4

1.1.3

(1) 10-100nm
10-70m2/g
(2)
1063 2nm 300
(3)

(4)
1-0.8
(5) -
5-50nm

(6)

45nm
TiO2

1.2
1.2.1
3

[16]

GaN/ZnO 1.1
ZnO GaN
ZnO GaN

1.1 GaN/ZnO
ZnO GaN
GaN ZnO
ZnO
[17]Guo
TiO2/ZnO
[18]

1
2
3.

1.2.2

[19-21]

1.2.2.1

[22] 1.1

1.2
1.2.2.1

[23]

1.3
5

1.3

1 Et
2 Et 1

3 Et
4 Et
3
1.2.2.3

[22]
1.2.2.4
-

[23]

1.3
1.3.1

[24],[25]

1871 Houston Houston

[26]

1959 Morin
[27-31]

[32],[33] 80

[34]

[35]
VO2
VO2 67
67VO2
VO6
67VO2 VO2

1.3.2

1.3.2.1
7

1.4
25

1.4
1.3.2.2

CuHgI4

[36]

[37](CH3)2CHNH3CuCl

5 6[38] Febinteanu Marilena

[Ni(AA)3-n(BB)n][PdX4] Ni2+
8

Cu2+ Cl AA
[Ni(AA)3-n(BB)nCl2][39]
1.3.2.3

CrO42-
Pb2+ Pb4+ Pb2+
Pb4+
Pb4+ Pb4+
[40] 100

1.3.3

(
)

Del Sol 80
TC
Licritherm
,

Nature

1.4 AgI
1.4.1

1925 Sheppard

[41]

[42]

10

TiO2

TiO2 [43]

1.5 AgBr/TiO2
1.5 AgBr/TiO2
2.6eV TiO2 3.2eV
TiO2

Zang TiO2(P25)
/TiO2
[44]Kakuta
/
[45]Zhang
MX-5B
[44]Li
Ag/AgBr/SFN 7
[45]

11

1.6AgI/TiO2 TEM HRTEM

AgI Zhang
/
[46] Li
// AgI/TiO2 Li
-
4- 1.6 [47]

1.4.2 AgI
AgI , 147
-AgI
AgI
147 AgI
-AgI -AgI
-AgI
ABABAB ABCABC

1.5 AgI
a-AgIb-AgIc-AgI
147-AgI
12

-AgI
[48] -AgI
-AgI
[49-52]
-AgI 1-1cm-1
Makiura AgI
[53]

1.5
AgI AgI

-AgI
[49-52] -AgI
1-1cm-1
AgI

AgI TiO2 AgI

AgI/TiO2

(1) AgI/TiO2
(2) AgI/TiO2
(3) HRTEMTEMSEMXRD
DRUVPALS

13

AgI/TiO2
2.1
AgI , 147

147-AgI -AgI[48]
-AgI
-AgI
[49-52] -AgI
1-1cm-1
Makiura AgI
[53] AgI

[54-56] AgI

AgI

AgI

AgI/TiO2
DSCXRDTEM

2.2
2.2.1

14

ECF1-8-13

202-OAB

79-1

KQ-400KDE

TG328A

YZ15W

MC-100l

XQM-0.4

IKAC-MAG HP7

GYZ-125

2.2.2

C16H36O4Ti

AR

99.5

AgNO3

KI

TiO2(P25)

TiO2

AR

C2H5OH

99.7

2.3
2.3.1 TiO2
(1) 10.62g TiCl4 200ml

(2) 40 3

(3) 150
TiO2

2.3.2 TiO2

15

(1)
(2)
10
(3) 10 200
TiO2

2.3.3 TiO2(P25) AgI

(1) 1.000g TiO2P25 100ml
A
(2) 0.078g KI 10ml B
(3) 0.080g AgNO3 10ml C
(4) B A
(5) C A
30
(6) 80

TiO2 TiO2 AgI

2.4 AgI/TiO2
2.4.1
STA449CX XRD
Rigaku D/Max-IIIA X Cu K
TEM JEM-100CX
UV-3600 Shimadzu
RF-5301 410 nm X
16

XPert PRO DY2198 X Cu K

10

2.4.2

2-1
(1) AgI/TiO2

(2)
(3)

2.5
2.5.1

17

2-2 AgI/TiO2(P25)TG5/min

2-3 AgI/ TiO2 TG5/min

18

2-4 AgI/ TiO2 TG5/min

2-22-32-4 50TiO2(P25) TiO2
TiO2 AgI
150
AgI
AgI

2.5.2 XRD

19

2-5 AgI/TiO2 XRD

2-6 AgI/TiO2(P25) XRD a)25 oC, b)70 oC, c)100 oC, d)120
o
C, e)140 oC, f)155 oC.

2-7 AgI/ TiO2 XRD a) 25 oC, b) 70 oC, c) 100 oC,

d) 120 oC, e) 150 oC
2-5 AgI/ TiO2 P25 XRD
TiO2 PDF
20

83-20450 4 22.38, 23.70, 39.28, 46.28 -AgI

100
002(110),(112) AgI/TiO2 AgI

2-8 AgI/ TiO2 XRD a)25 oC, b)70 oC, c)100 oC,
d)120 oC, e)150 oC
-AgI -AgI 150 -AgI
XRD 2-62-72-8
AgI/ TiO2 P25AgI/ AgI/ TiO2
XRD AgI/ TiO2
150 -AgI 100
002 -AgI 150
AgI/P25 -AgI 100002
-AgI 110200 -AgI
150 -AgI AgI/ AgI/
150 -AgI -AgIAgI
XRD 150
-AgI AgI

TiO2 -AgI110

AgI -AgI 110 AgI/

AgI/ AgI -AgI 110

21

2.5.3 TEM HRTEM

2-9 AgI/TiO2(P25) TEMA HRTEMBAgI/ TiO2 TEM

C HRTEMDAgI/ TiO2 TEME
2-9 AgI/TiO2(P25) TEMA HRTEMBAgI/
TiO2 TEMC HRTEMD AgI/ TiO2 TEME
2-9A -AgI TiO2
TiO2 11-33nm -AgI 10-28mm
2-9CTiO2 0.32nm TiO2110
AgI 0.23nm -AgI110
22

AgI/ TiO2 P25 -AgI110/

TiO2110/ TiO2101
AgI TiO2(P25)
-AgI TiO2 110
TiO2(P25)

2-9D D AgI/ TiO2 TEM-AgI

TiO2 TEM
AgI/ TiO2 -AgI110/ TiO2101
2-9E AgI/ TiO2 TEMAgI
TiO2
-AgI/ TiO2

2.5.4

23

2-10 AgI AgI/TiO2(P25)a) 25 oC, b)

70 oC, c) 100 oC, e) 155 oC.
2-10 AgI/TiO2 AgI
2-11 AgI/TiO2 25 oC100 oC
155 oC
AgI/TiO2

hv=A(hvEg)1/2
, v, Eg, A [63],[64]
AgI/TiO2

25 oC

100 oC

155 oC

2-11 AgI/TiO2
24