1
Supporting Information
Effective Nonmetal Incorporation in Black Titania with Enhanced
Solar Energy Utilization
Tianquan Lin,1,2 Chongyin Yang,1,2 Zhou Wang,1,2 Hao Yin,1 Xujie Lü,1 Fuqiang Huang,1,2,*
Jianhua Lin,2 Xiaoming Xie,3 and Mianheng Jiang3
1 CAS Key Laboratory of Materials for Energy Conversion, Shanghai Institute of Ceramics,
Chinese Academy of Sciences, Shanghai 200050, P.R. China; 2 College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P.R.
China; 3 State Key Laboratory of Functional Materials for Informatics, Shanghai Institute of
Microsystem and Information Technology, Chinese Academy of Sciences, Shanghai 200050,
P.R. China.
Content
1. The formation mechanism of black TiO2-x
2. Preparation of X-doped TiO2 (X=N, S, I) following the literature methods
3. XRD patterns, HRTEM images and elemental abundances of titania samples
4. The calculation of solar absoption of TiO2-N
5. VB XPS and magnetic field dependence of magnetization of TiO2-X
6. Experimental details of H2 generation
7. The photocatalytic activities of nonmetal-doped titania prepared by the literature
methods
8. References
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1. The
Plenty
oxygen-
furnace
H2-redu
The Ell
reduced
for exam
lines in
stability
standard
metal ca
For exam
the H2
tempera
It is
tempera
Any
partial p
will be o
reduced
e formatio
of oxyge
-deficient t
. More eff
uced sample
lingham dia
d to a metal
mple, M+½
n the Ellingh
y of oxides.
d condition
an reduce t
mple, the 2
+ O2 H
ature.
a conveni
ature using t
combinatio
pressure. If
oxidized; in
d. In this res
on mechan
n vacanci
itania (TiO
ficient redu
es previous
agram used
l. The stand
½O2 MO
ham diagra
It is possib
ns by observ
the oxides o
Ti2O3 + O2
H2O line, so
Figure S1
ient way to
the followin
on of values
the oxygen
n contrast, if
search, the m
nism of b
es are fir
O2-x) by the
uction can
report, con
d to show
dard Gibbs
. This valu
am (Figure
le to visuali
ving the rel
of all other
4TiO2 li
o elemental
. Ellingham
o obtain th
ng equation
( G0, T) in
partial pres
f it is lower
melted Al at
2
black TiO2
rst introdu
reduction
be achiev
nsistent with
the conditi
free energy
ue, G , is
S1) represe
ize directly
lative positi
metals who
ine lies abo
Al can red
m diagram o
he equilibri
n:
n the diagra
ssure is high
r than the eq
t 800 C can
0 lG RT
2-x
uced in T
of melted
ed in our
h Ellingham
ions under
y of formati
plotted aga
ent the func
the affinitie
ions of the
ose lines lie
ove 4/3Al +
duce TiO2 t
of G versus
ium oxygen
am represent
her than the
quilibrium v
n effectively
2ln Op
TiO2 nanoc
Al in an e
Al-reduced
m diagram sh
which a m
ion of the o
ainst tempe
ction G0 (
es of metals
lines in the
e above the
O2 2/3A
to Ti2O3 bu
s temperatu
n partial p
ts a particul
e equilibrium
value then th
y decrease o
crystals to
evacuated tw
d sample t
shown in Fi
metal oxide
oxide is con
erature. The
(T) and the
s for oxygen
e diagram.
eirs on the d
Al2O3 line bu
ut H2 canno
ure.
pressure at
lar value of
m value, the
he oxide wi
oxygen part
obtain
wo-zone
than the
gure S1.
e can be
nsidered,
e straight
relative
n in their
A given
diagram.
ut below
ot at low
a given
f oxygen
e metal
ill be
tial
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pressure
the TiO
2. Prep
The
Typical
(67%)/A
The
At 40
(20%) w
vigorou
transfer
slowly t
remove
The
method
0.05mol
autoclav
washed
Figure
reductio
(TiO2-H
black tit
500 C
treatmen
e. When the
2 is readily
paration
N-doped T
ly, the com
Ar gas flow
S-doped T
C, a soluti
was added
us stirring.
rred into a
to 240 C f
the residua
I-doped T
.S3 In the ty
l/L) under
ve and reac
with deioni
S2. The equ
on of TiO2
H) in a therm
tania (TiO2
for 4 h, r
nt of TiO2-x
e oxygen pa
reduced.
of X-dope
TiO2 (N:TiO
mmercial TiO
at 1 atm fo
TiO2 (S:TiO
ion containi
into a solu
After being
100 mL au
for 2 h. The
al organic co
TiO2 (I:TiO
ypical proce
stirring. T
cted at 100
ized water,
uipment sch
(TiO2-x) in
mal plasma
-S, I) by th
respectively
x powder at
artial pressur
ed TiO2 (X
O2) was pre
O2 (Deguss
r 3 h.
2) sample w
ing 10 mL
ution contain
g aged for
utoclave co
e solid was
ompounds t
O2) sample
edure, 2.5 g
The resultan
0 C for 24
followed by
hematics of
n a two-zon
furnace by
e reaction o
y. (d) Prepa
500 C for
3
ure of TiO2 i
X=N, S, I)
epared acco
sa P25) pow
was prepare
ethanol an
ning 40 mL
24 h at 40
ontaining 25
then furthe
to obtained
e was prep
g Ti(SO4)2 w
nt white s
4 h. The re
y calcinatio
f preparation
ne furnace.
y hydrogen p
of the as-pre
aration of N
4 h with a N
is much low
) followin
ording to pr
wder were t
ed according
nd 2.5 mL
L ethanol a
0 C, the a
5 mLCS2/E
er calcined
S-doped Ti
pared acco
was dissolv
lurry was
esultant yel
on at 300 C
n samples. (
(b) Prepara
plasma. (c)
epared TiO2
N-doped bl
NH3:Ar=2:1
wer than its e
ng the liter
eviously rep
treated at 60
g to the foll
dilute HNO
and 10 mL
as-prepared
EtOH solutio
at high tem
O2 (S:TiO2)
rding to p
ved in potas
transferred
low powde
C for 2 h.
(a) Schemat
ation of H-d
Preparation
2-x with S an
lack titania
1 gas flow.
equilibrium
rature me
eported proc
00 C unde
lowing proc
O3 aqueous
Ti(O-C4H9
d TiO2 xero
on and wa
mperature fo
).
previously
ssium iodate
to a Tefl
er was cen
atic low-tem
doped blac
n of S- and
and I2 atmos
a (TiO2-N)
m value,
ethods
cedure.S1
er a NH3
cedure.S2
solution
9)4 under
ogel was
s heated
or 8 h to
reported
e (KIO3,
lon-lined
trifuged,
mperature
k titania
I-doped
sphere at
by heat
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The
compari
TiO2-N,
Figure
TiO2-N,
3. XRD
sample
Figure
doped T
color of T
ison, the ph
, TiO2-S, Ti
S3. The pho
, TiO2-S, Ti
D pattern
es
S4. (a f) TE
TiO2, respec
TiO2-X sam
hotos of al
iO2-I, H:TiO
otos of all th
iO2-I, H:TiO
ns, HRTE
EM image a
ctively. The
mple varies
l the titania
O2, N:TiO2,
he titania sa
O2, N:TiO2,
M images
and HRTEM
se nanocrys
4
s with the
a samples (
, S:TiO2, an
amples (inc
, S:TiO2, an
s and elem
M images o
stals are ave
doping ele
(including p
nd I:TiO2) w
luding prist
nd I:TiO2) fo
mental ab
f pristine Ti
eragely 25
ment of X
pristine TiO
was provided
tine TiO2, T
or comparis
bundances
iO2, TiO2-x
nm in diam
X (H, N, S,
O2, TiO2-x,
d in Figure
TiO2-x, TiO2
son.
s of titani
and nonmet
meter.
, I). For
TiO2-H,
S3.
-H,
ia
tal-
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Figure
confirm
Figure
I). (b) E
that pri
nonmeta
exhibits
as-resul
S5. Energy
ming the exis
S6. (a) XRD
Enlarged vie
istine TiO2
al-doped Ti
s a larger l
lted disorde
dispersive
stence of no
D patterns o
ew of the (1
2 (Degussa
iO2-X (X = N
linewidth t
r-induced la
spectroscop
onmetal elem
of TiO2 bef
101) XRD p
a P25, a m
N, S, I) rem
han pristin
attice strain
5
pic (EDS) s
ments in the
fore and afte
peak of anat
mixture of
main high cr
ne TiO2, wh
ns.
pectra of Ti
e nonmetal-
er the Al re
tase. The st
anatase a
rystallinity.
hich is der
iO2-x and Ti
- doped blac
duction and
rong diffrac
and rutile),
Neverthele
rived from
iO2-X (X=N
ck titania.
d TiO2-X (X
ction peaks
black TiO
ess, the blac
oxygen va
N, S, I),
X = N, S,
indicate
O2-x and
ck TiO2-x
acancies,
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The
photoele
S7.
4. The
We obta
solar ab
where A
(W m-2
sample
Therefo
nonmetal
ectron spec
Table S1.
Sample
TiO2 (P2
TiO2-x
TiO2-N
TiO2-S
TiO2-I
e calculati
ained the ab
bsorption of
A is the sola
nm-1), show
absorption
ore, we can o
element
ctroscopy (X
. Elemental
s Ti
25) 27.8
28.
N 27.6
S 26.7
28.0
Figur
ion of sola
bsorbance o
f the TiO2-N
ar absorption
wn in Figure
of solar spe
obtained the
contents i
XPS) measu
l abundanc
i O
85 72
1 70
65 65
73 66
04 66
re S7. Full-s
ar absopti
of titania sam
N is given by
A
n; T is reflec
e S8; is th
ectral irradia
e solar abso
6
in titania
urements, a
ces determi
O
2.3
0.8
5.73
6.76
6.31
scale XPS s
ion of TiO
mples by U
y the equati
(1 )T S
S d
ctance of th
he waveleng
ance.
orption of th
samples w
as listed in T
ined by XP
N
-
-
6.62
-
-
spectra of T
O2-N
UV-Vis-IR d
ion:
d
he sample, S
gth (nm). He
he TiO2-N w
were observ
Table S1 an
PS in titania
S
-
-
-
5.12
-
iO2-X.
diffuse refle
S is solar spe
ere, the (1 T
was approxi
ved in the
nd shown in
a samples.
I
-
-
-
-
4.31
ectance spec
ectral irradi
T) S represe
imate 85%.
e X-ray
n Figure
ctra. The
iance
ents the
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Figure
Equatio
(1 T) S)
Figure
Al-redu
S-doped
5. VB
Figu
S8. The abs
on 1) and Ti
S).
S9. Diffuse
uction; black
d TiO2 samp
XPS and
ure S10. XP
sorbance of
O2-N absor
e reflectance
k titania obt
ples (N:TiO
magnetic
PS valence
f TiO2-N (bl
rption of sol
e spectra of
tained by hi
O2, S:TiO2) f
c field dep
band spectr
7
lack line), s
lar spectral
f pristine TiO
igh-pressure
following th
pendence
ra of prisitin
olar spectra
irradiance (
O2; our blac
e H2 anneali
he literature
of magne
ne, TiO2-x an
al irradiance
(filled with
ck TiO2-x pr
ing (HP-TiO
e preparation
etization o
nd TiO2-X (
e (red line, S
canary yell
repared by
O2); N- and
ns.
of TiO2-X
(X = H, N, S
S in
ow,
X
S, I).
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Figure
and pris
6. Exp
Figure
Xe lamp
Hyd
Pyrex re
ultrason
sacrifici
in the su
S11. Magn
stine TiO2.
perimenta
S12. Exper
p irradiation
drogen prod
eaction cell
nic for 2 m
ial reagent.
uspension. T
netic field d
al details o
rimental setu
n and a clos
duction by p
l as shown
min in a 20
0.5% Pt we
Then the su
dependence
of H2 gene
up for H2 pr
sed gas circu
photocatalyt
in Figure S
00 mL aqu
ere loaded i
uspension w
8
of magneti
eration
roduction fr
ulation syst
tic H2 gene
S12. 100 m
ueous solut
in situ by im
was thorough
ization of T
rom water o
em.
eration was
g photocata
tion contain
mpregnation
hly degasse
TiO2-x, TiO2
over the pho
carried out
alyst powde
ning 40 mL
n 0.05 mL o
ed by pure N
2-I, TiO2-N
otocatalyst u
in a top-irr
er was disp
L methano
of H2PtCl6
N2 and irrad
, TiO2-S
under
radiation
ersed by
ol as the
(10 g/L)
diated by
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a 300 W
confirm
solution
determi
photoca
7. The
literat
Figure
H-doped
is TiO2-
W Xe lamp
med by UV-
n was maint
ned using
atalytic activ
Figure S1
e photoca
ure meth
S14. (a) U
d TiO2 (H:T
-H > H:TiO
p with 400
-vis absorpt
tained at roo
a gas ch
vities were c
13. Transm
atalytic ac
ods
UV-light and
TiO2) and o
O2 > TiO2 dri
0 nm cut-o
tion spectru
om tempera
hromatograp
compared b
ittance of th
ctivities o
d (b) visible
our TiO2@T
iven by UV
9
on filter. Th
um in Figu
ature by a fl
ph (Shangh
by the avera
he 400 nm c
of nonmet
e-light driv
TiO2-H (TiO
V or visible l
his filter ca
ure S13. Th
low of wate
hai, GC-79
age H2 evolu
cut-on filter
tal-doped
ven decomp
O2-H). The t
light.
an cut off
he temperat
er. The evolv
900, TCD,
ution rate in
used in our
titania p
osition of m
trend of pho
>99.9% U
ture of the
lved H2 amo
N2 carrie
n the first 3
r research.
prepared
methyl oran
otocatalytic
UV light,
reaction
ount was
er). The
h.
by the
nge over
c activity
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Figure
I-doped
TiO2-I >
Figure
S-doped
TiO2-S
TiO2-x >
Figure
N-doped
TiO2-N
TiO2-x >
S15. (a) U
d TiO2 (I:T
> TiO2-x > I
S16. (a) U
d TiO2 (S:T
> TiO2-x >
> TiO2 drive
S17. (a) U
d TiO2 (N:T
> TiO2-x >
> TiO2 drive
UV-light and
TiO2) and T
I:TiO2 > TiO
UV-light and
TiO2) and T
> S:TiO2 > T
en by visibl
UV-light and
TiO2) and T
> N:TiO2 > T
en by visibl
d (b) visible
TiO2@TiO2-
O2 driven by
d (b) visible
TiO2@TiO2
TiO2 driven
e light.
d (b) visible
TiO2@TiO2
TiO2 driven
e light.
10
e-light driv
-I (TiO2-I)
y UV or vis
e-light driv
2-S (TiO2-S
n by UV lig
e-light driv
2-N (TiO2-N
n by UV lig
ven decomp
. The trend
ible light.
ven decomp
S). The tren
ght while th
ven decomp
N). The tren
ght while th
osition of m
d of photoc
osition of m
nd of photo
he trend is
osition of m
nd of photo
he trend is T
methyl oran
catalytic ac
methyl oran
ocatalytic ac
TiO2-S > S
methyl oran
ocatalytic ac
TiO2-N > N
nge over
ctivity is
nge over
ctivity is
S:TiO2 >
nge over
ctivity is
N:TiO2 >
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11
8. References S1. Asahi, R.; Morikawa, T.; Ohwaki, T.; Aoki, K.; Taga, Y., Science 2001, 293, 269.
S2. Li, H.; Zhang, X.; Huo, Y.; Zhu, J., Environ. Sci. Technol. 2007, 41, 4410.
S3. Su, W.; Zhang, Y.; Li, Z.; Wu, L.; Wang, X.; Li, J.; Fu, X., Langmuir 2008, 24, 3422.
S4. Di Valentin, C.; Pacchioni, G.; Selloni, A.; Livraghi, S.; Giamello, E. J. Phys. Chem. B
2005, 109, 11414.
S5. Barolo, G.; Livraghi, S.; Chiesa, M.; Paganini, M. C.; Giamello, E. J. Phys. Chem. C 2012,
116, 20887.
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