Supporting Information Effective Nonmetal Incorporation in ... · PDF fileSupporting...

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

Electronic Supplementary Material (ESI) for Energy & Environmental ScienceThis journal is © The Royal Society of Chemistry 2013

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


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


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-


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,


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


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).


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


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


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 >


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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