DIPARTIMENTO DI CHIMICA FISICA

ED ELETTROCHIMICA

Effects of surface modification and doping on

the photocatalytic activity of TiO2

Elena Selli
elena.selli@unimi.it
 TiO2 electronic excitation

Reduction
A
Conduction A + e-CB A-
band -
O2 ads + eCB O2ads

A-
Energy

hn Eg
D
Oxidation
Valence D + h+VB D+
band
+
OHads + h+VB OH
D+ ads

Recombination
e-CB + h+VB heat
 Main Applications

Down-hill reactions, e.g. oxidative

degradation

Up-hill reactions, e.g. water splitting

 TiO2 modification

The photocatalytic efficiency of semiconductors is greatly

affected by surface modifications, by altering
The adsorption properties of inorganic and organic species
Electron transfer paths occurring at the semiconductor
surface under irradiation

Effects of
Noble metal particles deposition
Surface fluorination and doping with fluorine

Investigated reactions
Photocatalytic degradation of organic molecules
Hydrogen production from water vapour
 TiO2 preparation and characterization

Sol-gel synthesis
Synthetic methods
Flame spray pyrolysis

Deposition-precipitation (DP)
Surface modification Deposition of stabilised noble
by NM deposition metal (NM) nanoparticles
Photodeposition

XRD
HRTEM
Characterization DR UV-vis spectroscopy
XPS
BET
photocatalytic activity tests
 Down-hill reactions:
Photocatalytic oxidative degradation on TiO2

Acid Red 1 (AR1)

Formic Acid (FA)
OH NHCOCH 3
HCOOH
N=N

Ion
SO3Na
SO3Na
Chromatography
Spectrophotometric analysis
0.7
lmax = 531 nm
0.6 Evolution of H2O2,
0.5
generated from O2 reduction by eCB
Absorbance

0.4

0.3

0.2
Indirect spectrofluorimetric
0.1 analysis
0.0
200 300 400 500 600 700 800
l (nm)
 Photocatalysis on Au/TiO2
2H+

CB e- Au H2
hn
TiO2
Bandgap

H 2O

VB h+ 1/2 O2 + 2H+

Gold metal nanoparticles capture photopromoted

electrons because their Fermi level is lower than CB of TiO2

efficiency of electron- interface electron

hole pairs separation transfer
 Au/TiO2 characterisation

Uv-vis diffuse reflectance spectra

2.5 DP 2.5%
DP 0.5%
DP 0.38%
DP 0.13%
2.0
DP 0.06%
DP 0%
P25
1.5
A

1.0

0.5

0.0
200 300 400 500 600 700 800
l (nm)

Au weight PERCENT
PLASMONIC BAND
(550 nm) Au nanoparticles DIMENSIONS
 HRTEM

NaBH4 1%

H2 1.3 %

DP 0.5%

DP UREA 0.5%
 AR1 photodegradation
NaBH4 SERIES
k0 /k0 P25
DP urea H2 SERIES
1.00 0.98
1.0 DP SERIES SERIES
0.91 0.90
0.9 0.85
0.79 0.79
0.8 0.76 0.76
0.74
0.69 0.68
0.7 0.66 0.64
0.61
0.6

0.5

0.4

0.3

0.2

0.1

0.0
P25 DP DP DP DP DP DP UREA UREA UREA NaBH4 NaBH4 H2 H2 H2
0% 0.06% 0.13% 0.38% 0.5% 2.5% 0% 0.5% 2.5% 0% 1% 0% 1.3% 1.3%
150C 200C

No Au/TiO2 sample more efficient than P25

Negligible Au deposition effects

M.V. Dozzi, L. Prati, P. Canton, E. Selli, PCCP, 2009, 11, 7171

 H2O2 evolution during AR1 photodegradation

10
P25
DP 0%
DPU 0%
8
DPN 0%
DPH 0%
[H2O2].105(M)

DP 0.5%
6
DP 2.5%
DPU 2.5%

0
0 2000 4000 6000 8000 10000 12000 14000 16000
time (s)

Increase in H2O2 production rate in the presence of gold

nanoparticles

Controversial effect of Au on TiO2: favored eCB- transfer to O2

leading to H2O2, but not parallel increase of AR1 photodegradation
 HCOOH photocatalytic mineralization
0 0
k /k P25 NaBH4 H2 SERIES
1.6 SERIES
1.44
1.36
1.4
DP SERIES
DP UREA 1.13
1.2 SERIES
1.05 1.04 1.08
1.00 1.01
1.0 0.93 0.88
0.85
0.81 0.78
0.8
0.61
0.6 0.53

0.4

0.2

0.0
P25 DP DP DP DP DP DP UREA UREA UREA NaBH4 NaBH4 H2 H2 H2
0% 0.06% 0.13% 0.38% 0.5% 2.5% 0% 0.5% 2.5% 0% 1% 0% 1.3% 1.3%
150C 200C

Best performance for NaBH4 and H2 reduced Au/TiO2 samples

Calcination at 450C reduces the photocatalytic activity
Beneficial role of Au in HCOOH degradation
Optimal Au loading
 H2O2 evolution during FA photodegradation
30 105 [H2O2]max/M
P25
DP 0%
25 DP 0.06%
DP 0.13%
AR1 FA
DP 0.38%
20 P25 2.9 0.07
[H2O2]105 (M)

DP 0.5%
DP 2.5% DP 0.06% 3.2 0.52
15
DP 0.13% 3.6 1.1

10 DP 0.38% 4.1 21.7

DP 0.5% 7.9 27.9
5 DP 2.5% 7.4 24.4
DPU 2.5% 3.8 26.9
0
0 2000 4000 6000 8000 10000 12000 14000 DPN 1% 3.3 25.4
time (s)
DPH 1.% 2.4 0.61

No H2O2 could be detected during FA mineralization on bare TiO2

Relatively high H2O2 amounts, increasing with gold content up to
0.5%, could be detected on Au/TiO2
H2O2 concentrations much higher than those detected during
AR1 degradation were attained

M.V. Dozzi, L. Prati, P. Canton, E. Selli, PCCP, 2009, 11, 7171

 HCOOH photomineralization mechanism

Prevailing photodegradation mechanism:

direct oxidation through valence band
holes at the TiO2 surface

HCOO-ads + h+VB CO2- + H+

CO2- + O2 CO2 + O2-

Reduction path:

O2 + e-CB O2-
O2- + e-CB + 2 H+ H2O2
 AR1 photodegradation mechanism

PROCESS MEDIATED BY OH RADICALS

h+VB + H2O OH + H+
E (V)
vs NHE
pH 7

RED-OX at Au/TiO2 interface -0.50 eCB
-0.33 O2 /O2

Au0 AuI oxidation

+1.68 Au 0 /Au
h+VB + Au Au+ +1.99 OH / OH

OH + H+ + Au Au+ + H2O
+2.64
hVB

AuI Au0 reduction

AR1
e-CB + Au+ Au
PHOTODEGRADATION
INHIBITED
 Limiting factors of TiO2 photocatalytic efficiency

1. The band gap of TiO2 is 3.2 eV, i.e. it absorbs light in the UV
region, so that only a small portion (5%) of the sunlight can
be used for photocatalytic processes.

ANION DOPING with p-BLOCK elements (B, C, N )

inserted in the TiO2 structure

POSSIBLE CREATION OF DIFFERENT TYPES OF INTRA BAND GAP STATES

 Preparation of S/F doped TiO2

Sol gel synthesis

S-doped TiO2 F-doped TiO2

Dopant: Thiourea Dopant: NH4F

Reference
Undoped TiO2
E_0 series
Dopant/Ti molar ratio Calcination
20 500 C
8 600 C
2 700 C

M.V. Dozzi, S. Livraghi, E. Giamello, E. Selli,

Photochem. Photobiol. Sci. 2011, 10, 343
 Characterisation of S/F doped TiO2

XRD analysis

F_20_700

F_20_600

F_20_500

20 30 40 50 2q 60 70 80

E_0_700

Both types of doping

inhibit the phase transition
E_0_600

from anatase into rutile

E_0_500

20 30 40 50 2q 60 70 80
 Characterisation of S/F doped TiO2

HRTEM analysis

F_20_700 E_0_500
 Characterisation of S/F doped TiO2
BET analysis
Surface area decreases with increasing calcination temperature
Doping seems to limit particles sintering effects, especially in case
of samples calcined at 500C

2 -1 B.E.T Specific Surface Area OF F - DOPED TiO2 SAMPLES

SSA (m g )
80.0
500C
63
600C
60.0 700C

43
40.0
31
23 21
20.0 15 16
12 12
9 7 6

0.0
E_0 F_20 F_8 F_2
Photoactivity of S/F doped TiO2 in FA degradation
0 7 -1
k 10 (Ms ) F - DOPED
3.0 500C TiO2
600C
2.5 700C
2.0 2.0
2.0 UNDOPED S - DOPED
TiO2 TiO2
1.5
1.0
0.9
1.0 0.9
0.7
0.6
0.5 0.5
0.4 0.4 0.4 0.4 0.4
0.5 0.4 0.3 0.3 0.3 0.4
0.1 0.1
0.0
E_0 S_20 S_8 S_2 F_20 F_8 F_2

S-doped TiO2 show a photocatalytic activity quite similar to that of

undoped materials. Insertion of S appears rather difficult
Beneficial role of F-doping: bulk modification of TiO2
Reaction rate increase with increasing calcination temperature:
high cristallinity of F-TiO2 samples composed of pure anatase
thermal energy can trigger the introduction of F- for O2-
low surface area and possible formation of Ti3+ centers

High doping levels limit photoactivity

 EPR characterisation

Detected species:
nitric oxide (NO) radical in
micro-voids
S20-500
?
nitrogen atoms (N) trapped in
S20-600
the bulk
3+
Ti (I)
S20-700 Ti3+ species
*10

3250 3300 3350 3400 3450 3500 3550 3600

B/Gauss 10mw 77K

F_2 S_2
E F_8 F_2 S_8 S_2
EPR spectra of S-doped samples at 77 K 0 0
NO NO
NO NO
500C - N N NO NO
Ti3+ N
Ti3+ Ti3+
N NO NO NO
600C - NO NO
Ti3+ Ti3+ Ti3+ Ti3+

M.V. Dozzi, S. Livraghi, E. Giamello, E. Selli, NO NO NO

700C - NO NO Ti3+
Photochem. Photobiol. Sci. 2011, 10, 343 Ti3+ Ti3+ Ti3+
 Photoactivity of NH4F-doped TiO2

LIQUID PHASE GAS PHASE

ACETIC ACID PHOTOOXIDATION ACETALDEHYDE PHOTOOXIDATION
1.5 8
P25 500C P25 500C
rate (mmolCO2 min )

A45 600C 600C

-1

1.2 A45
6 5.5

rate102 (min-1)
JRC-8 1.0 700C 700C
0.9 4.7
0.9 0.9
4.0 4.1
0.7 0.6 4 3.6 3.4 3.5
0.6
0.6 3.1 3.0
0.6 0.5
0.4 0.4 0.4 0.4 0.5
0.3 0.3 0.3 1.6 1.7
0.3 2 1.1
1.5 1.3
0.3 0.2 1.2 1.1
0.3
0.0 0
Commercial D_0 D_3 D_5 D_12 D_25 Commercial D_0 D_3 D_5 D_12 D_25

Beneficial effect of NH4F doping

Reaction rate increase with increasing calcination temperature:
NH4F - doping inhibits the anatase into rutile phase transition
high crystallinity of NH4F-TiO2 samples composed of pure anatase

Home made NH4F-doped samples more active than commercial ones

Too high doping levels limit the TiO2 photoactivity

M.V. Dozzi, B. Ohtani, E. Selli, PCCP, 2011, 13, 18217

 Action spectra analysis: AcOH photooxidation
CH COOH 2 O 2 CO 2 H O
3 2 2 2

Substrate: transparent acetic acid

Wavelength range: 370-460 nm
Samples: D_5, D_12 and D_25
Wavelength step: 10 nm
20 20
20
D_5_500 D_12_500 D_25_500
15 D_5_600 D_12_600 15 D_25_600
15

Fapp (%)
Fapp (%)

D_5_700 D_12_700 D_25_700

Fapp (%)

10 10
10

5 5
5

0 0
0
360 370 380 390 400 410 420 430 440 450 460 470 360 370 380 390 400 410 420 430 440 450 460 470
360 370 380 390 400 410 420 430 440 450 460 470
l (nm) l (nm)
l (nm)
1.0 1.0 1.0
D_5_500 D_12_500 D_25_500
0.8 0.8 D_12_600 0.8 D_25_600
D_5_600
Absorption
Absorption

Absorption
D_5_700 D_12_700 D_25_700
0.6 0.6 0.6

0.4 0.4 0.4

0.2 0.2 0.2

0.0 0.0 0.0

250 300 350 400 450 500 550 250 300 350 400 450 500 550 250 300 350 400 450 500 550
l (nm) l (nm) l (nm)
 DRS spectra: comparison model vs. calculation
BAND A BAND B

500C 0 Maximum
Active BAND A (365 nm)
600C Small Small Inactive BAND B (420 nm)
700C Maximum 0

0.3 0.3
D_5_500 D_12_500
BAND B
BAND B D_5_600 D_12_600
BAND A

Absorption
Absorption

0.2 D_5_700 0.2 D_12_700

BAND A

0.1 0.1

0.0 0.0
300 350 400 450 500 550 300 350 400 450 500 550
l (nm) l (nm)
0.3
BAND B D_25_500
BAND A
D_25_600
Absorption

0.2
D_25_700 Experimental action spectra
results well fit with the
0.1
qualitative model
0.0
300 350 400 450 500 550
l (nm)
 Correlation between DRS and action spectra
Subtraction of the action spectra obtained with samples calcined at 500C
from those obtained with samples calcined at 600 and 700C
6.0 6.0
D_5_700 - D_5_500 D_12_700 - D_12_500

4.0 D_5_600 - D_5_500 4.0 D_12_600 - D_12_500

D Fapp (%)
D Fapp (%)

2.0 2.0

0.0 0.0

-2.0 -2.0
360 380 400 420 440 460 360 380 400 420 440 460
l (nm) l (nm)

6.0 Band B absorption in the Vis

region is not photoactive in AcOH
D_25_700 - D_25_500
4.0 D_25_600 - D_25_500
decomposition
D Fapp (%)

2.0
Band A is responsible for the
0.0 enhanced photoefficiency obtained
-2.0 with samples calcined at 700C
360 380 400 420 440 460
l (nm)
 Conclusions

Photoactivity improvement of F-doped materials must be related to

bulk modifications that ensure a better charged separation, most
probably related to high crystallinity; in fact only surface
fluorination was shown to produce a marked decrease of FA
oxidation rate

Inactive band B, being most evident in the absorption spectra of

doped samples calcined at 500C and decreasing in intensity with
increasing the calcination temperature, can safely be attributed to
nitrogen doping

Band A, and the activity in acetic acid decomposition, increased

with increasing the calcination temperature. It might be attributed
to extrinsic absorption originating from surface oxygen vacancies or
surface defects

M.V. Dozzi, B. Ohtani, E. Selli, PCCP, 2011, 13, 18217

 Up-hill reactions: photocatalytic water splitting

TiO2 H2O (pH 7)

anatase
-1
- ECB
2H+ -0,5 4H+ + 4 e- 2H2
e-
CB e- 0
hn

Potential / V V
H2
TiO2 0,5
2H2O O2 + 4H+ + 4e-
hn
Bandgap 1

H 2O 1,5
e-
2
VB h+
1/2 O2 + 2H+ 2,5 + E
VB

TiO2 1
H 2O 2 h H 2 O 2 G = +237 kJ mol-1
2
Reforming of organics
G 9.3 kJ mol 1
h
CH 3OH H 2O 3 H 2 CO 2
 HRTEM analysis

Flame-made TiO2 photocatalyst

containing 0.5 wt.% Pt

e e e
e e
5 nm
FP-0.5%Pt/TiO2 EF
h NM
B

h
TiO2
1.0 wt.% Ag deposited on P25 TiO2

5 nm 1%Ag/TiO2
 TEM investigation of Au/TiO2

FP- 1 wt% Au/TiO2 THPC 1 wt% Au/TiO2

 Photocatalytic H2 production from vapor

H2 in A = Photoreactor
H2 out E2
B = Photocatalyst
hn bed
emission spectrum
Cthe
of =light
Pyrex-
source glass
window

Counts / a.u.
E1 PI
TI D = GC or QMS
detector
D
F = pump
H2O out
M N
N2 out G = thermostated
L 340 360 380 400 420 440 460
bubbler
l nm

H
30C N2 in C Reaction conditions:
B 14 mg of catalyst on
F G A sieved quartz
T = 60C
H2O in P = 1.2 bar
Feeding mixture:
40 ml min-1 of 1.8%
CH3OH/3.1% H2O/N2

G. L. Chiarello, L. Forni, E. Selli, Catal. Today, 2009, 144, 69

 Effects of methanol addition and of Au on TiO2

20
purging
Reforming of organics
FP-Au/TiO2
CH x H 2O H 2 CO 2
in the dark h
16
mmol H2 / g catalyst

12

8 In the presence of methanol, the H2

production rate increased up to 60
4
FP-TiO2 times for FP-TiO2 and up to 150 times
for FP-1% Au/TiO2 photocatalysts
0
0 1 2 3 4 5 6 7 8
irradiation time / h
ca 200 Nml H2 gcat-1 h-1
in H2O + 6 vol% CH3OH

Photocatalyst H2 production
Relative Relative rate with respect
rate
(mol H2 g-1 h-1) rate to H2O splitting

TiO2 (P25) 160 1.0 56

FP-TiO2 290 1.7 59
FP-1%Au/TiO2 7900 46.8 151

G.L. Chiarello, L. Forni, E. Selli, Catal. Today, 2009, 144, 69

 Reaction Sequence

hn , TiO
CH3OH
2 H2CO + H2 (1)

hn , TiO
H2CO + H2O
2 HCO2H + H2 (2)

hn , TiO
HCO2H
2 CO2 + H2 (3)

hn , TiO
H2CO
2 CO + H2 (4)

hn , TiO
2 CH3OH
2 HCO2CH3 + 2 H2 (5)

hn , TiO
2 CH3OH
2 CH3CHO + 2 H2 (6)

hn , TiO
2 CH3OH
2 CH3OCH3 + H2O (7)
 Time Profile of Products Evolution

25 350
H2
CO2 300
20
CO 250
15
mmol gcat-1

GC peak area
200

10 150
H2CO
100
5 HCO2H
50

0 0
0,0 0,5 1,0 1,5 2,0 2,5 0,0 0,5 1,0 1,5 2,0 2,5
Irradiation time / h Irradiation time / h

H2, CO2 and CO accumulate at constant rate in the re-circulating gas

phase
H2CO and HCOOH were identified in the gas phase, but they did not
accumulate there, but in the liquid phase

G. L. Chiarello, M. H. Aguirre, E. Selli, J. Catal., 2010, 273, 182

 Production rates and selectivity

Selectivity in relation to H2 production

Production rate / mmol h-1 gcat-1
/%
Photocatalyst H2 CO2 CO H2CO HCO2H CH4 CO2 CO H2CO HCO2H Sum
TiO2 0.36 0.013 0.032 0.25 tr. 9.1 10-4 10.7 17.7 69.4 - 98
FP-TiO2 0.72 0.022 0.044 0.48 tr. 7.6 10-4 9.1 12.2 67.0 - 88
1%Ag/TiO2 1.17 0.032 0.056 0.81 0.06 1.1 10-3 8.2 9.6 68.8 11.0 98
1%Au/TiO2 13.30 1.61 0.479 5.17 0.84 1.2 10-3 36.3 7.2 38.9 12.7 95
1%Au-
1%Ag/TiO2
12.82 1.24 0.603 5.23 1.11 1.6 10-3 29.0 9.4 40.8 17.3 96

1%Pt/TiO2 18.60 2.88 0.468 7.16 1.23 8.7 10-3 46.4 5.0 38.5 13.2 103
0.5%Pt/TiO2 7.75 0.45 0.322 4.40 0.58 4.4 10-3 17.5 8.3 56.7 14.9 98
0.5%Pt/FP-TiO2 8.36 0.70 0.190 4.65 0.49 2.8 10-3 25.1 4.6 55.6 11.8 97
FP-0.5%Pt/TiO2 14.23 1.02 0.078 7.85 1.44 2.3 10-3 21.6 1.1 55.1 20.3 98

3 rCO2
SCO2 100 Good mass balance agreement !
rH2

G. L. Chiarello, M. H. Aguirre, E. Selli, J. Catal., 2010, 273, 182

 H2 production rate and selectivities
100 20
rH2

rH2 / mmolH2 h-1 gcat-1

80 SCO2 16

Selectivity / %
SCO
60 12

40 8

20 4

0 0

0. Pt/ 2
Au iO2
-A iO2

t/T 2
2
Ag O2

-0 P- 2
Pt 2
2
1% /TiO

0. 5% TiO
iO

FP t/F iO

% iO
iO
1% Ti
1% /T
Au /T
-T

.5 T
/T
g
FP

5% P
P
rH2 greatly increased upon NM deposition
Ag (F = 4.74 eV) is the poorest co-catalyst, followed by Au (5.31 eV) and Pt (5.93 eV)
rH2 doubled upon doubling the Pt amount on TiO2
FP-made photocatalysts perform better than those prepared by deposition of NM nanoparticles
 Effects of doping and of NM loading

NH4F-doped TiO2 The rate of H2 and CO2

production greatly increased
upon 0.5 wt.% Au or Pt
nanoparticles deposition
H2 CO2 CO
20 Pt is a better co-catalyst
0.6
Au or Pt/P25 compared to Au, in
16 NAKED 0.4
agreement with the work
rate / mmol h-1 gcat-1

0.2
function values (Pt) = 5.93
12 D0 D5 D7 D12 P25
0.0 Pt/TiO2 eV and (Au) = 5.31 eV
Doping of TiO2 enhanced
8 the H2 production rate, with
an identical bell-shaped
Au/TiO2
4
trend with increasing the
dopant content for the
naked, Au- and Pt-modified
0
titania series
25
0

12

25
12
u/D

u/D

u/D

t/D

t/D

t/D

u/P
u/D

t/D

t/P

5% NH4F-doped TiO2 (D5)

%P

%P

%P
%A

%A

%A

%P

%P
%A
%A

0. 5

0. 5

0. 5

was the best photocatalyst

0. 5

0. 5

0. 5

0. 5

0. 5
0. 5
0. 5

within each series

 Effect of methanol molar fraction x

rH2 SCO2 SHCO2H

100 20 100 20
FP-0.5%Pt / TiO2 1%Au / TiO2

rH2 / mmolH2 h-1 gcat-1

rH2 / mmolH2 h-1 gcat-1

80 16 80 16
Selectivity / %

Selectivity / %
60 12 60 12

40 8 40 8

20 4 20 4

0 0 0 0
0. 5
0. 9
0. 3
0. 7
0. 0
0. 9
0. 0
0. 0
0. 0
0. 4
1. 6
0

0. 5
0. 9
0. 3
0. 7
0. 0
0. 9
0. 8
0. 0
0. 0
0. 4
1. 6
0
00
00
02
04
10
22
40
64
80
89
95
00

00
00
02
04
10
22
30
64
80
89
95
00
0.

0.
CH3OH molar fraction (x) CH3OH molar fraction (x)

SSA = 70 m2 g-1 SSA = 48 m2 g-1

53% anatase, 47% rutile 80% anatase, 20% rutile

G. L. Chiarello, M. H. Aguirre, E. Selli, J. Catal., 2010, 273, 182

 Effect of methanol molar fraction x
FP-0.5%Pt/TiO2
20

H2 10
H2CO
16
8

g cat
g cat

-1
-1

12

-1
-1

rate / mmol h
rate / mmol h

8
4

4 2

0 0
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0

CH3OH molar fraction CH3OH molar fraction

2,5 2,5

HCO2H CO2
2,0 2,0
g cat

g cat
-1

-1
1,5 1,5
-1

-1
rate / mmol h

1,0
rate / mmol h
1,0

0,5 0,5

0,0 0,0
0,0 0,2 0,4 0,6 0,8 1,0 0,0 0,2 0,4 0,6 0,8 1,0

CH3OH molar fraction CH3OH molar fraction

G. L. Chiarello, M. H. Aguirre, E. Selli, J. Catal., 2010, 273, 182

 Reaction Mechanism

H2Oads + h+VB OHads + H+ads

H 2 CO (g)
CH 3 OH (g)

HCO 2 H (g)

CH 3 OH ad H 2 CO ad HCO 2 H ad CO 2 ad CO 2 (g)

h VB + (or OH) h VB + + H 2 O ad h VB + (or OH)

TiO 2 surface
(or OH )
H+ (or H 2 O) H + (or H 2 O) H + (or H 2 O)

2 H+ads + 2 e-CB H2
G. L. Chiarello, D. Ferri, E. Selli, J. Catal., 2011, 280, 168
 Reaction Mechanism

By assuming that
the rate of each oxidation step occurring on the photocatalyst
surface is the sum of the rates of the direct and of the hydroxyl-
radical mediated paths
the steady state concentration of photopromoted electrons equals
that of photoproduced holes
the intermediate surface coverage can be expressed according to
the Langmuir adsorption isotherm
the activity coefficients can be calculated by the van Laar equation
an expression is obtained for the rate of the oxidation products
formation via the OH radical mediated path with a maximum located
at very low x values, followed by a decay trend with increasing x.
The hole-mediated oxidation path exhibits a typical saturation
behaviour with increasing x.
A water-mediated path is at work!

G.L. Chiarello, D. Ferri, E. Selli, J. Catal., 2011, 280, 168

 Effect of methanol molar fraction x
10 10
H2CO _ FP-0.5%Pt / TiO2 H2CO _ 1%Au / P25
8 8
rate / mmolH CO h-1 gcat-1

-1
rate / mmolH CO h gcat
-1
6 6
2

2
4 4

2 2

0 0
Each elementary step
2.0 HCO2H _ FP-0.5%Pt / TiO2 2.0 HCO2H _ 1%Au / P25 occurs through either
-1
-1

rate / mmolHCO H h gcat an indirect OH radical

rate / mmolHCO H h gcat

1.5 -1 1.5
-1

mediated path (.)

2
2

1.0 1.0

0.5 0.5 a hole mediated direct

0.0 0.0
path (-----)
2.5
CO2 _ FP-0.5%Pt / TiO2
3.0 CO2 _ 1%Au / P25
a water assisted path
(_ _ __ )
-1

-1

2.5
rate / mmolCO h gcat

rate / mmolCO h gcat

2.0
-1

-1

2.0
2

1.5
2

1.5
1.0
1.0
0.5
0.5

0.0 0.0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
CH3OH molar fraction CH3OH molar fraction

G.L. Chiarello, D. Ferri, E. Selli, J. Catal., 2011, 280, 168

 Acknowledgements

Thank you!
Cariplo Foundation for financial support