I Io. Chemical Physics Letters: Votr N C

Votr~n~c
I IO.
number 1
CHEMICAL
THE MECHANIShl
PRODUCTION
OF PHOTOCATALYTIC
OF Hz AND ALDEHYDE
PHYSICS
LETTERS
REACTION
OVER Pt/l?02:
FROhf GASEOUS ALCOHOL
AND WATER
Maki KAWAI *:, Tornoji KAWAI **, Sbuichi NAITO and Kenzi TAMARU
I _ Introduction
The pbotocatalytic
reaction using smiconductor
powder as a catalyst 113sbeen one of tbc most important systc~ns
in the field of catalysis and solar-energy
conversion. In particular, hydrogen production from
alcoltofs and water over plafinized TX& is known to
be a very effective system for converting UV light to
energy in the form of hydrogen [ 1.2 J. III fact. the
quantum yield of Hz production from CH,OH and
If20 over PtfTi02 exceeds 40% for ~~~o~~ocI~ro~~~atIc
380 nnl iigllt 1I ] .
hi spite of tllc importance
of tllis reaction, tile
mcchnnism of tlxse photocatalytic
reactions has not
been studied in detail. ~urtIlerr~~orc~ tbc detcmining
fxtors for tbc activity and selectivity of this reaction
have not been elucidated. WC bavc rccentiy studied
tlx 11vx1m11isn1 of the photocatalytic
reaction between
gaseous n~clbanol and water over Pt/TiO, [3]. From
observation of IR spectra lt~ld from volumetric studies,
wc have show~i that Ihcrc arc time reaction paths coexisting in t&s system f3 1. Tbc reaction mec1m~ism.s
arc shown below.
(A) Direct reaction of pbysisorbcd CI1~OH with a
* ircscnt sddrcss:
Ruscarch Center, Osaka Gas Co. Ltd., 619-9 Torishima,

~onoII~lniI-~U, O&GI 554. Japan.
** Institute
crIS&ntific
2nd Industri;~I Rcscorclr. Osnkn University, Ibarnki. Osaka 567, Japan.
58
l~ole produced
pistol-l(g)
CH30H(ad)
on
the
semiconductor
--j. ~I~~~H~d~
+ 3p+
surfxe:
HCI-IO -I-2H+ ,
3-I+ + 2Z.e
- l-i-/_(B) CO, production process_ Reaction
Cl-l,O(ad) and -OH produced from H,O:
II,0
between
+ p -+ *OH -I-H+ ,
CH,OH(&
-+ CH,O(ad)
f H&d) .
CH30(ad)
I- 5 -01-I + CO2 + 4H,O
ii+ 3-c --f $I$ *

(C) Reaction
bctwcen
CH,OI-I and *OH:
H20+p--OH+H+,
In this paper, we have focused our attention on

the relat~ol~s~lip between the reactivity of various alcobols and the electronic state of tlte adsorbed species,
and found that the valence band levelsof the adsorbed
species are very important in determining the reactivity and selectivity of these reactions. This is because
tlte hole produced by irradiation of the catalyst read0 0092614/84/S
(Norti~-HoIIand
03.00 0 Elsevier Science Publisiiers

Physics Puhlisbing Division)
B.V.
Volun~e 110. nunlber 1
ClIEXlICAL
ily reacted with the species with a shallower

Icvel.
PIIYSLCS
energy
LETTERS
mlSTP
0.3-
2. Experimental
The Pt/TiO, catalysts were prepared
previously [3]. Platinum was supported
as described
on TiO-,
0.2-
(Aerosil P 25, n-type) by photodeposition

from aqueous K,PtCI,
solution. The catalyst, Pt/TiO, (2 wt%),
thus prepared
400C
was oxidized
by 100 Torr of 0,
for 20 h followed by evacuation
at
at 458C
for
1 11in a reactor before use. The reaction was carried
out using a closed glass circulation system and the
products were analyzed by gas chromatography.

The
light source for the photocatalytic
reaction was a 500
W Xe lamp (Ushio Electric Co.) or a 200 IV Xe lamp
giving ody wavelengths between 350 and 400 nm
through a colored glass filter. IR spectra were observed
by using an FT-IR (Nicolct
0.1 -
0
.
. co2
0)
1.0
Co.) spectrometer.
2.0
hr
TIME
3. Results and discussion

The photocatalytic
reactions of a series of alcol~ols
and water were examined by the volumetric method
and by IR measurement.
Compared with the reaction
of methanol, which was previously reported [3], the
reaction of ethanol showed quite different behaviour.
In fig. 1, the changes in the amount of reaction products when 2.8 cm Hg of C?H,OH and 0.1 cm Hg of
Hz0 vapor were introduced aver Pt/TiO, under irradiation are shown. As is shown in fig. 1) Hz 2nd
CHJCHO were produced at identical rates. No other
products, such as CO, or CH,, were detected in the
gas phase. This wx e&rely different from the reaction
of CH,OH and water, where CO, was produced in
addition to HCHO and H,. When gaseous ethanol and
water were trapped by liquid N1, the reaction immcdiately stopped, wlicll suggests that the physisorbed
species is active in this photocatalytic
reaction.
The influence of the I-I,0 vapor pressure on this
reaction was examined. Fig. 2a shows the rate of production of Hz and CH,CHO versus H20 pressure. Even
when the Hz0 pressure was changed by more than one
order of magnitude, the activity of H, and CH,CHO
production was independent
of the H,O vapor
pressure. Moreover, these products were not affected
11.
0,.
0.5
H,O
1.0
cmHg
PRESSURE
Fig. 2. The cffcct of 1110 lxcssurc

lytic reaction
bctwccn aIco11olsand
on the rate of pllotocatawater owr It/TiO-.. (a)
Solid lint. Rates of 112 (0) and C11$310 (0) prodaction lion1
ethanol and water. 13llanol press~~cwas 1.9 cnl 11~.(b)
Broken line. Ratcsol
II;
from alethanol and water.
(0)
and CO? (A X l/10) production

hlcthnol
prcssurc was 2.9 cm II::.
59
Volume 110. wmbcr
4000
CHEMICAL
PllYSlCS
.
3600
3200
2800
Wavenumbers
2400
(cm-)
2000
1600
by chnnges in the H,O pressure (fig_ ?a). On the

other hand, in the case of the reaction between methanol
and
water, Hz and CO2 production
rates depcndcd greatly on Hz0 pressure (fig. 2b), since they were
accclcrated via reaction paths (B) and (C) [3].
An IR spccrroscopic study showed that there are
physisorbed and cbernisorbed species of ethanol under
tlrc reaction conditions. Chemisorbed ethanol showed
absorption bands of the adsorbed ethoxy group
(fig.
3 j at 2975 and 2874 CIII -I due to the C-H stretching
vibration of Cl-I,, 2930 and 2850 IX-~ due to CH?
species, and at 1 120 cm-*
due to the C-O stretching.
The sharp IR band at 3733 cm-
due to the surface
011 of the Pt/TiO? catalyst decreased and the broad
1wru.l
around 3500 CI~-~
increased. This was due to
WI i~wease
in the surface hydrogen bonding by an incrcasc of the OH species on the surface by the absorption of ethanol
in the manner EtOH + EtO(ad)
+ OH(ad).
When the gas phase was trapped by liquid N?, the
physisorbed species desorbed and only the ethoxy
and the OH groups remained on the surface. These
surface cthoxy and OH groups were quite stable under
irradiation of the catalyst in the absence of water,
at 41
60
LETTERS
14 Scprcnlbcr
1984
where the IR spectra did not change in frequency or

in intensity. This shows that the surface ethoxy species (chemisorbed ethanol) itself was inactive under
the irradiation. This was similar to the case of methanol. Although the adsorbed ethoxy species reacted
with Hz0 to produce CH3CHO and Hz in the absence
of physisorbed or gaseous ethanol, this reaction did
not occur in the presence of gaseous ethanol. In the
case of methanol, the reaction between adsorbed
methoxy species and water took place even in the
presence of gaseous alcohol. From these observations,
we see that only reaction path (A) is dominant for
ethanol even in the presence of water, i.e. the reaction with -OH radicai (paths (B) and (C)) is negligibly
small in the ethanol-water
system.
For the photocatalytic
reaction between alcohols
and water, the reaction process can be divided into
four parts: (1) production and separation of an electron and a hole in a Pt/Ti02 particle by irradiation;
(2) diffusion of the electron and the hole to an active
site; (3) reaction between hole and the surface active
species (oxidation); and (4) reaction between H+ and
the electron to produce Hz (reduction).
The differences in the reactivity for the different alcohols used
in the photocatalytic
reaction ir. the presence of water
must be due to differences in process (3), because an
alcohol acts as the reducing agent in this reaction.
Since the reactive species in the presence of gaseous
alcohols and water were the physisorbed ones, process
(3) is considered to be strongly dependent on the electronic states of the physisorbed alcohoIs.
In fig. 4, the position of the peak maximum of the
valence band spectra of various alcohols obtained by
UPS are shown together with that of Hz0 [4,5] _These
values were taken from the literature, for alcohols on
CU(110) [4] and for Hz0 on Pt(lll)
[5]. These UPS
spectra were taken at 110 K for monolayer physisorbed
species. In a system where alcohol and water coexist,
it is more stable if a hole reacts with the species which
has the shallower donor level. Consequently,
in the
case of methanol and water, where the energy levels
of valence bands for the physisorbed species are similar as shown in fig. 4, a hole reacts with either methanol or water to almost the same extent. Accordingly,
a Hz0 pressure effect is observed, and reactions (A),
(B) and (C) take place siniultaneously.
On the other
hand, in the case of ethanol, where the donor level of
physisorbed ethanol is much shallower than that of
Ef
Table
T
-iso-PrOH
EtOH
MeOH
n-PrOH
Trrblc 1
.-t: 5.5
-0
.f
H20
6.0 -I
Hz0 (fig. 4). the Role reacts selectively wit13 ethanol

m3d the I-l20 pressure effect is not observed, and 0131~
production of CH3CHO and Hz occurs.
On the basisof this consideration,
the reactions be-
tween isopropanol and water, and iI-propanol and

water were examined. As shown in fig. 4, isopropanol
has a 1nuc11 shallower donor level and n-propanol has
a deeper level than H,O. A difference in tl3e Hz0 effect for these alcohols is espected. The results for tl3e
HZ0 pressure effect a33d tl3e kind of products are
shown in table I_ As expected, the reaction between
isopropanol and H,O did not show an HZ0 vapor pressure dependence, and the one between n-propanol
and HZ0 was strongly dependent 013 the HZ0 pres-
sure. Furthernlore,
for the alcohols that did not show
the I-I20 pressure effect, only the deliydrogenatcd
species and H, were obtained. Only CH,CHO (acetaldehyde) and Hz were produced in the case of ethanol
and water, and (CH&CO
(acetone) and H2 for isopropanol and water. On the other hand, for alcollols
with the Hz0 pressure effect, lower carbon-number
species such as CO2 were obtained (table 1). It is well
known that -OH and hi are produced when physisorbed HZ0 is oxidized with a hole in Pt/TiO, [6] _
These facts suggest that the HZ0 effect on the reactivity and the breaking of the C-C bond of alcol~ols is
connected with the -OH.
The reactiorl mechanisms for the different kinds of

alcohols we have discussed are sumniarized in table 2.
There arc two types of reacrion mechanism in the
photocatalytic
reaction of alcohols and water over
Pt/TiO?. One is the direct reaction of a physisorbed
alcohol species with the hole . The other is the reaction of the adsorbed species with the *OH which is
produced by the oxidation of adsorbed Hz0 by the
hole. In the direct reaction with a hole, aldehyde and
H, were produced. On the other hand, in the reaction
with *OH. further oxidized species such as CO, were
produced. These selectivities are controlled by the relative energy position of the adsorbed alcol~ols against
that of H,O.
4. Conclusion
In the photocatalytic reaction between alcollols
and water, the reaction is initiated by the oxidation
In the
direct
in table 1,
reactioli of physisorbed ~llcol~Asa13dthe ltolc
the current doublii
process wn be included.
61
Volume 1 IO. number 1
CHEMICAL
of the physisorbed species (alcohols and water) by a

hole, and that hole selectively reacts with the physisorbed species which has a shallower donor level. Consequently, for alcohols which have a shallower donor
level than H20, direct reaction of physisorbed alcohol species with the hole dominates, and for alcohols
with deeper donor levels, the hole reacts with Hz0 to
produce -OH. The adsorbed alcohol species then reacts with this radical to produce aldehydes. The selectivity of these reactions is reasonably understood by
taking this phenomenon
into consideration_ The -OH
also reacts with the chemisorbed species and produces
some smaller carbon-number
products or CO?. In the
case of methanol, -OH reacted with methoxy and
produced CO2 and Hz. Here we have found that the
valence bar.3 energy level of the physisorbcd species
PHYSICS LETTERS
14 September
1984
is one of the most important factors determining the

activity and selectivity of photocatalytic
reactions between alcohols and water.
References
[ l] T. Ikwai and T. Sakata, J. Chem. Common. (1980) 694.
[2] P. Pichat, J.-M. Hcrrmann, J. Diddier, H. Courbon and
M.-N. hfozzanga, Now. J. Chim. 5 (1981) 627.
[ 31 31. Kawai, T. Kawai, S. Naito and K. Tamaru, Chem.
Phys. Letters 98 (1983) 377.
[4] M. Bowker and R.J. hladh, Surface Sci. 95 (1960) 190;
116 (1982) 549.
[5 ] C.B. Fisher and J.L. Gland, Surface Sci. 94 (1980) 446.
[6] C.D. Jaeger and A.J. Bard, 3. Phys. Chem. 83 (1979)
3146.

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Votr~n~c

FROhf GASEOUS ALCOHOL

Ruscarch Center, Osaka Gas Co. Ltd., 619-9 Torishima,

I- 5 -01-I + CO2 + 4H,O

ii+ 3-c --f $I$ *

CH,OI-I and *OH:

In this paper, we have focused our attention on

03.00 0 Elsevier Science Publisiiers

Volun~e 110. nunlber 1

ily reacted with the species with a shallower

(Aerosil P 25, n-type) by photodeposition

for 20 h followed by evacuation

products were analyzed by gas chromatography.

by using an FT-IR (Nicolct

3. Results and discussion

Fig. 2. The cffcct of 1110 lxcssurc

on the rate of pllotocatawater owr It/TiO-.. (a)

and CO? (A X l/10) production

Volume 110. wmbcr

by chnnges in the H,O pressure (fig_ ?a). On the

where the IR spectra did not change in frequency or

Hz0 (fig. 4). the Role reacts selectively wit13 ethanol

tween isopropanol and water, and iI-propanol and

The reactiorl mechanisms for the different kinds of

reactioli of physisorbed ~llcol~Asa13dthe ltolc

the current doublii

Volume 1 IO. number 1

of the physisorbed species (alcohols and water) by a

is one of the most important factors determining the

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