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18 August 1995
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CHEMICAL
PHYSICS
LETTERS
ELSEVIER Chemical PhysicsLetters 242 (1995) 315-319

Titanium(IV) oxide photocatalyst of ultra-high activity for

selective N-cyclization of an amino acid in aqueous suspensions
Bunsho Ohtani a, Kunihiro Iwai a, Hiroshi Kominami h, Takeshi Matsuura b,
Yoshiya Kera b, Sei-ichi Nishimoto a
" Division of Energy and Hydrocarbon Chemistry, GraduateSchool of Engineering, Kyoto University, Kyoto 606-01, Japan
b Departmentof Applied Chemistry, Faculty of Science and Engineering, Kinki University, Kowakae, Higashiosaka 577, Japan
Received 2 March 1995; in final form 26 June 1995

Abstract

Titanium(IV) oxide (TiO 2) powder was prepared by the high-temperature hydrolysis of titanium(IV) tetrabutoxide in
toluene as anatase crystaUites of average diameter ~ 15 nm. They were platinized by impregnation from aqueous
chloroplatinic acid solution followed by hydrogen reduction. The catalyst was suspended in an aqueous L-lysine (Lys)
solution and photoirradiated under argon at ambient temperature to obtain L-pipecolinic acid (PCA). Among several
platinized commercial TiO 2 powders, the present TiO 2 showed the highest photocatalytic activity for both Lys consumption
and PCA production. This result is attributed to both the higher activity owing to the larger surface area with lesser defects
and the higher dispersion of platinum deposits acting as an efficient reduction site for a Schiff base intermediate into PCA.

1. I n t r o d u c t i o n In a previous investigation, the authors suggested

Among many kinds of semiconducting materials
used as photocatalyst, titanium(IV) oxide (TiO 2)
powders have been used widely and successfully
[1,2]. The photocatalytic activities of almost all the
known crystal structures of TiO2: anatase [3-8],
rutile [9-11], brookite [12] and TiO2(B) [13], as well
as its amorphous form [14,15], have been examined.
Generally, powders containing anatase or brookite
crystallites show relatively higher activity while ru-
tile shows lower or negligible activity. However, it is
also welt known that a significantly large difference
in photocatalytic activity can be seen among parti-
cles of the same crystal structure, indicating that
factor(s) other than crystal structure may be domi-
nant for photocatalytic activity.
a rate expression for TiOE-induced photocatalytic
reactions as a function of the rates of electron-posi-
tive hole recombination and the capture of a pho-
toexcited electron and positive hole by surface-ad-
sorbed substrates [11,16-18]. In this context, the best
photocatalyst should be of large surface area to
adsorb a larger amount of substrates and, at the same
time, of small surface area to prevent recombination,
since the electron-positive hole recombination may
proceed preferentially at the particle surface and,
thereby, be enhanced by an increase in surface area.
As a result, amorphous TiO 2 without crystallites of
anatase a n d / o r rutile shows negligible photocatalytic
activity when suspended in aqueous alcoholic solu-
tions despite its large surface area [14,15], presum-
ably due to the greater number of surface sites

0009-2614//95/$09.50 1995 Elsevier Science B.V. All rights reserved

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316 B. Ohtani et a L / Chemical Physics Letters 242 (1995) 315-319

inducing recombination. These contradictory claims
require us to prepare TiO 2 crystallites of well-bal-
anced structure, being well grown but of small parti-
cle size.
One of the most convenient and popular methods
of TiO 2 preparation is the precipitation of
titanium(IV) hydroxide from titanium(IV) halide or
alkoxide followed by dehydration into TiO 2 at high-
temperature calcination. The latter process leads to
dehydration and the growth of crystallites (predomi-
nantly anatase); both crystallite content and particle
size increase by the calcination. Furthermore, the
calcination induces a crystal transformation from
anatase into rutile, decreasing the activity as de-
scribed above. Therefore, it seems difficult to obtain
small but well grown (anatase) crystallites by this
conventional liquid-phase process. Some of the pre-
sent authors have found that the high-temperature
hydrolysis of titanium alkoxide with a small amount
of water dissolved in organic solvents leads to the
formation of ultra-small particles of TiO 2 [19]. In the
organic solvent, crystallite growth of small TiO 2
particles produced by hydrolysis would be sup-
pressed and the dehydration of each particle en-
hanced to yield small anatase crystallites with fewer
defects. Furthermore, the TiO 2 particles retain their
larger surface area, i.e. smaller particle size, even
after post-preparation annealing at high temperature,
suggesting successful photocatalytic activity. This
Letter describes the results of the photocatalytic reac-
tion by TiO 2 particles and shows significantly higher
activity for the production of a cyclic amino acid in
their aqueous suspension.
2. Experimental
TiO 2 powder was synthesized by the high-tem-
perature hydrolysis of titanium tetrabutoxide (TNB)
dissolved in an organic solvent such as toluene [19].
The method will be called hydrothermal crystalliza-
tion in organic media (HyCOM) in this Letter. The
toluene solution (70 cm 3) of TNB (6.0 g) was heated
at 573 K for 2 h in an autoclave in the presence of
water (15 cm 3) which was not in contact with the
toluene solution. This process resulted in the forma-
tion of small anatase crystallites of average diameter
-~ 15 nm. They were washed repeatedly with ace-
tone, dried, and further annealed in air at 823 K to
remove organic residue on the surface. Some of their
physical properties have been reported elsewhere
[19]. Commercial samples of TiO 2 powders were

Table 1
Photocatalytic activity of TiO 2 particles platinized by impregnation for the N-cyclization of L-lysine in aqueous solutions
TiO2 a Pt-impreg. b BET area Pt area irrad. H2 conversion c selectivity d %ee-L e
(wt%) method b (m 2 g - 1 ) ( m2 g~-a~) (h) (Ixmol) (%) (%) (%)

HyCOM 0.5 evapo. 67 0.20 0.5 44 99 64 59

HyCOM 0.5 incip. 67 0.34 0.5 35 92 77 58
P-25 0.5 evapo. 50 f 0.10 1 55 84 32 61
P-25 2 evapo. 50 f 0.57 1 13 68 77 52
P-25 0.5 incip. 50 f 0.04 0.5 28 37 8 - g
UV 2 evapo. > 250 f 0.16 1 54 92 42 57
M 2 evapo. 13 0.07 3 57 69 24 38
IS 2 evapo. 65 f _ h 1 24 76 30 49
W 2 evapo. 23 < 0.002 1 0.3 3 0 -
a HyCOM: TiO 2 particles prepared by hydrothermal crystallization in organic media - P-25: Degussa P-25, UV: Sachtleben Hombikat
UV-100, M: Merck (anatase), IS: Ishihara RAC (ruffle) and W: Wako (rutile).
b Method of Pt impregnation - evapo: a mixture of TiO 2 and an aqueous solution of H2PtC16 were stirred and evaporated to dryness, incip:
incipient wetness. Powders obtained by both methods were subjected to H 2 reduction at 773 K.
c Conversion of L-lysine.
d Selectivity of PCA yield based on L-lysine consumption.
e Enantio excess percentage of L-PCA.
f Data reported by suppliers, showing the area before platinization procedure.
g Because of negligible formation of D-PCA, %ee-L could not be evaluated with sufficient accuracy.
h Not measured.
 B. Ohtani et al. / Chemical Physics Letters 242 (1995) 315-319 317

used as reference photocatalyst without further pre- L-lysine(Lys) COOH

treatment or activation. Platinization was performed
by impregnation from an aqueous solution of chloro- H2N/~-~NH2
platinic acid (H2PtCI6.6H20; Wako Pure Chemi-
cals) followed by hydrogen (H 2) treatment at 773 K. 2h .2H
The impregnation was made by either incipient wet-
ness or the evaporation method [20,21]. The specific
surface area of the loaded platinum (Pt) was evalu- COOH COOH
ated by volumetric H 2 adsorption measurements
[18,22]. The platinized photocatalyst (50 mg) was HN~/~NH2 H2N/~//~NH
suspended in an aqueous solution (5.0 cm 3) of Lys
(100 ~mol) and photoirradiated at wavelengths H20I-NH3 H20~'NH3
> 300 nm under argon atmosphere at 298 K with COOH COOH
vigorous magnetic stirring (1000 rpm). Details of the
HOC"v ~ v L NH2 H2N/~~O
photoirradiation and product analyses have been re-
ported elsewhere [23]. I'H20 I-H20
cyclbaseicSchiff
3. Results and discussion
COOH COOH
Table 1 shows the results of the photocatalytic
reaction of Lys in an aqueous suspension of pla- 2e, 2H+ 1 (Pt) 2e, 2H+~ (Pt)
tinized TiO 2 particles. All these powders gave PCA
from Lys, along with by-products such as ammonia, pipecolinic
H 2 and piperidine. The optical purity, i.e. enantio acid (PCA)
excess percentage of the L-isomer (%ee-L), of PCA COOH COOH
H H
was not so influenced by the origin and platinization
conditions of TiO2, as reported previously [24]. Thus, racemic
50-60%ee-L product was obtained except for the Scheme 1.
case of the less active Merck TiO 2. It has been
proven that the position in the Lys molecule, a- or
e-amino group, undergoing oxidation by positive solid phase. P-25 TiO 2 has been used therein as a
holes (h+), decides the %ee-L; oxidation at the a- reference catalyst because of its relatively high activ-
and e-positions give, respectively, racemic and L- ity. To the best of our knowledge, only two reports
PCA, as shown in Scheme 1. have shown that commercial TiO 2 powders
As clearly seen in Table 1, the HyCOM-TiO 2 (Sachtleben Hombikat UV-100 [25] and Tioxide
exhibited a higher rate of Lys consumption as well HC90 and A-HR [26]) exhibit photocatalytic activity
as higher selectivity of L-PCA production. Note that higher than P-25 for the photocatalytic removal of a
almost complete consumption of Lys could be pollutant in water under aerated conditions. On the
achieved by half-hour irradiation while the other other hand, we could find no reports showing photo-
TiO 2 catalysts required an hour or more. Further- catalytic activity higher than P-25 under deaerated
more, the loading of a small amount of Pt through conditions. As shown in Table 1, the photocatalytic
incipient wetness (0.5 wt%) induced significant im- activity of Hombikat UV-100, loaded with 0.5 wt%
provement in the PCA selectivity to be ~ 80%, of Pt, was a little higher than or comparable to that
which was the highest among the photocatalysts used of P-25. Hence, the superior photocatalytic activity
for this N-cyclization. There have been many articles of HyCOM-TiO 2 is unambiguous. Furthermore, the
reporting the photocatalytic activity of TiO 2 powders present TiO 2 have significantly higher photocatalytic
toward various types of reactions in the liquid, gas or activity not only for the reaction leading to N-cycli-
318 B. Ohtani et al. / Chemical Physics Letters 242 (1995) 315-319
zation products, but also for the dehydrogenation of
2-propanol to yield acetone and H 2 [27], indicating
the wide applicability of HyCOM-TiO 2 to liquid-
phase photocatalytic reactions under deaerated condi-
tions. Further investigation on the applicability to
aerated conditions is now in progress.
In the absence of loaded small Pt particles, all the
TiO 2 powders listed in Table 1 showed negligible
photocatalytic activity. Such a behavior has been
commonly observed for deaerated photocatalytic re-
action systems, in which the photoexcited electrons
are consumed for reactions other than the reduction
of molecular oxygen into the superoxide anion radi-
cal. In the presence of Pt deposits on the TiO 2
surface, photoexcited electrons ( e - ) transfer to Pt
unless they recombine with positive holes, and re-
duce H to yield H 2 or hydrogenated products such
as PCA [28]. The reason for the negligible photocat-
alytic activity of bare TiO 2 powders is the poor
reduction ability of their photoexcited electrons.
Therefore, the difference in photocatalytic activity of
platinized TiO 2 should be accounted for not only by
the essential activity of TiO 2 but also by the effi-
ciency of electron transfer through the TiO2-Pt in-
terface; particle size a n d / o r contact of Pt with the
TiO 2 surface must influence the photocatalytic activ-
ity.
Fig. 1 shows the variations in %ee-L of PCA, Lys
conversion and the selectivity of PCA as a function
of the amount of loaded Pt up to 0.5 wt%. Again,
100
80
: 60
_o
~ 40
2O
I I I I I
0.1 0.2 0.3 0.4 0.5
amount of loaded Pt / wt%
Fig. 1. Variation in consumption of Lys (O), selectivity of PCA
(O), and enantio excess percentage of PCA ( D ) as a function of
the amount of Pt loaded on HyCOM-TiO 2 powder. Platinization
was made by incipient wetness from an aqueous H~ PtC16 solution
followed by H 2 treatment at 773 K.
%ee-L of PCA was insensitive to the Pt amount and
almost constant ( = 60%). This is consistent with the
proposed reaction scheme showing that the optical
purity of PCA is decided in the first oxidation stage
[24] and that loaded Pt catalyzes not the oxidation
but the reduction by photoexcited electrons. On the
other hand, the Lys conversion was drastically in-
creased by the Pt loading, as described in Section 2,
and attained its maximum by 0.2 wt% loading. A
further increase in the Pt loading gave a slightly
negative effect on the Lys conversion. A similar
behavior has been reported in several papers
[9,28,29]. We studied such a behavior for Pt loaded
on P-25 TiO 2 and found that the maximum rate of
Lys consumption was obtained by a Pt loading of
--~ 0.5 wt%. For the HyCOM-TiO 2 powders, a
smaller amount of Pt is required for the saturation of
reaction rate. It was proved that the appropriate Pt
content corresponds to an amount of Pt enough to be
distributed to each TiO 2 particle, i.e. a TiO 2 particle
is expected to have at least one Pt deposit on its
surface, and the overall rate is independent of the Pt
content at the saturated Pt loadings [18]. Conse-
quently, as long as we compare the saturated photo-
catalytic activities, the observed difference can be
attributed to the essential photocatalytic activity of
the TiO 2 themselves. On the assumption that the
amounts of Lys adsorbed on HyCOM-TiO 2 and P-25
are comparable, according to the similar BET area,
the significantly superior photocatalytic activity of
HyCOM-TiO 2 should be attributed to the suppressed
recombination of electron-positive hole pairs. The
post-preparation annealing in air (at 823 K in the
present experiments) may produce a surface of less
defects as recombination centers, without the accom-
panying considerable decrease in surface area.
Fig. 1 also shows that the selectivity of PCA
formation was markedly improved by a Pt loading of
up to 0.5 wt% to be = 80%. Similar improvement
has also been observed for P-25 TiO2, but a larger
amount of Pt ( = 2 wt%) was required to obtain such
high selectivity. In the investigation of P-25 TiO 2,
we found that the selectivity increases along with the
increase in specific surface area of Pt. The expected
increase in Pt surface area, though we have not
measured it yet, may account for the results depicted
in Fig. 1. It is notable that the surface area of Pt on
HyCOM-TiO 2 was twice as large as that on P-25 to
 B. Ohtani et al. / Chemical Physics Letters 242 (1995) 315-319
result in a higher PCA selectivity, despite them both
being prepared by the same procedure (evaporation).
This may be caused by the difference in surface
properties of the TiO 2. A further higher Pt surface
area could be obtained by the incipient wetness
procedure giving the best photocatalyst for PCA
synthesis. This should be stressed as one of the
advantages of HyCOM-TiO 2, since P-25 TiO 2 has
presumably negligible pores [30] to absorb the
H2PtC16 impregnation solution so that the impregna-
tion through incipient wetness gave a rather smaller
Pt surface area and poorer photocatalytic activity, as
shown in Table 1.
4. Conclusion
Platinized HyCOM-TiO 2 powders showed mark-
edly higher photocatalytic activity for N-cyclization
of Lys to give PCA as compared to several commer-
cial TiO 2 powders. The higher rate of Lys consump-
tion is attributable to the higher crystallinity for
lesser recombination of electron-positive hole pairs,
while the higher PCA selectivity is due to the ten-
dency of the larger surface area of Pt for the efficient
reduction with photoexcited electrons. Investigation
on the surface structure influencing both the recom-
bination process and platinization, as well as further
enhancement of the photocatalytic activity by con-
trolling the preparation conditions, is now underway.
Acknowledgement
We thank Mr. Mitsuru Ochiai (Nippon Aerosil),
Dr. Bernhand Becker (Sachtleben Chemie) and Mr.
Yoichi Takaoka (Ishihara Sangyo) for the gift of the
TiO 2 samples: Degussa P-25, Hombikat UV100 and
RAC, respectively. Mr. Hideshi Hamaguchi (Kyoto
University) is acknowledged for the BET surface
area measurement of some of the TiO 2 samples.
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