J. Org. C h e m .

1992,57,5087-5091 5087
or Dewar benzene (and to benzene via a secondary pro- since the diradical intermediate is unreactive and has an
cess‘). energy so high (because of the constraint of the u frame)
The differences between an intermolecular [2 + 21 cy- that it is of no chemical significance. Rather, the preferred
cloaddition (the [2 + 21 reaction of two ethylene molecules6 thermal mechanism for transformation of Dewar benzene
that we have studied previously) and the intramolecular to prismane corresponds to a two-stage asynchronous
[2 + 21 cycloaddition of Dewar benzene to prismane merit process. In the [2 + 21 cycloaddition of two ethylene
some brief comment. The differences ought to be capable molecules the ‘transition state” on this pathway haa two
of rationalization from behavior of the Coulomb energy imaginary frequencies; however, the constraint of the u
Q (i.e., to steric effects that arise from the u bond frame- frame turns one of these negative directions positive in the
work) since the exchange energy T must have a similar Dewar benzene to prismane transformation. The electronic
topology in the two systems. While the coulomb energy factors that control the existence of the conical intersection
Q in the [2 + 21 cycloaddition of two ethylene molecules are present in both systems. However the geometry at the
is completely flat (seeFigure 4 of ref 6b) and plays almost conical intersection is so highly strained (large Q) for the
no role in the determination of the topology of the ground- transformation of Dewar benzene to prismane that this
and excited-state potential energy surfaces, as we have mechanism may not exist if steric factors are increased
seen, Q plays a crucial role in the mechanism of the consistent with the experimental observation that only the
transformation of Dewar benzene to prismane. Thus, in adiabatic photochemicalreaction is observeds in 1,CDewar
contrast to the [2 + 21 cycloaddition of two ethylene naphthalene.
molecules, where the lowest energy pathway involves an
asynchronous two-step process involving an anti attack, Acknowledgment. This work was supported by the
the Corresponding thermal pathway for the transformation SERC (U.K.) under grant numbers GR/F 48029, GR/F
of Dewar benzene to prismane involving a nonaromatic 46452, and GR/G 03335. I.J.P. is grateful to the SERC
transoid diradical intermediate is only a ‘formal” pathway for the award of a studentship.

Photoinduced Reduction of Aldehydes on Titanium Dioxide

Cheryl Joyce-Pruden, Jeffrey K. Pross, and Yuzhuo Li*

Department of Chemietry, Clarkson University, Potsdam, New York 13699-5810

Received April 6, 1992

Aromatic and aliphatic aldehydes are reduced to their corresponding alcohols using titanium dioxide as a
photocatalyst. The reduction proceeds through an electron transfer from the excited state of titanium dioxide
to the aldehydea and is followed by a protonation. The electron hole in the valence band of the excited semiconductor
causes concomitant oxidation of the alcohol solvent and production of hydrogen. The quantum efficiency for
the reduction is directly related to the half-wave potential of the aldehyde, the solvent, the nature of an electron
donor, and the presence of a strong acid or base.

Study of light-induced electron-transfer reactions on oxidations of organic compounds such as amines, carbox-
semiconductors has become one of the most active areas ylic acids, and aromatic olefins6on semiconductors ale0
of research in photochemistry. The reactions demonstrate have been fruitfully investigated. However, there are only
the possibilities of converting solar energy into chemical a few reports on the reduction of organic compounds wing
or electrical energy, providing new synthetic routes, and a semiconductor as a photocatalyst.’ Reduction of acet-
introducing new ways of photodegradation of industrial
wastes.’ Titanium dioxide is one of the most studied (1) (a) Kalyanasundaram,K. in Energy Resources Through Photo-
semiconductors due to ita ultraviolet-visible absorption chemistry and Catalysis; Grhtzel, M., Ed.;Academic Prese: New York,
band and chemical stability. Irradiation of titanium di- 1983; pp 217-260. (b)Pelizzetti, E.; Barbeni, M.; Pramauro, E.; Erh,W.;
Borgarello, E.; J a ” , M. A.; Serpone,N. Quimica Nova 1985,288. (c)
oxide promotes one electron from the valence band (VB) Halmann, M.; Zuckerman, K. In Homogeneom and Heterogeneow
to the conduction band (CB). The excited state of TiOz Photocatalysis; Pelietti, E., Serpone, N., Eds.;D. Reidel: Dordrecht,
can be expreewd as TiOz(e-,h+).2 The electron in the 1986; pp 521-532.
(2) (a) Wrighton, M. 5.Photochemistry, Chem. Eng. News, Sept 3,
conduction band is readily available for transference (-0.85 1979; pp 2*47. (b) Fox,M. A. Nouu. J. Chim. 1987,11,129.
eV vs SCE) while the electron hole in the valence band is (3) Kanno, T.; Oguchi,T.; Sakuragi, H.; Tokumaru, T. Tetrahedron
open for donation (2.4 eV vs SCE).3 A reactant that Lett. 1980,21,467.
(4) (a) Borgarello, E.; Peliizzetti, E. Chim. Znd. 1983, 65,474. (b)
receives the electron from TiOz would be reduced, while Teratani, S.; Nakamichi, J.; Taya, K.; and Tanaka, K. Bull. Chem. SOC.
a reactant that donates an electron to TiOz would be ox- Jpn. 1982, 55, 1688. (c) Sakata, T.; Kawai, T. In Energy Resources
idized. Based on this redox scheme, a variety of organic Through Photochemistry and Catalysk, Gritzel, M., Ed.;Academic
Press: New York, 1983; pp 331-358. (d) Noudek, L.; Sedlacek, J. J.
reactions can be catalyzed by semiconductors. For exam- Catal. 1975,40, 34.
ple, oxidation of protic organic compounds or biomass to (5) (a) Matthem, R. W. Wat. Res. 1990,24, 653. (b) Frank, S. N.;
produce hydrogen‘ and photodegradation of polychloro- Bard, A. J. J. Am. Chem. SOC.1977,99,7729. (c) Pelizmtti, E.; Serpone,
aromatic compounds have been explored.s Photo- N.; Borgarello, E. In Photocatalysis and Environment; Schiavello, M.,
Ed.; Kluwer Academic: New York, 1988, pp 469-497.
(6) (a) Xu, 2. Q.; Tongbao, X. Hwxue Tongbao 1989,10,26. (b) Fox,
M. A,; Chen, C.-C. Tetrahedron Lett. 1983,24,547. (c) Ohtani, B.; OaaLi,
* Author to whom correspondence should be addressed. H.; Nishimoto, 5.; Kagiya, T. Chemistry Lett. 19811,1075.

0022-3263192f 1957-5087$03.00/0 0 1992 American Chemical Society

5088 J. Org. Chem., Vol. 57, No. 19, 1992 Joyce-Pruden et al.
Table I. Photoreduction of Benzaldehyde in TiOz
Suspension
yield (%)
reaction photolysis hydro-
media time (h) PhCHO PhCH20H benzoin
ethanol"" 0 100 0 0
ethanol"," 2 100 0 0
ethanol"" 2 26.0 52.0 7.4
ethanol"# 4 3.0 82.0 6.8
2-propanol"" 2 58.6 17.6 7.4
methanol"" 2 49.2 34.0 5.5
ethanolbgSe 2 100 0 0
ethanoleJa
ethanoW
ethanoleJ"
ethanolef"
ethanolPJJ
2
18
2
18
2
58.0
0
62.4
20.1
0.0
11.8
35.0
5.8
17.8
18.4
d
d
d
d
4.2
'"1
o
0
! .
20
, . ,
40
. ,
60
. ,
80
. ,
100
. I
120
ethanolpfd 2 20.2 54.6 7.2 Photolysis Time (hours)
"Purged with nitrogen before photolysis. bPurged with oxygen Figure 1. Photocatalytic reduction of heptanal (-o-, DIPA
during photolysis. e Colloidal TiOz. Not detected. e Trace added; -v-, DIPA and NaOH added; -A-, NaOH added; 4,
amount of benzoic acid also detected. f Acetal formation makes up no NaOH or DIPA added).
the rest of mass balance. 80.001 M HC1 is present in solution. h O . l
M HC1 is present in solution. "No TiOz added. PParticulate Ti02,
anatase (Degussa, P-25). 'Diisopropylamine added (0.1 M). jN,- Table 11. Photoreduction of Heptanal in TiOI Suspensions
N-Dimethylaniline added (0.1 M). heptanol pH after
[Ht] or pH before yield (%) photolysis
aldehyde to ethanol in water by illuminated ZnS has been [OH-] added photolysis (30 h) (30 h)
reported. However, when platinized Ti02was used under [Ht] = 3.66 5 3.65
similar conditions, only negligible amounts of ethanol were IHtl = lo-' 6.03 12 5.70
... .

produced? We report here the photoreduction of aromatic iH+j = 10-5 6.20 15 5.92
and aliphatic aldehydes to their corresponding alcohols [Ht] = 10" 6.04 18 6.18
water 6.00 19 6.35
using Ti02 as a catalyst. wateP 6.00 20 5.45
[OH-] = 10" 6.24 19 6.00
Results [OH-] = 6.28 24 6.43
A suspensionof titanium dioxide (anatase) in 2-propanol [OH-] = lo-' 6.38 26 5.77
containing benzaldehyde is purged with nitrogen and ir- [OH-] = 7.00 26 6.54
radiated with 350-nm light. The photolysis produces [OH-] = 10.28 0 9.14
benzyl alcohol, acetone, hydrobenzoin, and hydrogen (eq " No aldehyde is added in this run.
1). Irradiation of a similar suspension saturated with
In the cases of ethanol and methanol, the solvents were
oxidized to acetaldehyde and formaldehyde, respectively.
The comparison shows that the photoinduced reduction
is most efficient when ethanol is employed as the solvent.
oxygen gives no benzyl alcohol but yields a trace amount Methanol offers slightly higher quantum efficiency than
of benzoic acid as the only primary product (Table I). 2-propanol (Table I). The analyses based on the UV-vis
Irradiation of a Ti02 suspension saturated with oxygen absorption spectra of aldehyde solutions and TiOz sus-
containing benzyl alcohol instead of benzaldehyde does not pensions indicate that the photoredox reaction is halted
give any detectable benzoic acid or any other oxidation when the aldehyde becomes predominant in light ab-
product from benzyl alcohol. Direct photolysis of benz- sorption; Le., there is a higher limit in aldehyde concen-
aldehyde with a 350-nm light in the absence of TiOz does tration for the reduction. The quantum efficiencies also
not produce any benzyl alcohol. In a control experiment, depend on the electronic nature of the aldehydes. Pho-
the suspension is kept in the dark but saturated with toredudions of electron-deficientp-acetobenzaldehydeand
hydrogen to simulate the presence of hydrogen during phalobenzaldehydeain the suspensionsof TiOzare at least
photolysis. The aldehyde is not reduced under this con- 20 times more efficient than that of anisaldehyde and
dition. These findings are also true for several other aliphatic aldehydes (Figure 1, Table I).
aromatic and aliphatic aldehydes such as p-cyanobenz- The photoreduction is selective for several multifunc-
aldehyde, p-acetobenzaldehyde, p-chlorobenzaldehyde, tional compounds. The aldehyde group is reduced in
p-bromobenzaldehyde,isonicotinaldehyde,heptanal, and p-cyanobenzaldehyde and p-acetobenzaldehydewhile the
octanal. cyano and aceto groups are retained. The nitro group,
The photoinduced reduction was conducted in three however, is reduced more readily than the aldehyde group
different alcohol media, ethanol, methanol, and 2-propanol. when p-nitrobenzaldehyde is employed as a substrate.
Selective photoreduction of the nitro group in bifunctional
compounds on semiconductors (eq 2) will be the focus of
(7) (a) Taniguchi, Y.;Toneyama, H.; Tamura, H. Chem. Lett. 1983,
269. (b) Pichat, P.; Mozzanega, M.-N.; Courbon, H. J. Chem. SOC., a forthcoming paper?
Faraday Trans. 1 1987, 83, 697. (c) Weng, Y.; Wang, F.; Lin, L. Acta
Energ Sol. Sin. 1989,10(3), 259. (d) Al-Ekabi, H. In Photochemistry in 702 NH2
Organized and Constrained Media; Ramamurthy, V., Ed.; VCH Pub-
lishers: Weinheim, 1991; pp 495-534. (e) Cuendet, P.; Gratzel, M. J.
Phys. Chem. 1987,91,654. (0Kormann, C.; Bahnemann, D. W.; Hoff- li0:EtOH '
man, M. R. Enuiron. Sci. Techno[. 1988,22,798. X
(8) Yanagida, S.; Ishimaru, Y.; Miyake, Y.; Shiragami, T.; Pac, C.;
Hashimoto, K.; Sakata, T. J . Phys. Chem. 1989,93, 2576. x = n cno. OCH,. NQ. m,
Photoinduced Reduction of Aldehydes J. Org. Chem., Vol. 57, No. 19, 1992 5089
Scheme I. Oxidation of Alcohols Using Ti02 as a
Photocatalyst
hv
no2 TiOz(e-,h+)
-H+ h+

0
on
-
0- 0.

2 ~

02 -
.
e.
H2

02'
-

Scheme 11. Photoreduction of Aldehydes Using TiOzas a

Catalyst
w.

pH (calculated)
Figure 2. Photoinduced reduction of benzaldehyde and heptanal
in the presence of NaOH and HCl (4, benzaldehyde; -0-,
heptanal). x I I
x k X X
A B
When a small amount of a strong base, e.g., NaOH, is
added into a TiOz suspension, the photoreduction effi- X = H, Br, Cl, (3.
COcH,; X \ W 3
ciency is increased (Figure 1,Table II).lo But, the pH of
the suspension does not increase significantly. The pH of
the suspension increases only when excess base is added.
The increase in pH is accompanied with a sharp decrease
in the photoreduction efficiency. Therefore, there is pensions in dry acetonitrile containing aldehydes do not
generally an optimum for the added OH- concentration. give any photoreduction products. Irradiation of a sus-
For most aldehydes this concentration is ca.lW3 M (Figure pension of TiOz in dry acetonitrile containing p-bromo-
2). Addition of a strong acid, HC1, to the suspension of benzaldehyde gives benzaldehyde, a debromination prod-
TiOz does not decrease the pH until the added [HCl] uct (eq 4). Addition of ethyl alcohol changes the reaction
reaches M (Table 11). The decrease in pH is also toward reduction of the carbonyl group and production of
accompanied by a sharp decrease in the reduction effi- bromobenzyl alcohol. Irradiations of suspensions con-
ciency. Photoreduction of benzaldehyde was also carried taining bromobenzene or chlorobenzaldehyde,however, do
out in colloidal TiOz containing 0,001or 0.1 M HCl. The not give any dehalogenation products.
acidic condition is required to stabilize the colloids.
Compared to the suspensions with large particles, these Discussion
colloids are much more transparent and therefore expected It is known that alcohols can be oxidized to aldehydes
to have higher redox quantum efficiencies. On the con- or ketones on TiOz upon irradiation accompained by a
trary, our mults (Table I) indicab that the reduction rates production of hydrogen (Scheme I).4 In the absence of
for these systems are at least 50% slower than those of the oxygen or other electron acceptor, this oxidation praceeda
reactions carried out in large TiOz particle suspensions until enough electrons are accumulated in the conduction
(Degussa P25). band 80 that the electrons efficiently compete with alcohol
Addition of diisopropylamine (DIPA) accelerates the for electron hole quenching. In the presence of oxygen,
photoreduction of aldehydes. However, addition of N f l - the electrons in the conduction band of the excited TiOz
dimethylaniline (DMA) does not increase the reduction are captured by oxygen to give a series of oxidative species
efficiency noticeably (Table I). A suspension that contains such as hydrogen peroxide and atomic oxygen. These
diisopropylamine (0.1 M) and its optimal [OH-] has a species are capable of oxidizing the adsorbed aldehyde to
higher reduction efficiency compared to the suspension a carboxylic acid." Our control experiments clearly
containing optimal [OH-] only. A suspension that contains demonstrate that the photoreduction of an aldehyde is
only diisopropyl amine (0.1 M)has the highest efficiency initiated by the excitation of the semiconductor rather than
for the reduction (Figure 1). by the excitation of the aldehyde in a Norrish type I1
Irradiation of Ti02-benzaldehyde in 0-deuterated reaction or by a direct hydrogenation.
ethanol (C,H,OD) gives a product labeled with two deu- However, there are still two alternative pathways for the
terium atoms (eq 3). irradiations of various TiOz sus- generation of the a-hydroxyl radical (B)as shown in
Scheme 11. It could be formed from either the addition
of a hydrogen atom (Scheme I) to the aldehyde or by a
(3) single electron transfer from the excited state of TiOz to
the aldehyde followed by a protonation. If the first
pathway is followed, all aldehydes should react regardless
of their electronic nature. Our results, however, show that
(4) the reduction occurs only to the electron-deficient aldeh-
I I I ydes. The quantum efficiency for the reduction strongly
H Br Br
depends on the reduction potentials of the aldehydes. For
example,the reduction potentials for the electron-deficient
(9) Madahvi, F.; Bruton, T.; Chandra, R.; Partch, R.; Li, Y. Unpub-
lished results, manuscript in preparation.
(10)Sato, S.; White, J. M. J . Catal. 1981,69, 128. (11) Kamat, P.; Dimitrijevic, N. Solar Energy 1990,44, 83.
5090 J. Org. Chem., Vol. 57, No.19, 1992 Joyce-Pruden et al.
aldehydes, including benzaldehydes, are near the con- increase because the hydroxy groups on the surface of Ti02
duction band energy of Ti02(-0.85 eV vs SCE). These consume most of the added base; i.e., the hydroxide ions
aldehydes can be easily reduced on the semiconductor are completely absorbed onto the ~urface.'~When an
particles. The reduction potentials for the anisaldehyde excess amount of the base is added, the hydroxide ion
and the aliphatic aldehydes are significantly lower (from concentration exceeds the number of the absorption sites
-1.48 to -1.90 eV v8 SCE).I2 Theae electron-richaldehydes on the surface of the semiconductor. The ex- hydroxide
are much lees reducible because of their lesser abilities to ions remain in the suspension and cause an increase in pH
accept a single electron from Ti02 In the cases of heptanal and shortage of protons. The shortage of protons trans-
and octanal, the radical anions A (X= hexanyl and hep- lates to a lees effective protonation which slows down the
tanyl) would be particularly unstable due to the lack of reduction process. The balancing of the need for a proton
resonance compared to aromatic aldehydes. The demon- in reduction and the need for a hydroxide to prevent fast
strated competition between the aldehydes and molecular electron-electron hole recombination results in an optimal
oxygen also indicates that the reduction is initiated by an OH- concentration (ca. M).
electron transfer from Ti02 to the aldehyde. Addition of an amine to a suspension containing optimal
There are also two possible pathways for the formation [OH-] does not produce any additional anionic sites on the
of alcohol product from radical B. The radical may be surface of semiconductor but gives higher reduction effi-
reduced to give the same fmal product either by a second ciency compared to the suspension containing optimal
electron transfer from Ti02followed by a protonation or [OH-] only. This clearly indicates that the amine does not
by a hydrogen abstraction from the solvent. Irradiation rely on adsorption onto the surface or the deprotonation
of TiOz-benzaldehyde in the presence of 0-deuterated of the hydroxy ten-ters on the surface to increase the re-
ethanol (CzHSOD)gives a product labeled with two deu- duction efficiency; it donates an electron to the electron
terium atoms (eq 3). This indicates that the reduction hole directly. Unlike strong base, a higher amine con-
occurs through two stages of electron transfer and pro- centration can be used without decreasing the proton
tonation. If hydrogen abstraction occurs instead of elec- availability significantly. As a result, the highest efficiency
tron transfer and protonation, the hydrogen source would for the reduction can be obtained in a suspension that
most likely be the secondary hydrogen on ethanol. The contains only diisopropylamine (Figure 1).
product, then, would be labeled with only one deuterium. Similar analysis can be made for the acidic TiOz SUB-
According to the reaction mechanisms illustrated in pensions. The low quantum efficiency in these low pH
Schemes I and II, the oxidation of an alcoholic solvent and suspension perhaps due to the fact that a higher proton
the reduction of the aldehyde substrate are logically cou- concentration converts more TiOz particles to positively
pled. The protons produced from the oxidation are com- charged species.I6 The recombination of an electron and
pletely consumed in the reduction. The proton concen- an electron hole on a positively charged TiOa particle is
tration, therefore, remains essentially the same during the much faster than on a neutral one. The quantum effi-
photolysis (Table 11). Assuming no side reaction is in- ciency for reduction or oxidation is, therefore, reduced in
volved, a balanced equation can be written for a two- a more acidic solution. The buffer effect on the absorption
photon event (eqs 5-7).
PhCHO + 2e- + 2H+ PhCH20H - sites on the Ti02surface retards the impact of the added
strong acid on the pH of the suspension.

2CH3CH20H + 2h+ - 2CH3CHO + 2H+ + H2 (6)

(5) The differences among the three alcohols can also be
explained by a similar analogy considering their proton-
donating and electron hole-quenching capabilities. For
PhCHO + 2CH3CH20H-?L2CH3CH0 + H2 (7) isopropyl alcohol, having the highest pK,, the lowest
concentrations of protons and alkoxy anions are available
This equation is consistent with our observation that the for the protonation and the electron hole quenching.
reduction of an aldehyde is enhanced by the oxidation of Although methanol has the smallest pK, and provides
solvent. When the suspension is irradiated without an more protons than the other alchohols, the m e t h w radical
'aldehyde, the reduction that consume8 the protons (eq 6) is.kinetically much lees stable. Ethanol provides the best
is absent. The proton concentration is increased during combination of both aspects. Therefore, the photore-
the photolysis (Table 11). duction carried out in ethanol is most efficient.
The most important event that reduces the quantum When irradiation of a semiconductor suepension is
efficiency of a photoredox reaction on a semiconductor is carried out in an aprotic solvent such as acetonitrile, there
the fast recombination of the electron in the conduction is neither a proton nor an electron hole quencher available.
band and the electron hole in the valence band.13 For In the absence of an electron hole quencher, the electron
photoreduction, a sacrificial donor can be added to quench and electron hole recombination on the semiconductorwill
the electron hole and prevent the recombination. An be so rapid that the competitive electron transfer to an
amine can be considered a better electron donor than an organic substrate would be almost impossible. In the ab-
alcohol. The fact that addition of N,N-dimethylaniline sence of a proton source, even if electron transfer from a
does not significantly affect the reduction may be due to semiconductor to an organic substrate occurs, the radical
the fact that it is a weaker electron donor than DIPA. anion of the substrate would return to ita neutral state very
When a small amount of strong base, NaOH, is added quickly via back-electron transfer. The reduction is,
to a TiOz suspension containing heptanal, the photore- therefore, stopped. Irradiation of bromobenzaldehyde in
duction efficiency of the aldehyde increases (Figure 1, acetonitrile containing titanium dioxide gives a radical
Table 11). However, the pH of the suspension does not anion A (X = Br) as illustrated in Scheme 11. In the
absence of a proton source, the radical anion debrominates
(12) Handbook of Organic Chemistry; Dean, J. A., Ed.;McCraw Hill: to give a radical. The radical then abstracts a hydrogen
New York, 1987. from the solvent to give benzaldehyde. Irradiation of a
(13) (a) Henglein, A. Top. Curr. Chem. 1988,143,113-180. (b) Pel-
izzetti, E.: Visca, M. Bifunctional Redox Catalvsia: Svnthesis and OD-
eration in- Water-Cleavage Reactions. In Energy R&ources Through (14) Matijevic, E.;Budnik, M.; Meites, L. J. Colloid Interface Sei.
Photochemistry and Catalysis: Gritzel. M.. Ed.: Academic Press: New 1977,61, 302.
York, 1983; pp 261-296. (15) Wang, C.; Mallouk, T. J. Phys. Chem. IBW,94,4276.
Photoinduced Reduction of Aldehydes J. Org. Chem., Vol. 57,
-
No. 19, 1992 8091
similar suspension containing bromobenzene instead of mL of TiOz suspension in 95% ethauol(10.0 g/L). The vial was
bromobenzaldehyde does not give debromination product. sealed with a rubber septum and purged with nitrogen for five
This indicates that an electron-deficient functional group min. The mixture was irradiated and filtered with an 0.2."
such as an aldehyde is required to accept an electron in- HPLC syringe filter to remove the TiOz particles. Two mL of
itially. Then the electron is transferred from the aldehyde the reaction mixture were mixed with 2 mL of a 0.02 M solution
of tekalin (aninternal standard) and analyzed with GC-MS and
group to bromine. Bromobenzene has a reduction poten- HPLC. All alcohol products were identified by their GC-MS
tial at -1.9 eV (vs SCE) and cannot effectively accept an spectra and confirmed by comparison with authentic samples
electron from the conduction band of TiOz. Although the obtained commercially or prepared according to literature pro-
d u c t i o n potential of p-chlorobenzaldehyde is high enough cedures.Is
(-1.1 eV vs SCE)12to undergo electron-transfer reaction Percent Yield Determination. Six solutions of known con-
with the semiconductor, the chloride atom is not a good centrations of an aldehyde or its alcohol ranging from 5 x lo-'
enough leaving group. The dechlorination process, to 5 X 10" M with 0.0097 M tetralin were analyzed using the GC
therefore, is much less efficient. or HPLC. Area ratios of the alcohol to tetralin or the aldehyde
to tetralin were then determined. Using these data, a standard
Conclusion curve of area ratio VB alcohol or aldehyde concentration was
constructed. From these graphs, concentrations of reactant and
The most fundamental yet difficult issue in semicon- product could be determined after photolysis.
ductor-mediated photochemical transformations is how to PhotolysisUsing Colloidal TiO+" To a "Lvolumetric
logically and practically couple the reductive and the ox- flask were added 25 mL of 100% ethanol and efficient HC1 to
idative aspects of the catalyst together in one system, so achieve desired proton concentration. Titanium(IV) iaopropoxide
that an electron can be completely recycled. In our ex- (4.61 g, 16.2 "01) was then added to the solution dropwise while
periments, the reduction of organic functional groups is stirring. The solution was then diluted to 250 mL with 95%
logically coupled with the oxidation of an alcoholic solvent. ethanol and stored at room temperature for 3 days for complete
hydrolysis. The general procedure for photolysis deacribed above
There are at least two advantages of using alcohols as the was followed except that the suspension of TiOzin ethyl alcohol
solvents: (1) compared to water, alcohols offer better was substituted by a TiOz solution. After the photolysis, TiOz
solubility for an organic substrate and a better suspension was precipitated with the addition of 5 mL of water. The products
for T i 0 2 particles by providing closer interaction between were extraded with ethyl ether (3 X 3 mL). The ether solution
aldehydes and the T i 0 2 surface, and (2) compared to was then analyzed with GC or GC-MS.
acetonitrile, alcohols are better proton donors. Depro- Photolysis with Deuterated Solvent. TiOp suspensions
tonation of alcohols generates alkoxy anions that are ex- containing 5 X M of benzaldehyde were irradiated as de-
cellent electron hole quenchers which prevents recombi- scribed in the general procedure except CZH~OD was used as the
nation between electron holes and electrons on the surface solvent. The mixture was photolyzed and analyzed. The GGMS
spectrum showed a molecular ion of 110 for the benzyl alcohol,
of the photocatalyst. indicating the structure of PhCHDOD. The reduction was ale0
carried out in C&OD using tri-n-butyltin hydride as the reducing
Experimental Section agent. GC-MS analysis revealed a molecular ion of 109 for the
General. GC-MS measurements were carried out on a Hew- benzyl alcohol, indicating the structure PhCHzOD.
lett-Packard Model 5890 series I1 GC with a Model 5971A maas Detection of Hydrogen Formation. The formation of hy-
spectrometer. Yields were determined on a Perkin-Elmer Sig- drogen from the photolysis of a TiOz suspension was analyzed
ma-2000 GC with an FID detector and a Hewlett-Packard 1050 with a hydrogenation experiment The suspension is continuously
series HPLC. Photolyses were carried out in a Rayonet photo- purged with nitrogenwhile it is irradiated,and the nitrogen stream
chemical reactor equipped with 3Wnm bulbs. pH measurements coming out of the suspension is introduced into a round-bottom
were preformed with a Chemtrix type 6OA pH meter equipped flaek containing hexane, &"aldehyde, and R/C. The hexane
with an SCE electrode. Benzaldehyde (reagent grade), 1,2,3,4- solution was analyzed before and after photolysis. After the
tetrahydronaphthalene (practical),p-chlorobenzaldehyde, and photolysis, the aldehyde is partially reduced to 3-phenylpropanal
p-anisaldehyde (reagent grade) were obtained from Eastman- and 3-phenylpropanol. When a similar setup is used for a control
Kodak Co. Diisopropylamineand isonicotinaldehyde were ob- experiment, without photolysis, cinnamaldehydeis not reduced.
tained form Lancaster Synthesis Ltd. Benzyl alcohol (reagent)
and Nfl-dimethylaniline (reagent) were obtained from Baker. Acknowledgment. We wish to thank Clarkson Univ-
pNitrobenzaldehyde (reagent),heptaual, octanal,and O-ethanol-d ersity for providing a Start-up fund to this research and
(C2H30D)were obtained from Aldrich. Titanium dioxide (P-25 Degussa Corp. for donating T i 0 2 samples.
anatase)was obtained from Degussa Corp. All reagents were ueed
without further purification except p-chlorobenzaldehyde which
was recrystalliied twice from ethyl alcohol. (16) Larock, R. C. Comprehensiue Organic tramformtiom;A Guide
to Functional Group Preparation; VCH: New York, 1989; pp 134-154.
General Procedure for Photolysis with Particulate TiOp (17) (a) Harrie, M. T.;Byers, C. H. J. Non-Cryst. Solids 1988,103,49,
In a 5mL shell vial equipped with a magnetic stir bar were mixed (b)Matijevic, E.; Budnik, M.; Meites, L. J. Colloid Interface Sci. 1977,
2 mL of aldehyde solution in 95% ethanol (1.0 X M)and 2 61,302.