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Abstract
Degradation of cyanuric acid in aqueous suspensions of Degussa P25 TiO2 has been achieved by the addition of fluoride ion at low pH.
Consistent with the work of Minero and Pelizzetti [Langmuir 16 (2000) 2632, Langmuir 16 (2000) 8964], it is suggested that this is due
to the formation of homogeneous phase hydroxyl radicals. Support for this hypothesis is brought from successful degradations using other
hydroxyl-generating conditions and the successful degradation of 4-t-butylpyridine, another organic compound previously shown to be
resistant to TiO2 -mediated photocatalytic degradation.
2004 Elsevier B.V. All rights reserved.
Keywords: Photocatalytic degradation; Titanium dioxide; Fluoride; Cyanuric acid
1. Introduction OH O
N N HN NH
Nearly every organic molecule ever tested is degraded to
CO2 , H2 O, and appropriate inorganic ions when exposed HO N OH O N O
H
to TiO2 -mediated photocatalytic degradation conditions in
Cyanuric Acid, 1 Isocyanuric acid
oxygenated water. This mineralization process is the basis
upon which the use of TiO2 and other semiconductors for Cl
water purification is built. N N
One of the very few organic molecules known to survive N
i-Pr Et
such treatment is cyanuric acid, (1). This is of both fun- N N N
4-t-Butylpyridine, 2 HAtrazine H
damental and practical interest. The latter is true because
of the large family of triazine herbicides in popular usage,
O O O
most notably atrazine. Several studies have all shown that
atrazine and other triazine herbicides are all degraded to cya- H2N N NH2 H2N NH2
H
nuric acid in the presence of irradiated TiO2 suspensions, Biuret Urea
but that no further degradation takes place [38]. While it
is known that cyanuric acid is generally difficult to chem-
ically hydrolyze or oxidize [9], this result is still remark- In neutral to acidic solution, (1) exists predominantly in
able given the extreme generality of the TiO2 photocatalytic the tautomeric form known as isocyanuric acid [9], which is
degradation method. In contrast, biologically based degra- related to cyanuric acid by a series of keto-enol equilibria.
dations using Pseudomonas sp. bacteria have been success- (For convenience, we will consistently refer to the mixture
ful. These degradations proceed through biuret and urea, of tautomers as cyanuric acid.) The pKa values are 6.9, 11.4,
both of which are intermediates that are formally products and 13.5, and most evidence suggests that the anion that is
of hydrolysis reactions [1013]. Similarly, hydrolysis can formed is that of the cyanuric acid tautomer. This suggests
be catalyzed by alumina in the range of 300 C [14] or in that cyanuric acid, were it adsorbed to TiO2 , would probably
supercritical water at even higher temperature and pressure be in the enolic form, but there is no direct evidence on this
[15]. point.
A few reasonable hypotheses might be proposed to ac-
count for the stability of (1) to TiO2 -mediated photocat-
Corresponding author. Tel.: +515-294-4711; fax: +515-294-9623. alytic degradation, which generally occurs by electron trans-
E-mail address: wsjenks@iastate.edu (W.S. Jenks). fer reactions and the action of adsorbed hydroxyl radicals.
1010-6030/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/S1010-6030(03)00372-1
324 Y.-C. Oh, W.S. Jenks / Journal of Photochemistry and Photobiology A: Chemistry 162 (2004) 323328
the Minero hypothesis, this time using a very simple observ- are not clear. However, it would be consistent with the cur-
able: removal of cyanuric acid from solution at least three rent results to speculate that their immobilization procedure
orders of magnitude more rapidly than without the fluoride. provides for binding sites that are more attractive to cya-
Moreover, the observation of ordinary hydroxylation nuric acid in addition to immobilizing the TiO2 particles.
intermediates in the TiO2 /F-mediated degradation of (2) is Reactions between the TiO2 and cyanuric acid might then
consistent with our explanation for the lack of observable take place.
intermediates in the degradation of (1). There is no reason to
believe that compound (2) is considerably less reactive than
any of its obvious derivatives towards HO . Thus, the rate 5. Conclusions
of intermediate formation is not grossly lower than that of
intermediate degradation early in the course of the reaction, The addition of fluoride to aqueous suspensions of titania
and the steady state concentration initially builds up. In con- has proved to be an important mechanistic tool in unravel-
trast, as in the homogeneous oxidations, the intermediates ing a long-standing conundrum in photocatalytic degrada-
from TiO2 /F degradation of (1) are consumed more rapidly tion. By using this method in parallel with other methods for
than they are formed and are thus not detected. An unfortu- producing homogeneous hydroxyl-type reagents, it is shown
nate corollary of this is that, although the expected reactivity that cyanuric acid is susceptible to degradation under easily
of hydroxyl radicals with (1) would presumably be by addi- accessible conditions. The comparatively unrelated, but not
tion to the carbon atoms, any further mechanistic discussion as generally unreactive, 4-t-butylpyridine (which is also al-
is too speculative to be fruitful. most untouched by ordinary TiO2 photolysis conditions) is
The pH sensitivity of the degradation of (1) under TiO2 /F also degraded by TiO2 /F. It gives predictable hydroxylated
conditions is also consistent with Minero. By working at pH intermediates, and thus supports the hypothesis that the in-
2, it is reasonable to suggest that we have not maximized the duced reactivity is due to the formation of homogeneous
amount of surface fluoride coverage (which peaks at slightly HO . The reason that cyanuric acid is ordinarily inert to
higher pH according to them), though we used a higher TiO2 -mediated photocatalytic degradation appears to be that
[NaF] than Minero. However, the considerably lower rate at it simply is not bound to the reactive portions of the TiO2
pH 7 is consistent with their prediction of still lower surface surface to any measurable extent, perhaps in combination
coverage by fluoride, and the complete lack of degradation with its lower reactivity evident from other reactions. Its in-
at pH 12 is consistent with their prediction of negligible flu- herent chemical resistance to degradation is still exhibited in
oride coverage. An important secondary conclusion to draw the inability to observe intermediate degradation products,
from this work is that the formation of free hydroxyl radicals regardless of degradation method, because the intermediates
apparently does not depend on complete fluoride coverage. are consumed more rapidly than they are formed.
While undoubtedly more homogeneous HO is formed with
higher fluoride coverage, some appears to remain even at
pH values where coverage is incomplete. The exact form of Acknowledgements
the pH dependence is beyond the modest scope of this pa-
per, but it is clear that an accurate assessment of the level of The support of this research by the IPRT Center for
fluoride coverage would be required 2 . Finally, it should be Catalysis and, in part, the National Science Foundation is
noted that we have not optimized the rate of cyanuric acid gratefully acknowledged.
degradation with respect to lamp output, pH, TiO2 concen-
tration, [NaF], etc., and it is possible that relative rates could
be significantly improved with sufficient effort. References
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