FTIR Results and Discussion. The IR spectrum of
the pure P25 TiO2 specimen shown in Figure 7 shows
î(OH) stretching bands in the region between 3740 and
3300 cm -1. The sharp bands observed between 3630 and
3680 cm-1 and the broader bands at 3500 and 3420 cm-1
have been reported in the literature9 and are attributed
to hydroxyl groups on different sites and to varying
interactions between hydroxyl groups on TiO2. Ammonia
readily interacts with the most acidic hydroxyl groups
and remains on the surface of the particles even after
evacuation of the reaction chamber as evidenced by the
significant reduction of the IR intensity of the î(OH) band
upon exposure of the pure P25 TiO2 to ammonia and the
concomitant appearance of î(NH) stretching bands at 3346
and 3400 cm-1. The intensities of the bands at 3500 and
3420 cm-1, which have been attributed to a monodentate
hydroxyl group and a bridging hydroxyl group, respectively,
were reduced completely by the ammonia. The
residual intensity of the band in the 3630-3680 cm-1
region of the spectrum is attributed to weak Lewis and
Brønsted sites from which the ammonia desorbed after
evacuation of the chamber.10
The IR spectrum of the surface-modified hydrophobic
T805 TiO2 specimen shows î(CH) stretching modes from
the -CH2- and CH3- of the TMOS in the region of 3000
and 2800 cm-1 (Figure 8). Although the specimen is
hydrophobic, the broad band appearing from 3420 to 3680
cm-1 indicates the presence of hydroxyl groups. In contrast
to unmodified P25 TiO2, however, the absence of the sharp
bands in the region of 3630-3680 cm-1 suggests that the
hydroxyl groups represented by these bands are completely
modified by theTMOSvia surface modification. The band
for the bridging hydroxyl group, 3420cm-1, is still evident,
but the band for the monodentate hydroxyl group, 3500
cm-1, is not resolved. The integrated intensity of the î-
(OH) band, between 3740 and 3300 cm-1, is greater for
modified than for unmodified TiO2, in agreement with
the XPS results. The silanol î(OH) band of TMOS is
centered near 3500 cm-1 and explains the relatively high
IR intensity in this region compared to the spectrum of
the unmodified TiO2.
Exposure of modified TiO2 to ammonia and subsequent
evacuation caused a reduction in intensity over the entire î(OH) stretching band, 3740 and 3300 cm-1, and the
appearance of the î(NH) stretching band, 3345 and 3400
cm-1. The changes in intensity of the î(OH) band are not
distinct enough to estimate the relative extent of reaction
of ammonia with the silanols of adsorbed TMOS and the
accessible hydroxyl groups on the modified TiO2 surface.
The comparable intensities of the î(NH) bands upon
ammonia adsorption on both the modified and unmodified
TiO2 suggests that some of the silanols, indeed, react with
ammonia. An estimation of the free hydroxyl groups on
modified TiO2 by ammonia is ambiguous owing to the
presence of TMOS silanols, which also react with ammonia.
Because the largerOLOA370 molecule would have
limited access to these silanols, OLOA 370 adsorption is
a more reliable method for determining the number of
free hydroxyl groups.