I. Photochem. Photobiol. A: Chem.

, 66 (1992) 355-366 355

A comparison of 254 nm and 350 nm excitation of TiOz

in simple photocatalytic reactors

Ralph W. Matthews and Stephen R. McEvoy

CSIRO Division of Coal and Energy Technology, Lucas Heights Research Laboratoties, PMB 7,
Menai, NSW 2234 (Australia)

(Received November 4, 1991; accepted February 7, 1992)

Abstract

Photocatalytic reactors of simple annular design were manufactured from blacklight flu-
orescent tubes and germicidal tubes of identical dimensions and electrical power requirements.
Salicylic acid and phenol selected as model water contaminants were analysed at various
illumination times and TiO, loading conditions to determine degradation rates. The shorter
wavelength 254 nm radiation is considerably more effective in promoting degradation than
radiation centred at 350 nm and the optimum rate occurred with a lower catalyst loading
than that required at 350 nm. However, even with 350 nm radiation, in oxygenated solutions
containing 94 ppm of phenol and greater, the phenol was degraded at a rate of approximately
2400 ppm I-’ kWh_’ and was mineralized at the equivalent of 820 ppm total organic
carbon destroyed 1-l kWh_l. Phenol and Degussa P25 TiOZ catalyst provide a basis for
future comparative photocatalytic reactor performance evaluations.

1. Introduction

Photocatalytic oxidation (PCO) is one of the most promising water treatment

processes to emerge during the last decade [l]. The majority of organic contaminants
are converted to carbon dioxide and other mineral products without the need for
expensive oxidizing chemicals. The photocatalyst may be activated by electrically
generated light or natural sunlight. The rapidly increasing documentation [2] deals
mostly with the destruction of individual contaminants or families of compounds and
the identification of degradation products. There is at present considerable debate
concerning the precise mechanism of the primary photocatalytic attack on solutes
[3-121 but it is evident that, regardless of the mechanistic details, the reaction is a
powerful wet oxidation that will find other useful applications. The photoreactors used
in many of these studies are primarily designed to facilitate sampling and analysis of
products. Maximizing photon efficiency has been of minor or secondary importance.
However, for the process to compete with or supplant existing water treatment
technologies, attention needs to be given towards developing (1) catalysts with greater
activities and (2) photoreactors that take into account the optical properties of these
heterogeneous systems with a view to maximizing photon efficiencies [13]. Furthermore,
these reactors need to be of simple design and economical to construct. Annular and
failing film reactors would seem to be the most appropriate for high opacity photocatalyst
suspensions.
In the prior literature various light sources were used with a high proportion of
medium pressure mercury lamps with major emission at 365 nm, but some workers

lOlO-6030/92/$5.00 Q 1992-Elsevier Sequoia. All rights reserved

356

use broad spectrum soIar simulators. In contrast, the photochemical reactors with
chemical oxidants in established water treatment technologies use shorter wavelength
W-B or UV-C radiation [14]. In this report the performance of a single photocatalyst
(Degussa P25 titanium dioxide) for PC0 was compared in two simple photoreactors
virtually identical except that one used a 15 W (electrical) “blacklight” fluorescent
tube as the light source and the other a 15 W germicidal tube. The relative merits
of these two light sources are considered with photoreactor performance in view, with
the intention of stimulating further improvements in the area.

2. Experimental details

2.2. Mater&d
Titanium dioxide was Degussa P2.5, BET surface area 50 m2 g-l, primary particle
size 30 nm, crystalline form mostly anatase, used without further treatment. Salicyclic
acid was supplied by British Drug Houses and phenol by Ajax Chemicals. Both were
analytical reagent grade and were used as supplied. The phenol concentrations in
stock solutions were checked by total organic carbon (TOC) analysis. Solutions were
prepared using water from a Millipore Milli Q water purification system. Instrument
grade air was taken directly from the cylinder and industrial grade oxygen was first
passed through an activated carbon trap. Both gases were supplied by Commonwealth
Industrial Gases. Optical absorption spectra were recorded with a Varian model DMS
300 spectrophotometer.

2.2. Analyses
Salicyclic acid and phenol were analysed by the spectrofluorimetric method described
previously [15] after filtration through Microfiltration Systems 0.45 m cellulose acetate
discs. TOC analyses were carried out by the PC0 method described elsewhere 1161.
After salicyclic acid or phenol analysis the filtrate was returned to the bulk of the
solution so that the volume was essentially constant throughout the experiments in
which only the solute concentration was monitored. In the case of the high concentration
runs in which both solute and TOC were determined, 1 ml samples were taken and
diluted with no return to the bulk. It was estimated that the volume decrease was
less than 20 ml from 0.5 1 during the course of the experiment and no corrections
were made for this.

2.3. Photoreactors
The basic photoreactor geometry is shown in Fig. l(a). The reactors were 406
mm long by 32 mm outside diameter borosilicate glass surrounding NEC 15 W blacklight
fluorescent and germicidal lamps 436 mm long with 25.5 mm outside diameter. The
annulus between the lamps and the reactor walls was 2.25 mm, sealed at each end
with ‘Nitrite’ ‘0’ rings. The inlet and outlet tubes were located approximately 15 mm
from each end of the reactors. The solution or suspension (0.5 1) was pumped through
the reactor and back to the reservoir by means of a peristaltic pump using Viton and
glass tubing in the arrangement shown in Fig. l(b). Unless otherwise stated the rate
of pumping was 300 ml min- l. The suspension was stirred magnetically. Air or oxygen
was bubbled through the suspension by means of a fine stainless steel frit for high
solute concentrations but no gas was bubbled at low solute concentrations.
 357

a
.
F
I

A
.J

0
E
Fig. 1. (a) Photoreactor geometry for both germicidal and blacklight blue fluorescent lamps, see
text for other dimensions; (b), arrangement of photoreactor relative to reservoir and pump, A
800 ml beaker, B peristaltic pump, C photoreactor, D gas sparger, E magnetic stirrer, F clock
glass cover.

3. Results and discussion

3.1. Optical density of suspensions

The optical absorption spectra of 0.05% and 0.10% suspensions determined in
a 1 mm path length cell are shown in Fig. 2. It can be seen that for the 0.05%
suspension there appears to be a maximum at about 325 nm. Neither lamp has a
major emission at this wavelength. The germicidal lamp emits monochromatic light
at 254 nm and the blacklight fluorescent lamp emits between 300 and 425 nm with
a peak at 350 nm [17]. However, it can be seen that for a 0.04% suspension at 254
nm or a 0.1% suspension at 350 nm practically no photons capable of exciting TiOz
(band gap 380 nm) are transmitted beyond the 2.25 mm annulus because of absorption
and scattering. Hence a layer beyond this depth is photocatalytically inert at these
suspension loadings.

3.2. Effect of suspension loading on photocatalytic oxidation

The effect of various suspension loadings on the salicyclic acid destruction in 0.5
1 of initial concentration 50 FM is shown in Fig. 3. Essentially no catalyst exciting
photons are transmitted through the annulus for loadings above 0.1% TiOz, but it is
seen that the rate‘of destruction increases marginally with suspension loading above
0.1%. The enhanced rate must be caused by a greater availability of photo-activated
reaction sites. However, it has been observed elsewhere [18] that increasing the catalyst
loading does not always lead to increasing PC0 rates, as an increasing proportion of
solute may be adsorbed by non-illuminated catalyst particles out of the photo-active
volume.
This may be the situation shown by the highest loading results in Fig. 4 (0.10%).
These results display the effect of suspension loading on salicyclic acid destruction
358

A
0.0 I I 1 I I

250 300 350 LOO L50

WAVELENGTH (nml

Fig. 2. Optical absorption spectra for TiOz suspensions in 1 mm path length cell: A water, 3
0.025% (w/v) TiOz, C 0.05% (w/v) TiOz.

under the same conditions as for Fig. 3 but in this case the light source is 254 nm
radiation from the germicidal lamp. When TiOt is absent the destruction is trivial
(upper line). A sub s tantial rate was observed when a 0.02% TiOz loading was present.
The rate was about twice as fast as that obtained with the same loading and 350 nm
radiation. This increase in rate could be partly caused by the greater light absorption
occurring with the 254 nm light. However, for loadings of 0.04% and above, essentially
all photons are retained within the reactor and the rates with the 254 nm light are
still substantially greater than the rates at the corresponding loading with 350 nm
light. In the case of the 0.04% suspension the rate is about 2.5 times faster with 254
nm light than with 350 nm light. The difference is not as great for 0.1% suspensions:
about 1.6 times faster. The optimum loading for 254 nm light has been exceeded at
0.1% since the rate is slightly less than that at 0.04%. This contrasts with the observation
of increasing rate between 0.04% and 0.1% loading in the case of the 350 nm light
and is probably a result of the greater optical density in 254 nm light.

3.3. Effect of pumping speed

Since it is known that rates of destruction by PC0 are very dependent on solute
concentration at these low concentrations, localized depletion of solute could occur
at low pumping speeds, This could be a source of low photocatalytic efficiency in
poorly stirred large volume immersion reactors. Therefore, we investigated the effect
of pumping speed. The results are shown in Fig. 5. It is seen that at low pumping
speeds (150 ml min-‘) the rate for salicyclic acid destruction is lower than at higher
pumping speeds. There appears to be a marginal increase in rate when the pumping
speed is increased from 300 ml min-’ to 450 ml min-‘. The effect of pumping speed
is expected to be greater at low solute concentrations and less at high solute con-
centrations.
 359

0 10 20 30 LO

TIME (min 1
Fig. 3. Effect of TiOz suspension on salicyclic acid destruction with blacklight fluorescent lamp:
0 0.02% (w/v), (ID0.04% (w/v), 0 0.10% (w/v), a, 0.20% (w/v).

3.4. Effect of solute concentration

The effect of solute concentration on PC0 rates has been studied elsewhere for
many solutes [2]. The dependence invariably follows apparent Langmuir-Hinshelwood
kinetics [19]. That is, at low solute concentrations the rate follows a first-order dependence
on solute concentration but at high solute concentration, zero-order kinetics are
observed [9]. The concentration dependences or the rates of destruction of phenol
for initial concentrations of 10, 50 and 100 p.M are shown in Fig. 6. The open circles
show results for 0.04% suspensions in which no air or oxygen was added to the
suspension via the bubbler but the surface of the suspension in the reservoir was open
to the atmosphere. Evidently diffusion of atmospheric oxygen into the suspension
across the surface was insufficient to keep pace with that depleted by oxidation at
the 100 PM concentration. The rate of the reaction progressively decreased with
increasing illumination times at this concentration. When oxygen was bubbled through
the suspension (tilled circles) the rate became apparently greater than first order at
longer illumination times. Similar results were observed for the effect of different
initial salicyclic acid concentrations on the destruction rate.
Since these results suggested that at an initial concentration of 50 fl the
suspension might also be depleted sufficiently in oxygen to inhibit the PC0 rate to
some degree at the longer illumination times, the effects of air and oxygen bubbling
vs. no bubbling were investigated more closely. The beneficial effect of increased
oxygen concentration has been reported earlier [ZO]. Also, to compare results for
phenol destruction between the two lamps, we used the blackfight-fluorescent lamp
360

I 1 I I I 1 I
Cl 5 10 15 20 25

TIME (min)
Fig. 4. Effect of Ti02 suspension loading on salicyclic acid destruction with germicidal lamp:
8 no Ti02, 0 0.02% (w/v), CD0.04% {w/v), 0 0.10% (w/v).

in this study. The results are shown in Fig. 7. With 0.1% suspensions, when air (half-
filled circles) or oxygen (filled circles) was bubbled through a suspension containing
an initial concentration of phenol of 50 PM, the rate was significantly enhanced
although the difference between the two was only marginally in favour of oxygen.
When the initial concentration of phenol was 100 NM the improvement in rate in
the presence of 100% oxygen bubbling was more pronounced.

3.5. Infiuence of experimental parameters

To obtain a more quantitative comparison of the relative rates of destruction the
data from Figs. 3-7 are summarized in Table 1. The to.5values were the illumination
times required to decrease the concentration measured in the solution bulk at time
zero to 50%. A downward curvature in the semilog plots is apparent in most of the
figures, especially at low concentrations. This has been discussed elsewhere [21].
However, the plots are approximately pseudo-first-order to the disappearance of 50%
of the solute. The d[S]ldt values at the initial concentrations were calculated by
multiplying the concentrations by the corresponding first-order decay constants. From
a consideration of these rates the following observations can be made:
(1) at equivalent TiOz loading, 254 nm light is much more effective in degrading
the solute than 350 nm light (experiments C&8 compared with experiments l-3);
(2) the maximum rate of degradation of 50 PM salicyclic acid using 254 nm light
was achieved with a 0.04% TiOz loading;
(3) the maximum rate of destruction of 50 PM s&cyclic acid using 350 nm light
was achieved with a 0.2% Ti02 loading but this rate was significantly below the
maximum obtained with 254 nm light;
 361

I-
O 2.5 5.0 7.5 IO.0 125 15.0

TIME (min)

Fig. 5. Effect of pumping speed on salicyclic acid destruction with 0.04% (w/v) TiOz and
germicidal lamp: 0 150 ml min-*, l 300 ml min-‘, CD450 ml min-‘.

(4) phenol is degraded at about a 30% lower rate than salcyclic acid under
equivalent conditions (experiments 10 and 17 compared with experiments 3 and 7);
(5) the rate of degradation increases with increasing initial concentration of phenol
(experiments 9-M), markedly at low concentrations and not so markedly at high
concentrations;
(6) the rate of degradation of phenol with 254 nm light and 0.04% TiOz loadings
is significantly greater than with 350 nm light and 0.1% loading (experiments 16-18
compared with experiments 9, 10 and 14).
(7) increasing the oxygen concentration enhances the phenol degradation rate
(experiments 10-12).

3.6. Improved eflectiveness of 254 nm light

The most noteworthy feature of these observations is the much greater apparent
_ _
effectiveness of 254 nm light in promoting the PCO. Both lamps have a nominal
electrical power rating of 15 W. According to the manufacturer the radiative output
of the germicidal lamp is 3.0 W whereas the radiative output of the blacklight lamp
is 2.4 W. The germicidal lamp is 25% more efficient than the fluorescent lamp in
terms of radiative power output but the degradation rate increases are much greater
than 25% (almost a factor of 2 in some cases). Therefore, the increased rates cannot
362

cl 5 IO 15 20 25 30
TIME (min 1
Fig_ 6. Effect of initial concentration on phenol destruction with 0.04% (w/v) TiOz and germicidal
lamp: 0 air saturated suspensions, no bubbling, 0 oxygen bubbling.

be attributed solely to the higher radiative efficiency of the germicidal lamp. Interestingly,
because of the higher energy of 254 nm photons (112.6 kcal einstein-I) ws. the energy
of 350 nm photons (81.7 kcal einstein -‘) the greater photon flux comes from the
fluorescent lamp (420 pmol min-’ vs. 382 ,umol min-‘). The maximum degradation
rate observed in the present experiments was 8.0 pmol mine1 (0.5 1 at 16.1 PM min-‘)
for phenol at an initial concentration of 100 PM in the presence of 0.04% TiOl.
Assuming that all photons were absorbed by the suspension, a quantum yield of 2.1%
is calculated for this rate. The parallel calculation for the blacklight lamp (assuming
that the 2.4 W is all emitted at 350 nm) gives a quantum yield of 1.1%. There is
thus plenty of scope for improvements to photocatalyst activity.
There are at least three possible explanations for the improved effectiveness of
254 nm 21s.350 nm light.
(1) The shorter wavelength light is absorbed more strongly by the TiOz particles
than the longer wavelength light, hence the penetration distance of photons into the
particle is shorter and photoelectrons and holes are formed closer to the surface of
the particle. Therefore, they take less time to migrate to the surface of the particle
and hence have less time to participate in energy wasting recombination reactions
before useful surface (or near-surface) reactions take place.
 363

TIME (min)

Fig. 7. Effect of air and oxygen bubbling on phenol destruction at different initial concentrations
with 0.10% (w/v) TiOz and blacklight blue lamp: @ air bubbling, l oxygen bubbling, 0 air
saturated suspensions, no bubbling.

(2) Although light scattering processes will be greater at 254 nm than at 350 nm
the back scattered light can pass through the germicidal lamp to the suspension
surrounding the lamp. Backscattered light to the fluorescent lamp would probably be
absorbed by the phosphor and lost as heat.
(3) Many organic molecules are excited by 254 nm light and are degraded as a
result of direct action. In the case of salicyclic acid there is absorption at 254 nm but
not at 350 nm. The direct action degradation rate is small compared with the rate
in the presence of photocatalyst (Fig. 4). However, the enhanced photocatalytic effect
at 254 nm may reflect a more facile photocatalytic oxidation of excited salicyclic acid
species than that of ground state species. Future analysis and experiments on these
and other proposals will reveal the relative importance of the various processes accounting
for the improvements observed here with 254 nm light.
In practice, it may be debatable whether the improvements obtained will warrant
the additional expense and hazards associated with short-wavelength lamps. The opacity
of most materials to short-wavelength WV light is a disadvantage. Borosilicate glass
sleeves separating lamps from Iiquids are comparatively cheap. Quartz is expensive.
364

TABLE 1
Effect of TiOz loading and different lamps on solute destruction under various conditions

Experiment Solute Initial TiOz Wavelength to.5 d[S]/dt”

concen- loading (nm) (min) (pM min-‘)
tration (% w/v)
(PM)

1 Salicyclic acid 50 0.02 350 8.8 3.94

2 Salicyclic acid 50 0.04 350 6.5 5.33
3 Salicyclic acid 50 0.10 350 4.5 7.70
4 Salicyclic acid 50 0.20 350 3.5 9.90
5 Salicyclic acid 50 0.00 254 >60 < 0.58
6 Salicyclic acid 50 0.02 254 4.5 7.70
7 Salicyclic acid 50 0.04 254 2.5 13.9
8 Salicyclic acid 50 0.10 254 2.7 12.8
9 Phenol 10 0.10 350 3.0 2.31
10 Phenol 50 0.10 350 5.5 6.30
11 Phenol (air bubble) 50 0.10 350 5.0 6.93
12 Phenol (0, bubble) 50 0.10 350 4.7 7.37
13 Phenol (air bubble) 100 0.10 350 8.8 7.88
14 Phenol (0, bubble) 100 0.10 350 7.5 9.24
15 Phenol (0, bubble) 1000 0.10 350 55 12.6
16 Phenol 10 0.04 254 2.3 3.01
17 Phenol 50 0.04 254 3.1 11.2
18 Phenol (0, bubble) 100 0.04 254 4.3 16.1

‘d[S]/df= 0.693[S]“/t,,.

3. Z Photoreactor efickncy
The goal of water treatment processes for organically contaminated water is to
decrease the TOC content to acceptable levels. The cost of the treatment will be
strongly dependent on the electrically consumed. Therefore, a logical expression of
efficiency for a photochemical water treatment process is TOC destroyed per litre per
kilowatt hour as used by Braun [14]. In photochemical and photocatalytic processes
the reporting of quantum yield is vital information concerning the photochemical
processes but does not give the overall efficiency of the photoreactor. It was of interest,
therefore, to express the performance of the present reactor arrangement in terms of
solute degraded and TOC destroyed per litre per kilowatt hour.
The results of phenol destruction and carbon dioxide formation for 1mM phenol
containing 0.1% TiOz illuminated with the blacklight lamp are shown in Fig. 8. In
this experiment (listed as 15 in Table 1) the pH was adjusted to 4.0 with perchloric
acid before illumination commenced. Oxygen was bubbled continuously during the
experiment so that COz was purged from the system. The TOC measurements were
made on the suspension and the CO2 formation curve was calculated by difference.
The time taken to oxidize 50% of the phenol to CO2 was 87 min giving a rate of 5.7
PM min-’ ( e q uivalent to 0.41 ppm TOC min-l). Since the working volume was 0.5
1 this translates to 820 ppm TOC 1-l kWh_l.
The initial rate of phenol degradation at a concentration of 1 mM was 12.6 PM
min-l. Under the experimental conditions this converts to 2370 ppm 1-l kWh_l.
Increasing the initial concentration of phenol to 10 mM made no significant difference
to either the rate of phenol degradation or the rate of mineralization. That is, at 1
 365

CD

z 600_
5

s 500_

w’
z LOO -
U

300 -

200 -

loo_

I I
30 60

TIME (min)

Fig. 8. Phenol destruction and mineralization with 0.1% (w/v} TiOz and blacklight blue lamp,
oxygen bubbling: 0 phenol destruction, l phenol converted to CO2 from TOC measurements.

mM phenol the rates are in the region independent of solute concentration. At high
light intensities a dependence of photocatalytic degradation rates on the square root
of intensity has been reported merging into first-order dependence at low intensities
[20]. In the present experiments the radiative intensity at the surface of the fluorescent
tube is 2~ 1016 photons s-l cmm2.
The phenol degradation rates and mineralization rate obtained here appear to
represent a substantial improvement over previously reported rates. Even greater rates
can be expected if 254 nm fight is used instead of 350 nm. Phenol is a common
contaminant in industrial wastewaters with “middle of the road” oxidation rates in
photoactivated TiOa suspensions [22]. Phenol and Degussa PZ5 TiO, seem to be a
suitable solute and photocatalyst for evaluating the performance of any photocatalytic
reactor.

4. Conclusions

Photocatalytic reactors of simple annular design were constructed around blacklight

fluorescent and germicidal tubular lamps. The design allowed a direct comparison to
be made between the relative efficiencies, based on electrical power requirements, of
254 nm radiation vs. blacklight radiation for the PC0 of salicyclic acid and phenol
as model wastewater contaminants. The shorter wavelength 254 nm radiation is
significantly more effective in promoting the PC0 of these solutes than blacklight
366

radiation. The degradation rates obtained with these reactors was significantly greater
than most rates previously reported. With more attention to reactor design further
improvements can be anticipated.

Acknowledgment

This work was partially funded by a grant from the Australian Land and Water
Resources Research and Development Corporation.

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