Applied Catalysis A: General 262 (2004) 105110

Intrinsic kinetics of photocatalytic oxidation of formic and oxalic acid on immobilised TiO2 lms
T.A. McMurray a , J.A. Byrne a, , P.S.M. Dunlop a , J.G.M. Winkelman b , B.R. Eggins a , E.T. McAdams a
b

NIBEC, University of Ulster at Jordanstown, Newtownabbey BT37 0QB, Northern Ireland, UK Department of Chemical Engineering, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The Netherlands Received in revised form 12 November 2003; accepted 14 November 2003

Abstract Titanium dioxide (TiO2 ) photocatalysis is a possible alternative/complementary technology to conventional water treatment methods. The TiO2 catalyst may be used as slurry or it may be immobilised onto a supporting substrate. With immobilised TiO2 lms mass transfer problems occur in most photocatalytic reactors, which results in a reduction of reactor efciency and in the accuracy of measured catalyst efciency and kinetics. In order to determine the real intrinsic kinetics of photocatalytic reactions on immobilised TiO2 lms a stirred tank reactor (STR) was used. The reactor incorporated a propeller and a bafe, thus providing good mixing and efcient mass transfer to the TiO2 lm. Degussa P25 was immobilised onto borosilicate glass by a dip coating method and the kinetics of the photocatalytic degradation of the model pollutants, formic acid and oxalic acid were investigated as a function of catalyst loading, initial pollutant concentration and propeller rotation speed. The rate of degradation, of either acid, was not mass transfer limited at propeller speeds greater than 1000 rpm. The rate of formic acid degradation was dependent upon catalyst loading up to a maximum loading above which a decrease in the degradation rate was observed. The apparent quantum yield for the photocatalytic degradation was 5% for oxalic acid and 10% for formic acid. This compares very well with usual reported apparent quantum efciencies for photocatalysis which are 1%. The photocatalytic oxidation of both acids could be described using a LangmuirHinshelwood kinetic model. 2003 Elsevier B.V. All rights reserved.
Keywords: Titanium dioxide; Photocatalysis; Formic acid; Oxalic acid; Kinetics

1. Introduction Titanium dioxide (TiO2 ) photocatalysis is a possible alternative/complementary technology to conventional water treatment methods [13]. When TiO2 is illuminated with light < 400 nm, electronhole pairs are generated. The valence band holes are strongly oxidising and can react with water or hydroxide ions at the interface to produce hydroxyl radicals. Hoffman et al. [1] reviewed the evidence for both direct hole transfer and indirect hole transfer via surface bound hydroxyl radical, and signicant body of literature was found in support of both mechanisms. Both hydroxyl radicals and valence band holes are powerful and indiscriminate oxidizing species and will attack organic pollutants at
Corresponding author. Tel.: +44-289-36-8941; fax: +44-289-36-6863. E-mail addresses: ta.mcmurray@ulster.ac.uk (T.A. McMurray), j.byrne@ulst.ac.uk (J.A. Byrne).

the surface to yield carbon dioxide, water, and the respective mineral acids or salts [4]. Carraway et al. [5] reported evidence for direct hole oxidation of tightly bound electron donors such as formate at the semiconductor surface. The catalyst may be used either as an aqueous slurry or it may immobilised onto a supporting substrate [6]. Suspension or slurry type reactors have been reported to be efcient due to the large surface area of catalyst available for reaction and the efcient mass transfer within such systems [7]. However, due to the small particle size of the TiO2 particles, a post-treatment catalyst recovery stage involving microltration is necessary. Post-treatment catalyst recovery would be undesirable at industrial scale as it would add to the capital and operating costs of the treatment process. Alternatively, the TiO2 may be immobilised onto a supporting substrate such as glass [8]. With an immobilised system one can obtain a conguration in which all the catalyst is illuminated, therefore the thickness of the supported catalyst layer should be thin enough to enable the light to

0926-860X/$ see front matter 2003 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2003.11.013

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reach all the catalyst [9]. However, the use of immobilised TiO2 lms leads to mass transfer problems in most photocatalytic reactors which results in a reduction of reactor efciency and in the accuracy of measured catalyst efciency and kinetics [10,11]. In order to determine the real intrinsic kinetics of photocatalytic reactions on immobilized TiO2 lms, a stirred tank reactor (STR) was used. The reactor incorporated a propeller and a bafe, thus providing good mixing and efcient mass transfer to the TiO2 lm. The kinetics of the photocatalytic degradation of model pollutants, formic acid and oxalic acid, were investigated using TiO2 lms immobilized on borosilicate glass. The effects of operational parameters on the rate of degradation of the pollutants is reported, i.e. propeller rotation speed, catalyst loading, and initial pollutant concentration. The organic pollutant for a standard test system should be a recognised organic pollutant. It should be cheap, easily analysed, water soluble, photochemically inactive, non-volatile and readily and completely photomineralised using Degussa P25 TiO2 as the semiconductor photocatalyst [2]. Degussa P25 is reported to have a high photocatalytic activity, which is due to the mixed phase of anatase and rutile in P25 promoting charge-pair separation and inhibiting recombination [1]. Formic acid and oxalic acid were used as the model pollutants in this study because: (1) they are oxidised directly to CO2 without the formation of any stable intermediate products; (2) they are intermediate products in the photocatalytic degradation of other larger organic compounds; and (3) they have been used previously in photocatalytic studies [1214].

Fig. 1. Schematic representation of a stirred rank reactor.

2. Experimental 2.1. Immobilisation of TiO2 Borosilicate glass plates (110 mm 110 mm) were cleaned by sonication in hot detergent solution followed by several rinses in distilled water. The plates were then dried and weighed. TiO2 was dipcoated from a 5% TiO2 (Degussa P25) methanol suspension with a constant withdrawal rate 4.3 mm s1 . The plates were dried after each coat using an IR lamp. This procedure was repeated to produce plates with a range of TiO2 loadings. One side of the coated plate was cleaned to remove the TiO2 and the plates were annealed in air at 673 K for 1 h. Gravimetric analysis of the plates was used to determine the TiO2 loading. The borosilicate glass has a refractive index of 1.489 at = 365 nm, which gives a corresponding loss due to reection of a perpendicular beam of 3.8%. 2.2. Stirred tank reactor A major concern in designing photocatalytic reactors is to minimize mass transfer limitations within the reactor. Mass

transfer limitations considerably decrease the accuracy of measured catalyst efciency and kinetics. A stirred tank reactor was used due to the simplicity of the system and the ability to eliminate any mass transfer limitations. Good mass transfer behaviour is obtained as turbulent ow within the reactor can be created in order to transport the organic pollutant towards the coated TiO2 plate and disperse O2 from the headspace into the liquid. A schematic representation of the STR is given in Fig. 1 and corresponding dimensions in Table 1. The coated TiO2 glass plate was secured to the bottom of a water-jacketed walled vessel creating a reservoir. A stainless steel propeller was used in order to create a turbulent ow directed towards the coated glass plate were the reaction takes place and mass transfer rates should be maximised. The rotation of the propeller was achieved using a homogenator motor (Camlab Ltd., Tri-R Instruments model S63C) giving rotation speeds over the range 02500 rpm. The homogenator motor was calibrated using an optical tachometer. A stainless steel bafe was used to increase mixing within the reactor. The catalyst was illuminated from below using two PL-S 9W/10 UV-A uorescent lamps (Philips) with a stable output between 350 and 400 nm (peak emission at 370 nm), which were positioned at a distance of 2.5 cm away from the TiO2 glass plate. The light intensity entering the reactor was determined by potassium ferrioxalate actinometry [15]. Oxygen (99.5%) was added to the headspace of the reactor. The glass wall of the reactor consisted of a cooling jacket connected to a thermostatic bath for temperature regulation
Table 1 Specications of stirred tank reactor Dimensions of STR Outer diameter (including cooling jacket) (m) Inner diameter (excluding cooling jacket) (m) Height (m) Reactor volume (m3 ) Illuminated catalyst area (m2 ) Height of propeller from bottom (m) 1.00 8.50 9.50 5.40 5.67 4.00 101 102 102 104 103 102

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of the system (Grant FH5 ow heater and a Grant FC25 ow cooler). The reactor was kept at a constant temperature (20 2 C) throughout the experiments. 2.3. Determination of relative mass transfer coefcient Borosilicate glass was cleaned, weighed and coated with benzoic acid by pouring molten benzoic acid over the plate. Benzoic acid melts between 122 and 123 C, and partly sublimes at this temperature. On contact with the glass plate, the benzoic acid immediately solidied, yielding a thick uniform layer of benzoic acid on the plate. Once cooled, a circumference matching that of the base of the reactor was etched using a knife and the excess removed. The remaining benzoic acid layer, conforming to the catalyst lm geometry, was smoothed using a hot cloth and rinsed with distilled water. The plate was weighed to determine the amount of benzoic acid present. Experiments were carried out at propeller rotational speeds of 1000, 1500 and 2000 rpm. The benzoic acid coated plate was placed in the reactor and the reactor was lled with 200 cm3 of water. A 2.0 cm3 sample was taken immediately, then every 30 s in the rst 2 min, and then every minute there after for a total of 10 min. The benzoic acid concentration was determined by UV absorption at 272 nm (Perkin-Elmer, Lambda 11). 2.4. Photocatalytic experiments The UV lamps were allowed to stabilise for 20 min prior to commencing experiments. Aqueous solution (200 cm3 ) of formic acid or oxalic acid, with the desired initial concentration, was added to the reactor and the headspace purged with O2 . The propeller was switched on and adjusted to the required speed. A 1.5 cm3 sample was taken immediately (t = 0 s) and every 15 min thereafter, usually for 2 h. 2.5. Analysis The concentration of formic acid and oxalic acid were determined by Ion Exclusion HPLC with an Aminex HPX-87H Ion Exclusion Column (300 mm 7.8 mm i.d., Bio-Rad). Conditions were as follows: mobile phase was 1 103 mol dm3 H2 SO4 pH 1.5 at a ow rate of 0.8 cm3 min1 , column temperature was 30 C, injection volume was 100 l for formic acid and 20 l for oxalic acid, UV detection at = 210 nm.

Fig. 2. Benzoic acid concentration vs. time at different propeller rotational speeds. Table 2 Mass transfer coefcients calculated for benzoic acid at varying propeller rotational speeds Propeller speed (rpm) 1000 1500 2000 k1 (m s1 ) 105 2.48 3.54 3.90

a function of time for the three propeller speeds studied, i.e. 1000, 1500 and 2000 rpm. To determine the mass transfer coefcient (k1 ) from the concentration (C) versus time (t) curve the balanced Eq. (1) was used: dC V = k1 A(Cs C) (1) dt where V is the volume of water present in the reactor, A the area covered with benzoic acid, and Cs the solubility of benzoic acid in water (the saturated concentration of benzoic acid in water over solid benzoic acid). Using the data, the mass transfer coefcient for benzoic acid in this reactor was determined for each propeller speed (Table 2). The relative mass transfer coefcient for formic acid and oxalic acid (Table 3) was then determined using the diffusion coefcients for benzoic acid, formic acid and oxalic acid (Eq. (2)), where the exponent is valid for turbulent conditions [16]. k1,oxalic/formic =
0 Doxalic /formic 0 Dbenzoic 0.67

k1,benzoic

(2)

3. Results and discussion 3.1. Relative mass transfer coefcient The mass transfer coefcient was estimated at several rotational stirrer speeds by performing experiments with benzoic acid. Fig. 2 shows the concentration of benzoic acid as

Table 3 Calculated relative mass transfer coefcients for formic acid and oxalic acid Propeller speed (rpm) 1000 1500 2000 k1 formic acid (m s1 ) 105 3.83 5.47 6.01 k1 oxalic acid (m s1 ) 105 3.25 4.65 5.11

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Fig. 3. Effect of catalyst loading and apparent quantum yield on formic acid degradation rate.

Fig. 4. Effect of propeller rotational speed on formic acid and oxalic acid degradation rate.

The diffusion coefcient of benzoic acid (7.821010 m2 s1 ) and formic acid (1.49 109 m2 s1 ) were determined using the methods of Wilke-Chang and Le Bas [17] and the diffusion coefcient for oxalic acid used (1.17 109 m2 s1 ) was taken from Kulas et al. [11]. 3.2. Catalyst loading In the dip coating procedure it was found that the catalyst loading was directly proportional to the number of dips with 3.9 104 kg m2 of TiO2 deposited per dip. The rate of degradation of formic acid was measured as a function of catalyst loading in order to determine the optimum catalyst loading. The initial concentration of formic acid was 5.3 mol m3 and the degradation was observed to follow zero-order kinetics. Formic acid (99%) was degraded after 90 min of illumination using a catalyst loading of 1.17 102 kg m2 . For the lowest catalyst loading (1.2 103 kg m2 ), 91% degradation was achieved in 240 min. The rate of degradation increased with increasing catalyst loading, up to an optimum loading of approximately 1.17 102 kg m2 . It was found any further increase above this catalyst loading caused a decrease in the rate of degradation (see Fig. 3). This trend has been observed with other workers [18,19] and can be explained by the fact that as the catalyst lm becomes too thick the TiO2 will begin to effectively mask itself with the total irradiation being absorbed by only the initial layers of catalyst. The maximum rate, under the conditions of these experiments, will be achieved when all of the incident light is absorbed by the catalyst lm. This occurs, for I0 ( = 370 nm) = 3.5 104 Einstein m2 s1 , when the catalyst loading is approximately 1.17 102 kg m2 (see Fig. 3). 3.3. Rate as a function of propeller rotation speed The rate of degradation was examined as a function of propeller speed to determine if it was mass transfer limited. Experiments at three different propeller rotations, i.e. 2000,

1500 and 1000 rpm were performed. Fig. 4 shows the concentration versus time plot for the different rotation speeds for formic acid and oxalic acid. The rates for each of the propeller speeds were very similar with a coefcient of variance of 2% for formic acid and 3% for oxalic acid (Table 4). Therefore it was concluded that the photocatalytic degradation of formic acid and oxalic acid was not mass transfer limited under the conditions of the experiments. 3.4. Rate as a function of formic acid concentration The degradation of pollutants can be described by the LangmuirHinshelwood kinetic model [1,4,20]. Assumptions for the LH model have been described by Fox and Dulay [21] suggesting that: (1) only one substrate can bind at each surface site; (2) at equilibrium the number of surface adsorption sites is xed; (3) there is no interaction between adjacent adsorbed substrates; (4) the rate of surface absorption of the substrate is larger than the rate of any subsequent chemical reactions; and (5) the heat of absorption by the substrate is identical for each site and is independent of surface coverage. Two situations can exist: pseudo zero-order kinetics and pseudo rst-order kinetics. In the STR the degradation rate of formic acid and oxalic acid appeared to follow pseudo zero-order kinetics (see Fig. 5).
Table 4 Determined rates for formic acid and oxalic acid at varying propeller rotational speeds rpm Formic acid 1000 1500 2000 Oxalic acid 1000 1500 2000 Rate (mol m2 s1 ) 105 3.03 2.94 3.06 1.59 1.53 1.48 R2 Data points 7 7 7 13 13 13

0.946 0.990 0.986 0.991 0.993 0.990

T.A. McMurray et al. / Applied Catalysis A: General 262 (2004) 105110 Table 5 Initial rate of degradation for different initial concentrations of acid Initial concentration (mol m3 ) Formic acid 5.20 4.20 3.10 2.80 0.52 Oxalic acid 5.00 4.00 3.00 2.00 1.00 Fig. 5. Effect of initial concentration and apparent quantum yield on formic and oxalic acid degradation rate.

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Rate (mol m2 s1 ) 105 3.45 3.36 3.33 3.13 2.62 1.52 1.69 1.52 1.20 0.95

The rate law is shown in Eq. (3), where R is the initial rate of the disappearance of formic acid and [S] is the initial concentration. K is the Langmuir adsorption constant and k is the rate proportionality constant. R= kK[S ] 1 + K[S ] (3)

3.5. Quantum efciency Potassium ferrioxalate actinometry was carried out to determine the light intensity falling upon the TiO2 lm. The actinometer solution conforms to reactor dimensions and only measures the light that enters the reactor. The method used in this case is as that of Hatchard and Parker as given in Calvert and Pitts [15]. The incident photon ux on the TiO2 coated support was determined to be 3.5 104 Einstein m2 s1 . The apparent quantum yield (app ) of the reaction can be dened as the initial degradation rate (mol m2 s1 ) of pollutant divided by the photon ux (I0 ) (Einstein m2 s1 ) (Eq. (4)). app = rate I0 (4)

The usual method for obtaining values for K and k is to plot a double reciprocal plot of initial rate (R) versus initial concentration [S] (Fig. 6; rate data shown in Table 5). Such a plot should be linear if the LH rate form is representative. The intercept of this line corresponds to 1/k and the slope is equal to 1/kK. Therefore, if k is independent of reactant, the intercepts should be equal for all reactants degraded in the same reactor and under the same conditions [22]. For formic acid, k was determined to be 3.77 105 mol m2 s1 , and K to be 2.23 m2 mol1 . For oxalic acid, k was determined to be 1.99 105 mol m2 s1 and K to be 0.88 m2 mol1 . The rate constant k for formic acid is close to twice that measured for oxalic acid and therefore k, in this instance, is not independent of the reactant.

app increases with catalyst loading (Fig. 3) and reaches a maximum corresponding to the optimum lm thickness. The maximum app measured were 10% for formic acid and 5% for oxalic acid (see Fig. 5). This is an important nding as normally reported app values for photocatalytic systems are ca. 1% [3].

4. Conclusions The kinetics of the photocatalytic degradation of oxalic and formic acid on immobilized TiO2 lms were investigated under conditions of high mass transfer using a novel stirred tank reactor. The effect of operational parameters on the rate of degradation were investigated, i.e. propeller rotation speed, catalyst loading, and initial pollutant concentration. It was found that the rate of degradation was not signicantly dependent upon the propeller rotation speed and therefore not mass transfer limited. The degradation rate increased with increasing catalyst loading until an optimum was reached above which, the rate decreased. Both oxalic and formic acid degradation kinetics were found to obey a LangmuirHinshelwood type kinetic model. The

Fig. 6. Double reciprocal of rate vs. initial concentration for formic and oxalic acid.

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T.A. McMurray et al. / Applied Catalysis A: General 262 (2004) 105110 [7] M.F.J. Dijkstra, et al., Comparison of the efciency of immobilized and suspended systems in photocatalytic degradation, Catal. Today 66 (24) (2001) 487. [8] J.A. Byrne, et al., Immobilisation of TiO2 powder for the treatment of polluted water, Appl. Catal. B: Environ. 17 (12) (1998) 25. [9] A.K. Ray, A. Beenackers, Novel photocatalytic reactor for water purication, Am. Inst. Chem. J. 44 (2) (1998) 477. [10] A.K. Ray, A. Beenackers, Development of a new photocatalytic reactor for water purication, Catal. Today 40 (1) (1998) 73. [11] J. Kulas, et al., Photocatalytic degradation rate of oxalic acid on the semiconductive layer of n-TiO2 particles in the batch mode plate reactor. Part I. Mass transfer limits, J. Appl. Electrochem. 28 (8) (1998) 843. [12] R.J. Candal, W.A. Zeltner, M.A. Anderson, Effects of pH and applied potential on photocurrent and oxidation rate of saline solutions of formic acid in a photoelectrocatalytic reactor, Environ. Sci. Technol. 34 (16) (2000) 3443. [13] D.H. Kim, M.A. Anderson, Solution factors affecting the photocatalytic and photoelectrocatalytic degradation of formic acid using supported TiO2 thin lms, J. Photochem. Photobiol. A: Chem. 94 (23) (1996) 221. [14] D.H. Kim, M.A. Anderson, Photoelectrocatalytic degradation of formic-acid using a porous TiO2 thin-lm electrode, Environ. Sci. Technol. 28 (3) (1994) 479. [15] J.G. Calvert, J.N. Pitts (Eds.), Photochemistry, 1973, Wiley, New York, p. 783. [16] K.R. Westerterp, W.P.M. Van Swaaij, A.A.C.M. Beenackers (Eds.), Chemical Reactor Design and Operation, second ed., Wiley, New York, 1984, p. 399. [17] R.C. Reid, J.M. Prausnitz, B.E. Poling (Eds.), The Properties of Gases and Liquids, fourth ed., McGraw-Hill, New York, 1987, p. 577. [18] A. Mills, J.S. Wang, Photomineralisation of 4-chlorophenol sensitised by TiO2 thin lms, J. Photochem. Photobiol. A: Chem. 118 (1) (1998) 53. [19] H.T. Chang, N.M. Wu, F.Q. Zhu, A kinetic model for photocatalytic degradation of organic contaminants in a thin-lm TiO2 catalyst, Water Res. 34 (2) (2000) 407. [20] R.W. Matthews, Kinetics of photocatalytic oxidation of organic solutes over titanium-dioxide, J. Catal. 111 (2) (1988) 264. [21] M.A. Fox, M.T. Dulay, Heterogeneous photocatalysis, Chem. Rev. 93 (1) (1993) 341. [22] C.S. Turchi, D.F. Ollis, Photocatalytic reactor designan example of mass-transfer limitations with an immobilized catalyst, J. Phys. Chem. 92 (23) (1988) 6852.

maximum apparent quantum yield for oxalic acid was 5% and that for formic acid was 10%, under the conditions of the experiments. This compares well with other studies reporting ca. 1% for photocatalytic reactions. Further work will investigate the effect of light intensity, pH and ionic strength on the degradation kinetics.

Acknowledgements The authors would like to thank Degussa for supplying samples of P25, Henk Giller, Philips lighting, The Netherlands, for supplying UV lamps, the engineering technical staff of the University of Ulster for reactor construction, the European Commission for funding under the 4th and 5th Framework Programmes for PCATIE ENV4-CT97-0632 and PEBCAT EUK1-CT-2000-00069 respectively. Also to, the Department of Higher and Further Education Training and Employment, Northern Ireland, for funding T.A. McMurray.

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