Photocatalytic properties of porous titania grown by oblique angle deposition

M. J. Riley, B. Williams, G. Y. Condon, J. Borja, T. M. Lu et al. Citation: J. Appl. Phys. 111, 074904 (2012); doi: 10.1063/1.3699370 View online: http://dx.doi.org/10.1063/1.3699370 View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v111/i7 Published by the American Institute of Physics.

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JOURNAL OF APPLIED PHYSICS 111, 074904 (2012)

Photocatalytic properties of porous titania grown by oblique angle deposition

M. J. Riley, B. Williams, G. Y. Condon, J. Borja, T. M. Lu, W. N. Gill, and J. L. Plawskya)
Department of Chemical and Biological Engineering, Rensselaer Polytechnic Institute, Troy, New York 12180, USA

(Received 2 November 2011; accepted 2 March 2012; published online 5 April 2012) High surface area nanorods of titanium dioxide were grown by oblique angle deposition on a transparent substrate to investigate their effectiveness as photocatalytic agents for the destruction of organic contaminants in air and water. Optical transmission measurements were made that allowed for an estimation of the porosity of the lm (75%-78%). Comparing transmission measurements with those from a dense anatase lm showed that the penetration depth for the light into the nanorod lm was 2.5 times that in a dense, anatase lm. The photocatalytic degradation of indigo carmine dye on the porous lms was shown to depend on lm thickness and annealing conditions. The effectiveness of the lm was assessed by observing the change in absorbance of the dye at 610 nm over time and quantifying the lm performance using a pseudo-rst-order reaction rate model. Reaction rates increased as the lm thickness increased from 600 nm to 1000 nm, but leveled out or decreased at thicknesses beyond 1500 nm. A transport/reaction model was used to show that there exists an optimal geometry that maximizes the overall reaction rate and that such a geometry can be simply produced using glancing angle deposition. The nanorod lms were benchmarked against nanoparticle lms and were shown to perform as well as 0.73 g/L of C 25-nm-diameter anatase nanoparticles with surface area of 50 m2/g. V 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3699370]
kh

INTRODUCTION

TiO2 hv ! e h ; OH h ! OH ; O 2 e ! O : 2
ka kd

(1) (2) (3)

Titanium dioxide (titania) is used commonly as a pigment in paint and in sunscreen. In the presence of UV radiation, it also acts as a photocatalyst, causing organic molecules to decompose. This property is of great interest for air and water purication, since contaminants that adsorb to the titania surface can be eliminated or broken down into less harmful substances.1 The number of publications on this subject has proliferated since the early 1970s. Initial work concentrated on hydrogen production and eventually expanded into environmental solutions for wastewater treatment and air quality as more practical applications for titania became evident.1 A key concern is designing a system that brings the light, the contaminant, and the surface of the titania together to maximize the reaction rate needed in applications where the ow rate or exposure to the catalyst is limited. The effectiveness of the titania depends on the catalyst surface area, crystalline structure, the bandgap (3.2 eV), and the intensity of UV radiation.2 Anatase has better photocatalytic activity than rutile due to a higher indirect band-gap and the tendency to contain many lattice defects, which act as electron traps and delay recombination.2 When conditions are favorable, electron and hole pairs are generated by the excitation of UV light that have a lifetime long enough to migrate to the surface and react with water to produce hydroxyl radicals, depicted in Fig. 1. The creation of surface radicals is expressed by the following:

The super oxide, O , facilitates the photocatalytic activity 2 by preventing exciton pair recombination, and the hydroxyl radicals are unstable and will pull hydrogen atoms from organic compounds. The radicals initiate a series of reactions, depending on the complexity of the molecule, that eventually lead to the evolution of CO2 or other innocuous compounds,3,4 as shown in Eq. (4). OH pollutant O ! products CO2 ; H2 O; etc:: (4) 2 The Langmuir-Hinshelwood mechanism is most often used to describe the overall reaction rate on the photocatalyst surface, ) Adye STiO2 ( AS;
ka ka kp

(5) (6) (7)

AS ( BS; )
ks

ks

BS ( Bproducts S: )
kb

kb

a)

Author to whom correspondence should be addressed. Electronic mail: plawsky@rpi.edu.

Equations (5)(7) describe the adsorption of an organic reactant, its degradation, and the desorption of the product from the surface, respectively. It is assumed that the forward and
C V 2012 American Institute of Physics

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related to the surface area of the nanorods available for adsorption, while kS contains information on hydroxyl radical concentrations, which depends on exciton generation rate for a given UV radiation intensity. In 2005, J.-M. Hermann showed that a linear relationship between light ux and reaction rate exists, except close to the high light ux regime, where electron-hole recombination is favored, and the rate is proportional to the square root of ux.5 For consideration here, a simple proportionality is assumed, and the constants are lumped together as kLH. CA represents the initial concentration of indigo carmine dye in the experiments.
FIG. 1. The absorbed photons produce electron-hole pairs, some of which react with O2 and OH on the surface.

dC kLH KA CA kLH h0 : 1 KA CA dt

(15)

reverse steps in Eqs. (5) and (7) are in equilibrium, and, as such, the relationships can be expressed as kA CA CS kA CAS : Dening KA to equal kA/KA transforms Eq. (8) to CAS KA CA CS : The same process can be used for desorption, kB CBS kB CB CS ; transforming Eq. (10) by dening KB as kB/kB. CBS KB CB CS : (11) (10) (9) (8)

The total active site balance (CT total number of available sites) is CT CS CAS CBS : (12)

CAS and CBS from the rate equations are then substituted into the site balance, Eq. (12), to solve for CS, CS CT : 1 KA CA KB CB (13)

Now we consider the reaction step rate of Eq. (6). We assume that the degradation of indigo carmine is irreversible and that this step is rate-limiting. The nal substitution for CS yields the rate expression for the rate-limiting reaction step, rs ks AS ks BS % ks AS C T ks K A C A : 1 KA CA KB CB (14)

Equation (14) is simplied by recognizing that the reaction product(s) is/are only weakly adsorbed on the surface, rendering KBCB ( 1, KACA, and thereby eliminating the term KBCB. The constants CT and ks contain information on how the surface of the nanorods provides reaction sites based on the pore structure and UV light intensity. The two parameters are functions of the depth within the lm and can be affected by changing the tilt angle during growth. CT is

The kinetics of the breakdown of several dyes have been studied and shown to accurately follow a pseudo rst-order rate law, which we can approximate in Eq. (15) when KACA( 1 and the illumination is constant.68 Nanoparticles and solid lms of titania are the prevalent forms in existing catalytic systems. The nanoparticles used in this work were of anatase phase and have a reported surface area of 50 m2/g. In loose form, they must be immobilized in a matrix and irradiated remotely, so are utilized in enclosed reactors, where the uid to be cleansed is forced over or through them.9 A difculty associated with irradiation using a remote source is that much of the light intensity is lost as it passes through the medium to be cleansed, and as it gets dissipated within the titania, an effect Gogate calls the shadow effect.10 Not only does the intensity of radiation decay with distance from the source as 1/d2, but a layer of catalyst too thick will also absorb a portion of the light. Solid lms are easy to deposit and are mechanically robust, but lack the surface area required to promote high reaction rates.1 A lm which can harvest the light efciently by providing direct contact to its illumination source and that maintains a high rate of reaction would expand the type of environment and devices that could use photocatalysis. Thin lms of discrete titania nanorods, fabricated using glancing angle deposition, offer the possibility of high surface area, exible geometry, and high illumination efciency. The deposition method allows for direct contact of the titania to the light source, and so a substrate, such as a UV light-emitting diode (LED), would provide a low prole and versatile photocatalytic solution. The nanorod lm would be designed such that the amount of UV radiation escaping the lm would be controlled, so that such a device could potentially operate in inhabited areas. Pyun et al. studied some of the basic parameters of deposition of TiO2 by oblique angle deposition; specically, the crystallographic structure of anatase was veried and the deposition angle that provides the highest catalytic activity was determined.11 The method they used to gather optical constants and estimate the porosity of their lms, ellipsometry, is a standard tool for characterizing thin solid lms, but poses a modeling challenge when trying to characterize thick porous lms with high surface roughness. We present two alternative methods to measure porosity simply using transmittance. This work also reveals how lm thickness and annealing conditions are

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This deposition method has been used to make antireection coatings and photonic crystals14,15 and is slowly nding its way into other areas for sensors and photocatalysis.11,16 Importantly, Pyun et al. established that deposition incident angles up to 60 increased the PCA, after which there was a decline in activity.11 The paper considers this result and compares the PCA of nanorod lms of thickness from 600 nm to 1500 nm against nanoparticles to provide an estimate of surface area.
EXPERIMENTAL METHODS

FIG. 2. Electron beam evaporator with oblique angle deposition conguration, with 2-axis control of the orientation of the substrate with the vapor.

important factors in determining the photocatalytic activity (PCA) and compares reaction rate constants of nanorods with that of nanoparticles to demonstrate their competitive performance. We also offer an explanation for why we observe differences in catalyst effectiveness as a function of nanorod length and deposition angle. Oblique or glancing angle deposition is used to deposit high surface area nanorods on a solid substrate. Applications of thin lms grown using this method are relatively new, but are increasing, since the technique offers a level of porosity control not available using other methods.12 Figure 2 shows the e-beam deposition system apparatus that creates porous lms by mounting the substrate at an angle relative to the incoming vapor ux. The angle of incidence and rotation can be controlled independently during deposition to change the porosity and rod direction, respectively.13 As the lm grows, the incoming particles have limited access to the surface, since areas that nucleate rst dominate the growth, depicted in Fig. 3. As growth continues, rods form from the nucleated areas and grow toward the normal. Spirals are made by rotating the sample around its normal axis, which changes the direction of the rod growth.

Films were prepared by e-beam evaporation of TiO2 (99.95% purity) in the presence of oxygen onto conventional soda-lime glass microscope slides. The substrates were unheated and mounted 0.3 m from the source at an angle of 70 relative to the ux for 2/3rds of the deposition time and 80 for the nal 1/3rd. Higher angles result in higher porosity. The change in incident angle was intended to increase the porosity at the rod tips to allow for easier diffusion of dye into the lm, while helping to extend the reach of the UV light. A range of thicknesses across one slide was achieved by mounting the long side of the slides vertically in the chamber such that higher deposition rates occur on the end closer to the source of the vapor. Film thicknesses varied continuously from 580 nm to 1600 nm, as conrmed by a Dektak prolometer and SEM cross-section images like that shown in Fig. 4. Photocatalytic measurements were made at thicknesses of 600 nm, 1000 nm, and 1500 nm. The lms were subjected to rapid thermal annealing (RTA) in an oxygen environment at 550  C for 0, 30, 45, and 60 min. The as-deposited lms were optically clear, but turned opaque after annealing. The anatase phase was conrmed by x ray diffraction of the annealed lms using a Panalytical XPert Pro x ray diffractometer. Transmittance measurements were made on a Jasco 600 spectrometer for each annealing time and at multiple lm thicknesses. Photocatalytic activity was measured using the degradation of indigo carmine dye in water. The dye has a high solubility in water, is safe, degrades within several hours, and has a strong absorption peak at 610 nm that can be easily

FIG. 3. Competitive growth caused by shadowing of the vapor ux results in porosity in the form of tilted nanorods.

FIG. 4. SEM cross-section and top view (inset) of nanorod lm used for photocatalytic testing.

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FIG. 5. Experimental setup for testing of photocatalytic activity.

used to monitor its destruction. An initial dye concentration, C0, of 0.02 g/L (43 lM) was used because it was within the detection limits of the photospectrometer and demonstrated complete breakdown of the dye in a reasonable time. Dye bleaching was measured using the apparatus shown in Fig. 5. The solution was placed inside a square well created by sandwiching a 1 cm2 1 mm window of polydimethylsiloxane, PDMS, between two slides; the bottom slide contained the lm. It was enclosed to prevent evaporation during testing and provide a controlled volume. A halogen lamp supplied the visible light to measure the characteristic absorption peak of indigo carmine at 610 nm, while a uorescent black light with a peak wavelength of 365 nm was used as the UV source for photocatalysis. The photocatalytic activity (PCA) was observed as an absorbance drop recorded over time at 610 nm. The concentration change is proportional to dye absorbance, and since the initial concentration is known, the concentration change can be calculated as it drops from C0 to zero. The geometry of the setup prevented shining the UV source from below, while simultaneously measuring the 610-nm peak, so the breakdown times of the dye were measured when the lm was facing up and also ipped over, to verify that results from front lighting the lm did not differ measurably from backlighting it. A trial was also run in the absence of UV light for 2 h to verify that the absorbance at 610 nm was constant and did not change as a result of adsorption effects not associated with photocatalysis. The decay of the absorption peak t a rst order reaction prole, and the reaction rate was calculated by tting the curve to Eq. (16),   C (16) R0 t: ln C0 Photocatalytic testing of the anatase nanoparticles was conducted using the same setup as above, except for the preparation of the lm. The nanoparticles, with a reported average particle diameter of 25 nm, were stirred into suspension in ethanol at concentrations of 0.14, 0.35, 0.57, and 0.94 g/L. These concentrations were chosen to provide decay times that spanned the timescales of the nanorod tests. The suspension was sonicated for 1 h to help disperse any agglomerates, then 50 l L was pipetted to the PDMS well on a glass slide and air dried. Addition of dye solution and testing then proceeded in the same manner as for the nanorods lms.

FIG. 6. XRD 2-Theta plot for as-deposited and annealed lm (60 min), demonstrating conversion to anatase phase.

RESULTS AND DISCUSSION

The x ray diffraction 2-theta measurements of the asdeposited lm and the 60-min annealed lm are shown in Fig. 6. Each peak in the annealed lm line corresponds to the anatase phase; the (101) plane is the highest. Transmittance measurements of a glass reference slide were made to establish it as an adequate substrate for high transmission (> 86%) at 350 nm and above, a necessary condition for the 365-nm UV lamp. Figures 7 and 8 show the transmission spectra of the lms for various annealing times and lm thicknesses, respectively. Interference fringes are evident, corresponding to constructive and destructive interference occurring in the lm, with periods dependent on the thickness and index of refraction of the porous titania. The spacing between individual fringes is a factor of the index of refraction and the lm thickness related by Eq. (17).17 d Dm 2n2 sin2 h2 Dvif
1

(17)

Here, Dm number of fringes, n index of refraction, h light angle of incidence, and Dvif wavenumber range, over which Dm is counted.

FIG. 7. Transmittance measurements at 0, 15, 30, and 60 min of O2 annealing of the 1000-nm-thick lm.

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FIG. 8. Transmittance measurements of the 60-min annealed lm at various lm thicknesses.

Since the lm thickness is known, the porosity of the lm can be calculated from the index at theta 0, since transmittance was measured at normal incidence. Equation (17) was rearranged, and the index was calculated for the unannealed lm using wavelengths above 500 nm to avoid the increase in index that occurs close to titanias band edge. The index, evaluated at 5 lm thicknesses, had an average value of 1.54 with a range of 0.19. The porosity was found from this by comparison of the lm index with that of dense TiO2 (2.54) and using an effective medium approximation, Eq. (18).18 This approach gives a porosity of 75%. Porosity 1 n2 1 : n2 1 d (18)

the thickest and thinnest lms tested is 8% to 14%, which corresponds to nearly 1 absorbance unit. x The skin depth function in the form of T=T0 ek was t to each annealing time in Fig. 9. k is the optical depth describing the point where 63% of the light is absorbed or scattered. This value can be used to determine the lm thickness needed to control the amount of UV light that escapes the lm. The inverse of k is the absorption coefcient of the nanorods lm at this level of porosity. SCOUTV thin lm modeling software by W. Theiss was used to recreate the optical depth for a dense lm of anatase TiO2, shown in Fig. 9 as the gray curve. An optical depth of 83 nm was determined from this, which, in comparison, is 2.5 times less than the 206-nm value for the 60-min annealed nanorods. This demonstrates how porosity signicantly enhances the ability of the UV to penetrate through the lm. The Bruggeman effective medium approximation (EMA) was then used to estimate the porosity. It assumes spherical inclusions (air in this case) in the lm that alter the dielectric constant according to Eq. (19),
R

1 f

em eeff ep eeff f 0; em 2eeff ep 2eeff

(19)

The absorption at 365 nm, which is the peak of the black lights output wavelength increased with lm thickness and annealing time. The penetration depth at this wavelength was calculated by plotting the transmittance at 365 nm against lm thickness and annealing time and is shown in the transmission plot, Fig. 9. It is evident that most of the effects of annealing on transmission occur within the rst 30 min (over a 44% drop), after which the next 30 min results only in an additional 17% drop or less. The difference between

where f fraction air (porosity), em dielectric constant of TiO2, ep dielectric constant of air, and eeff effective dielectric constant. Using SCOUTV software, f was varied until the optical thickness was equal to 206 nm for the 60-minute annealed lm. This yielded a porosity of 78%, close to the value obtained using Eqs. (17) and (18). Both methods of estimation do not consider that the porosity varies from the top to the bottom of the lm, and this gradient of index would affect the transmittance measurements. At the same time, this feature inherent in the deposition process may be helpful for optimizing the photocatalytic activity of the lm. The absorbance of the indigo carmine dye was monitored over time and normalized. Figure 10 shows the degradation of the dye signature for 3 lm thicknesses and 60 min of annealing. An increase in the reaction rate is evident at
R

FIG. 9. The transmittance of the lms in Figs. 6 and 7 at 365 nm plotted vs thickness for different annealing times.

FIG. 10. The decay of indigo carmine dye over time for the 3 tested thicknesses of titania nanorods as indicated by an absorbance drop at 610 nm. A 1st order reaction function was t to each curve before and after the rate change using Eq. (16). The inset shows the logarithmic concentration dependence.

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FIG. 11. The rate constant for 3 lm thicknesses of the 60-min annealed sample, 3 consecutive runs for each, as well as the unannealed sample.

FIG. 12. Reaction rate of dye degradation on anatase nanoparticle lms at various particulate concentrations.

around 10 min. This was observed before by Barka et al. who also used indigo carmine as a test dye.19 They attributed this to either competition for adsorption sites between the dye and intermediary products or loss of dissolved oxygen in the water. Both results, however, show higher reaction rates after the change compared to before, which is not consistent with this explanation and will require further investigation. This was observed in all runs to varying degree, except in the unannealed samples. Equation (16) was t to each run before and after the change in rate. The rate constant R0 was taken from each t and describes the ability of the nanorods to break down the dye, a higher value indicating a faster reaction. The same was done for 600-nm and 1500-nm rods, and the rate constants were plotted in Fig. 11 as a function of lm thickness. The activity appears to level off for lms 1000 nm and taller. The shorter lm had a lower activity, likely limited by lower surface area available for reactions to occur. The unannealed samples degraded the dye over a much longer time scale of 3 to 6 h and had a steady rate constant, as indicated by the blue stars at the bottom of the plot. The next analysis would naturally be to understand how the surface area of the nanorods affects the photocatalytic activity; however, the surface area is not easily determined experimentally for a lm with strong adhesion to a surface, since the most common technique, the Brunauer-EmmettTeller (BET) technique, requires a signicant mass of sample in particle form. Another method was therefore considered that provides a comparison. The activity was evaluated for various concentrations of commercially available anatase nanoparticles by calculating the reaction rate constants in the same manner as the nanorods. The reaction rates were plotted as a function of particle concentration, as shown in Fig. 12. The concentration of particles with comparable reaction rates to the rods was found by interpolation of the red line. The rate constant of 0.2 min 1 was chosen as an average value to represent the activity of the nanorods grown by oblique angle deposition. This corresponded to 0.73 g/L of nanoparticles (7.3 lg in the test well) or 36.5 m2 of area per liter (3.65 10 3 m2 in the test well), assuming the reported value of 50 m2/g for the particles. An estimation of the mass

of the nanorods, using the porosity, can be made to suggest a possible surface area per gram. Using the 75% porosity value from above and the density of anatase, 3.89 g/cm3, the 1micron-thick by 1 cm2 layer of nanorods has a mass of $ 95 lg and therefore 38 m2/g of active surface (calculated using 3.65 10 2 m2 of equivalent surface area).
REACTION/DIFFUSION MODEL

A model was created to represent the diffusion of dye into the thin lm and its reaction on the titania surface, with consideration that the light intensity in the lm changes, making the reaction rate a factor of lm thickness. The purpose of the model was to discover how lm thickness and pore dimensions change the catalyst effectiveness. Since the porosity of a lm can be adjusted during growth, this provides a predictive tool to determine if a porosity distribution would be benecial and how the porosity distribution should be varied. It can then be understood how the changes in deposition angle described in Pyun et al. affect the reaction rates measured by photocatalysis. The simplest version of the model presented here assumes a cylindrical pore with catalytic walls of titania. The dye enters from the pore mouth and reacts on the surface, as depicted in Fig. 13. The initial concentration of dye in the pore is ca 0, except at x 0, where ca is constant at ca0. The light enters from the opposite end of the pore with intensity u0 and decays inside the lm as it is absorbed. This conguration anticipates how we would normally illuminate a lm deposited atop a transparent substrate. The intensity of light along the pore wall is given by

FIG. 13. Modeled geometry of diffusion of dye into a pore of the titania nanorod lm.

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ux u0 expaL x;

(20)

TABLE I. Parameters used to model diffusion inside pore (Systeme International units). ks /0 L a D rp 1 10 6 (m/Ws) 2.5 10 2 (W) 3 10 6 (m) 3 106 (m 1) 1 10 6 (m2/s) 3 10 8 (m)

where a is the absorption coefcient that was measured experimentally. Assuming a dilute solution, the reaction rate can be re-written as a simple bimolecular expression (Hermann, 2005), ra ks uca : The continuity equation for the pore is   d dca Pd ks u0 expaL xca 0; DAc dx dx (22) (21)

where D is the diffusivity of the dye inside the pore, Ac is the cross sectional area of the pore, and Pd is the perimeter of the inside surface of the pore. Both Ac and Pd may be functions of x; however, in the simplest case, we assume a cylindrical pore with constant radius, rp. This reduces Eq. (22) to   d 2 ca 2ks u0 expaL xca 0: (23) dx2 Drp The boundary conditions for this problem assume that the dye concentration at the pore mouth is constant and that the opposite end of the pore is sealed so there is no ux through that surface. x0 xL ca ca0 ; dca 0: dx (24) (25)

a range of lm thicknesses (0.1 to 10 microns) normally accessible via oblique angle deposition. While the catalyst effectiveness is a monotonically decreasing function of lm thickness, as expected due to increased mass transfer resistance in longer pores, the overall rate of reaction passes through a maximum with pore length. Thus, there is an optimum pore length to maximize the destruction of the contaminant and this conrms, qualitatively, the behavior we are seeing in Fig. 11. The overall reaction rate is also sensitive to pore radius, but that is not as straightforward to model as the dependence on pore length. Following Poxson et al. 2008, the porosity of a lm grown by oblique angle deposition can be represented by20 P hTanh ; c hTanh (31)

We dene the following dimensionless variables and substitute them into the differential equation to yield: v ca cao x e ; L (26)

  d2 v 2ks /0 expaLL2 expaLev 0; DrP d 2 e2 e 0 v 1; dv 0: de

(27)

(28)

where c is a constant that depends upon the material being deposited, h is the deposition angle, and P is the porosity. Due to the shadowing effect, and assuming that the volume of an individual nanorod is independent of deposition angle, then the change in deposition angle leads to a change in nanorod density and hence a change in effective pore diameter. Thus, as the lm is made more porous, there is less surface area available for reaction, even though what surface area there is becomes more accessible. This will lead to a peak in overall reaction rate similar to what we see as a function of nanorod length at a given porosity and similar to the ndings of an optimum deposition angle by Pyun et al.

e1

(29)

The overall catalyst effectiveness can be dened as L g

0

ra Pd dx

L ks uca Pd dx
0

ra;max Pd L

ks u0 ca0 Pd L
R

(30)

The model was solved using ComsolV and the model parameters used are shown in Table I. The absorption coefcient was taken directly from the experimental data of Fig. 9. Figure 14 shows how the overall reaction rate on the surface, the numerator of Eq. (30), and the catalyst effectiveness vary as a function of lm thickness. The model was run over

FIG. 14. Overall reaction rate and catalyst effectiveness for the nanorod surface approximated by Fig. 13.

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1

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CONCLUSIONS

The photocatalytic performance of TiO2 nanorods grown by oblique angle deposition was measured using the rst order reaction rate constant. Transmission measurements on the lms at various annealing times showed a signicant increase in absorption over 60 min as the titania converted from amorphous to anatase. Interference fringes were observed in measurements made at several thicknesses and were used to estimate the porosity, calculated to be 75%. The porosity was also calculated using the change in penetration depth of 365nm UV light. The penetration depth was calculated to be 208 nm for 60-min annealed lm as compared to 83 nm for a modeled dense anatase lm. The porosity was found to be 78% using the Bruggeman effective medium approximation to adjust the optical depth of the modeled lm until it matched that of the 60-min annealed lm. The photocatalytic activity of the lms was measured by tting the decay of indigo carmines absorption peak at 610 nm to a rst order kinetics expression. It was found that, for the 3 thicknesses evaluated, the 1000-nm and 1500-nm thicknesses had similar reaction rates, both higher than the 600-nm lm, suggesting that thicker lms lack access to UV light or absorbed reactants across their entire surface area. A simple reaction diffusion model showed that the pore dimensions affect the overall reaction rate and catalyst effectiveness and that an optimal lm thickness exists. Altering catalyst porosity as a function of lm thickness is something easy to achieve using oblique angle deposition. Reaction rates for the nanorod lm were compared with rates using anatase nanoparticles at varying concentrations. It was shown that reaction rates for the rods were comparable to 0.73 g/L of nanoparticles, corresponding to 3.54 10 3 m2 per cm2 of coated surface. An estimation of the mass of the nanorods lm gives a surface area per gram of 38 m2/g as compared with 50 m2/g for the nanoparticles.
ACKNOWLEDGMENTS

This work was supported in part by the Engineering Research Centers Program of the National Science Foundation under NSF Cooperative Agreement No. EEC-0812056 and in part by New York State under NYSTAR contract C090145. This material is also based upon work supported by the National Science Foundation under Grant No. 0333314.