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MODELING OF PRACTICAL PHOTOELECTROCHEMICAL REACTORS

1 INTRODUCTION
The desire to convert solar energy to usable energy for both commercial and consumer use is an important goal, especially as global energy forecasts worsen. Photo-electrochemical systems, which are capable of producing molecular hydrogen and oxygen gas directly from water, are an appealing solution that allow for both energy conversion and storage. Over the last 30 years, scientists and engineers have focused mainly on developing materials that are highly efficient at capturing solar radiation and relatively inexpensive to manufacture (for example, TiO2 has been well studied). While such studies are the key to ultimately developing models that can compete against other forms of energy production, commercial reactors at the consumer or industrial scale will require further design work with regards to kinetics and transport processes, at the bulk semiconductor, interfacial, and bulk fluid scales. These studies can take place in parallel to the development of new materials. This study aimed to develop a first-order model of a complete photo-electrochemical reactor. A variety of phenomena were incorporated, including flow and transport within the electrolyte fluid, kinetics at electrode interfaces, and electronic effects within the semiconductor electrodes. All of these processes have been studied in typical (non-photo) electrochemical cells, but have not yet been applied to practical photoelectrochemical reactor designs. To ensure that the design was practical and verifiable, all geometries and materials were chosen to mimic a recently developed flow-through photo-electrochemical reactor. Most importantly, this model will provide insight into the limiting physics of the reactor design, be it transport, kinetics, or materials design. Finally, it can provide insight into the design of the next generation of reactors.

2

REACTOR GEOMETRY AND CONFIGURATIONS

A recently developed photo-electrochemical reactor design was chosen as the basis for this study. The reactor was designed to test photo electrodes in a flow reactor, similar to what a commercial reactor might resemble. This design can thus act as a stepping stone in the scale up from the lab bench to a full design. The reactor in a typical configuration is demonstrated in Figure 1. The reactor was composed of a series of milled PVDF plates, providing a variable number of flow channels. Plates A and F provide the top and bottom of the reactor, with plate A having a central hole to allow light to enter the reactor. Electrodes B and E represent the photo-anode and cathode (not necessarily in that order). Plate C represents a flow channel, with electrolyte entering from the hole at the top of the plate and leaving through an identical hole at the bottom. Finally, D is a thin membrane acting to separate the anodic and cathodic products while allowing the transfer of the supporting electrolyte. The modular design of the reactor allows for a variety of reactor configurations. A typical configuration, analogous to the exploded view, is shown in Figure 2. Electrolyte flows through the two channels, and exits through the opposite side of the channels. In the presented case, light enters through the top of the reactor, passes through the solution, and strikes the photo-anode layer lying at the bottom. However, a variety of other configurations are possible. The simplest consists of just the top and bottom plate (A and F), the electrodes (B and E), and a single channel (C). As long as electrochemical current flow is low, the combustion

In addition. 2009). the addition of photosensitive dyes. Modern possibilities under investigation include new semiconductor materials.0-2. on both TiO 2 and on newer materials have since been conducted. corresponding to an upper wavelength threshold of 620 nm. hematite has a conduction band energy lower than required for the evolution of hydrogen. Both single and double channel systems were considered within this study. encompassing a large portion of the solar spectrum. The band gap of hematite in various forms has been measured to be 2. restricting the active regions of hematite films to just next to the film/solution interface. Most importantly. . a single channel design greatly simplifies the design. A B C D C E W F Figure 1: A schematic of the reactor configuration. hematite is an abundant and cheap material. Unfortunately.of hydrogen and oxygen gases should not be an issue. about 2-4 nm (Kennedy and Frese 1978). 3 MATERIAL SELECTION FOR THE PHOTO-ANODE Previous efforts have established a large number of candidate materials for the photo-anode in a water splitting device. Figure 2: The active region within the reactor. the diffusion length of minority carriers (photo-generated electrons and holes) is extremely short. Polycrystalline silicon-doped hematite ( -Fe2O3) was chosen as the primary material to compose the photo anode for several reasons. both disassembled and assembled.2 eV (Cesar. The first relatively efficient material discovery was for TiO2 (Fujishima and Honda 1971). constructed from the exploded view in Figure 1. et al. A huge number of studies. making it extremely economical. Furthermore. requiring an additional small bias voltage. and the use of complex surface morphologies.

5 5. models were developed both for the full 3D reactor and for 2D cross sections of the reactor (parallel to the mean flow direction). as detailed later. The flow of fluid through the reactor was highly dependent on the entrance and exit regions. However. Other groups have proposed the use of several stacked thin hematite sheets (mentioned as a solution in most hematite studies. 2003) among others. 2009). the transport of dissolved gases and ions in solution required boundary layer computational meshes. Instead. Additionally. simplifying model development. (a) Triangular mesh for fluid flow calculations (b) Logarithm-spaced mesh for transport calculations Figure 3: Demonstration of hybrid meshing method used to solve for both fluid flow and flow-dependent transport phenomena. et al. 2009). Representative studies include doping with Si (Cesar. 2009). et al. 4 COMPUTATIONAL METHODS Due to the complexity of the model and the non-ideal geometry of the reactor. et al. The inner rectangular mesh of (b) corresponds to the region on which the electrode sits. Several of the desired models were already provided within the software. Unless specified otherwise. solution time for each aspect of the model was on the scale of minutes. et al. which was then transferred to a more detailed mesh incorporating only the reactor region around the electrodes. Steinfink and White 1982). Formal and Gratzel 2009). Another approach is to layer small amounts of hematite onto a structured host film. Ge and Mg (Sanchez. Furthermore. which added too much complexity to the nonlinear flow calculations. Reactors with either one chamber or two chambers separated with a membrane were considered. Finally. but should be applicable to similar packages. Nb (Sanchez. analytical solutions to the various design equations were not possible. nanostructured films have been proposed and tested (Cesar. et al. A hybrid method was instead used. et al. demonstrated in Figure 3. Numerical meshes were refined until results did not change with increased meshing or until memory usage exceeded 4 Gb. a variety of dopants and dyes have been used to modify the electronic structure and absorb higher wavelength light. Obtaining solutions to the 2D case were straightforward. The description of the model will be in the context of the COMSOL model. such as in (Cesar. 2009). et al. such as tungsten oxide (Sivula. 1986) and Ti (Sartoretti. 2008). the flexible numerical PDE package COMSOL was used.Silicon doped hematite thin films without catalytic surface sites were used throughout this study. Mo and Cr (Kleiman-Shwarsctein. where a regular (relatively coarse) mesh was used to solve for the flow profile. but additional considerations were necessary for the 3D case. although many possibilities have been tried in literature. et al. various catalytic additives have been deposited on hematite to improve performance such as Cobalt-Phosphate (Gamelin. 2009)). Recent efforts have been made to incorporate nanotube synthesis strategies (increasingly common throughout materials science) (Rangaraju. Several models with varying geometries and numbers of dimensions (2D/3D) were developed to assess fully understand the modeled phenomena.1 DOMAIN MODELING GENERAL OVERVIEW . To compensate for the short carrier diffusion length. and memory usage was on the order of gigabytes.

A simplified view of the reactor setup can be seen in Figure 4. At the cathode. there is a uniform potential in the cathode. with the flow generally being laminar (justified later). Figure 4: A simplified view of the various physical phenomena considered and their interactions. spread over several orders of magnitude in both time and space. The electrolyte flow in each channel was considered to be independent. with a fixed voltage source applying a potential difference between it and the anode (and providing electrons). both the valence and conduction bands are bent due to the semiconductor/solution interface. A membrane separated the two channels to prevent the diffusion of H2 and O2 into the opposite compartments. the electrons were used to + convert aqueous H into gaseous H2. The mesh cathode was treated as a standard electrode. Finally. The expected potential distribution across the cell for the system in Figure 4 using a Fe2O3 anode is shown in Figure 5. there is a second sharp change in potential across the cathode / solution interface. The electronic band gap for iron oxide is shown in shaded yellow. Within the photo-anode. . There is a large potential change across the interface. Models for all of these phenomena are considered throughout this report. but due to the highly conductive nature of the metal. At the electrode surface. followed by small resistive changes across the solution and membrane. the electronic structure of the photo-anode was considered (with corresponding light absorption and electron conduction) and used to evaluate the kinetics of oxygen evolution at its surface. the ideal material would have a conduction band just above the H2O/H2 potential and a valence band just below the H2O/O2 potential (with enough excess to achieve reasonably fast kinetics). While the bandgap is relatively narrow. suggested that each region within the reactor should be treated separately and coupled together.The wide range of phenomena present within the photo-electrochemical reactor.

rather than in the context of each particular section and interface.Figure 5: Overview of the potential losses for the entire two-chamber reactor. The figure is not drawn to scale. most reactor limitations occur either within the semiconductor or at the semiconductor/solution interface.2 TOTAL POTENTIAL DROP AND THERMODYNAMIC TREATMENT The potential distribution across the reactor is critical to understanding all aspects of the photoelectrochemical reactor. The potential drop across the entire reactor is: The potential drop across each of the interfaces is: . As described later. and is shown in Figure 3. The total potential drop is described here as it is best described in an overall manner. 5.

is potential loss due to band bending in a semiconductor. and is the partial pressure of the relevant gas (H2 or O2). 5. A comparison of the density and viscosity at 25 C of sea water (ionic concentration of 0. In addition. and is the overpotential. the electrolyte would be recycled through a reservoir. was modeled first to obtain an understanding of both the fluid dynamics and the distribution of ions (both the supporting electrolyte and the pH gradients). If the reaction is contributing to bubble formation. will be atmospheric pressure plus a diameter-dependent contribution from the curved bubble/solution interface. the balance for the interface becomes: When the thermodynamic potential and band bending potential can be estimated from local conditions (pH and such) the overpotential can be calculated. such as 1M sodium sulfate. In the actual implementation.97 o . Inc 2008-2009) Pure Water Salt Walter Density at 25 C (kg/m ) 997 1023 o 3 Viscosity at 25 C (cP) 0. was taken to be atmospheric pressure in all cases.Where is the thermodynamic potential.3 BULK ELECTROLYTE The bulk electrolyte. Thus. Table 1: Comparison of the density and viscosity of sea water to pure water (CRC Press. The thermodynamic terms for the anode are cathode were thus: [ ] [ ] When a potentiostat is used to control the potential drop across one of the interfaces. where such control could take place.3. A high concentration of supporting electrolyte was assumed.1 ELECTROLYTE FLUID FLOW PROFILES The first aspect to be considered was the flow profile of the fluid within the central region of each o reactor. the entire potential drop will be: ( ) ( ) The thermodynamic potentials can be obtained from the Nernst equation. and the fluid flow profile does not affect the flow profile of a fully developed laminar flow. In many electrochemical experiments. 5. a potentiostat is used to control the interfacial potential drop. Since the values for each were similar. it was assumed that the pH of the inlet electrolyte could be well controlled. and are additional constants. the temperature dependent values for water were used. critical to the understanding of any electrochemical reactor.89 0. For the purposes of this study.66 molal) of to that of pure water is shown in Table 1. using well known constants for the separate reactions at the anode and cathode: Where is the equilibrium potential.

the flow regime throughout most of the reactor was assumed to be laminar (the entrance region would become turbulent at lower flow rates). Diffusion of solutes within the solution was assumed to have no impact on the flow profile. with the appropriate momentum balance with no body forces: ( ) [ ( ) ] The boundary conditions for the inlet and outlet of the three-dimensional model were a laminar inflow and outflow. | |. 5. Both the 2-dimensional (trivial.3. To accommodate the rectangular cross section. only one quarter of the channel was modeled (and the solution transferred to the rest of the channel). Along each surface (and along the electrode and membrane). the hydraulic diameter was used in the calculation: [ ] [ The corresponding volumetric flow rate for this velocity was: [ ] ] [ ] [ ] This flow rate is quite large (and greater than the capability of the pump employed in the reactor system. Since each flow channel was symmetric in both directions perpendicular to the length of the reactor. Of particular importance was the distribution of flow over the surface of the electrode (and the corresponding design of the inlet region). no-slip conditions were used. Figure 6: The fluid velocity profile. The laminar flow profile was calculated using the full Navier-Stokes equation for incompressible fluids. parabolic) case and 3dimensional case (using the full reactor) was solved. although diffusion influenced convection could be possible. for the two-channel reactor configuration at low flow rates. The solution of the fluid flow profile for the two-channel reactor scenario is shown in Figure 6.The flow regime of the electrolyte solution was determined through an analysis of the transition flow rate for the central region of the flow channel. Thus.2 MASS TRANSPORT OF GASEOUS PRODUCTS .

At moderate current densities. the flux is given by: Where is the species diffusion coefficient. + The most widely accepted method for calculating ion transport within the reactors is the NernstPlanck equations. In either case. The problem is still being developed in literature. making inclusion in this first-order model difficult. including ion/ion interactions.The transport of products formed at each electrode. 9. electric potential. Cl . the Farraday constant. (CRC Press. the reactor was always run so that no bubble formation occurred and simple diffusive/convective flow dominated. Table 2: Diffusion coefficients and saturation concentrations for molecular hydrogen and oxygen. The diffusion coefficients for the various ions considered are (in + + units ( ): Na . diffusion induced convection. where semi-analytical solutions were developed for a variety of electrochemical geometries based on uniform activation potentials (which would not be true for semiconductor electrodes). OH . the electric potential. H . For + + each ion in solution (for example. Some studies in the past have considered the effect of bubble formation on surface activity. with a zero inlet concentration. The boundary conditions for the each species were coupled to the kinetics of the surface reactions on the electrode. 2. Example calculations and determination of the maximum current density before bubble formation is shown later. While reactors can be designed to account for bubble formation. Inc 2008-2009). The saturation concentration and diffusion coefficients for hydrogen and oxygen in water are shown in Table 2. molecular hydrogen and oxygen. Cl . or trapped in the upper section of each channel.33. The species mobility was related to the species diffusion coefficient through the Nernst-Einstein equation: . H and OH ) is greatly complicated by the electric potential applied across the reactor channel. Previous successes in the field include (Wang 2004).03. reaction. (Basha 2006).0. the semiconductor/solution surface area becomes unsteady and complicated. where a full computational model including induced convection for a PEM fuel cell was developed and experimentally verified. is called the tertiary current distribution. and convection. were modeled separately from the electrolyte concentration.0 (CRC Press. where natural convection was included in the solution. which model transport due to diffusion. for example (Vogt 1980). any bubbles produced in this design would either be swept along with the flow. To simplify the model and experimental methods. the species mobility constant. The system was modeled as follows: Where is the concentration of either oxygen of hydrogen and is the velocity field from the bulk electrolyte flow.3 ION CONCENTRATION AND POTENTIAL DISTRIBUTION Determining concentration gradients of important ions in an electrolyte solution (in this case. The resulting solution of the complex interactions that arise. the concentration of these species at the surface of the electrodes will exceed the thermodynamic saturation concentration and form bubbles within the flow.1. the species charge. and the flow velocity as calculated above. the species concentration. OH ). H . Saturation concentrations were related to temperature through Henry’s law (in equilibrium with a partial pressure of 1 atm) and empirical relation for the constant. Na . and (Chung 2000). and electromagnetic/ion interactions. the species concentration.3. Inc 2008-2009) Saturation Concentration [ Hydrogen (H2) Oxygen (O2) [ [ ( ( [ ] [ ] ] )] )] Diffusion Coefficient at 25 C [ o ] 5. 5.

For the hydroxide and proton species.5. The rate constant ( [ ] ) was chosen so that it was neither too high (causing numerical instability) or too low (allowing out of equilibrium proton/hydroxide concentrations). they must be energetic enough to promote electrons from the valence to the conduction band ( ).1 ELECTRONIC STRUCTURE The ability of a semiconductor to absorb light at various wavelengths is entirely determined by its electronic structure. a pseudo chemical reaction was included. At the same time.5. For the examples provided. allowed the differential equation for one of the ions in solution to be replaced by an algebraic relation rather. the valence band holes will be below the potential of the oxygen evolution potential so as to drive the production of oxygen gas. the following term was used: [ ] ( [ ][ ]) Where was the equilibrium constant of water ( ). The membrane would become especially important when trying to model the separation of gases produced from the anode and cathode (H2 and O2). For photons to be absorbed. this potential was set to 0.5 BULK CHARACTERISTICS OF THE SEMICONDUCTOR PHOTO-ANODE 5.The transient balance for an infinitesimal fluid element in the reactor is then: ( ) Where is the total production or consumption from chemical reactions for species . At steady state. The total charge of all species was related through: ∑ This conservation equation. this becomes: ( ) In the fluid bulk (that is. greatly simplifying the solution.4 MEMBRANE The membrane for the reactor was assumed to contribute to the reactor model only through a small ohmic potential loss. . any fluid element can be assumed to be neutral. namely the position of the valence and conduction bands ( and ). 5. a mixture of which would be highly explosive. 5. typically called the electroneutrality condition. In order to include the proton/hydroxide/water equilibrium. 5. the potential of conduction band electrons should be high enough to drive the production of hydrogen gas at the (non-photo) cathode.2 ELECTRON AND HOLE MOBILITY AND RECOMBINATION RATES . excluding molecular-width boundary layers). Ideally. This constant needed slight adjusting depending on the pH gradients involved in the solutions.

A complete model of the propagation of light through the semiconductor interface should include effects from both absorption and scattering processes. 5. anatase. and others have even encouraged the phenomena to improve performance (Sheng. there are significant differences in the absorption coefficient at any specific wavelength. and the recombination rate. the light intensity at absorbable wavelengths should reach zero. the reliability of literature UV/VIS data for TiO 2. especially when the semiconductor/solution interface is coated with particulate or porous catalyst material. et al. . o o PLD. generated using four techniques (pulsed layer deposition. a full understanding requires knowledge of transport parameters within the bulk semiconductor. et al. 2002) are shown for rutase. Although there is rough agreement in the distribution of the absorption coefficients (the shape of the curve). the spatial distribution of photo-generated electron/hole pairs becomes important. Before attempting to identify absorption coefficients for the materials used in this study. and (Koelsch. 2009). a well-studied material. and that absorption coefficient curves will need to be collected with UV/VIS instrumentation for each new photo-anode prepared. 1997). 2002). Electron diffusion lengths have been reported of 2-4nm (Kennedy and Frese 1978) or 20nm (Dare-Edwards. While models of the semiconductor/solution interface can be restricted to this low current case. 1983). Literature parameters for -Fe2O3 vary widely. and is the distance from the electrode/solution interface into the semiconductor film. The most widely used parameters to characterize this type of transport is the diffusion length of holes and electrons.3 LIGHT ABSORPTION When the transport of electrons and holes within the semiconductor photo-anode is potentially limiting. 2008). although recent studies tend to cite (Kennedy and Frese 1978) more frequently. However. The light intensity will be largest near the electrolyte/solution surface of the photo-anode (in the configuration shown in Figure 4) and decrease as photons are absorbed. as a simplification and because of the availability of UV/VIS absorption data for a range of materials. and sol-gel). ALD. This suggests that attempting to find literature absorption coefficients that correspond to newly developed samples will be unsuccessful. is shown in Figure 4. generated at two temperatures (100 C and 300 C) and at various concentrations. atomic layer deposition. et al. was the surface light intensity. Absorption coefficients from (Aarik. where UV/VIS was conducted on samples of known thickness and absorption coefficients calculated. only light absorption was considered. Data from three studies. et al. and are assumed to be independent of hole/electron energies and isotropic in nature. and brookite TiO2. Diffusion lengths for electrons and holes tend to be equated and represented as minority carrier diffusion lengths (roughly justified as both are effectively electron movement). was the experimentally measured effective absorption coefficient. Some recent studies have included scattering effects (Reyes-Coronado.Performance of the photo-electrochemical cell can be limited by transport effects of the minority carriers if the current is close to the limiting value. was investigated. The intensity profile was thus taken to be of the form: ( ) ( ) Where was the surface reflectivity. et al. If the photo-anode is thick enough. et al. Despite many studies over the past two decades no improvements to these measurements have been made.5. (Sumita.

2002) did not specify units. the electron/hole transport properties in the bulk semiconductor will most likely dominate (since the generation of photons is usually lower than the maximum current that can be sustained through mass transport in the solution) (Bockris and Reddy. et al. where the conductive nature ensures the potential is nearly uniform everywhere inside.Figure 7: Comparison of literature values for the absorption coefficient of TiO 2 films made through a variety of techniques. Assuming that these catalytic materials do not significantly alter the electronic structure of a semiconductor photomaterial. and are thus shown separately. Modern Electrochemistry 2B 1998).6. Kiwi and Grätzel 1987). 5. Discuss effect of porosity of semiconductor 5. However. et al. This is further evidenced by the effectiveness of adding large amounts of catalytic surface sites (Thampi. there will be a much larger potential change depending on the local electric fields. below the limiting current the interface may play a large role. even in the gas phase with a known chemical pathway (Prasad. DFT-based first-principles studies of TiO2 surfaces have been conducted recently (Valds. 2008). their impact will be purely kinetic. but make no attempt at predicting the effects of additives or different morphologies at the reactor scale. Near the limiting current for a photo-electrochemical cell. 5. Give examples of absorption lengths. For example. (Koelsch.2 ELECTRIFIED INTERFACE (ELECTRONIC DOUBLE LAYER) The potential distribution at a semiconductor/solution interface is complicated by a relatively slow transition from the bulk material potential to the bulk solution.1 CATALYTIC SURFACE SITES The use of catalytic additions to photo materials to increase the rate of surface reactions is extremely common. as intensity assumed to have linear effect on rate of generation of electrons and holes. 2009). However. there will only be a small potential change approaching the surface. quantitatively determining the impact of various catalytic materials is complex. However. and .6 PHOTO-ANODE AND SOLUTION INTERFACE The kinetic and thermodynamic treatment of the reactions and charge profiles of the photo-anode and solution interface are necessary for a complete understanding of the photo-electrochemical process in Figure 4. Kiwi and Grätzel 1987). et al. Ruthenium and Ruthenium oxides were used to enhance the rate of a TiO 2-based photomethanation of CO2 (Thampi. in the transport controlled flows of the semiconductor.6. the consumption rate at the surface. Thus. the role of catalytic sites for this model must be confined to the kinetic rate constant from the Butler-Volmer method and will be fitted to experimental data. In a metal.

Bartlett and Dare-Edwards 1981). on the order of 10 mV for normal electrochemical systems. et al. The importance of electronic effects within photo-electrochemical reactors depends strongly on the operating conditions. Most work was conductor for planar geometries. the Butler-Volmer equation is sufficient. (Kay. Effectively. beginning with (Bockris and Uosaki 1977). but are usually limited instead by transport within semiconductor electrodes (Bockris and Reddy 1998). Cesar and Gratzel 2006) was the first of a series of efforts by . Extensive progress has been made in describing the coupling of these interactions mathematically. When the current is close to the limiting current in a standard electrochemical reactor. where normal Tafel relations were identified with medium currents below the limiting current and well above zero current. If bubble formation is avoided.3 BUTLER-VOLMER KINETICS The most popular method of estimating the kinetics of charge transfer at an electrode/solution interface is the Butler-Volmer equation. the current density simplifies to: At the opposite extreme (high overpotentials). Photoelectrochemical reactors could be limited by these effects. However. developing with (Albery. When the current is well below the limiting current. The equation relates the current density to an overpotential based on a potential barrier argument (similar to that of an Arrhenius-type rate equation). but some models also took into account spherical interfaces (Albery and Bartlett 1984). and that perhaps the Co-phosphate additions were doing more than providing surface sites for improved reaction rates. Although the semiconductor/solution interface is far more complicated than the simple model on which the Butler-Volmer equation is based. the constants and ( can be determined. The deviant line shows that the type of catalyst can greatly affect electrode scaling. traditional charge transport kinetics take over. Data for 10 electrodes from four sources are shown. performance is limited by traditional mass transport effects at the electrode/solution interface. To test this observation and identify the scaling of Si-doped Fe2O3 electrode performance with respect to potential. 2008). et al. which is derived with discussion in (Bockris and Reddy 1998). the current density simplifies to: ( ) ⁄ This equation forms the physical grounding for Tafel plots. for similar environments. (Gamelin. data electrode performance data from a variety of recent sources were collected and are presented in Figure 8. is an empirical constant representing the position of the potential barrier with respect to the width of the Helmholtz layer. The full equation. 5.the local diffusion and mobility constants of the relevant charge carriers. and largely completed with (Khan and Bockris 1984). where the overpotential is plotted versus the ) log of the current density. More recent work has largely focused on quantum mechanical effects for understanding of highly idealized surfaces inappropriate for the work here (Valds. This phenomenon was first confirmed experimentally for semiconductors using a p-GaP electrode (Uosaki and Kita 1981). 2009) developed electrodes with and without an added layer of Co-phosphate catalyst. When is sufficiently small.6. with only the potential applied across the electrode/solution interface changing. and is the overpotential. Tafel lines are observed when photocurrents are sufficiently low (Uosaki and Kita 1981). the limitations due to mass transport of the product dissolved gases will limit the operating current well below the limiting current for the cell. is as follows: ( ⁄ ( ) ⁄ ) Where is the exchange current density. The exchange current density is further dependent on the concentration of reactants depending on the order of the reaction.

hydrogen gas evolution. The cathode in this reactor is not photo-active. below the limit of applicability of the observed Tafel relations. Tafel relations were sufficient to represent the kinetics until bubble formation begins (estimated to be on the order of 1 ). and experiments using WO 3 as a substrate to deposit Fe2O3 onto. corresponding to . A follow-up study with variations in preparation method. These relations also show how much the kinetics can vary depending on the synthesis conditions. 5. Formal and Gratzel 2009) show similar behavior. Figure 8: Tafel plots for a variety of Si-doped -Fe2O3 electrodes from literature. The average Tafel slope (excluding the outlier) was calculated to be . et al. (Cesar. even when considering a single material composition. resulting in an average (excluding the one clear outlier where large amounts of surface catalyst were added) linear slope of . especially if the materials complement each other by having different bandgaps (and thus having different absorbance spectra). this value is quite close to the naïve assumption of used in many electrochemical studies and derivations (Bockris and Reddy 1998). with of all of the major physics (electronic bandgaps and electron/hole generation and mobility) directly based on the material of the photo-anode. All 10 electrodes exhibited Tafel relationships below approximately . (Sivula. it has been suggested that photo-anode/photo-cathode pairs be used. The fitted Tafel relation is then: Calculating from this relation (assuming all experiments conducted at approximately 298K): Interestingly. was disregarded for the setup listed in Figure 4 for several reasons. However. Data from 10 samples among four publications are shown. the kinetics of the alternate electrode should not be the rate limiting process.7 BULK CHARACTERISTICS OF THE CATHODE The kinetics and modeling of the cathodic reaction. 2009). Since the preparation technique and morphology of the photo-anode has been shown in numerous instances to have a large effect on the performance of photo-catalytic reactors (a somewhat obvious observation). Thus. such as those .the Gratzel lab to improve Si-doped iron electrodes with nano-patterning. will need to be a fitted variable for every material. Bubble formation is estimated to occur at approximately 1 A/m2.

Due to the low resistance metallic nature of the cathode. was calculated so that the total current at the cathode was equal to the total current at the anode. the overpotential was variable and calculated through: The cathode potential.demonstrated in (Licht. The current density at the cathode/solution interface was modeled with a simplified Buttler-Volmer relation (Tafel kinetics): ( ) ⁄ Where was a fitted parameter and the remaining terms were the same as shown above for the anode/solution interface. et al. However. terms for the current density and potential drop at the cathode solution interface were required to solve for the ion distribution within the reactor. 5. Using the overpotential relation in the kinetic relationship: [( )( ) ⁄ ] [( [( )( )( ) ⁄ ) ⁄ ] ] The total current at the cathode was then: ∮ [( [( )( )( ) ⁄ ) ⁄ ] ] Moving constant terms outside of the integral: [( )( ) ⁄ ] ∮ [ ( )( ) ⁄ ] The cathode current was then related to the anode current: ∮ ∮ [ ( )( [( ) ⁄ )( ] ) ⁄ ] The cathode potential could then be calculated directly as a function of the total anode current and the total effect from the thermodynamic potentials: ( ) * ∮ ∮ [ ( )( ) ⁄ ] + ( ) 6 6.8 CATHODE AND SOLUTION INTERFACE While hydrogen evolution at the cathode was assumed not to be the rate limiting process. a uniform flow pattern was desired. with a 4 mm radius) needed . These new systems would require additional considerations similar to those presented here for the photo-anode.1 RESULTS IMPROVEMENTS OF THE ELECTROLYTE FLOW PROFILES To ensure maximum activity across the entire surface of each electrode. 1998). the potential was considered to be an arbitrary uniform value . The electrolyte flow from the relatively small inlet regions (tubular inlet.

A series of posts at the inlet are used for flow distribution over the entire reactor. 1[ml/min] 300 [ml/min] ) | | Figure 9: Flow distribution for the default reactor design. The initial design called for a series of posts to be used in the entrance region to spread the flow. most of the flow would occur down the centerline of each channel. At the upper flow rate (a reasonable rate for an electrochemical reactor of this sort). with a 1[ml/min] inlet flow (left) and 300[ml/min] flow (right). | | Figure 10: Recommended modifications to improve flow profile at 300[ml/min]. with the remaining regions becoming dead volume. this design is insufficient at high flow rates and leads to non-uniform flows in the main channel region. Several methods were attempted to improve the flow situation. there is a noticeable minimum in the profile along the centerline of the reactor (in both the original and improved designs). Also.2 MAXIMUM SUSTAINABLE CURRENT BEFORE BUBBLE FORMATION | | ( | | . there is uneven flow within the reactor.to be distributed across the 10cm X 10cm electrode. However. The resulting flow profiles for inlet rates of [ ] and [ ] are shown in Figure 9. The flow past the top most post is directed towards the upper edge of the reactor. The final recommended design chosen for its improved profile and ease of modification (only a small amount of milling necessary) is shown in Figure 10. However. and along the upper half the flow with simple modifications (shaving part of the corners in the inlet region). including the removal of the corners along the edges of the inlet region and the addition of extra posts. Without a suitable mechanism to spread the incoming flow. 6. A small reduction in the diameter of the first center post would likely improve this situation. Shown on the lower half of the channel is the profile of the original design. there is still substantial spatial variation in the flow pattern. making the flow more even.

Figure 12: Diffusion coefficient. which can be calculated through the numerical model. fluid flows from the left with zero gas saturation. which could result in further improvements to the current flow. and maximum sustainable current density as a function of temperature. Since the diffusion coefficient and saturation concentration are both strongly dependent on temperature. (C) shows that of uniform flux. and gradually picks up oxygen until saturation conditions are barely reached in the upper region where flow is slower. First. (A) shows the overall profile. with overlaid velocity profile. saturation o concentration. All quantities are scaled to the respective values at 25oC. (A) (B) (C) Figure 11: Hydrogen concentration profiles for the determination of maximum current density before bubble formation. and current density. (B) shows the case of uniform saturated concentration. Two methods were used to determine this limiting density. a .64A.1 mm away) of the anode is shown for two different uniform current densities. Transport calculations for the dissolved gas were extended to the full reactor geometry in the single chamber case (one flow section with both the anode and cathode). Calculated profiles are shown in Figure 11. the maximum current density was calculated to be 0. the highest uniform flux was found so that no point along the reactor channel reached saturation concentrations. bubble formation will impede the operation of the reactor. Additionally. The increase in the diffusion coefficient at higher temperature more than makes up for the corresponding drop in the saturation concentrations. saturation concentration. Figure 12 shows the diffusion coefficient. the maximum current density was 0. For uniform surface concentration. all normalized to values at 25 C for a range of temperatures. the mass flux of gaseous species at the outlet of the reactor was calculated assuming a saturated liquid at the electrode/solution interface along one side of a single channel. Secondly. For uniform flux. and the model and experimental studies were run so that bubble formation was minimal. The results can be seen in Figure 13 The oxygen saturation near the surface (0. Temperature changes will also have an effect on the surface kinetics and properties of the semiconductor. the limiting current density should as well. However.78A. this places a limit on the average current density. At .As described above.

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