Gas-phase vs. material-kinetic limits on the redox response of nonstoichiometric oxides

Cerium dioxide, CeO_(2−δ), remains one of the most attractive materials under consideration for solar-driven thermochemical production of chemical fuels. Understanding the rate-limiting factors in fuel production is essential for maximizing the efficacy of the thermochemical process. The rate of response is measured here via electrical conductance relaxation methods using porous ceria structures with architectural features typical of those employed in solar reactors. A transition from behavior controlled by material surface reaction kinetics to that controlled by sweep-gas supply rates is observed on increasing temperature, increasing volume specific surface area, and decreasing normalized gas flow rate. The transition behavior is relevant not only for optimal reactor operation and architectural design of the material, but also for accurate measurement of material properties

Interplay of material thermodynamics and surface reaction rate on the kinetics of thermochemical hydrogen production

Production of chemical fuels using solar energy has been a field of intense research recently, and two-step thermochemical cycling of reactive oxides has emerged as a promising route. In this process, the oxide of interest is cyclically exposed to an inert gas, which induces (partial) reduction of the oxide at a high temperature, and to an oxidizing gas of either H_2O or CO_2 at the same or lower temperature, which reoxidizes the oxide, releasing H_2 or CO. Thermochemical cycling of porous ceria was performed here under realistic conditions to identify the limiting factor for hydrogen production rates. The material, with 88% porosity and moderate specific surface area, was reduced at 1500 °C under inert gas with 10 ppm residual O_2, then reoxidized with H_2O under flow of 600 sccm g^(−1) of 20% H_2O in Ar to produce H_2. The fuel production process transitions from one controlled by surface reaction kinetics at temperatures below ∼1000 °C to one controlled by the rate at which the reactant gas is supplied at temperatures above ∼1100 °C. The reduction of ceria, when heated from 800 to 1500 °C, is observed to be gas limited at a temperature ramp rate of 50 °C min^(−1) at a flow of 1000 sccm g^(−1) of 10 ppm O_2 in Ar. Consistent with these observations, application of Rh catalyst particles improves the oxidation rate at low temperatures, but provides no benefit at high temperatures for either oxidation or reduction. The implications of these results for solar thermochemical reactors are discussed

Implications of Exceptional Material Kinetics on Thermochemical Fuel Production Rates

Production of chemical fuels by solar-driven thermochemical cycling has recently generated significant interest for its potential as a highly efficient method of storing solar energy. Of particular interest is the thermochemical process using non-stoichiometric oxides, such as ceria. In this process a reactive oxide is cyclically exposed to an inert gas, typically at 1500 °C to induce the partial reduction of the oxide, and then exposed to an oxidizing gas of either H_2O or CO_2 at a temperature between 800–1500 °C to oxidize the oxide and release H_2 or CO. Conventional wisdom has held that material kinetics limit the fuel production rates. Herein we demonstrate that, instead, at 1500 °C the rates of both reduction and oxidation of ceria, and hence also the global fuel production rate, are limited only by thermodynamic considerations for any reasonable set of operating conditions. Thus, in terms of materials design, significant room exists for sacrificing material kinetics in favor of thermodynamic characteristics

Maximizing fuel production rates in isothermal solar thermochemical fuel production

Production of chemical fuels by isothermal pressure-swing cycles has recently generated significant interest. In this process a reactive oxide is cyclically exposed to an inert gas, which induces partial reduction of the oxide, and to an oxidizing gas of either H_2O or CO_2, which reoxidizes the oxide, releasing H_2 or CO. At sufficiently high temperatures and sufficiently low gas flow rates, both the reduction and oxidation steps become limited only by the flow of gas across the material and not by material kinetic factors. In this contribution, we develop a numerical model describing fuel production rates in this gas-phase limited regime. The implications of this behavior are explored under all possible isothermal pressure-swing cycling conditions, and the outcome is optimized in terms of fuel production rate as well as fuel conversion and utilization of input gas of all types. Fuel production rate is maximized at infinitesimally small cycle times and attains a value that is independent of material thermodynamics. Gas utilization is maximized at infinitesimally small gas inputs, but the values can be made independent of cycle time, depending on manipulation of flow conditions. Gas-phase conditions (temperature, oxidant and reductant gas partial pressures, and CO_2 vs H_2O as oxidant) have a strong impact on fuel production metrics. Under realistic, finite cycle times, material thermodynamics play a measurable role in establishing fuel production rates

Impact of enhanced oxide reducibility on rates of solar-driven thermochemical fuel production

Two-step, solar-driven thermochemical fuel production offers the potential of efficient conversion of solar energy into dispatchable chemical fuel. Success relies on the availability of materials that readily undergo redox reactions in response to changes in environmental conditions. Those with a low enthalpy of reduction can typically be reduced at moderate temperatures, important for practical operation. However, easy reducibility has often been accompanied by surprisingly poor fuel production kinetics. Using the La_(1−x) Sr_x MnO_3 series of perovskites as an example, we show that poor fuel production rates are a direct consequence of the diminished enthalpy. Thus, material development efforts will need to balance the countering thermodynamic influences of reduction enthalpy on fuel production capacity and fuel production rate

High-temperature structural stability of ceria-based inverse opals

The use of ceria-based inverse opals as a catalyst system for the thermochemical production of fuels from sunlight offers the potential of improved fuel production kinetics over materials with random porosity. Quantitative methods for characterizing ordered porosity are lacking, thus limiting the ability to predict the lifetime of ordered structures at elevated temperatures. In the present work, Fourier transform image analysis was used to determine the effect of composition and temperature on ordered porosity for a series of CeO_2-ZrO_2 inverse opals having pore sizes ranging from 300 nm to 1 μm. An order parameter, γ, derived from the image analysis, was applied to scanning electron microscopy images and used to determine the degree of order in the inverse opal. The thermal stability studies indicate that loss of ordered porosity is highly dependent on temperature and that gas cycling effects have a minor effect on periodicity. A minimum Zr content of 20 at.% is necessary to retain periodicity for annealing up to 1000°C with pore diameters larger than 1 μm. These results show that CeO_2-ZrO_2 inverse opals can be used at higher temperatures than previously thought for efficient thermochemical hydrogen production without loss of the benefits associated with ordered porosity

Impact of enhanced oxide reducibility on rates of solar-driven thermochemical fuel production

Two-step, solar-driven thermochemical fuel production offers the potential of efficient conversion of solar energy into dispatchable chemical fuel. Success relies on the availability of materials that readily undergo redox reactions in response to changes in environmental conditions. Those with a low enthalpy of reduction can typically be reduced at moderate temperatures, important for practical operation. However, easy reducibility has often been accompanied by surprisingly poor fuel production kinetics. Using the La_(1−x) Sr_x MnO_3 series of perovskites as an example, we show that poor fuel production rates are a direct consequence of the diminished enthalpy. Thus, material development efforts will need to balance the countering thermodynamic influences of reduction enthalpy on fuel production capacity and fuel production rate