Metal Ferrite Spinels for Solar-Thermal Water Splitting Redox Cycles

"There is a need to develop cost effective renewable energy processes for the production of clean fuels that can simultaneously mitigate the U.S. energy/global environmental security issue. If H2 can be obtained cost effectively via the splitting of water using concentrated sunlight, then it’s possible to operate a fuel cell using renewable H2 or to synthesize other fuels based on renewable H2 for generating electricity or for running internal combustion engines. For example, H2 can be reacted with sequestered carbon dioxide (CO2) to produce syngas (H2/CO) via reverse water gas shift (RWGS), i.e. H2 + CO2 ? CO + H2O. The syngas can be catalytically methanated to form synthetic natural gas (SNG) or it can be catalytically reformed to produce liquid fuels such as “green” gasoline via the MTG process (syngas? methanol ? gasoline). The desert SW United States is home to world class sunlight. Fundamental ferrite thermodynamics will be reviewed, an example of the beneficial effect of ferrite surface area on reaction kinetics will shown, and process economics will be investigated for a 100,000 kg/day facility to produce H2.Introduction and Background ThermodynamicsSpinel ferrites of the form MxFe3-xO4, where M generally represents Ni, Zn, Co, Mn, or other transition metals, have been shown to be capable of splitting water according to the two step cycle shown below:MxFe3-xO4 + solar thermal energy ? xMO + (3-x)FeO + 0.5 O2 (1)xMO + (3-x)FeO + H2O ? MxFe3-xO4 + 2H2 (2)This is an inherently clean and sustainable process, as the only net inputs are solar energy and water, and the net outputs are hydrogen and oxygen. Ferrite water splitting cycles are advantages compared to other high temperature water splitting cycles, such as the ZnO/Zn and Mn2O3/MnO cycles, because thermal reduction has been demonstrated at significantly lower temperatures[1, 2]. As a result, overall efficiency may be increased due to the fact that radiation losses increase as the fourth power of temperature, and material considerations for reactor design should be more flexible. Additionally, cycle repeatability has been demonstrated with relative ease as compared to other thermochemical cycles [3-6]. However, the amount of hydrogen per mole that is generated is significantly less than for other high temperature thermochemical cycles due to the fact that only Fe3+ is capable of being reduced at the temperatures of interest[6]. In addition, water oxidation kinetics appear to be very slow, likely due to diffusion or surface area limitations created by near surface oxidation [6, 7]."