Vincent Wheeler edited section_introduction_The_emerging_field__.tex  over 7 years ago

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The emerging field of high-temperature solar thermochemistry holds tremendous promise to disrupt the conventional paths of producing fuels, energy-intensive commodity materials and generating dispatchable power. Direct solar irradiation is concentrated by mirrors, captured by a receiver, converted into high-temperature process heat, often exceeding $\mathrm{1000K}$, and used to drive highly-endothermic processes for production of chemical fuels and materials including synthesis gas, carbon black, ammonia, lime, and metals \cite{bader2016solar}\cite{Fletcher_2001}\cite{Steinfeld_2003}\cite{Kodama_2003}. Production of the components of synthesis gas, $\mathrm{H_2}$ and $\mathrm{CO}$, can be achieved in a single thermal dissociation step (thermolysis) followed by a high-temperature gas separation. However, the excessively high temperatures required for such chemistry pose serious limitations for practical implementation. For example, the thermolysis of $\mathrm{H_2O}$ and $\mathrm{CO_2}$ require temperatures exceeding $\mathrm{2500K}$ in order to obtain significant $\mathrm{H_2}$ and $\mathrm{CO}$ concentrations, respectively \cite{bader2016solar}. Alternatively, thermochemical cycles can be employed, in which active materials undergo cyclic reduction and oxidation (redox) reactions, with the net effect of splitting $\mathrm{H_2O}$ and $\mathrm{CO_2}$. In addition to lowering process temperatures, the added process steps can be leveraged to eliminate energetically expensive gas-phase separation requirements.   High-temperature solar thermochemical reactors are designed for maximum solar-to-chemical energy conversion efficiency, to minimise the required size of the optical concentrators, and thus to improve the economic viability of the process \cite{Palumbo_2004}. The rapid and efficient transfer of energy from a concentrated solar source to the redox material---i.e. the transfer of energy from photons to chemical bonds---is therefore a core critical research aspect towards achieving an high-output and efficient reactor design. To this end, we study here the performance of a class of porous particles of cerium dioxide redox materials under highly-concentrated, direct solar irradiation. We believe these materials to hold promise for efficient energy transfer for a number of reasons we outline here. More specifically, we answer the questions: Why particles? Why porous? Why ceria? (\text{i}) Unlike bulk materials, particles can have an absorption efficiency (potentially much) greater than unity.   Note that this may seem impossible given the fact absorption efficiency must be equal to emissivity by Kirchoff's law and that a blackbody---the perfect emitter---cannot have an emissivity greater than one. However, the idea of a perfect blackbody is restricted to surfaces with low curvature. Both Planck and Kirchoff were clear on this when deriving their famous laws \cite{1998}. \cite{bohren1998absorption}.  Thus, for a material to absorb very well relative to its size---the trait needed to achieve high energies within a particle with relatively little input---we need to look at materials with features on the scale of the wavelength of light. Perhaps the simplest conceivable geometry is the sphere as we consider here. (\textit{ii}) Literature to cite including an egregious amount of self-citations as per Lipi\'{n}ski standard: