- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
Synergy of the catalytic activation on Ni and the CeO <sub/>2</sub> –TiO <sub/>2</sub> /Ce <sub/>2</sub> Ti <sub/>2</sub> O <sub/>7</sub> stoichiometric redox cycle for dramatically enhanced solar fuel production
摘要： Solar thermochemical approaches to CO2 and H2O splitting have emerged as an attractive pathway to solar fuel production. However, efficiently producing solar fuel with high redox kinetics and yields at lower temperature remains a major challenge. In this study, Ni promoted ceria–titanium oxide (CeO2–TiO2) redox catalysts were developed for highly effective thermochemical CO2 and H2O splitting as well as partial oxidation of CH4 at 900 1C. Unprecedented CO and H2 production rates and productivities of about 10–140 and 5–50 times higher than the current state-of-the-art solar thermochemical carbon dioxide splitting and water splitting processes were achieved with simultaneous close to complete CH4 conversions and high selectivities towards syngas. The underlying mechanism for the exceptional reaction performance was investigated by combined experimental characterization and density functional theory (DFT) calculations. It is revealed that the metallic Ni and the Ni/oxide interface manifest catalytic activity for both CH4 activation and CO2 or H2O dissociation, whereas CeO2–TiO2 enhances the lattice oxygen transport via the CeO2–TiO2/Ce2Ti2O7 stoichiometric redox cycle for CH4 partial oxidation and the subsequent CO2 or H2O splitting promoted by catalytically active Ni. Such findings substantiate the significance of the synergy between the reactant activation by catalytic sites and the stoichiometric redox chemistry governing oxygen ion transport, paving the way for designing prospective materials for sustainable solar fuel production.
关键词： thermochemical CO2 splitting,solar fuel production,density functional theory,Ni promoted ceria–titanium oxide,thermochemical H2O splitting,methane partial oxidation,redox catalysts
更新于2025-09-19 17:15:36
-
Experimental framework for evaluation of the thermodynamic and kinetic parameters of metal-oxides for solar thermochemical fuel production
摘要： The two-step metal oxide redox cycle is a promising and thermodynamically attractive means of solar fuel production. In this work, we describe the development of a high-temperature tubular reactor in which the fundamental thermodynamic and kinetic behaviour of thermochemical materials can be readily assessed. This reactor system is capable of operating at temperatures up to 1873 K, total pressures ranging from vacuum to ambient, and oxygen partial pressures (pO2) as low as 10-29 atm. Compared to off-the-shelf systems like thermogravimetric analyzers (TGA) or indirect conductivity-based measurement systems, this system has three inherent benefits: (1) the flexibility to control the sample morphology (e.g. powder, packed bed, reticulated porous ceramic, or pellet), (2) the potential for a well-developed and characterized flow, and (3) the ability to readily customize the system on demand (e.g. easy integration with a steam generator to control and operate at very low pO2). The reactor system and experimental methods were validated by performing isothermal relaxation experiments with undoped ceria, wherein the sample environment was rapidly altered by stepwise changes in the delivered H2O vapor concentration, and comparing measured oxygen nonstoichiometries with accepted data available in the literature. Data was measured at temperatures from 1173-1473 K and pO2 from 4.54×10-18-1.02×10-9 atm. The measured equilibrium data displayed strong agreement with the literature and the expected trends were preserved. Kinetic data was extracted by first transforming reactant concentrations measured downstream of the reaction zone using a tanks-in-series mixing model to account for gas dispersion. Next, a mechanistic kinetic model distinguishing surface and bulk species concentrations was fit to the data to extract pertinent thermodynamic and kinetic parameters. The model assumed a two-step reaction mechanism mediated by the formation of an intermediate hydroxyl species on the surface. Activation energies and defect formation enthalpies and entropies for the forward and reverse reactions were found to be in good agreement with previous modelling efforts, providing further validation of the use of this system to explore thermodynamic and kinetic behaviour of emerging thermochemical materials.
关键词： thermodynamic and kinetic parameters,undoped ceria,solar fuel production,metal oxide redox cycle,high-temperature tubular reactor
更新于2025-09-09 09:28:46