Nonstoichiometric ceria(CeO2−δ) is a candidate reaction medium to facilitate two step water splitting cycles and generate hydrogen. Improving upon its thermodynamic suitability through doping requires an understanding of its vacancy thermodynamics. Using density functional theory(DFT) calculations and a cluster expansion based Monte Carlo simulations, we have studied the high temperature thermo...

The rapid increase in the use of engineered nanoparticles [ENPs] has resulted in an increasing concern over the potential impacts of ENPs on the environmental and human health. ENPs tend to adsorb a large variety of toxic chemicals when they are emitted into the environment, which may enhance the toxicity of ENPs and/or adsorbed chemicals. The study was aimed to investigate the adsorption and d...

We use density functional theory calculations with Hubbard corrections (DFT+U) to investigate electronic aspects of the interaction between ceria surfaces and gold atoms. Our results show that Au adatoms at the (111) surface of ceria can adopt Au(0), Au(+) or Au(-) electronic configurations depending on the adsorption site. The strongest adsorption sites are on top of the surface oxygen and in ...

The oxidation of methane, ethane, propane, and n-butane has been studied over CeO2 and Ce0.8Sm0.2Ox (SDC) catalysts. The rates for methane and ethane were found to be indistinguishable over the two catalysts, while the rates for propane and n-butane were much higher on ceria compared to SDC. The difference between n-butane oxidation over ceria and SDC is shown to result from a low-temperature r...

An FTIR study of CO adsorption from 120 K up to room temperature on a series of Au–ceria samples is presented. Samples with low gold content (0.7 and 0.6 at%) were prepared by urea gelation/co-precipitation and by cyanide leaching of the high-gold content (5.8 at%) material prepared by deposition–precipitation on La-doped CeO2. The samples were subjected to different pretreatments to collect in...

The grain coarsening in dense nanocrystalline gadolinia-doped ceria (CGO) and CeO2 was studied for the grain size regime from 10 to 250 nm. Dense ceria-based thin films were prepared by spray pyrolysis and pulsed laser deposition on sapphire substrates. The small grain-sized CGO and CeO2 microstructures were surprisingly stable and showed self-limited grain growth and relaxation of the microstr...

Reduction of SO, by CO to elemental sulfur on fluorite oxide and transition metal/fluorite oxide composite catalysts is discussed within the redox framework. The oxygen vacancies on the fluorite oxide are active catalyst sites and their creation is a key step to initiate the redox reaction. Transition metal/fluorite oxide composites demonstrate a strong synergism for the reaction. A reduction k...

We investigate the dopant distribution and its influence on the oxygen ion conductivity of ceria doped with rare earth oxides by combining density functional theory and Monte Carlo simulations. We calculate the association energies of dopant pairs, oxygen vacancy pairs and between dopant ions and oxygen vacancies by means of DFT + U including finite size corrections. The cation coordination num...

We present the activities and selectivities of Pt/Al2O3-based catalysts in the production of hydrogen from methanol through catalytic decomposition. For the decomposition reaction, the Pt and Pd catalysts promoted by ceria exhibit similar activity reaching 100% conversion at 315 C. Promoting with ceria had a positive effect on activity and selectivity. Among all catalysts, the 9% Pt– 10% CeO2/A...

Oxygen nonstoichiometry and thermodynamic characterization of Zr doped ceria in the 1573 – 1773 K temperature range