Cerium dioxide (CeO2, ceria) is becoming an ubiquitous constituent in catalytic systems for a variety of applications. 2016 sees the 40th anniversary since ceria was first employed by Ford Motor Company as an oxygen storage component in car converters, to become in the years since its inception an irreplaceable component in three-way catalysts (TWCs). Apart from this well-established use, ceria is looming as a catalyst component for a wide range of catalytic applications. For some of these, such as fuel cells, CeO2-based materials have almost reached the market stage, while for some other catalytic reactions, such as reforming processes, photocatalysis, water-gas shift reaction, thermochemical water splitting, and organic reactions, ceria is emerging as a unique material, holding great promise for future market breakthroughs. While much knowledge about the fundamental characteristics of CeO2-based materials has already been acquired, new characterization techniques and powerful theoretical methods are dee...

Fundamentals and Catalytic Applications of CeO2-Based Materials

CO2 conversion covers a wide range of possible application areas from fuels to bulk and commodity chemicals and even to specialty products with biological activity such as pharmaceuticals. In the present review, we discuss selected examples in these areas in a combined analysis of the state-of-the-art of synthetic methodologies and processes with their life cycle assessment. Thereby, we attempted to assess the potential to reduce the environmental footprint in these application fields relative to the current petrochemical value chain. This analysis and discussion differs significantly from a viewpoint on CO2 utilization as a measure for global CO2 mitigation. Whereas the latter focuses on reducing the end-of-pipe problem “CO2 emissions” from todays’ industries, the approach taken here tries to identify opportunities by exploiting a novel feedstock that avoids the utilization of fossil resource in transition toward more sustainable future production. Thus, the motivation to develop CO2-based chemistry does...

Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment

Atomic layer deposition (ALD) is gaining attention as a thin film deposition method, uniquely suitable for depositing uniform and conformal films on complex three-dimensional topographies. The deposition of a film of a given material by ALD relies on the successive, separated, and self-terminating gas–solid reactions of typically two gaseous reactants. Hundreds of ALD chemistries have been found for depositing a variety of materials during the past decades, mostly for inorganic materials but lately also for organic and inorganic–organic hybrid compounds. One factor that often dictates the properties of ALD films in actual applications is the crystallinity of the grown film: Is the material amorphous or, if it is crystalline, which phase(s) is (are) present. In this thematic review, we first describe the basics of ALD, summarize the two-reactant ALD processes to grow inorganic materials developed to-date, updating the information of an earlier review on ALD [R. L. Puurunen, J. Appl. Phys. 97, 121301 (2005)], and give an overview of the status of processing ternary compounds by ALD. We then proceed to analyze the published experimental data for information on the crystallinity and phase of inorganic materials deposited by ALD from different reactants at different temperatures. The data are collected for films in their as-deposited state and tabulated for easy reference. Case studies are presented to illustrate the effect of different process parameters on crystallinity for representative materials: aluminium oxide, zirconium oxide, zinc oxide, titanium nitride, zinc zulfide, and ruthenium. Finally, we discuss the general trends in the development of film crystallinity as function of ALD process parameters. The authors hope that this review will help newcomers to ALD to familiarize themselves with the complex world of crystalline ALD films and, at the same time, serve for the expert as a handbook-type reference source on ALD processes and film crystallinity.

Crystallinity of inorganic films grown by atomic layer deposition: Overview and general trends

The controllable synthesis of nanostructured CeO2-based materials is an imperative issue for environment- and energy-related applications. In this review, we present the recent technological and theoretical advances related to the CeO2-based nanomaterials, with a focus on the synthesis from one dimensional to mesoporous ceria as well as the properties from defect chemistry to nano-size effects. Seven extensively studied aspects regarding the applications of nanostructured ceria-based materials are selectively surveyed as well. New experimental approaches have been demonstrated with an atomic scale resolution characterization. Density functional theory (DFT) calculations can provide insight into the rational design of highly reactive catalysts and understanding of the interactions between the noble metal and ceria support. Achieving desired morphologies with designed crystal facets and oxygen vacancy clusters in ceria via controlled synthesis process is quite important for highly active catalysts. Finally, remarks on the challenges and perspectives on this exciting field are proposed.

Nanostructured ceria-based materials: synthesis, properties, and applications

CO2 conversion into value-added chemicals and fuels is considered as one of the great challenges of the 21st century. Due to the limitations of the traditional thermal approaches, several novel technologies are being developed. One promising approach in this field, which has received little attention to date, is plasma technology. Its advantages include mild operating conditions, easy upscaling, and gas activation by energetic electrons instead of heat. This allows thermodynamically difficult reactions, such as CO2 splitting and the dry reformation of methane, to occur with reasonable energy cost. In this review, after exploring the traditional thermal approaches, we have provided a brief overview of the fierce competition between various novel approaches in a quest to find the most effective and efficient CO2 conversion technology. This is needed to critically assess whether plasma technology can be successful in an already crowded arena. The following questions need to be answered in this regard: are there key advantages to using plasma technology over other novel approaches, and if so, what is the flip side to the use of this technology? Can plasma technology be successful on its own, or can synergies be achieved by combining it with other technologies? To answer these specific questions and to evaluate the potentials and limitations of plasma technology in general, this review presents the current state-of-the-art and a critical assessment of plasma-based CO2 conversion, as well as the future challenges for its practical implementation.

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Plasma technology - a novel solution for CO2 conversion?

Solar syngas production from H2O and CO2 is experimentally investigated using a two-step thermochemical cycle based on cerium oxide redox reactions. A solar cavity-receiver containing porous ceria felt is directly exposed to concentrated thermal radiation at a mean solar concentration ratio of 2865 suns. In the first endothermic step at 1800 K, ceria is thermally reduced to an oxygen deficient state. In the second exothermic step at 1100 K, syngas is produced by re-oxidizing ceria with a gas mixture of H2O and CO2. The syngas composition is experimentally determined as a function of the molar co-feeding ratio H2O:CO2 in the range of 0.8 to 7.7, yielding syngas with H2:CO molar ratios from 0.25 to 2.34. Ten consecutive H2O/CO2-splitting cycles performed over an 8 hour solar experimental run are presented.

Syngas production by simultaneous splitting of H2O and CO2via ceria redox reactions in a high-temperature solar reactor

A solar cavity-receiver containing a reticulated porous ceramic (RPC) foam made of pure CeO2 has been experimentally investigated for CO2 splitting via thermochemical redox reactions. The RPC was directly exposed to concentrated thermal radiation at mean solar flux concentration ratios of up to 3015 suns. During the endothermic reduction step, solar radiative power inputs in the range 2.8–3.8 kW and nominal reactor temperatures from 1400 to 1600 °C yielded CeO2−δ with oxygen deficiency δ ranging between 0.016 and 0.042. In the subsequent exothermic oxidation step at below about 1000 °C, CeO2−δ was stoichiometrically reoxidized with CO2 to generate CO. The solar-to-fuel energy conversion efficiency, defined as the ratio of the calorific value of CO (fuel) produced to the solar radiative energy input through the reactor’s aperture and the energy penalty for using inert gas, was 1.73% average and 3.53% peak. This is roughly four times greater than the next highest reported values to date for a solar-driven d...

Solar Thermochemical CO2 Splitting Utilizing a Reticulated Porous Ceria Redox System

Oxygen exchange materials for solar thermochemical splitting of H2O and CO2: a review

A thermodynamic and experimental investigation of a new class of solar thermochemical redox intermediates, namely, lanthanum–strontium–manganese perovskites, is presented. A defect model based on low-temperature oxygen non-stoichiometry data is formulated and extrapolated to higher temperatures more relevant to thermochemical redox cycles. Strontium contents of x = 0.3 (LSM30) and x = 0.4 (LSM40) in La1–xSrxMnO3−δ result in favorable reduction extents compared to ceria in the temperature range of 1523–1923 K. Oxidation with CO2 and H2O is not as thermodynamically favorable and largely dependent upon the oxidant concentration. The model is experimentally validated by O2 non-stoichiometry measurements at high temperatures (>1623 K) and CO2 reduction cycles with commercially available LSM35. Theoretical solar–fuel energy conversion efficiencies for LSM40 and ceria redox cycles are 16 and 22% at 1800 K and 13 and 7% at 1600 K, respectively.

Lanthanum–Strontium–Manganese Perovskites as Redox Materials for Solar Thermochemical Splitting of H2O and CO2

The thermodynamics of ceria-based metal oxides MxCe1–xO2, where M = Gd, Y, Sm, Ca, Sr, have been studied in relation to their applicability as reactive intermediates in solar thermochemical redox cycles for splitting H2O and CO2. Oxygen nonstoichiometry was modeled and extrapolated to high temperatures and reduction extents by applying an ideal solution model in conjunction with a defect interaction model. Subsequently, relevant thermodynamic parameters were computed and equilibrium H2 and CO concentrations determined as a function of reduction conditions (T, PO2) and ensuing oxidation temperature. At 1 atm and above 1673 K, the degree of reduction is negatively correlated to dopant concentration, regardless of the type of dopant considered. Consequently, at a given reduction temperature, more H2 and CO is generated at equilibrium for pure ceria compared to any of the other doped ceria materials considered. Although the reduction enthalpy decreases as the dopant concentration increases, the overall solar-...

Jonathan R. Scheffe

Papers

Syngas production by simultaneous splitting of H2O and CO2via ceria redox reactions in a high-temperature solar reactor

Solar Thermochemical CO2 Splitting Utilizing a Reticulated Porous Ceria Redox System

Oxygen exchange materials for solar thermochemical splitting of H2O and CO2: a review

Lanthanum–Strontium–Manganese Perovskites as Redox Materials for Solar Thermochemical Splitting of H2O and CO2

Thermodynamic Analysis of Cerium-Based Oxides for Solar Thermochemical Fuel Production