Special Issue "Cerium-based Materials for Energy Conversion"

A special issue of Inorganics (ISSN 2304-6740). This special issue belongs to the section "Inorganic Solid-State Chemistry".

Deadline for manuscript submissions: closed (30 September 2017)

Special Issue Editors

Guest Editor
Prof. Dr. Ulrich F. Vogt

1. Empa, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, 8600 Dübendorf, Switzerland
2. Albert-Ludwigs-University Freiburg, Crystallography, Institute of Earth and Environmental Sciences, Hermann-Herder-Str. 5, D-79104 Freiburg i.Br., Germany
Website 1 | Website 2 | E-Mail
Phone: +41 58 765 4160
Interests: materials for energy conversion; CeO2 redox reactions; perovskites; power-to-gas; H2 electrolysis (SOEC, AWE)
Guest Editor
Prof. Paolo Fornasiero

Universita’ degli Studi di Trieste, Department of Chemical and Pharmaceutical Sciences, Trieste, Italy
Website | E-Mail
Phone: +390405583973
Fax: +39 40 558 3903
Interests: material chemistry; functional metal oxides; hybrids and nanostructured catalysts; energy applications; environmental applications; heterogeneous catalysis

Special Issue Information

Dear Colleagues,

Ceria (CeO2) plays a key role in many catalytic processes. Due to its excellent oxygen storage capacity (OSC), ceria and ceria-based mixed oxides are widely used for industrially-relevant applications, like three-way catalysis, catalytic oxidation in exhaust converters, hydrocarbon reforming, SOFC fuel cells, SOEC electrolysis, photocatalysis, water–gas shift reactions, or thermochemical water splitting. Doping and formation of nanocomposites and solid solutions allow to enhance the excellent redox properties of ceria, and to significantly improve its high temperature- and chemical stability. Consistently, ceria-based materials are ideal materials, even for demanding high temperature catalytic reactions.

While there is no doubt that ceria, as with any catalyst, is able to reduce the energetic requirements of the catalytic process where it is applied, particularly relevant are the direct application of ceria-based materials in the energy sector.  This is the case of ceria-based materials used as electrolytes in SOFS, as co-catalyst in anodes of SOFC or in DAFC, as active components in the formulation of reforming catalysts for hydrogen production or in thermochemical applications. Applications of ceria-based materials in photo- or photoelectrochemical processes for solar fuel production are also exponentially growing.

The goal of this Special Issue aims is to bring together the actual status of research on the use of ceria-based materials for energy-related applications in an openly-accessible way, in order to allow better communication of this topic to a wider audience. Therefore, we invite you to contribute with a paper in the above-mentioned areas and allow your research to inform and influence the next generation of scientist to keep the field as vibrant as it is today.

Prof. Dr. Ulrich F. Vogt
Prof. Dr. Paolo Fornasiero
Guest Editors

Manuscript Submission Information

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Keywords

  • Ceria oxygen exchange mechanism
  • CeO2–y oxygen storage capacity
  • Ceria oxygen exchange mechanisms
  • ceria-based mixed oxides
  • thermochemical water splitting
  • thermochemical syngas production
  • dopand solubility limit
  • solar fuels
  • ceria based FC
  • photocatalytic water splitting

Related Special Issue

Published Papers (6 papers)

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Research

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Open AccessArticle The Role of Neodymium in the Optimization of a Ni/CeO2 and Ni/CeZrO2 Methane Dry Reforming Catalyst
Received: 8 March 2018 / Revised: 27 March 2018 / Accepted: 28 March 2018 / Published: 3 April 2018
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Abstract
The development of a sustainable economy based on the use of renewable resources and the reduction of greenhouse gases emissions is an important mandate in modern societies to minimize the global warming. The CO2-reforming of methane through a conversion of CO
[...] Read more.
The development of a sustainable economy based on the use of renewable resources and the reduction of greenhouse gases emissions is an important mandate in modern societies to minimize the global warming. The CO2-reforming of methane through a conversion of CO2 and CH4 to syngas is a suitable process for this purpose and there is growing interest in the development of new catalysts for this process’ application at an industrial scale. This study is the first to investigate methane dry reforming activity of nickel supported on CeO2 and CeO2–ZrO2 solid solutions doped with neodymium. The supports were synthesized using a surfactant-assisted co-precipitation method and characterized through several analytical techniques to understand the role of synthesis parameters in the distribution of the dopant as well as in the properties of the supports. Co-doping with Zr and Nd resulted in an enhancement of dry reforming activity of ceria due to a higher dispersion of Ni and changes in the strength of basic sites. It was also shown that the addition of Nd helped to mitigate coking issues by increasing the mobility of surface oxygen in ceria and ceria–zirconia oxides and, accordingly, the rate of oxidation of carbonaceous deposits. Full article
(This article belongs to the Special Issue Cerium-based Materials for Energy Conversion)
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Open AccessArticle Ceria: Recent Results on Dopant-Induced Surface Phenomena
Received: 27 September 2017 / Revised: 26 October 2017 / Accepted: 27 October 2017 / Published: 8 November 2017
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Abstract
Redox studies on dense zirconia-doped ceria pellets were carried out by thermogravimetric investigations and dilatometry. Up to 1600 K reduction parameters determined by both methods correspond to each other. At higher temperatures, however, thermogravimetry overestimates the degree of reduction since mass loss is
[...] Read more.
Redox studies on dense zirconia-doped ceria pellets were carried out by thermogravimetric investigations and dilatometry. Up to 1600 K reduction parameters determined by both methods correspond to each other. At higher temperatures, however, thermogravimetry overestimates the degree of reduction since mass loss is not only due to oxygen exsolution but also to selective evaporation of CeO2 whose vapour pressure is considerably higher than that of ZrO2. As a consequence surface segregation of zirconia occurs in (Ce,Zr)O2−δ pellets leading to a porous surface zone of Ce2Zr2O7 pyrochlore which gradually grows in thickness. Surface enrichment of zirconia is detrimental for splitting CO2 or H2O since re-oxidation temperatures of (Ce,Zr)O2−δ are known to be shifted towards lower temperatures with increasing ZrO2 content. Thus, very harsh reduction conditions should be avoided for the (Ce,Zr)O2−δ redox system. The kinetics investigations comprised the high temperature reduction step (T ≅ 1600 K) and the “low” temperature oxidation reaction with a carbon dioxide atmosphere (T ≅ 1000 K). The reduction kinetics (at around 1600 K and an oxygen activity of 7 × 10−4 in the gas phase) directly yield the (reduction) equilibrium exchange rate of oxygen in the order of 10−7 mol·O/(cm3·s) as the kinetics are surface controlled. The oxidation step at around 1000 K, however, occurs in the mixed control or in the diffusion control regime, respectively. From oxygen isotope exchange in combination with SIMS depth profiling oxygen exchange coefficients, K, and oxygen diffusivities, D, were determined for so-called equilibrium experiments as well as for non-equilibrium measurements. From the obtained values for K and D the (oxidation) equilibrium exchange rates for differently doped ceria samples were determined. Their dependency on the oxygen activity and the nature and the concentrations of a tetravalent dopant (Zr) and trivalent dopants (La, Y, Sm) could be semi-quantitatively rationalised on the basis of a master equation for the equilibrium surface exchange rate. Full article
(This article belongs to the Special Issue Cerium-based Materials for Energy Conversion)
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Open AccessArticle Synthesis of 1,3-Diols from Isobutene and HCHO via Prins Condensation-Hydrolysis Using CeO2 Catalysts: Effects of Crystal Plane and Oxygen Vacancy
Received: 28 September 2017 / Revised: 27 October 2017 / Accepted: 2 November 2017 / Published: 7 November 2017
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Abstract
We herein report the synthesis of 3-methyl-1,3-butanediol from isobutene and HCHO in water via a Prins condensation-hydrolysis reaction over CeO2, which is a water-tolerant Lewis acid catalyst. The CeO2 exhibits significant catalytic activity for the reaction, giving 95% HCHO conversion
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We herein report the synthesis of 3-methyl-1,3-butanediol from isobutene and HCHO in water via a Prins condensation-hydrolysis reaction over CeO2, which is a water-tolerant Lewis acid catalyst. The CeO2 exhibits significant catalytic activity for the reaction, giving 95% HCHO conversion and 84% 3-methyl-1,3-butanediol selectivity at 150 °C for 4 h. The crystal planes of CeO2 have a significant effect on the catalytic activity for the Prins reaction. The (110) plane shows the highest catalytic activity among the crystal planes investigated (the (100), (110), and (111) planes), due to its higher concentration of Lewis acid sites, which is in line with the concentration of oxygen vacancies. Detailed characterizations, including NH3-TPD, pyridine-adsorbed FT-IR spectroscopy, and Raman spectroscopy, revealed that the concentration of Lewis acid sites is proportional to the concentration of oxygen vacancies. This study indicates that the Lewis acidity induced by oxygen vacancy can be modulated by selective synthesis of CeO2 with different morphologies, and that the Lewis acidity and oxygen vacancy play an important role in Prins condensation and hydrolysis reaction. Full article
(This article belongs to the Special Issue Cerium-based Materials for Energy Conversion)
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Open AccessArticle Investigation of the Thermodynamic Properties of Surface Ceria and Ceria–Zirconia Solid Solution Films Prepared by Atomic Layer Deposition on Al2O3
Received: 29 August 2017 / Revised: 11 October 2017 / Accepted: 11 October 2017 / Published: 15 October 2017
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Abstract
The properties of 20 wt % CeO2 and 21 wt % Ce0.5Zr0.5O2 films, deposited onto a γ-Al2O3 by Atomic Layer Deposition (ALD), were compared to bulk Ce0.5Zr0.5O2 and γ-Al
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The properties of 20 wt % CeO2 and 21 wt % Ce0.5Zr0.5O2 films, deposited onto a γ-Al2O3 by Atomic Layer Deposition (ALD), were compared to bulk Ce0.5Zr0.5O2 and γ-Al2O3-supported samples on which 20 wt % CeO2 or 21 wt % CeO2–ZrO2 were deposited by impregnation. Following calcination to 1073 K, the ALD-prepared catalysts showed much lower XRD peak intensities, implying that these samples existed as thin films, rather than larger crystallites. Following the addition of 1 wt % Pd to each of the supports, the ALD-prepared samples exhibited much higher rates for CO oxidation due to better interfacial contact between the Pd and ceria-containing phases. The redox properties of the ALD samples and bulk Ce0.5Zr0.5O2 were measured by determining the oxidation state of the ceria as a function of the H2:H2O ratio using flow titration and coulometric titration. The 20 wt % CeO2 ALD film exhibited similar thermodynamics to that measured previously for a sample prepared by impregnation. However, the sample with 21 wt % Ce0.5Zr0.5O2 on γ-Al2O3 reduced at a much higher P O 2 and showed evidence for transition between the Ce0.5Zr0.5O2 and Ce0.5Zr0.5O1.75 phases. Full article
(This article belongs to the Special Issue Cerium-based Materials for Energy Conversion)
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Open AccessArticle Stabilization of ZrO2 Powders via ALD of CeO2 and ZrO2
Received: 30 August 2017 / Revised: 19 September 2017 / Accepted: 27 September 2017 / Published: 3 October 2017
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Abstract
ZrO2 powders were modified by atomic layer deposition (ALD) with CeO2 and ZrO2, using Ce(TMHD)4 and Zr(TMHD)4 as the precursors, in order to determine the effect of ALD films on the structure, surface area, and catalytic properties
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ZrO2 powders were modified by atomic layer deposition (ALD) with CeO2 and ZrO2, using Ce(TMHD)4 and Zr(TMHD)4 as the precursors, in order to determine the effect of ALD films on the structure, surface area, and catalytic properties of the ZrO2. Growth rates were measured gravimetrically and found to be 0.017 nm/cycle for CeO2 and 0.031 nm/cycle for ZrO2. The addition of 20 ALD cycles of either CeO2 or ZrO2 was found to stabilize the surface area of the ZrO2 powder following calcination to 1073 K and to suppress the tetragonal-to-monoclinic transition. Shrinkage of ZrO2 wafers was also suppressed by the ALD films. When used as a support for Pd in CO oxidation, the CeO2-modified materials significantly enhanced rates due to interactions between the Pd and the CeO2. Potential applications for modifying catalyst supports using ALD are discussed. Full article
(This article belongs to the Special Issue Cerium-based Materials for Energy Conversion)
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Open AccessErratum Erratum: Knoblauch, N. et al. Ceria: Recent Results on Dopant-Induced Surface Phenomena . Inorganics 2017, 5, 76
Received: 15 June 2018 / Accepted: 15 June 2018 / Published: 19 June 2018
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Abstract
The authors would like to add Stefan Beschnitt, who performed SIMS line scans, to the authors’ list in 5th position of their paper published in Inorganics[...] Full article
(This article belongs to the Special Issue Cerium-based Materials for Energy Conversion)
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