Cerium(IV) oxide

Last updated
Cerium(IV) oxide
Cerium(IV) oxide.jpg
Ceria-3D-ionic.png
Names
IUPAC name
Cerium(IV) oxide
Other names
Ceric oxide,
Ceria,
Cerium dioxide
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.013.774 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/Ce.2O/q+4;2*-2 Yes check.svgY
    Key: OFJATJUUUCAKMK-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/Ce.2O/q+4;2*-2
    Key: OFJATJUUUCAKMK-UHFFFAOYAX
  • [O-2]=[Ce+4]=[O-2]
Properties
CeO2
Molar mass 172.115 g/mol
Appearancewhite or pale yellow solid,
slightly hygroscopic
Density 7.215 g/cm3
Melting point 2,400 °C (4,350 °F; 2,670 K)
Boiling point 3,500 °C (6,330 °F; 3,770 K)
insoluble
+26.0·10−6 cm3/mol
Structure
cubic crystal system, cF12 (fluorite) [1]
Fm3m, #225
a = 5.41 Å [2] , b = 5.41 Å, c = 5.41 Å
α = 90°, β = 90°, γ = 90°
Ce, 8, cubic
O, 4, tetrahedral
Hazards
NFPA 704 (fire diamond)
NFPA 704.svgHealth 1: Exposure would cause irritation but only minor residual injury. E.g. turpentineFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
1
0
0
Related compounds
Related compounds
 Cerium(III) oxide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Cerium(IV) oxide, also known as ceric oxide, ceric dioxide, ceria, cerium oxide or cerium dioxide, is an oxide of the rare-earth metal cerium. It is a pale yellow-white powder with the chemical formula CeO2. It is an important commercial product and an intermediate in the purification of the element from the ores. The distinctive property of this material is its reversible conversion to a non-stoichiometric oxide.

Contents

Production

Cerium occurs naturally as oxides, always as a mixture with other rare-earth elements. Its principal ores are bastnaesite and monazite. After extraction of the metal ions into aqueous base, Ce is separated from that mixture by addition of an oxidant followed by adjustment of the pH. This step exploits the low solubility of CeO2 and the fact that other rare-earth elements resist oxidation. [3]

Cerium(IV) oxide is formed by the calcination of cerium oxalate or cerium hydroxide.

Cerium also forms cerium(III) oxide, Ce
2O
3, which is unstable and will oxidize to cerium(IV) oxide. [4]

Characteristics

CeO2 is one of the most widely studied oxides of Cerium. CeO2 is the most-oxidized form of Cerium, 4f states strongly hybridizes with the O 2p states making 4f electrons delocalized. These states form a wide dispersive band, extending over a region of some eV, which can be correctly detected using theoretical methods accurately. [5]

Structure and defect behavior

Cerium oxide adopts the fluorite structure, space group Fm3m, #225 containing 8-coordinate Ce4+ and 4-coordinate O2−. At high temperatures it releases oxygen to give a non-stoichiometric, anion deficient form that retains the fluorite lattice. [6] This material has the formula CeO(2−x), where 0 < x < 0.28. [7] The value of x depends on both the temperature, surface termination and the oxygen partial pressure. The equation

has been shown to predict the equilibrium non-stoichiometry x over a wide range of oxygen partial pressures (103–10−4 Pa) and temperatures (1000–1900 °C). [8]

The non-stoichiometric form has a blue to black color, and exhibits both ionic and electronic conduction with ionic being the most significant at temperatures > 500 °C. [9]

The number of oxygen vacancies is frequently measured by using X-ray photoelectron spectroscopy to compare the ratio of Ce3+
to Ce4+
.

Defect chemistry

In the most stable fluorite phase of ceria, it exhibits several defects depending on partial pressure of oxygen or stress state of the material. [10] [11] [12] [13]

The primary defects of concern are oxygen vacancies and small polarons (electrons localized on cerium cations). Increasing the concentration of oxygen defects increases the diffusion rate of oxide anions in the lattice as reflected in an increase in ionic conductivity. These factors give ceria favorable performance in applications as a solid electrolyte in solid-oxide fuel cells. Undoped and doped ceria also exhibit high electronic conductivity at low partial pressures of oxygen due to reduction of the cerium ion leading to the formation of small polarons. Since the oxygen atoms in a ceria crystal occur in planes, diffusion of these anions is facile. The diffusion rate increases as the defect concentration increases.

The presence of oxygen vacancies at terminating ceria planes governs the energetics of ceria interactions with adsorbate molecules, and its wettability. Controlling such surface interactions is key to harnessing ceria in catalytic applications. [14]

Natural occurrence

Cerium(IV) oxide occurs naturally as the mineral cerianite-(Ce). [15] [16] It is a rare example of tetravalent cerium mineral, the other examples being stetindite-(Ce) and dyrnaesite-(La). The "-(Ce)" suffix is known as Levinson modifier and is used to show which element dominates in a particular site in the structure. [17] It is often found in names of minerals bearing rare earth elements (REEs). Occurrence of cerianite-(Ce) is related to some examples of cerium anomaly, where Ce - which is oxidized easily - is separated from other REEs that remain trivalent and thus fit to structures of other minerals than cerianite-(Ce). [18] [15] [16]

Applications

Cerium has two main applications, which are listed below.

The principal industrial application of ceria is for polishing, especially chemical-mechanical planarization (CMP). [3] For this purpose, it has displaced many other oxides that were previously used, such as iron oxide and zirconia. For hobbyists, it is also known as "opticians' rouge". [19] [20]

In its other main application, CeO2 is used to decolorize glass. It functions by converting green-tinted ferrous impurities to nearly colorless ferric oxides. [3]

Other niche and emerging applications

Catalysis

CeO2 has attracted much attention in the area of heterogeneous catalysis. It catalyses the water-gas shift reaction. It oxidizes carbon monoxide. Its reduced derivative Ce2O3 reduces water, with release of hydrogen. [21] [22] [23] [24]

The interconvertibility of CeOx materials is the basis of the use of ceria for an oxidation catalyst. One small but illustrative use is its use in the walls of self-cleaning ovens as a hydrocarbon oxidation catalyst during the high-temperature cleaning process. Another small scale but famous example is its role in oxidation of natural gas in gas mantles. [25]

A glowing Coleman white gas lantern mantle. The glowing element is mainly ThO2 doped with CeO2, heated by the Ce-catalyzed oxidation of the natural gas with air. Glowing gas mantle.jpg
A glowing Coleman white gas lantern mantle. The glowing element is mainly ThO2 doped with CeO2, heated by the Ce-catalyzed oxidation of the natural gas with air.

Building on its distinct surface interactions, ceria finds further use as a sensor in catalytic converters in automotive applications, controlling the air-exhaust ratio to reduce NOx and carbon monoxide emissions. [26]

Energy & fuels

Due to the significant ionic and electronic conduction of cerium oxide, it is well suited to be used as a mixed conductor. [27] As such, cerium oxide is a material of interest for solid oxide fuel cells (SOFCs) in comparison to zirconium oxide. [28]

Thermochemically, the cerium(IV) oxide–cerium(III) oxide cycle or CeO2/Ce2O3 cycle is a two-step water splitting process that has been used for hydrogen production. [29] Because it leverages the oxygen vacancies between systems, this allows ceria in water to form hydroxyl (OH) groups. [30] The hydroxyl groups can then be released as oxygen oxidizes, thus providing a source of clean energy.

Optics

Cerium oxide is highly valued in the optics industry for its exceptional polishing capabilities. [31] It effectively removes minor scratches and imperfections from glass surfaces through both mechanical abrasion and chemical interaction, producing a smooth, high-gloss finish. [32] Cerium oxide can also enhance the durability of optical surfaces by forming a protective layer that increases resistance to scratches and environmental wear. [33]

Cerium oxide has also found use in infrared filters and as a replacement for thorium dioxide in incandescent mantles [34]

Welding

Cerium oxide is used as an addition to tungsten electrodes for Gas Tungsten Arc Welding. It provides advantages over pure Tungsten electrodes such as reducing electrode consumption rate and easier arc starting & stability. Ceria electrodes were first introduced in the US market in 1987, and are useful in AC, DC Electrode Positive, and DC Electrode Negative.

Safety aspects

Cerium oxide nanoparticles (nanoceria) have been investigated for their antibacterial and antioxidant activity. [35] [36] [37] [38]

Nanoceria is a prospective replacement of zinc oxide and titanium dioxide in sunscreens, as it has lower photocatalytic activity. [39]

See also

Related Research Articles

<span class="mw-page-title-main">Zirconium dioxide</span> Chemical compound

Zirconium dioxide, sometimes known as zirconia, is a white crystalline oxide of zirconium. Its most naturally occurring form, with a monoclinic crystalline structure, is the mineral baddeleyite. A dopant stabilized cubic structured zirconia, cubic zirconia, is synthesized in various colours for use as a gemstone and a diamond simulant.

<span class="mw-page-title-main">Praseodymium</span> Chemical element with atomic number 59 (Pr)

Praseodymium is a chemical element; it has symbol Pr and the atomic number 59. It is the third member of the lanthanide series and is considered one of the rare-earth metals. It is a soft, silvery, malleable and ductile metal, valued for its magnetic, electrical, chemical, and optical properties. It is too reactive to be found in native form, and pure praseodymium metal slowly develops a green oxide coating when exposed to air.

<span class="mw-page-title-main">Thorium dioxide</span> Chemical compound

Thorium dioxide (ThO2), also called thorium(IV) oxide, is a crystalline solid, often white or yellow in colour. Also known as thoria, it is mainly a by-product of lanthanide and uranium production. Thorianite is the name of the mineralogical form of thorium dioxide. It is moderately rare and crystallizes in an isometric system. The melting point of thorium oxide is 3300 °C – the highest of all known oxides. Only a few elements (including tungsten and carbon) and a few compounds (including tantalum carbide) have higher melting points. All thorium compounds, including the dioxide, are radioactive because there are no stable isotopes of thorium.

<span class="mw-page-title-main">Solid oxide fuel cell</span> Fuel cell that produces electricity by oxidization

A solid oxide fuel cell is an electrochemical conversion device that produces electricity directly from oxidizing a fuel. Fuel cells are characterized by their electrolyte material; the SOFC has a solid oxide or ceramic electrolyte.

A "photoelectrochemical cell" is one of two distinct classes of device. The first produces electrical energy similarly to a dye-sensitized photovoltaic cell, which meets the standard definition of a photovoltaic cell. The second is a photoelectrolytic cell, that is, a device which uses light incident on a photosensitizer, semiconductor, or aqueous metal immersed in an electrolytic solution to directly cause a chemical reaction, for example to produce hydrogen via the electrolysis of water.

<span class="mw-page-title-main">Bismuth(III) oxide</span> Chemical compound

Bismuth(III) oxide is a compound of bismuth, and a common starting point for bismuth chemistry. It is found naturally as the mineral bismite (monoclinic) and sphaerobismoite, but it is usually obtained as a by-product of the smelting of copper and lead ores. Dibismuth trioxide is commonly used to produce the "Dragon's eggs" effect in fireworks, as a replacement of red lead.

<span class="mw-page-title-main">Birnessite</span> Manganese hydroxide mineral

Birnessite (nominally MnO2·nH2O), also known as δ-MnO2, is a hydrous manganese dioxide mineral with a chemical formula of Na0.7Ca0.3Mn7O14·2.8H2O. It is the main manganese mineral species at the Earth's surface, and commonly occurs as fine-grained, poorly crystallized aggregates in soils, sediments, grain and rock coatings (e.g., desert varnish), and marine ferromanganese nodules and crusts. It was discovered at Birness, Aberdeenshire, Scotland.

<span class="mw-page-title-main">Fast-ion conductor</span>

In materials science, fast ion conductors are solid conductors with highly mobile ions. These materials are important in the area of solid state ionics, and are also known as solid electrolytes and superionic conductors. These materials are useful in batteries and various sensors. Fast ion conductors are used primarily in solid oxide fuel cells. As solid electrolytes they allow the movement of ions without the need for a liquid or soft membrane separating the electrodes. The phenomenon relies on the hopping of ions through an otherwise rigid crystal structure.

<span class="mw-page-title-main">Solid oxide electrolyzer cell</span> Type of fuel cell

A solid oxide electrolyzer cell (SOEC) is a solid oxide fuel cell that runs in regenerative mode to achieve the electrolysis of water by using a solid oxide, or ceramic, electrolyte to produce hydrogen gas and oxygen. The production of pure hydrogen is compelling because it is a clean fuel that can be stored, making it a potential alternative to batteries, methane, and other energy sources. Electrolysis is currently the most promising method of hydrogen production from water due to high efficiency of conversion and relatively low required energy input when compared to thermochemical and photocatalytic methods.

<span class="mw-page-title-main">Cerium(III) oxide</span> Chemical compound

Cerium(III) oxide, also known as cerium oxide, cerium trioxide, cerium sesquioxide, cerous oxide or dicerium trioxide, is an oxide of the rare-earth metal cerium. It has chemical formula Ce2O3 and is gold-yellow in color.

<span class="mw-page-title-main">Electrocatalyst</span> Catalyst participating in electrochemical reactions

An electrocatalyst is a catalyst that participates in electrochemical reactions. Electrocatalysts are a specific form of catalysts that function at electrode surfaces or, most commonly, may be the electrode surface itself. An electrocatalyst can be heterogeneous such as a platinized electrode. Homogeneous electrocatalysts, which are soluble, assist in transferring electrons between the electrode and reactants, and/or facilitate an intermediate chemical transformation described by an overall half reaction. Major challenges in electrocatalysts focus on fuel cells.

<span class="mw-page-title-main">Cerium</span> Chemical element with atomic number 58 (Ce)

Cerium is a chemical element; it has symbol Ce and atomic number 58. It is a soft, ductile, and silvery-white metal that tarnishes when exposed to air. Cerium is the second element in the lanthanide series, and while it often shows the oxidation state of +3 characteristic of the series, it also has a stable +4 state that does not oxidize water. It is considered one of the rare-earth elements. Cerium has no known biological role in humans but is not particularly toxic, except with intense or continued exposure.

Gadolinium-doped ceria (GDC) (known alternatively as gadolinia-doped ceria, gadolinium-doped cerium oxide (GCO), cerium-gadolinium oxide (CGO), or cerium(IV) oxide, gadolinium-doped, formula Gd:CeO2) is a ceramic electrolyte used in solid oxide fuel cells (SOFCs). It has a cubic structure and a density of around 7.2 g/cm3 in its oxidised form. It is one of a class of ceria-doped electrolytes with higher ionic conductivity and lower operating temperatures (<700 °C) than those of yttria-stabilized zirconia, the material most commonly used in SOFCs. Because YSZ requires operating temperatures of 800–1000 °C to achieve maximal ionic conductivity, the associated energy and costs make GDC a more optimal (even "irreplaceable", according to researchers from the Fraunhofer Society) material for commercially viable SOFCs.

<span class="mw-page-title-main">Ceria-zirconia</span>

Ceria-zirconia is a solid solution of cerium(IV) oxide (CeO2, also known as ceria) and zirconium oxide (ZrO2, also known as zirconia).

<span class="mw-page-title-main">Cerianite-(Ce)</span> Oxide mineral

Cerianite-(Ce) is a relatively rare oxide mineral, belonging to uraninite group with the formula (Ce,Th)O
2. It is one of a few currently known minerals containing essential tetravalent cerium, the other examples being stetindite and dyrnaesite-(La).

<span class="mw-page-title-main">Mixed conductor</span>

Mixed conductors, also known as mixed ion-electron conductors(MIEC), are a single-phase material that has significant conduction ionically and electronically. Due to the mixed conduction, a formally neutral species can transport in a solid and therefore mass storage and redistribution are enabled. Mixed conductors are well known in conjugation with high-temperature superconductivity and are able to capacitate rapid solid-state reactions.

Praseodymium(III,IV) oxide is the inorganic compound with the formula Pr6O11 that is insoluble in water. It has a cubic fluorite structure. It is the most stable form of praseodymium oxide at ambient temperature and pressure.

<span class="mw-page-title-main">Heterogeneous gold catalysis</span>

Heterogeneous gold catalysis refers to the use of elemental gold as a heterogeneous catalyst. As in most heterogeneous catalysis, the metal is typically supported on metal oxide. Furthermore, as seen in other heterogeneous catalysts, activity increases with a decreasing diameter of supported gold clusters. Several industrially relevant processes are also observed such as H2 activation, Water-gas shift reaction, and hydrogenation. One or two gold-catalyzed reactions may have been commercialized.

Electro-oxidation(EO or EOx), also known as anodic oxidation or electrochemical oxidation (EC), is a technique used for wastewater treatment, mainly for industrial effluents, and is a type of advanced oxidation process (AOP). The most general layout comprises two electrodes, operating as anode and cathode, connected to a power source. When an energy input and sufficient supporting electrolyte are provided to the system, strong oxidizing species are formed, which interact with the contaminants and degrade them. The refractory compounds are thus converted into reaction intermediates and, ultimately, into water and CO2 by complete mineralization.

Cerium compounds are compounds containing the element cerium (Ce), a lanthanide. Cerium exists in two main oxidation states, Ce(III) and Ce(IV). This pair of adjacent oxidation states dominates several aspects of the chemistry of this element. Cerium(IV) aqueous solutions may be prepared by reacting cerium(III) solutions with the strong oxidizing agents peroxodisulfate or bismuthate. The value of E⦵(Ce4+/Ce3+) varies widely depending on conditions due to the relative ease of complexation and hydrolysis with various anions, although +1.72 V is representative. Cerium is the only lanthanide which has important aqueous and coordination chemistry in the +4 oxidation state.

References

  1. ↑ Pradyot Patnaik. Handbook of Inorganic Chemicals. McGraw-Hill, 2002, ISBN   0-07-049439-8
  2. ↑ E. A. Kümmerle and G. Heger, “The Structures of C-Ce2O3+δ, Ce7O12, and Ce11O20,” Journal of Solid State Chemistry, vol. 147, no. 2, pp. 485–500, 1999.
  3. 1 2 3 Reinhardt, Klaus; Winkler, Herwig (2000). "Cerium Mischmetal, Cerium Alloys, and Cerium Compounds". Ullmann's Encyclopedia of Industrial Chemistry . Weinheim: Wiley-VCH. doi:10.1002/14356007.a06_139. ISBN   978-3527306732..
  4. ↑ "Standard Thermodynamic Properties of Chemical Substances" (PDF). Archived from the original (PDF) on October 29, 2013.
  5. ↑ Herper, Heike C; Vekilova, Olga Yu; Simak, Sergei I; Di Marco, Igor; Eriksson, Olle (2020-02-25). "Localized versus itinerant character of 4f-states in cerium oxides". Journal of Physics: Condensed Matter. 32 (21): 215502. doi:10.1088/1361-648x/ab6e92. ISSN   0953-8984.
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  7. ↑ Defects and Defect Processes in Nonmetallic Solids By William Hayes, A. M. Stoneham Courier Dover Publications, 2004.
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  38. ↑ Hussain S, Al-Nsour F, Rice AB, Marshburn J, Yingling B, Ji Z, Zink JI, Walker NJ, Garantziotis S (2012). "Cerium dioxide nanoparticles induce apoptosis and autophagy in human peripheral blood monocytes". ACS Nano. 6 (7): 5820–9. doi:10.1021/nn302235u. PMC   4582414 . PMID   22717232.
  39. ↑ Zholobak, N.M.; Ivanov, V.K.; Shcherbakov, A.B.; Shaporev, A.S.; Polezhaeva, O.S.; Baranchikov, A.Ye.; Spivak, N.Ya.; Tretyakov, Yu.D. (2011). "UV-shielding property, photocatalytic activity and photocytotoxicity of ceria colloid solutions". Journal of Photochemistry and Photobiology B: Biology. 102 (1): 32–38. Bibcode:2011JPPB..102...32Z. doi:10.1016/j.jphotobiol.2010.09.002. PMID   20926307.
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