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J O U R N A L O F M A T E R I A L S S C I E N C E 3 8 (2 0 0 3 ) 4661 – 4675
0022–2461
C 2003 Kluwer Academic Publishers 4661
CHEMICAL AND BIO-CERAMICS
solution. Examples of homogeneous catalysts include
transition metal ions, transition metal complexes, in-
organic acids/bases and enzymes. In a heterogeneous
reaction, the catalyst is in a different phase from the
reactants, where the reaction occurs at the surface of a
solid (catalyst) particle in contact with the gaseous or
liquid solution. The main disadvantage associated with
heterogeneous when compared with homogeneous cat-
alyst operation is the lower effective concentration of
catalyst as the reaction occurs only on the exposed ac-
tive surface. Catalyst recovery and reuse is, however,
far more facile in the case of heterogeneous operation.
The prototypical example of heterogeneous catalysis
is the formation of hydrocarbons from the reaction of
Figure 1 Energy diagram for a catalyzed and uncatalyzed chemical hydrogen and carbon monoxide over a suitable solid
reaction.
catalyst. The simple methanation reaction
Figure 2 Simple schematic showing (a) physisorption and (b) chemisorption involving (i) associative and (ii) dissociative interactions.
Commercial catalysts must possess sufficient mechan- prise clusters, thin surface mono- or multi-layers or
ical strength to resist losses as a result of crushing (in small crystallites where interaction with the support
packed bed operation) or attrition (in reactors involv- can impact on surface reactivity. The major active com-
ing vigorous agitation). High surface areas can be at- ponent is typically expressed on a percentage weight
tained either by fabricating small particles or clusters basis (e.g., 10% w/w Pd/Al2 O3 ) where the crystallo-
where the surface-to-volume ratio of each particle is graphic form of the support (e.g., γ -Al2 O3 ) should
high, or by creating materials where the void surface be given. Secondary components or additives are in-
area (pores) is high compared to the amount of bulk cluded (or doped) and serve as promoters where this
support material. Many catalysts are porous solids of modification may be directed towards enhancing ac-
high surface area that is both “external” and “inter- tivity/selectivity, poison resistance or textural proper-
nal,” the former represented by the envelope surround- ties. The determination of the surface chemical com-
ing discrete particles. The internal surface comprises position and structural properties, as opposed to bulk
the walls of the pores/channels/cavities and the total characteristics, can call upon a range of complimen-
surface area equals the sum of the external and internal tary surface science techniques: established techniques
areas. Gas adsorption methods, notably the Brunauer- with the pertinent obtainable information are identified
Emmett-Taller (BET) approach, are widely used to de- in Table I. The structures of catalyst surfaces are no-
termine surface areas [14, 15]. Porosity is a measure of toriously difficult to elucidate due to the involvement
the fraction of the bulk volume that is occupied by pore of microscopic and even macroscopic regions with dif-
or void space. Pore size distribution is an important ferent compositions, phases and structures, each bear-
characteristic of porous catalysts where pores of di- ing a diversity of imperfections. A detailed discussion
ameter in excess of 50 nm are considered macropores, of each of the techniques listed in Table I is outside
those less than 2 nm are termed micropores and pores of the scope of this Review. It should, however, be
of intermediate size are denoted mesopores [7, 16]. It noted that each surface analytical technique typically
must be stressed that a wide range of pore sizes, span- employs high vacuum conditions and catalyst struc-
ning both mico- and macro-porosity is characteristic ture under standard operating (reaction) conditions is
of standard solid catalysts. The pore size distribution often impossible to determine. Adsorption/desorption
is an important factor in controlling diffusion of reac- measurements provide indirect structural information
tants/products within any catalyst pore network and is while transmission electron microscopy is applicable
an essential characteristic property of the catalyst. A for surface analysis down to tenths of a nanometer. In
distinction must then be drawn between the true cata- terms of catalysis, the atomic scale structure is criti-
lyst density (solid mass to volume ratio excluding all cal, i.e., the arrangement of atoms involved in chemical
pores and voids) and bulk or packing density. The lo- bonding with reactants. X-ray diffraction is applicable
cation of the catalytically active component within the to measurement of crystallite sizes and identification of
porous structure and the manner in which pores inter- the crystalline phases present. Electron spectroscopies,
connect can have a profound effect on the accessibility notably AES, XPS and SIMS, facilitate measurement
of reactants to the catalytically active site, and to the of the chemical composition of reactive surfaces. Each
removal of products. This effect is illustrated in Fig. 4 technique involves bombardment of the surface with
where n-butane can be seen to have ready access to high energy (electron, X-ray or ion) beams with an
the internal silicalite matrix while the movement of the energy analyzer (or mass spectrometer in the case of
more bulky iso-butane isomer is hindered. SIMS) as detector. Instrumentation developments are
The catalyst particle can be a complex entity com- directed towards detection of finer detail, i.e., atomic
posed of a porous solid serving as a support for one or spacial resolution, ever smaller energy resolution and
more catalytically active phases. The latter may com- shorter time scales. A comprehensive characterization
4664
CHEMICAL AND BIO-CERAMICS
T A B L E I Common experimental analytical techniques used to characterize catalyst surface structure
Chemisortion/temperature programmed desorption (TPD) Active site concentration/adsorbate binding energies [17–19]
Fourier transform infrared spectroscopy (FTIR) Adsorbate/surface interactions, bonding geometry and strength [20, 21]
Transmission electron microscopy (TEM) Imaging technique, active site distribution, surface structure [22–24]
X-ray diffraction (XRD) Bulk diffraction and diffraction at extreme glancing angles, [25, 26]
bulk and surface structure
X-ray photoelectron spectroscopy (XPS) Near surface composition, oxidation states [17, 27–29]
Auger electron spectroscopy (AES) Near surface composition [17, 27, 30, 31]
Secondary ion mass spectrometry (SIMS) Surface composition [27, 32, 33]
Ultraviolet photoelectron spectroscopy (UPS) Bonding of surface species [17, 31, 34]
Scanning tunneling microscopy (STM) Surface topology, surface electronic structure [27, 35, 36]
Low energy electron diffraction (LEED) Surface atomic structure [37–39]
Extended X-ray absorption fine structure (EXAFS) Local surface structure, coordination numbers [17, 38, 40, 41]
Atomic force microscopy (AFM) Surface structure/topology [42, 43]
Electron energy loss spectroscopy (EELS) Electronic structure [17, 34, 44]
(atomic, molecular and electronic) of catalyst surfaces a kink can viewed as a ledge on a ledge. The growth
will result from a combination of the tabulated tech- of “terraces” of parallel atomic planes is largely due to
niques. In those cases where experimental characteriza- a small mismatch of atomic planes, i.e., a dislocation
tion techniques are impractical, theoretical calculations [47]. An adatom is a single atom sitting on a terrace
(ab initio, semi-empirical and force field methods) can and a vacancy is a single atom missing from a ter-
be instrumental in gaining a better understanding of cat- race. Ledges and kinks are termed “line defects” to dis-
alyst structure and the feasible transition states/reaction tinguish them from vacancies and adatoms, which are
pathways. denoted “point defects” [13]. Solid surfaces are hetero-
Certain catalytic reactions proceed at the same rate geneous on the atomic scale and the relative concen-
regardless of the nature of the reactive surface and are tration of atoms in the ordered domain (flat surface),
deemed to be structure insensitive, whereas other reac- in line defects and in point defects depends on surface
tions exhibit an appreciable structure sensitivity where preparation/pretreatment. Variation in catalytic particle
the rate can vary by orders of magnitude from one crys- size can result in a change in the distribution of sites
tal face to another [7]. Masel has noted [45] that all cat- and preponderance of a particular defect which may be
alytic reactions exhibit some degree of structure sensi- the source of observed structure sensitivity.
tivity under certain reaction conditions. Heterogeneous
catalysts cannot be regarded as representing a “model”
uniform reacting surface but display a distribution of
interaction energetics associated with the different ex- 2.2.1. Catalytic properties of ceramics
posed crystal faces, occurrence of dislocations, defects As ceramic materials withstand high temperatures, ex-
and other disturbances [46]. The simplest surfaces can hibit chemical durability and wear resistance, they have
be regarded as “flat” surfaces (see Fig. 5) and devi- unlimited potential as catalytic materials for use in a di-
ations from this ideal arrangement include “ledges,” versity of reactor configurations and over a range of op-
“kinks,” “adatoms” and “vacancies.” Ledges are the erating conditions. Ceramics applications in catalysis
steps formed at the borders of the pristine flat surface can be divided into (i) direct use as catalysts and (ii) use
while a kink is a defect formed at the end of a ledge; as support materials (substrates) to anchor and disperse
a variety of active metals. Taking a broad definition of
ceramics as “any inorganic nonmetallic material,” there
is a wide array of catalysts that can be termed, although
it is not common practice in the catalysis community,
ceramics. Ceramic catalysts and catalyst supports con-
stitute the largest market segment outside the electronic
ceramics, estimated to be $1.43 billion in 1998 with an
expected increase to $1.84 billion by the year 2003
[48]. Practical ceramic catalysts are typically complex
metal oxides containing at least two different cations
which offer enormous compositional flexibility. The
redox chemistry of these materials in the bulk and at
the surface may be very different from that expected
in solution, with the result that certain cations may be
held in unusually high oxidation states [49]. A selec-
tion of ceramic oxide catalysts that have been subjected
to rigorous characterization and/or catalytic (princi-
pally oxidation) reactions are provided in Table II. The
Figure 5 Diagram showing an ideal flat surface and ledge, kink, adatom surface redox behavior and defect structure is of cru-
and vacancy arrangements. cial importance in determining catalytic activity and
4665
CHEMICAL AND BIO-CERAMICS
T A B L E I I Representative ceramic oxide catalyst systems
Catalyst Reference
V2 O5 /SiO2 [50]
CeO2 /MgAl2 O4 [51]
CeO2 /ZrO2 [52]
V2 O5 /TiO2 [53]
CeO2 /Al2 O3 [54]
BaO/SrTiO3 [55]
Sr/La2 O3 [56, 57]
SrO/Nd2 O3 [58] Figure 6 Perovskite unit cell structure with Ti atoms at the corners, O
Sm2 O5 /MgO [59] atoms at midpoints of the edges and a Ca atom in the center; dark shades
N2 O/MgO [60] are used to indicate a layered effect.
La2 O3 /CaO [61]
resistance to reactive fluid flow, i.e., low associated Figure 8 Catalyst deactivation by coke deposition.
pressure drop [75]. Honeycomb structures are typ-
ically made of cordierite ((MgO)2 (Al2 O3 )2 (SiO2 )5 )
by means of a precise extrusion process, which al- strong chemical interaction with the active sites where
lows the production of various cell shapes and sizes catalytic activity cannot be recovered without a drastic
[76] with differing rheological characteristics [77]. change in the operating conditions [84, 85]. The time
Ceramic foams possess structural characteristics that dependent loss of activity can be linked to a migration
make them, in turn, suitable as substrates for hetero- of active species into the catalyst pellet, morphological
geneous catalysts. These features include high porosi- changes of surface crystallites of a given phase, change
ties with a significant degree of interconnectivity that in the number of steps, kinks and vacancies on the sur-
results in low pressure-drop while convection in the face and modifications to the surface/bulk composition
tortuous mega-pores provides enhanced mass and heat ratios.
transfer [78]. Activity loss due to coke formation is typical of re-
actions involving hydrocarbons and is due to reactant
or product degradation that produces a carbonaceous
2.3. Catalyst deactivation residue on the surface which is inactive for catalysis.
One of the major problems that have bedeviled the op- Coke that accumulates on a catalyst may cause deactiva-
eration of heterogeneous catalysis is a progressive loss tion either by covering active sites or by physical block-
of activity with catalyst use. Catalyst deactivation as ing of the pores in the catalyst, as shown in Fig. 8. Coke
a function of time is often unavoidable and the deac- deposits can amount to 15–20% w/w of the catalyst, de-
tivated catalyst must either be regenerated or replaced pending on the operating conditions and the nature of
[79]. The causes of catalyst deactivation are numerous the catalyst and reactant(s) [86]. Moreover, carbon de-
but they can be conveniently grouped into three gen- position on reactor tubes and heat exchanger surfaces
eral categories [80]: sintering, poisoning and coking. can adversely affect the performance of an array of unit
Sintering refers to a diminution of active site disper- operations associated with catalytic processing. Such
sion and can apply to all phases present in the catalyst, deposits invariably contain both carbon and hydrogen
i.e., active phases, modifiers and support. The overall with H/C ratios varying from almost zero up to 2 [87].
effect of sintering is a reduction in active surface area The carbonaceous byproduct deposits are a complex
per unit volume of catalyst and is normally the result mixture of amorphous, filamentous and graphitic struc-
of excessively high reaction temperatures [81]. Ceramic tures [88–90]. Forzatti and Lietti [86] and McCarty and
monoliths [82] and foams [83] exhibit far superior prop- Wise [91] have identified up to seven forms of “car-
erties in terms of thermal stability when compared with bon” associated with hydrocarbon processing, notably
more conventional catalyst systems and are resistant to “encapsulated” hydrocarbons, filamentous carbon and
deactivation by sintering. The presence of deactivating pyrolytic carbon. Considerable effort (use of promot-
species in the reactant feed (as impurities) or formed ers/catalyst regeneration) is expended to minimize car-
during reactant conversion (transformation of an inter- bon deposition and extend the productive lifetime of the
mediary and/or product) can induce a partial or total catalyst [87, 92, 93]. The catalyst regeneration strategy
loss of activity. Catalyst poisoning can be irreversible depends on the causes of deactivation [94, 95]. Deac-
(true poisoning), reversible or transient (inhibition) or tivation due to carbon deposition can be reversed by
may involve fouling agents which induce a mechani- heating the spent catalyst in air/oxygen which serves to
cal inhibition. The latter refers to non-covalent bonding “burn off” the carbon deposit. This oxidative (highly
(van der Waals interaction, hydrogen bonding, ionic in- exothermic) treatment must be carefully controlled in
teractions etc.) that serve to physically impede access order to avoid any possible sintering due to excessive
of reactants to the active sites. True poisoning involves high temperature fluctuations.
4667
CHEMICAL AND BIO-CERAMICS
4 1.2
5 2.0
6 2.8
8 4.5
10 6.3
Figure 9 (a) Structure of faujasite and (b) SEM micrograph showing 12 8.0
topographical features of a Na-Y zeolite.
4668
CHEMICAL AND BIO-CERAMICS
dimensions of the incoming molecule and the zeolite Na-Y can be shown as
cavities. For example, normal hexane with a kinetic
molecular diameter of about 5.1 Å can pass through H-Y + (H2 O)x−1 + Na+ + OH−
Na-Y + (H2 O)x
a 10-membered ring (or larger), whereas cyclohexane
(2)
with a kinetic molecular diameter of 6.9 Å would ex-
perience severe transport limitations. This size/sieving
The ion exchange of divalent metal (M2+ ) ions with
property is put to good effect in separation applications.
Na-Y can be represented by the equilibrium [96]
The void spaces in the crystalline structure of zeolites
present a high capacity for adsorbates and the internal + +
S + 2NaZ ↔ 2NaS + MZ
M2+ 2+
surface area typically provides the predominant con- (3)
tribution to the overall uptake. Adsorption in zeolites
is, as a direct consequence, strongly dependent on the where S and Z represent the solution and zeolite phases,
molecular dimensions of the adsorbate and configu- respectively. The degree of divalent ion exchange is de-
rational diffusion is often an important consideration pendent on the zeolite composition (Si/Al ratio), size
where mass transport control predominates. of the exchanging hydrated metal ions, metal ion con-
Recent developments have focused on materials vir- centrations and temperature [109]. The use of zeo-
tually identical to the classical zeolite i.e., oxides of lites for the sorption (separation) of non-electrolytes
metals other than silicon and aluminum which have has been covered to a more limited extent in the lit-
stretched the range of materials that are “zeolitic” in erature but there are a number of reported accounts
nature [100]. The vast majority of oxide structures with of the adsorption of organic compounds on zeolites
a well defined porous structure are now lumped to- [110, 111].
gether and classified as zeolites—the term “zeotypes” Metal ion exchange serves as a synthetic route to
has emerged as a generic description. supported metal catalysts where a reduction (in hydro-
Zeolites are unique among inorganic oxides because gen) of the divalent metal exchanged zeolite generates
of their uniform microporous character, high internal a supported zero valent metal phase according to the
surface area, high thermal stability and their ability to equilibrium [112, 113]
develop internal acidity. Zeolites are structurally resis-
+
z + H2 ↔ MZ + 2HZ
M2+ 0
tant to temperatures in excess of 723 K, can operate (4)
over a range of acid/alkaline conditions, are unaffected
by ionizing radiation and can be used in the uptake of Zeolite supported transition metal catalysts have
radioactive cations [101, 102]. The latter application found widespread use in a range of hydrogena-
draws on the ion exchange properties of zeolites. Sili- tion/dehydrogenation, hydroisomerization, dehydrocy-
con is tetravalent and aluminum is trivalent, which re- clization and hydrogenolysis reactions [114–117]. Two
sults in negatively charged zeolite framework structures surface hydroxyl groups (Brønsted acid sites) are gen-
where each mole of aluminum produces one equivalent erated for each reduced divalent metal and these im-
of cation exchange capacity for the zeolite framework. part a surface acidity that can be employed to promote
The net negative charge is balanced by an exchangeable catalytic transformations that require acid sites, e.g.,
cation (typically Na+ ), as shown in Fig. 11. Zeolites alkylation and dehydration [118, 119]. Brønsted acidity
are proven ion exchange materials where the indige- can also be introduced through hydrolysis (as shown in
nous charge balancing (sodium) cations are not fixed Scheme (2) above) and by zeolite exchange with NH+ 4
rigidly to the hydrated aluminosilicate framework and followed by thermal treatment [118, 120]. The ability of
are readily exchanged with metal cations in solution zeolites to preferentially sieve molecules can be put to
[96]. In environmental remediation applications, both good effect in catalytic applications in that the produc-
synthetic [103–105] and naturally occurring [106, 107] tion of a chemical of particular size and/or shape may be
zeolites have been used to remove a range of toxic heavy preferentially promoted [121], as is depicted in Fig. 12.
metals from water. Solution pH has a significant impact Where a reactant is sterically hindered in accessing the
on zeolite exchange properties where a sufficiently low active sites located within the zeolite pore network, then
pH can cause structural damage while metal hydroxide the product resulting from that reactant will also be re-
precipitation/deposition may predominate at high pH stricted, as shown in Fig. 12a for the case of a branched
[105]. Zeolite addition to water is accompanied by an hydrocarbon feed. Alternative, if a “bulky” product is
immediate solution pH increase as a result of a hydrol- formed within the zeolitic cavities, its intracrystalline
ysis of the zeolite [108], which in the case of zeolite diffusional transport will also be restricted, as arises
4669
CHEMICAL AND BIO-CERAMICS
alytic converter processes the exhaust gases by chemi-
cal reaction to treat pollutants such as carbon monox-
ide (CO), nitrous oxides (NOx ) and hydrocarbons
[124]. Sulfur oxides (SOx ), although polluting, are not
normally removed by post-combustion treatment and
the preferred approach to minimize sulfur emissions is
to lower the sulfur content in the fuel. In order to reduce
toxic emissions, modern car engines carefully control
the amount of fuel that is burnt, keeping the air-to-
fuel ratio very close to the stoichiometric point. During
engine operation the fuel mixture deviates significantly
from the ideal stoichiometric ratio where the mixture
can be “lean” (higher air content) or “rich” (higher
Figure 12 Schematics illustrating shape selectivity in zeolite catalysis: fuel content). The main emissions of a car engine
(a) rejection of branched chained hydrocarbons, (b) preferential produc- are:
tion of para-xylene during benzene methylation.
3.2. Catalytic converters The first three emissions are relatively benign although
The involvement of ceramics in the automobile indus- carbon dioxide emissions have been linked to global
try is far ranging. Indeed, without ceramics, one would warming and added CO2 emissions compound the envi-
not recognize or even be able to operate a modern auto- ronmental burden. The latter three emissions contribute
mobile. The windows, mirrors, spark plugs, lights and to smog and acid rain and are the main regulated emis-
electronics that control every function of a car’s op- sions, which catalytic converters are designed to re-
eration have some ceramic component. Moreover, re- duce. NOx emissions at less than ppm levels can affect
moval of ceramics would result in a malfunctioning persons with respiratory complaints while exposure to
air conditioner, water pump, loud speakers, seat belt 3 ppm NO2 can cause healthy persons to experience
buzzer, motors for the windshield wipers and power breathing difficulties [125]. Modern catalytic convert-
seats, radio/tape/CD deck; even the airbag would no ers are designated as “three-way converters” in refer-
longer function. Ceramics are used in a hundred differ- ence to the three regulated emissions that are treated
ent ways in the construction of the modern car but it (CO, HC and NOx ). The action of the three-way con-
is the role that ceramics play in the catalytic converter verter is shown in Fig. 13. A typical unit consists of
that is the focus of this Section. either a ceramic honeycomb monolithic structure (see
In the last sixty years, world vehicle usage has in- Fig. 7) or ceramic beads coated with precious metals
creased from about forty million vehicles to over seven (Pt, Pd and Rh). As the relative movement of parts re-
hundred million and each is a source of pollution; this sults in considerable attrition due to friction, ceramic
figure is projected to increase to nine hundred and monoliths (typically cordierite based) have now dis-
twenty million by the year 2010 [122]. Air quality, par- placed the original bead structure. The term monolith
ticularly in large cities remains grave cause for concern comes from the Greek “mono lithos” (single stone)
due to the excessive motor traffic. As a means of ad- and as the monolithic catalyst consists of one piece,
dressing these issues, cities, states and the federal gov- there is no attrition due to moving particles. The cat-
ernment have put in place “clean air” laws that restrict alytic metal component can be deposited on the surface
the amount of pollution that cars can produce [123]. of the monolith, directly or via an intermediate step,
The legislation imposed by the regulatory bodies is cer- termed washcoating [126]. The latter involves an ini-
tain to become increasingly more restrictive. This has tial deposition of a layer of high-surface-area oxide(s)
prompted automakers to redesign car engines and fuel onto the monolith. The active catalytic component is
systems where the incorporation of a catalytic converter incorporated into this layer either during the washcoat-
represents a major automobile refinement. Engine ex- ing step or after the washcoat has been applied using
haust gases consist of a complex mixture, the com- such established techniques as impregnation, adsorp-
position depending on such factors as type of engine tion, ion exchange, precipitation/co-precipitation, de-
(two- or four-stroke, spark- or compression (diesel)- position/ precipitation, sol-gel, slurry dip-coating and
ignited), driving conditions (urban vs. highway), vehi- in situ crystallization [127]. In every case, the for-
cle speed, acceleration/deceleration, etc. Located just mation of a strong bond between the support and
downstream of the engine’s exhaust manifold, the cat- the active phase is a key factor in avoiding catalyst
4670
CHEMICAL AND BIO-CERAMICS
Figure 13 Action of the “three-way converter” to treat CO, NOx and HC (hydrocharbons) in automobile exhaust.
deactivation. State-of-art washcoating composition can gen to facilitate an oxidation of unburned hydrocarbons
include [128–131]: and CO.
such as small portable generators, and remote and pre- electrical conductivity while Ce promotes hydrocarbon
mium power applications. The basic SOFC unit com- oxidation and also exhibits high ionic conductivity.
prises three oxide ceramic units: a fuel electrode; an Further advances in SOFC performance must now fo-
air electrode; a solid electrolyte. A simple schematic cus on materials development to elevate the electrical
outline of SOFC operation is shown in Fig. 14. Oxy- conductivity and catalytic performance of the anode.
gen in the air supply accepts electrons from the exter- Enhanced SOFC performance must include higher en-
nal circuit to form O2− ions at the cathode that travel ergy conversion efficiency, lower chemical and acous-
through the electrolyte to the fuel electrode (anode) to tical pollution, fuel flexibility, cogeneration capability
generate H2 O and/or CO2 (depending on the fuel used), and a rapid load response. While SOFCs now perform
releasing electrons to the external circuit [133]. Many adequately in terms of efficiency and fuel flexibility,
advanced ceramics display electrical properties supe- the high temperatures required for operation have lim-
rior to (or unattainable in) their metallic and polymeric ited the application options. The high temperature also
counterparts; these materials are known as electroce- demands that the system include significant thermal
ramics. One group of electroceramics, referred to as shielding to protect operating personnel and to retain
“fast ion conductors,” “rapid ion conductors” or “su- heat. While such requirements are acceptable in a utility
perionic conductors” are able to support a high flux application, they are not consistent with the demands of
of ions in the solid state. Ceramics that can rapidly most transportation applications nor do they lend them-
conduct oxygen ions (O2− ) are potential candidates in selves to small, portable or transportable applications.
SOFC developments. Ceramic materials have a decided role in the devel-
Today’s technology employs several ceramic ma- opment of lighter and more compact electrical power
terials as the active SOFC components. The anode sources for emerging applications.
is typically formed from an electronically conducting
nickel/yttria-stabilized zirconia (Ni/YSZ) cermet (i.e.,
a ceramic/metal composite). The cathode is based on 4. Concluding remarks: A look to the future
a mixed conducting perovskite, lanthanum manganate Until quite recently, ceramics were viewed as being
(LaMnO3 ). Yttria-stabilized zirconia (YSZ) is used for solely of artistic and domestic value. The industrial po-
the oxygen ion conducting electrolyte. To generate a tential of ceramics has yet to be fully exploited but
reasonable voltage, fuel cells are not operated as sin- future advances in ceramics will undoubtedly widen
gle units but as an array of units or “stack,” with a the potential applications. Taking the field of electron-
doped lanthanum chromite (e.g., La0.8 Ca0.2 CrO3 ) in- ics and communication, further developments will be
terconnect joining the anodes and cathodes of adjacent directed towards device (micro) miniaturization where
units. SOFCs based on a YSZ electrolyte have been a generation of new ceramic materials for component
developed for operation in the temperature range 900– manufacture with micro-applications in superconduc-
1000◦ C. SOFCs can in principle operate by direct elec- tors, sensors and memory storage devices represents
trochemical oxidation of a hydrocarbon fuel. Operation a myriad of applications. Indeed, the burgeoning in-
at elevated temperatures enables O2− diffusion through terest in nanotechnology will undoubtedly change the
the electrolyte and facilitates C H bond activation in way materials, in general, and ceramics, in particular,
the hydrocarbon reactant. However, the Ni component will be produced. Potentially, ceramics will have im-
in the composite catalyzes hydrocarbon decomposition proved mechanical, electrical and optical properties,
to solid carbon at such temperatures, leading to fouling and be lighter, stronger and cheaper to produce. De-
[135, 136]. Such anodes are not suitable for use with velopments in the medical field will see ceramic appli-
logistic fuels, i.e., kerosene, JP8, diesel or gasoline. cations in diagnostic instruments, bioceramics for bone
A reduction of the SOFC operating temperature would replacement, use in chemotherapy release capsules and
serve to broaden the choice of materials of construction advances in tissue engineering.
and lower the manufacturing costs. Recent develop- In terms of catalysis, the use of ceramics is still in a
ments have resulted in an SOFC unit that runs directly formative stage but the most far ranging viable appli-
on hydrocarbon (methane, ethane, l-butene, n-butane cation will be in the field of energy conservation and
and toluene) fuels and employs a YSZ anode with a environmental protection as catalytic materials/reactors
Cu/Ce content [137, 138]. Copper provides enhanced and fuel cells. Developments in heterogeneous catalysis
4672
CHEMICAL AND BIO-CERAMICS
have always required an understanding of reactivity at 12. S . N I S H I M U R A , “Handbook of Heterogeneous Catalytic Hy-
the nano-scale with the result that nanotechnology as drogenation for Organic Synthesis” (John Wiley, Chichester,
2001).
applied to ceramics production should lead to improved
13. G . A . S O M O R J A I , “Introduction to Surface Chemistry and
catalyst support properties. The latter can impact on Catalysis” (Wiley Interscience, New York, 1994).
catalytic converter performance that will meet increas- 14. V . P O N E C , Z . K N O R and S . C E R N Y , “Adsorption on
ing more stringent air quality demands. The ceramic Solids,” (Butterworth, London, 1974).
monolith unit that forms the core of the converter re- 15. A . W . A N D E R S O N , “Physical Chemistry of Surfaces,” 5th ed.
(Wiley & Sons, New York, 1990).
quires further optimization in terms of application (and
16. A . J . L E C L O U X , “Catalysis Science and Technology,” edited
composition) of the active phase and improvements in by J. R. Anderson and M. Boudart (Springer, Berlin, 1981) Vol. 2.
mass/heat transport properties to improve gas/surface 17. D . P . W O O D R U F F and T . A . D E L C H A R , “Modern Tech-
contact, achieving uniform flow within the honeycomb niques of Surface Science” (Cambridge Solid State Science Series,
while minimizing the occurrence of hotspots. Incor- Cambridge University Press, New York, 1986).
18. J . T . Y A T E S , in “Solid State Physics: Surfaces, Methods of
poration of advanced ceramic materials in combustion
Experimental Physics,” edited by R. L. Park and M. G. Lagally
engines and combustion power systems in general can (Academic Press, New York, 1985).
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