Chemical Papers 68 (9) 11541168 (2014)

DOI: 10.2478/s11696-013-0469-7

REVIEW

Diesel soot combustion catalysts: review of active phases

Ana M. Hernndez-Gimnez, Dolores Lozano Castell, Agustn Bueno-Lpez*

Department of Inorganic Chemistry, University of Alicante, E-03080 Alicante, Spain

Received 27 March 2013; Revised 13 June 2013; Accepted 24 June 2013

The most relevant information about the dierent active phases that have been studied for the
catalytic combustion of soot is reviewed and discussed in this article. Many catalysts have been
reported to accelerate soot combustion, including formulations with noble metals, alkaline metals
and alkaline earth metals, transition metals that can accomplish redox cycles (V, Mn, Co, Cu,
Fe, etc.), and internal transition metals. Platinum catalysts are among those of most interest for
practical applications, and an important feature of these catalysts is that sulphur-resistant platinum
formulations have been prepared. Some metal oxide-based catalysts also appear to be promising
candidates for soot combustion in practical applications, including ceria-based formulations and
mixed oxides with perovskite and spinel structures. Some of these metal oxide catalysts produce
highly reactive active oxygen species that promote ecient soot combustion. Thermal stability is an
important requirement for a soot combustion catalyst, which precludes the practical utilisation of
several potential catalysts such as most alkaline metal catalysts, molten salts, and metal chlorides.
Some noble metal catalysts are also unstable due to the formation of volatile oxides (ruthenium,
iridium, and osmium).

c 2013 Institute of Chemistry, Slovak Academy of Sciences

Keywords: diesel soot, DPF, DOC, soot combustion catalyst, Pt catalyst, ceria, perovskite

Introduction erated by soot combustion in order to avoid pressure

Soot particles are emitted by diesel engines to-
gether with NOx , CO, and unburned hydrocarbons
(HC) in gas streams with high O2 , CO2 , and H2 O
concentrations and temperatures typically below 500
550 C. Under these conditions, CO and HC oxidation
can be easily accomplished with a Diesel Oxidation
Catalyst (DOC), but both NOx and soot require com-
plex abatement strategies.
Diesel Particulate Filters (DPF) are used to re-
move soot particles from the exhaust stream (Neeft
et al., 1996a; van Setten et al., 2001a; Maricq, 2007;
Twigg, 2007). These lters usually consist of wall-ow
monoliths, that is, honeycomb-like structures with
50 % of the channels plugged at the gas entry side and
the remaining channels plugged at the exit. The gas
stream enters into the lter through the open channels
and is forced to pass through the porous walls where
the soot particles get stuck. DPF lters must be regen-
drop in the exhaust and several commercially avail-
able technologies have been designed for this purpose
(Fino & Specchia, 2008).
The PSA system consists of using metal-fuel addi-
tives to obtain soot particles with catalytically active
metals well-embedded in the structure. A DPF is used
to collect the metal catalyst-containing soot particles
and, once lter regeneration is required, extra fuel is
injected and its exothermic combustion initiates the
catalytic combustion of soot.
The Continuously Regenerating Trap (CRT) sys-
tem (by Johnson Matthey) consists of a DPF lter
located downstream of a Pt-containing DOC catalyst.
CO and HC are oxidised in the DOC, which also oxi-
dises NO to NO2 . NO2 is much more active in its ox-
idising reactions than NO and O2 and reacts rapidly
with the soot and initiates its ignition.
Some other lter regeneration strategies are un-
der investigation, such as modications of the CRT

*Corresponding author, e-mail: agus@ua.es

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 A. M. Hernndez-Gimnez et al./Chemical Papers 68 (9) 11541168 (2014)
systems that incorporate active phases in the lter
instead of, or in addition to, that in the previous ox-
idation catalyst or the Toyota Motors DPNR (Diesel
Particulate NOx Reduction) system for the simulta-
neous removal of NOx and soot.
Since the 1980s, intensive research eorts have
been applied to design and improve soot combustion
catalysts; the current review article seeks to compile
and discuss the most relevant information available on
the dierent active phases that have been studied for
the catalytic combustion of soot.
Table 1 gives a survey of the dierent active phases
that have been tested for the catalytic combustion of
soot. Comparison of the soot catalytic combustion re-
sults obtained at dierent laboratories is not easy be-
cause of the particular features of the soot oxidation
reactions:
i) Real soot is a heterogeneous material, therefore,
not suitable for catalysts-screening. Important dier-
ences can be found in the amount and type of ashes
(sometimes metals with potential catalytic activity),
the amount of adsorbed hydrocarbons and the degree
of graphitisation of the soot formed. Usually, a model
commercial carbon black is preferred for laboratory
studies, and the behaviour of a particular catalyst de-
pends on the model carbon material used to perform
the tests. Model carbon blacks typically have very low
or null amounts of adsorbed hydrocarbons and metal
compounds.
ii) The soot-catalyst contact signicantly aects
the results of the catalytic combustion, and it is not
always easy to ensure that the contact in experiments
performed at dierent laboratories is equal. It is gen-
erally accepted that loose contact mixtures of soot
and powder catalysts (soot and catalyst mixed with a
spatula, for instance) are more convenient for labora-
tory experiments than tight contact mixtures (soot
and catalyst mixed in a mortar, for instance), because
they are thought to more closely replicate the soot-
catalyst contact in a real DPF (van Setten et al.,
2000). However, some authors screen their catalysts
in the laboratory in tight contact with soot because
dierences in catalytic activity are more evident.
iii) Soot properties change with time during com-
bustion (amount of oxygen, size and shape of particles,
graphitic structure, surface area, etc.). For this rea-
son, the kinetic parameters of the catalysed soot ox-
idation reactions (reaction rates, activation energies,
pre-exponential factors) also change with time, and
they are only valid for very specic soot combustion
conditions. This drawback has had the result that, in
most articles devoted to the study of soot combustion
catalysts, kinetic parameters are not reported.
In addition to these particular features of the soot
combustion reactions, the reaction rate also depends
on general variables, such as temperature for isother-
mal reactions and heating rate for ramp experiments,
nature and partial pressure of gases in the stream,
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space velocity/residence time of gases in the solid bed,
soot-to-catalyst ratio, etc. In order to restrict the in-
formation contained in the literature to results with
a certain practical relevance, only data obtained with
catalysts tested in loose contact with soot and under
both NOx - and O2 -containing gas mixtures have been
considered in Table 1. However, despite these precau-
tions, it is not possible to arrive at realistic conclu-
sions as to the best and worst catalyst from the data
included in Table 1, nor is that the intention of this
review article but rather to compile the considerable
amount of information available in the literature and
to review this information identifying the strong and
weak points of each type of catalyst.
The survey given in Table 1 shows that many cat-
alysts have been reported to accelerate soot combus-
tion, including formulations with noble metals (mainly
Pt), alkaline metals and alkaline earth metals, transi-
tion metals that can accomplish redox cycles (V, Mn,
Co, Cu, Fe, etc.), and internal transition metals. In the
subsequent sections of this article, the most relevant
information reported on the behaviour of the dierent
types of soot combustion catalysts is presented and
discussed. The discussion is arranged into groups of
catalysts according to their composition or structure,
that is, platinum catalysts, non-platinum noble metals
and silver catalysts, perovskites, spinels, ceria-based
catalysts, metal chlorides, molten salts, and alkaline
metal catalysts.
Platinum catalysts
Pt is currently used in commercial soot removal
systems. The so-called CRT (Continuously Regener-
ating Trap) system, which is already in use on heavy
duty diesel vehicles such as trucks and buses, utilises
a platinum-containing DOC in front of a DPF lter to
control HC and CO emissions, and also to oxidise NO
to NO2 for the low temperature combustion of soot
in the downstream lter under the applicable driving
conditions (Twigg, 2006, 2007).
The role of platinum in the combustion of soot with
O2 has been presumed to be the spill-over of activated
oxygen (Neri et al., 1997) and, on NOx /O2 mixtures,
the catalytic oxidation of NO to NO2 (Setiabudi et al.,
2002). In the presence of both NO2 and O2 , it has also
been reported (Jeguirim et al., 2007) that, besides the
well-established catalytic oxidation of NO to NO2 , Pt
also has a catalytic eect on the cooperative carbon
NO2 O2 oxidation reaction. An overall mechanism in-
volving the formation of atomic oxygen over platinum
sites followed by its transfer to the carbon surface has
been proposed. It has been suggested that platinum
catalysts increase the surface concentration of surface
carbon oxygen complexes, which then react with NO2
leading to an enhanced carbon consumption.
The eect of the support oxide and platinum
precursor on the catalytic combustion of soot was
1156 A. M. Hernndez-Gimnez et al./Chemical Papers 68 (9) 11541168 (2014)

Table 1. Compilation of soot combustion catalytic tests results. Only catalysts tested in loose contact with soot and under both
NOx - and O2 -containing gas mixtures were considered; only results obtained with fresh catalysts are included.

Catalysts Ta Tbmax Relevant experimental details Reference

( C) ( C)

SiO2 661 500 mL min1 ; 10 mole % O2 +7 mole % H2 O + Oi-Uchisawa et al.

1%Pt/SiO2 312 0.1 mole % NO + 0.01 mole % SO2 in N2 ; ow reac- (1998)
1%Pt/Al2 O3 460 tor; 10 C min1 ; 5 mg of soot + 500 mg of catalyst;
1%Pt/ZrO2 408 carbon black (Nippon Tokai carbon 7350F)

SiO2 687 500 mL min1 ; 0.1 mole % NO + 10 mole % O2 + 7 Liu et al. (2001)
1%Pt/SiO2 562 mole % H2 O in N2 ; ow reactor; 10 C min1 ; 5 mg
V2 O5 /SiO2 555 of soot + 500 mg of catalyst; carbon black (Nippon
V2 O5 Pt/SiO2 518 Tokai carbon 7350F)
MoO3 /SiO2 535
MoO3 Pt/SiO2 475

-Al2 O3 (260 m2 g1 ) 650 100 mL min1 ; 0.2 mole % NOx + 5 mole % Castoldi et al.
1%Pt/-Al2 O3 (210 m2 g1 ) 550 O2 in He; ow reactor; 15 C min1 ; 66 mg (2006)
1%Pt/20%Ba/-Al2 O3 (160 m2 g1 ) 580 (m(soot) : m(catalyst) = 1 : 9); Printex U

2.5%Pt/4%K2 O/Al2 O3 150 375 200 mL min1 ; 0.06 mole % NOx + 10 mole % Krishna and Mak-
O2 in Ar; ow reactor; 1 C min1 ; 100 mg kee (2006)
(m(soot) : m(catalyst) = 1 : 4); 43000 h1 ; Printex U

Cs2 SO4 V2 O5 /foam lter 475 200 mL min1 ; 0.06 mole % NOx + 10 mole % O2 Setiabudi et al.
1%Pt/Al2 O3 415 in Ar; ow reactor; 0.6 C min1 ; Printex U (2002)

Ce0.8 Zr0.2 O2 (3DOM) 191 394 50 mL min1 ; 0.2 mole % NO + 5 mole % O2 in Ar; Wei et al. (2013)
1%Pt/Ce0.8 Zr0.2 O2 (3DOM) 231 354 ow reactor; 2 C min1 ; 10 mg of soot + 100 mg of
8%Pt/Ce0.8 Zr0.2 O2 (3DOM) 259 326 catalyst; Printex U

CeO2 (64 m2 g1 ) 88 518 500 mL min1 ; 0.05 mole % NOx + 5 mole % Atribak et al.
Ce0.76 Zr0.24 O2 (67 m2 g1 ) 85 521 O2 in N2 ; ow reactor; 10 C min1 ; 100 mg (2009)
Ce0.56 Zr0.44 O2 (31 m2 g1 ) 19 587 (m(soot) : m(catalyst) = 1 : 4); 30000 h1 ; Printex
Ce0.36 Zr0.64 O2 (8 m2 g1 ) 10 596 U
Ce0.16 Zr0.84 O2 (47 m2 g1 ) 0 606
ZrO2 (65 m2 g1 ) 24 582

CeO2 (49 m2 g1 ) 129 465 50 mL min1 ; 0.2 mole % NOx + 5 mole % Liu et al. (2011)
Ce0.8 Sm0.2 O2 (47 m2 g1 ) 128 466 O2 in He; ow reactor; 1 C min1 ; 100 mg
Ce0.8 Zr0.2 O2 (48 m2 g1 ) 125 469 (m(soot) : m(catalyst) = 1 : 10); Printex U
Ce0.8 V0.2 O2 (15 m2 g1 ) 100 494

Ce0.5 Zr0.5 O2 (132 m2 g1 ) 500 500 mL min1 ; 10 mole % O2 + 0.1 mole % NO + Zhu et al. (2007)
7mole % H2 O in N2 ; ow reactor; 10 C min1 ; 5 mg
of soot + 100 mg of catalyst; Printex U

CeO2 (2 m2 g1 ) 54 474 200 mL min1 ; 0.06 mole % NOx + 10 mole % Krishna et al.
Ce0.9 La0.1 Ox (16 m2 g1 ) 68 460 O2 in Ar; ow reactor; 0.6 C min1 ; 100 mg (2007a)
Ce0.9 Pr0.1 Ox (11 m2 g1 ) 109 419 (m(soot) : m(catalyst) = 1 : 4); 70000 h1 ; Printex
Ce0.9 Sm0.1 Ox (5 m2 g1 ) 35 493 U
Ce0.9 Y0.1 Ox (2 m2 g1 ) 24 504

Pt/Al2 O3 (commercial) 515 140 mL min1 ; 10 mole % O2 + 0.1 mole % NO + 3 Tikhomirov et al.
CeO2 (37 m2 g1 ) 550 mole % H2 O in N2 ; TGA reactor; 10 C min1 ; 5 mg (2006)
Mn0.25 Ce0.75 Ox (86 m2 g1 ) 460 of soot + 100 mg of catalyst; real soot
Mn0.50 Ce0.50 Ox (79 m2 g1 ) 590
Mn0.75 Ce0.25 Ox (89 m2 g1 ) 500
Mn2 O3 (24 m2 g1 ) 585

CeO2 (62 m2 g1 ) 465 500 mL min1 ; 0.1 mole % NO + 9.5 mole % O2 Wu et al. (2007)
CuOCeO2 (68 m2 g1 ) 420 in N2 ; ow reactor; 20 C min1 ; 5 mg of soot +
CeO2 ZrO2 (57 m2 g1 ) 478 100 mg of catalyst; Printex U
CuOCeO2 ZrO2 (51 m2 g1 ) 448

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Table 1. (continued)

Catalysts Ta Tbmax Relevant experimental details Reference

( C) ( C)

La2 CuO4 504 50 mL min1 ; 0.2 mole % NO+ 5 mole % Liu et al. (2008)
Pr2 CuO4 507 O2 in He; ow reactor; 2 C min1 ; 108 mg
Nd2 CuO4 518 (m(soot) : m(catalyst) = 1 : 5); Printex U
Sm2 CuO4 518
Gd2 CuO4 520
La1.3 Na0.7 CuO4 463

ZnAl2 O4 (133 m2 g1 ) 35 630 500 mL min1 ; 0.05 mole % NOx + 5 mole % Zawadzki et al.
5%CuO/ZnAl2 O4 (111 m2 g1 ) 65 600 O2 in N2 ; ow reactor; 10 C min1 ; 100 mg (2009)
Zn0.95 Cu0.05 Al2 O4 18 647 (m(soot) : m(catalyst) = 1 : 4); 30000 h1 ; carbon
(148 m2 g1 ) black (Vulcan XC72)

KCu/SrTiO3 (9 m2 g1 ) 188 495 500 mL min1 ; 0.05 mole % NOx + 5 mole % Lpez-Surez et
Sr0.8 K0.2 TiOx (5 m2 g1 ) 215 468 O2 in N2 ; ow reactor; 10 C min1 ; 100 mg al. (2009)
K/SrTiO3 (7 m2 g1 ) 195 488 (m(soot) : m(catalyst) = 1 : 4); 30000 h1 ; carbon
Cu/SrTiO3 (11 m2 g1 ) 78 605 black (Vulcan XC72)

LaCoO3 (9 m2 g1 ) 178 421 50 mL min1 ; 0.2 mole % NOx + 5 mole % Wang et al. (2008)
La0.90 K0.10 CoO3 (11 m2 g1 ) 201 398 O2 in He; ow reactor; 2 C min1 ; 180 mg
(m(soot) : m(catalyst) = 1 : 5)

LaFeO3 (3DOM) 153 432 50 mL min1 ; 0.2 mole % NO + 5 mole % O2 in Ar; Xu et al. (2010)
LaCo0.5 Fe0.5 O3 (3DOM) 188 397 ow reactor; 2 C min1 ; Printex U

LaMn0.95 Fe0.05 O3 (3 DOM) 392 50 mL min1 ; 0.2 mole % NO + 5 mole % O2 in Ar; Zheng et al. (2012)
ow reactor; 2 C min1 ; Printex U

a) Dierence between temperatures of non-catalysed and catalysed soot combustion; b) temperature of maximum soot combustion
rate, maximum COx emission, or temperature for 50 % soot conversion.

studied in a simulated exhaust gas with N2 , O2 ,
H2 O, NO, and SO2 (Oi-Uchisawa et al., 1998). The
platinum precursors compared were Pt(NH3 )4 (OH)2 ,
H2 PtCl6 6H2 O, Pt(NH3 )4 (NO3 )2 , and Pt(NH3 )4 Cl2 ;
the supports tested were SiO2 , Al2 O3 , and ZrO2 .
Pt/SiO2 prepared from Pt(NH3 )4 (OH)2 exhibited the
highest carbon oxidation activity, and it was observed
that platinum dispersion did not explain the cat-
alytic trends. The soot combustion activity was only
related to the catalytic oxidation of NO to NO2 .
In a later study (Oi-Uchisawa et al., 2000), the ef-
fect of support materials for platinum catalysts on
the oxidation of carbon black was revised, and sev-
eral platinum-supported metal oxides were evaluated
(Ta2 O5 , Nb2 O5 , WO3 , SnO2 , SiO2 , TiO2 , Al2 O3 , and
ZrO2 ). Pt/Ta2 O5 exhibited the highest activity in a
model diesel exhaust containing O2 , H2 O, NO, and
SO2 in N2 . Platinum catalysts supported on other
non-basic metal oxides such as Nb2 O5 , WO3 , SnO2 ,
and SiO2 exhibited similar high activities. The high
activity for these catalysts was attributed to their
non-basicity and negligible anity towards SO3 (or
H2 SO4 ), which reduced the poisoning of the supported
platinum. The MOx supports used for platinum cata-
lysts were further improved by using MOx TiO2 mix-
tures (Oi-Uchisawa et al., 2003), and the highest ac-
tivities were obtained with Pt/(TiO2 +SiO2 ) for molar
ratios of TiO2 /(TiO2 +SiO2 ) in the range from 0.4 to
0.7. This improvement was attributed to the enhanced
sulphur resistance.
The synergetic eect between platinum and some
other active components has also been reported. A se-
ries of SiO2 -supported MoO3 , V2 O5 , and/or platinum
catalysts was investigated (Liu et al., 2001), conclud-
ing that catalysts with both platinum and metal ox-
ides were more active than the single-component cata-
lysts. A synergistic reaction mechanism was proposed
in order to explain the eects of combining platinum
with the oxides, where platinum catalyses the oxida-
tion of NO with the gas phase O2 to NO2 , while MoO3
and V2 O5 catalyse the oxidation of carbon with NO2 .
Jelles et al. (1999a) also reported a synergetic eect
between platinum, used as a post-combustion catalyst,
and cerium introduced into the soot structure by us-
ing a fuel additive. The high soot combustion rate was
explained by a cycle of two catalytic reactions, where
platinum oxidises NO to NO2 , which subsequently ox-
idises soot using cerium as a catalyst, thus forming
NO which can participate in the reaction more than
once.

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1158 A. M. Hernndez-Gimnez et al./Chemical Papers 68 (9) 11541168 (2014)
Recently, three-Dimensionally Ordered Macrop-
orous (3DOM) Ce0.8 Zr0.2 O2 -supported platinum cat-
alysts have been synthesised (Wei et al., 2013). The
3DOM structure is presumed to improve the con-
tact eciency between catalyst and soot, and the
metal (Pt)support (Ce) synergistic eect increases
the amount of active oxygen species delivered to the
soot. The 3DOM Pt/Ce0.8 Zr0.2 O2 catalysts exhibited
a high catalytic activity and thermal stability for soot
combustion.
The synergistic eect between platinum and mag-
nesium (Liu et al., 2012) has also been reported to
enhance the NO oxidation activity and NOx storage
capacity of the PtMg/Al2 O3 catalyst. More NO2 is
produced in the temperature range of soot oxidation
on PtMg/Al2 O3 than on an Mg-free Pt/Al2 O3 cat-
alyst with a similar Pt particle size, which eciently
promotes the ignition of soot.
Soot combustion on NSR (NOx Storage and Re-
duction) catalysts has recently attracted attention
(Castoldi et al., 2006; Krishna & Makkee, 2006; Kus-
tov et al., 2009; Matarrese et al., 2009; Pieta et al.,
2010; Klein et al., 2012), in order to evaluate the po-
tential simultaneous removal of NOx and soot (DPNR
systems; Diesel Particulate NOx Reduction) and to
check the eect of soot on NSR catalysts performance.
NSR catalysts typically combine platinum with a ba-
sic oxide/carbonate (alkaline metal or alkaline earth
metal oxides/carbonates) and operate in cycles of O2 -
rich and O2 -lean atmospheres. NOx are chemisorbed
on the basic compounds during the O2 -rich cycles
and reduced during the lean periods attained by extra
diesel injection.
The potential utilisation of a typical PtBa/Al2 O3
NSR catalyst for the simultaneous removal of soot
and NOx was investigated and compared with that
of a Pt/Al2 O3 sample (Castoldi et al., 2006). It was
found that the PtBa/Al2O3 catalyst was able to re-
move both soot and NOx simultaneously, while the
Pt/Al2 O3 catalyst performed the soot oxidation eec-
tively but was incapable of signicantly removing the
gas phase NOx . These authors observed that the pres-
ence of soot did not signicantly aect NOx reduction
on the PtBa/Al2 O3 catalyst (Castoldi et al., 2006).
By contrast, Klein et al. (2012) also studied the eect
of soot on the performance of PtBa/Al2 O3 NSR cat-
alysts and reported that the presence of soot in the
catalytic bed led to a decrease in the NOx storage
capacity (NSC) of the catalysts. The involvement of
a direct reaction between carbon particles and NOx
storage sites to form carbonate adsorbed species was
proposed. However, the loss of NSC measured in the
presence of carbon varied as a function of the cata-
lyst composition. It was shown that the presence of
platinum limited the inuence of the carboncatalyst
contact. The key factor appears to be the proximity
between the storage sites, platinum sites and their con-
tact with carbon. During the carbon oxidation pro-
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cess, the ageing of catalysts caused by platinum sin-
tering and Ba agglomeration appears to occur. These
structural modications reduce the proximity between
the platinum and adsorption sites (Ba and/or Al),
resulting in a decrease in the NOx storage capacity
(Klein et al., 2013).
Soot oxidation activity and the deactivation of
Al2 O3 -supported NSR catalysts containing Pt, K, and
Ba were also studied (Krishna & Makkee, 2006). The
NSR catalysts were active in accelerating soot com-
bustion, and the reactions that were mainly responsi-
ble for such activity were soot oxidation with NO2 fol-
lowed by NO recycle to NO2 , and soot oxidation with
O2 assisted by NO2 . Only a part of the stored NOx
that was decomposed at high temperatures under lean
conditions was found to be useful in soot oxidation.
The NOx storage capacity of these NSR catalysts de-
creased on ageing under soot-oxidising conditions. The
Pt/KAl2 O3 catalyst was more active, but less stable
than Pt/BaAl2 O3 because the active species respon-
sible for synergism on Pt/KAl2 O3 are unstable and
cannot be regenerated (Krishna & Makkee, 2006). The
direct participation of the surface nitrates in soot ox-
idation on Pt/KAl2 O3 NSR catalysts, without the
requirement of the preliminary thermal decomposi-
tion of nitrates, has also been proposed (Matarrese
et al., 2013). This mechanism was presumed to occur
thanks to the mobility of the adsorbed NOx species
and is not promoted by platinum. This surface reac-
tion mechanism parallels the gas-phase soot oxidation
by NO2 and O2 evolved on decomposition of the stored
NOx . Potassium-based catalysts are more active than
Ba-containing catalysts due to the higher mobility of
the NOx species adsorbed on potassium compared to
those adsorbed on barium.
Non-platinum noble metals and silver
catalysts
Non-platinum noble metals have not been fre-
quently investigated as soot combustion catalysts, and
the literature contains few articles on the study of sil-
ver catalysts.
Na-Y zeolite-supported iridium, palladium, plat-
inum, and rhodium metals were screened as carbon
oxidation catalysts, and ruthenium was proposed as
the most active noble metal (Villani et al., 2006). How-
ever, it is known that ruthenium (and also iridium and
osmium) form volatile oxides, precluding its practical
application (Gandhi et al., 2003).
AuV-based catalysts have been studied for soot
combustion with special attention to the reaction
mechanism (Van Craenenbroeck et al., 2002). Gold
particles provide very active sites able to ignite soot
within the desired temperature range but retard the
oxidation process at high vanadium loadings because
of the diminished contact. Gold particles were pre-
sumed to promote the oxygen transfer from catalyst
 A. M. Hernndez-Gimnez et al./Chemical Papers 68 (9) 11541168 (2014)
to soot, which increases the activity in the combustion
of soot particles. However, this positive eect could be-
come negative because the same oxygen donor prop-
erty might be responsible for the formation of poly-
vanadate clusters instead of V2 O5 crystallites, dimin-
ishing the mobility of the catalyst.
The eect of 2 mass % of gold added to LaBO3
perovskite catalysts (B = Cr, Mn, Fe, and Ni) was
also studied in the simultaneous CO and soot com-
bustion (Russo et al., 2008a). The comparison of their
activity with that of the corresponding gold-free pure
perovskite conrmed that the presence of gold had
a good synergetic eect towards CO oxidation and a
negligible one towards carbon combustion.
Soot combustion over silver-supported catalysts
was studied by using Al2 O3 , CeO2 , and ZrO2 sup-
ports (Aneggi et al., 2009). The formation of Ag/Ag2 O
mixtures was observed in all supports and their rel-
ative abundance accords closely with the nature of
the support. Ceria was shown to stabilise silver oxide,
while metallic silver was preferentially formed with
ZrO2 and Al2 O3 . For this reason, it was proposed that
Ag/ZrO2 and Ag/Al2 O3 were active catalysts while
the bare ZrO2 and Al2 O3 supports were not. By con-
trast, the addition of silver to ceria had little benet,
because ceria itself is active in soot oxidation and sil-
ver forms an oxide of low activity. However, the prepa-
ration of a very active Ag/CeO2 catalyst with a novel
structure which consists of aggregates of ceria parti-
cles around a central silver metal core has recently
been reported (Kayama et al., 2010). It is proposed
that such a rice-ball nanostructure produces extremely
active oxygen.
Perovskite catalysts
ABO3 perovskite-type oxides (with A = La + Sr,
La + Li, La + K, or La + Cs and B = Co, Mn, Fe, Mn
+ Fe, Mn + Cu, or Cu + V) catalysed the simultane-
ous removal of NOx and diesel soot in the presence of
oxygen, and were superior to transition metal simple
oxides in the selectivity for NOx reduction (Teraoka
et al., 1995). The catalytic activity of perovskite-type
oxides depended on both A-site and B-site cations,
and the incorporation of potassium into the A sites
markedly promoted the oxidation of soot and the re-
duction of NOx . La1x Kx MnO3 perovskite catalysts
were also tested for the simultaneous removal of NOx
and soot (Teraoka et al., 2001). The solubility limit
of potassium in these mixed oxides was determined
as lying between x = 0.2 and x = 0.25, and the ac-
tivity and NOx reduction selectivity for N2 depended
signicantly on the potassium content, being highest
for compositions close to the solubility limit. ABO3
perovskites with A = La + K and B = Cu + V were
also eective for the simultaneous removal of soot and
NOx at 450500 C, but the stability at high temper-
ature (800 C) was poor (Fino et al., 2003a).
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LaCrO3 , LaFeO3 , and LaMnO3 perovskite cat-
alysts were compared and the highest activity for
soot combustion of the chromite catalyst was related
to its highest concentration of suprafacial, weakly
chemisorbed oxygen, which actively contributes to
soot combustion by spill-over in the temperature range
of 300500 C (Fino et al., 2003b). The introduction
of lithium into the chromium position of LaCrO3 soot
combustion perovskite catalysts has been shown to im-
prove the activity due to enhancement of the amount
of weakly chemisorbed oxygen O species (Fino et
al., 2006a). The simultaneous introduction of potas-
sium into the lanthanum position and copper into the
manganese position of the LaMnO3 perovskite also
enhanced the catalytic activity (Peng et al., 2007),
as also the partial substitution of lanthanum by al-
kaline metal cations (Wang et al., 2008; Russo et al.,
2008b) and cobalt by palladium (Yao et al., 2009) into
LaCoO3 .
Hirano et al. (2009) studied strontium-substituted
LaFeO3 perovskites for soot combustion; the activity
of these perovskites was reported to be only slightly
lower than that of a Pt/Al2 O3 reference catalyst.
Teraoka et al. (1996) also reported that Co, Mn, and
Fe perovskite-type and Cu-based K2 NiF4 -type oxides
(all with La3+ partially substituted by alkaline metal
or alkaline earth metal cations) catalyse the simul-
taneous removal of NOx and diesel soot particulates
and that these perovskite-related oxides are superior
to transition metal simple oxides and Pt/A12 O3 with
regard to their selectivity towards NOx reduction.
SrTiO3 perovskites doped with alkaline com-
pounds were investigated by Bialobok et al. (2007)
for soot combustion; the activity increased in the fol-
lowing order of alkaline metals: SrTiO3 ; Li/SrTiO3 ;
Cs/SrTiO3 ; K/SrTiO3 . It was also concluded that
substitution produced catalysts with higher activity
than catalysts with similar composition but prepared
by impregnation. However, the activity for soot com-
bustion in NOx /O2 of potassium-impregnated and
substituted SrTiO3 perovskite catalysts was studied,
concluding that fresh catalysts were active but that
they were progressively deactivated due to the loss of
potassium during consecutive reaction cycles (Lpez-
Surez et al., 2009).
The promoting eect of impregnated copper on the
SrTiO3 perovskite activity for the catalytic combus-
tion of soot has also been reported. The higher activ-
ity of Cu/SrTiO3 in comparison with Cu/Al2 O3 was
attributed to the improved redox properties of cop-
per originated by the Cu-support interactions, which
improve the catalytic oxidation of NO to NO2 . This
appears to be related to the presence of weakly-bound
oxygen in this sample, since the copper species present
on the Cu/SrTiO3 catalyst were more readily reduced
than those in other inert supports (Lpez Surez et
al., 2008).
Recently, several three-dimensionally-ordered
1160 A. M. Hernndez-Gimnez et al./Chemical Papers 68 (9) 11541168 (2014)
macroporous (3DOM) solids have been investigated
as soot combustion catalysts, some of them based
on perovskite structures. Xu et al. (2010) pre-
pared LaCox Fe1x O3 , Zhang et al. (2010a) prepared
La0.9 K0.1 CoO3 and Zheng et al. (2012) prepared
LaMn1x Fex O3 .
Particulate lters were coated with a number of
perovskite catalysts and the regeneration was eval-
uated. The CeO2 -supported PrCrO3 perovskite was
loaded on a catalytic wall-ow trap and pilot plant
tests were carried out on a diesel engine bench (Fino
& Specchia, 2004). The authors noted that this for-
mulation improved the performance of Pt/Al2 O3 cat-
alysts.
The La0.8 Ce0.2 MnO3 perovskite was used for the
microwave-assisted in-situ regeneration of diesel soot
lters (Zhang-Steenwinkel et al., 2005). This per-
ovskite has appropriate dielectric properties, i.e., a
high dielectric loss factor, and acts simultaneously as
an oxidation catalyst. The advantage of microwave
heating over conventional thermal heating is that
it is a bulk heating technique; hence it is rapid
and selective. A monolithic soot lter coated with
a La0.8 Ce0.2 MnO3 perovskite was fully microwave-
assisted regenerated with almost 100 % selectivity
towards CO2 . By contrast, the same lter with-
out any such coating was only partially regenerated,
and considerable amounts of CO were formed. The
La0.8 Ce0.2 MnO3 coating exhibited excellent temper-
ature shock resistance and thermo-chemical stability;
accordingly, the authors proposed that, once a suit-
able microwave cavity is designed, microwave-assisted
soot lter regeneration would be feasible.
However, the formation of perovskite structures
does not always have a positive eect on the soot
combustion activity of mixed oxides, and a few exam-
ples of catalyst deactivation due to perovskite struc-
ture formation have been reported. The stability of
Ba,K/CeO2 catalysts, which have been shown to be
very active in soot combustion, was studied and,
above 830 C, catalyst deactivation due to BaCeO3
perovskite structure formation was observed (Peralta
et al., 2006).
Spinel catalysts
Shangguan et al. (1996) investigated the simultane-
ous removal of NOx and diesel soot particulate in the
presence of excess oxygen with ternary AB2 O4 spinel
oxides. The catalytic performance was signicantly de-
pendent on the metal cations used, and CuFe2 O4 was
found to be the best catalyst. The performance of this
spinel catalyst was signicantly better than that of the
mechanical mixtures of the metal oxides. This conclu-
sion also extended to CuCr systems.
Nanostructured spinel-type oxide catalysts AB2 O4
(where A = Co and Mn, and B = Cr and Fe) were also
shown to be eective in the simultaneous removal of
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soot and NOx (Fino et al., 2006b). The activity or-
der for soot combustion was found to be CoCr2 O4 ,
MnCr2 O4 , CoFe2 O4 , whereas the activity order for
NOx reduction was CoFe2 O4 , CoCr2 O4 , MnCr2 O4 .
The best compromise between the simultaneous abate-
ment of soot and of nitrogen oxide was exhibited by
the CoCr2 O4 catalyst, which could promote soot com-
bustion and appreciable NOx reduction below 400 C.
The prevalent catalytic combustion activity of the
chromite catalysts could be explained by their higher
concentration of suprafacial, weakly chemisorbed oxy-
gen, which contributes actively to soot combustion by
spill-over. A CoAl2 O4 spinel catalyst also exhibited an
activity for soot combustion reaction similar to that of
a Pt/Al2 O3 reference catalyst (Zawadzki et al., 2011).
This high soot combustion activity of CoAl2 O4 was
attributed to its high NOx chemisorption capacity,
which aorded rapid NO oxidation to NO2 .
BaAl2 O4 spinel was also shown to be eective in
catalysing the reaction between soot and NOx under
lean-burn conditions, promoting simultaneous NOx
reduction to N2 and soot oxidation to CO2 (Lin et al.,
2009). The interaction of nitrates on BaAl2 O4 with
oxygenated intermediates C(O) on the soot surface
was found to be the key step in soot oxidation by
NOx over BaAl2 O4 .
Spinels were also shown to promote the activ-
ity of copper with regard to some other supports
such as alumina (Zawadzki et al., 2009). Copper-
containing ZnAl2 O4 spinels, 512 nm in size, were
tested for soot combustion. An impregnated catalyst
(5% CuO/ZnAl2 O4 ) was more active in soot com-
bustion than the bare support (ZnAl2 O4 ), a substi-
tuted catalyst (Zn0.95 Cu0.05 Al2 O4 ), and a 5% CuO/
-Al2 O3 catalyst, and was similar to that of copper
supported on a SrTiO3 perovskite. The activity of 5%
CuO/ZnAl2 O4 was attributed to the easy copper re-
ducibility.
Ceria catalysts
Cerium-based oxides are used as oxygen storage
components in Tree Way Catalysts of gasoline vehi-
cles that buer changes under the oxidising/reducing
conditions in the exhaust gas, promote the oxidation
of CO, and enhance dispersion of the supported noble
metals (Kapar et al., 1999).
Ceria in ceria-loaded Diesel Particulate Filters
(DPF) is also able to accelerate soot combustion and
cerium additives have been used to obtain cerium-
containing soot in order to promote the catalytic com-
bustion (Lahaye et al., 1996; Makkee et al., 2002; de
Sousa Filho et al., 2009).
The role of CeO2 in the catalysed combustion of
soot was studied (Setiabudi et al., 2004). CeO2 has
the potential to accelerate the oxidation rate of soot
due to its active oxygen storage capacity. It was pro-
posed that the formation of active oxygen was initi-
 A. M. Hernndez-Gimnez et al./Chemical Papers 68 (9) 11541168 (2014)
ated by NO2 in the gas phase. A synergetic eect was
observed as a result of the surface nitrate decompo-
sition, which resulted in the gas phase NO2 and the
desorption of active oxygen. Stored oxygen was pos-
tulated to exist in the form of surface peroxide or su-
peroxide (Setiabudi et al., 2004). Subsequently, ESR
characterisation conrmed the formation of superox-
ide ions (O 2 ) (Machida et al., 2008) and DRIFTS
analysis conrmed the presence of both peroxide and
superoxide groups on the ceria surface during the cat-
alytic combustion of soot (Gross et al., 2009, 2012).
Active oxygen is likely to play a role in the acceler-
ation of soot oxidation and to contribute more than
desorbed NO2 or NO2 from surface nitrate decomposi-
tion. Isotopic experiments (Bueno-Lpez et al., 2005;
Guilln-Hurtado et al., 2013) demonstrated that ceria
active oxygen was able to oxidise soot both directly
and via NO oxidation to NO2 , which reacted with
soot afterwards; these two reactions prevailed over the
direct oxidation of soot and NO by gas phase O2 . By
contrast, some other oxides, such as ZrO2 or TiO2 , for
instance, have a minor or null capacity to involve cata-
lyst oxygen in the soot combustion and their catalytic
activities are much lower than that of ceria (Atribak
et al., 2007).
Lahaye et al. (1996) produced soot by pyrolysis and
the oxidative pyrolysis of hydrocarbons doped with
cerium organometallic compounds; they observed that
the presence of cerium-based compounds had no eect
on the yield or morphology of soot but that they signif-
icantly decreased the ignition temperature of the soot.
It was also reported that cerium additives did not de-
teriorate the DPF lters, while some other additives
promoted chemical degradation (Montanaro, 1999).
The chemical interactions between sodium (as sul-
phite), iron, and cerium (as oxides), coming from fuel
additives, and a cordierite ceramic lter were stud-
ied (Montanaro, 1999); it was concluded that cerium
and iron oxides did not signicantly react with the
lter, whereas sodium led to a diuse etching start-
ing from low working temperatures. Several dierent
degradation mechanisms (solid state diusion, liquid
phase diusion, and evaporationcondensation) were
identied as functions of the temperature.
Dierent ceria-containing soot combustion cata-
lysts have been studied as active phases for DPF l-
ters. Harrison et al. (2003) studied ceria-supported
cobalt catalysts for the catalytic oxidation of diesel
soot with either O2 /He or NO/O2 He. Co3 O4 was
identied on these catalysts, and their catalytic ac-
tivity was correlated with the cobalt reducibility. A
redox-type mechanism assisted by oxygen spill-over
on the CeO2 support was proposed. By contrast,
cobalt supported on alumina, silica, and Sn4+ oxide
showed a much lower activity due to the presence
of dispersed Co2+ ions on these materials. Some of
these authors also proposed the Co,Ba,K/CeO2 sys-
tem as a potential candidate for the simultaneous
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1161
abatement of soot and NOx in diesel exhausts (Milt
et al., 2003).
Ceriazirconia-supported manganese oxides (Sn-
chez Escribano et al., 2008) and MnOx CeO2 mixed
oxides (Tikhomirov et al., 2006) were also studied for
the low-temperature oxidation of diesel soot. The ig-
nition temperature of soot for the MnOx CeO2 mixed
oxides was signicantly lower than those for the indi-
vidual oxides. This enhanced activity was attributed
to improved NO2 production. However, the addition
of SO2 to the model gas resulted in the catalyst de-
activation; this was traced to the loss of the NO ox-
idation activity. The sulphates could be decomposed
by heating the catalyst under reducing as well as ox-
idising conditions. However, the initial activity of the
catalyst could not be restored.
The promoting eect of ceria on the catalytic ac-
tivity of some other phases has also been studied. V
Ce and CuVCe were tested for the oxidation of soot
(Cousin et al., 2007). VCe oxides were active soot ox-
idation catalysts and increasing the vanadium content
enhanced their catalytic activity. This was correlated
with the formation of a V2 O5 phase. However, this
catalytic system (VCe) produced CO as soot com-
bustion product, and adding copper to the VCe oxide
to form a ternary system (CuVCe) had a benecial
eect on the CO2 selectivity.
Cu-containing ceria/ceriazirconia catalysts were
also successfully tested for soot combustion after age-
ing at 800 C in air (Liang et al., 2007). It was sug-
gested that the good catalytic properties of these ma-
terials may be related to the insertion of copper into
the ceria lattice and to the presence of well-dispersed
CuO on ceria, which promotes a strong synergistic
eect between copper and cerium species. In a later
study (Liang et al., 2008), the same authors prepared
copper- and manganese-doped ceria catalysts which
were tested for soot combustion. The results showed
that Mnx+ cations entered the ceria lattice to form
solid solutions which increased the amount of oxygen
vacancies and promoted surface oxygen chemisorp-
tion. Cux O clusters were postulated to be dispersed on
the surface of ceria particles, and the interaction be-
tween copper and cerium greatly enhanced the rapid
release of lattice oxygen.
The doping of soot-combustion ceria catalysts with
suitable cations, such as La3+ (Bueno-Lpez et al.,
2005), Zr4+ (Aneggi et al., 2006; Zhu et al., 2007;
Atribak et al., 2008a, 2008b), Hf4+ (Reddy et al.,
2008), and Pr3+/4+ (Krishna et al., 2007a, 2007b,
2007c), improves the features of this oxide.
Cex Zr1x O2 mixed oxides were studied for soot ox-
idation by NOx /O2 , and the catalytic activity was cor-
related with their NO oxidation capacity (Atribak et
al., 2009). The processes occurring on the catalysts
surface upon NO + O2 adsorption were studied by
in-situ DRIFTS and a dual role was attributed to the
zirconium dopant. On the one hand, zirconium pro-
1162 A. M. Hernndez-Gimnez et al./Chemical Papers 68 (9) 11541168 (2014)
motes the oxidation of the adsorbed nitrogen species
on the Cex Zr1x O2 surface (positive eect); on the
other hand, it enhances the adsorption strength of the
nitrogen groups and impedes NO2 release (negative
eect).
La3+ -doping also improved CeO2 catalytic activ-
ity for soot oxidation with O2 , and an optimum 5
mass % La3+ -loading was obtained for catalysts cal-
cined at 1000 C (Bueno-Lpez et al., 2005). This
improvement was related to the increase in BET
surface area and the change in the catalyst re-
dox properties of CeO2 resulting from doping with
La3+ . La3+ decreased the onset temperature of the
reduction of Ce4+ to Ce3+ by H2 and increased
the amount of Ce4+ that could be reduced by
H2 .
The eect of the doping of soot combustion ceria
catalysts with either La3+ or Zr4+ was recently com-
pared (Katta et al., 2010). It was reported that La3+
promoted the creation of oxygen vacancies/defects
in the ceria lattice more eciently than Zr4+ ; this
argument was used to explain the higher activity
for soot combustion of La3+ -doped ceria over pure
ceria and Zr4+ -doped ceria. The catalytic activity
for soot combustion of La3+ or Pr3+/4+ -doped ce-
ria was also compared. Pr3+/4+ -doping was more ef-
fective (Krishna et al., 2007a, 2007b, 2007c) because
these cations contribute to the redox mechanisms in-
volved in the combustion of soot, together with the
Ce3+/4+ , while La3+ only promotes the cerium per-
formance.
The size and structure of ceria catalysts also
play a role in soot combustion. Ce0.8 M0.2 O2 (M
= Sm, Zr, V) nanoparticles were recently prepared
and tested for soot combustion (Liu et al., 2011).
The results showed that the catalysts structures de-
pended on the dierent doped ions. Ce0.8 Sm0.2 O2 and
Ce0.8 Zr0.2 O2 preserved the face-centred cubic uorite
structure of CeO2 and the nanometer size, while sin-
tered CeVO4 crystallites were formed upon vanadium
doping. Nanometer Ce0.8 Sm0.2 O2 and Ce0.8 Zr0.2 O2
exhibited a higher catalytic activity than conventional
CeO2 and CeVO4 for soot combustion because their
nanometer size favours good soot-catalyst contact.
In addition, ceria doping with samarium or vana-
dium could enhance SO2 resistance. Ceria and ceria
zirconia catalysts were also recently characterised and
tested for soot combustion, and planes {100} and
{110} were proposed to be more active than the {111}
facets (Aneggi et al., 2012).
Three-dimensionally-ordered macroporous (3DOM)
Ce1x Zrx O2 solid solutions were prepared and suc-
cessfully tested for diesel soot combustion (Zhang et
al., 2010b). It was proposed that the microstructure
with open, interconnected macropores of this novel
catalyst facilitated the contact with soot and results
in a much higher catalytic activity than equivalent
disordered macroporous catalysts.
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Metal chlorides
Several metal chlorides were screened for the cat-
alytic oxidation of model soot in loose contact (Mul et
al., 1996). HgCl2 , CaCl2 , BaCl2 , CoCl2 , and NiCl2 ex-
hibited little activity, and hydrated BiCl3 and FeCl3
were converted in air into BiOCl and FeOCl, which
had a moderate soot-oxidation activity. MoCl5 was
converted into the corresponding metal oxide and also
exhibited a moderate loose contact activity. PbCl2 ,
CuCl2 , and CuCl were very active catalysts; the in situ
close contact between the soot and the metal chloride
via wetting and/or gas phase transport was sug-
gested. However, the application of metal chlorides in
the removal of soot from diesel exhaust was not rec-
ommended in practice, because they suer from insta-
bility or high vapour pressures.
Molten salts
Jelles et al. (1998a, 1998b) and van Setten et al.
(1999a) rst reported the study of molten salts as
diesel soot oxidation catalysts. Eutectic salt mixtures
of Cs2 O, V2 O5 , and MoO3 , with a low melting point,
were reported to be highly active soot combustion cat-
alysts. It was shown that some of the molten salts had
a high activity above their melting point of approxi-
mately 350 C. Activities up to ve times higher than
the activity of chemically-related solid oxide catalysts
were obtained, and this activity was observed during
the whole course of soot conversion. The high activity
was explained by the better contact between soot and
catalyst achieved by wetting of the soot by the liquid
catalyst (Jelles et al., 1999b).
Setiabudi et al. (2002) reported that molten salts
were more active soot oxidation catalysts than plat-
inum for O2 combustion, while platinum was more ac-
tive in the presence of NOx because molten salts were
less active than platinum in catalysing the oxidation
of NO to NO2 .
Open-pore ceramic foams were used as the sup-
port for molten-salt diesel soot oxidation catalysts (eu-
tectic mixtures of Cs2 O, V2 O5 , MoO3 , and Cs2 SO4 )
and the stable soot combustion rates obtained were
of the same order of magnitude as those measured for
catalytic fuel additives (van Setten et al., 1999b). A
molten salt (Cs2 SO4 V2 O5 )-based catalytic foam had
an onset temperature for catalytic oxidation of 320 C
(van Setten et al., 2001b). This was a promising tem-
perature for continuous lter-regeneration applica-
tions; however, the authors concluded that the liquid
state of the catalyst rendered it unt for the very ef-
fective wall-ow monolith lter. They concluded that
this molten salt required a foam lter as support, and
also that the onset temperature of the catalytic foam
of 320 C was still too high to justify a change from
wall-ow monolith to foam, as ceramic foam was a
less eective lter than the wall-ow monolith.
 A. M. Hernndez-Gimnez et al./Chemical Papers 68 (9) 11541168 (2014)
Another study (van Setten et al., 2003) reported
that the stability of the molten salt catalysts based
on Cs2 O, MoO3 , and Cs2 SO4 was also too low for ap-
plications. Due to partial evaporation, emission of the
catalyst compounds into the environment was proba-
ble and signicant deactivation of the catalytic phase
remained unavoidable. These active phases were also
found to be soluble in water, which might have serious
consequences in the event of condensation occurring in
the exhaust pipe.
Alkaline metal catalysts
Alkaline metals have been investigated in detail
for the gasication of carbon with H2 O, CO2 , and O2
(Gallagher & Harker, 1964; McKee, 1983; Moulijn et
al., 1984) and the activity of alkaline metals in this
reaction decreased in order Cs, K, Na, Li, similarly
to that reported for alkali metal compounds-catalysed
diesel soot combustion (Neeft et al., 1996b).
Alkaline metals have mainly been studied as pro-
moters of some other soot combustion catalyst phases,
such as ceria (Aneggi et al., 2008), spinels (CuFe2 O4
(Shangguan et al., 1998; An et al., 2004), CoFe2 O4
(An et al., 2004)), perovskites (LaCoO3 (Hong et
al., 1999; Wang et al., 2008), LaFeO3 (An et al.,
2004), LaCrO3 (Russo et al., 2005), LaMnO3 (Hong
& Lee, 2006), SrTiO3 (Bialobok et al., 2007; Ura
et al., 2011)), FeOx VOy /Al2 O3 (Neri et al., 2003),
VOx /MO (MO = SiO2 , TiO2 , ZrO2 , or Al2 O3 ) (Hong
& Lee, 2006; Liu et al., 2006), and Pt/Al2 O3 (Krishna
& Makkee, 2006), among others.
Dierent roles have been attributed to alkali pro-
moters. Bialobok et al. (2007) compared two groups
of SrTiO3 -based perovskites prepared by substitution
of alkaline metal cations in the A-position (strontium)
of the structure and by SrTiO3 impregnation with the
same amount of alkaline metals. They observed that
the substituted perovskites were more active due to
changes in basicity, desorption of oxygen, and surface
structure. Russo et al. (2008b) also concluded that
the improved activity of LaCoO3 upon alkali-doping
(mainly rubidium) was due to the distortions caused
by the intrusion of the relatively large rubidium ions
at the lanthanum site in the LaCoO3 perovskite lat-
tice.
The alkaline metal loading is an important issue to
be taken into account. Shangguan et al. (1998) stud-
ied the promoting eect of potassium on the catalytic
behaviour of Cu1x Kx Fe2 O4 spinels for the simulta-
neous removal of NOx and diesel soot particulates and
an optimum potassium loading was found to be x =
0.05, above which the CuFe active sites were covered
and deactivated.
The combustion of soot catalysed by alkaline
metals-promoted FeOx VOy /Al2 O3 was proposed to
occur through a redox mechanism, where the lattice
oxygen of the active phase is involved. Iron acts by
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1163
favouring the oxidationreduction process of the ac-
tive vanadium phase, through the participation of the
redox couple Fe2+ Fe3+ , and the promoting role of
alkaline dopants was attributed to the formation of
the low-melting phase on the catalyst. The enhanced
reduction of VOx /MO (MO = SiO2 , TiO2 , ZrO2 , or
Al2 O3 ) catalysts was also proposed to explain the pro-
moting eect of alkaline compounds (Hong & Lee,
2006; Liu et al., 2006). However, it was concluded that,
although the alkali-doped vanadium oxide systems ex-
hibited good activity, their application in praxis seems
not possible due to their low thermal stability (Neri
et al., 2003). Kureti et al. (2003) also reported the
deactivation of a Fe1.9 K0.1 O3 soot combustion cata-
lyst, which was attributed to the agglomeration of the
potassium promoter.
Thermal stability is one of the main drawbacks of
alkaline metals-containing soot combustion catalysts,
not only for the vanadium formulations referred to
above but also for most alkaline metals-containing cat-
alysts. Pt/KAl2 O3 was investigated and it was found
that platinum and potassium exhibited synergetic ef-
fects in soot combustion activity, but the active species
responsible for the synergism were found to be un-
stable and were not regenerated (Krishna & Makkee,
2006). The degradation of potassium catalysts due to
the sublimation of potassium compounds during the
soot combustion process was reported (An & McGinn,
2006; Lpez-Surez et al., 2009; Mul et al., 1995). A
Cu/K/Mo/Cl soot combustion catalyst was investi-
gated by Mul et al. (1995), and a catalytic cycle, in-
volving Cu2 OCl2 , was proposed to explain its high
activity in loose contact with soot. However, the ac-
tivity of this catalyst was only maintained as long as
Cu2 OCl2 was formed by the reaction of copper molyb-
dates with KCl, which served as a chlorine supplier.
Aneggi et al. (2008) studied the catalytic oxidation
of soot with alkaline metals-promoted ceria and found
a major drawback in the loss of metal and consequent
deactivation upon catalysts ageing, especially in a
water-containing atmosphere. To resolve this problem,
the preparation of soot combustion catalysts consist-
ing of alkaline metal carbonates stabilised on alumi-
nosilicates was recently reported (Kimura et al., 2011).
These novel catalysts were prepared by the ion ex-
change of alkaline compounds on zeolites, which were
nally allowed to collapse at high temperature; it was
noted that they overcame the drawback of the high
solubility of alkaline compounds in water.
Several authors have observed that transition el-
ements can moderate the loss of potassium (An &
McGinn, 2006). The stability of potassium in soot
combustion copper-containing SrTiO3 perovskite cat-
alysts was studied (Lpez-Surez et al., 2009), con-
cluding that the synthesis method used for potassium
addition (impregnation or substitution in the lattice)
notably aected the catalysts stability, and that the
substituted catalysts were more stable due to the lo-
1164 A. M. Hernndez-Gimnez et al./Chemical Papers 68 (9) 11541168 (2014)
cation of potassium inside the perovskite structure.
Despite the attempts to prepare stable alkaline
metal-containing soot combustion catalysts, the hy-
drothermal stability remains a major problem await-
ing solution for a practical use of alkaline metals in
soot combustion catalysts formulations.
Conclusions
The most relevant information available on the dif-
ferent active phases investigated for the catalytic com-
bustion of soot is reviewed and discussed in this ar-
ticle. Many catalysts have been reported to acceler-
ate soot combustion, including formulations with no-
ble metals, alkaline metals and alkaline earth metals,
transition metals that can accomplish redox cycles (V,
Mn, Co, Cu, Fe, etc.), and internal transition metals.
Platinum catalysts are among those of greatest in-
terest in practical applications. The main role of plat-
inum is to promote NO oxidation to NO2 , and one
important feature of these catalysts is that sulphur-
resistant platinum formulations have been prepared.
Some metal oxide-based catalysts are also promis-
ing candidates for soot combustion in practical appli-
cations, including ceria-based formulations and mixed
oxides with perovskite and spinel structures. In addi-
tion to catalysing the oxidation of NO to NO2 , some of
these metal oxide catalysts also produce highly reac-
tive active oxygen species. In this case, the DPF lter
must be loaded with the catalyst and dual bed con-
gurations (for instance, DOC + DPF such as in the
CRT system) are not appropriate.
Thermal stability is one important requirement for
a soot combustion catalyst, hence the practical utili-
sation of several potential catalysts such as most alka-
line metal catalysts, molten salts and metal chlorides
is precluded. Some noble metal catalysts are also un-
stable because they form volatile oxides (ruthenium,
iridium, and osmium).
Acknowledgements. The authors are grateful for the fi-
nancial support received from Generalitat Valenciana (Project
Prometeo 2009/047), the Spanish Ministry of Economy and
Competitiveness (Project no. CTQ2012-30703), and the EU
(FEDER).
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