Flame Spray Pyrolysis: An Enabling Technology For Nanoparticles Design and Fabrication PDF

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REVIEW www.rsc.org/nanoscale | Nanoscale
Flame spray pyrolysis: An enabling technology for nanoparticles design and

fabrication
Wey Yang Teoh,a Rose Amala and Lutz M€
adler*b
Received 11th January 2010, Accepted 4th March 2010
DOI: 10.1039/c0nr00017e
Combustion of appropriate precursor sprays in a flame spray pyrolysis (FSP) process is a highly
promising and versatile technique for the rapid and scalable synthesis of nanostuctural materials with
engineered functionalities. The technique was initially derived from the fundamentals of the well-
established vapour-fed flame aerosols reactors that was widely practised for the manufacturing of
Published on 17 May 2010 on http://pubs.rsc.org | doi:10.1039/C0NR00017E
simple commodity powders such as pigmentary titania, fumed silica, alumina, and even optical fibers.
In the last 10 years however, FSP knowledge and technology was developed substantially and a wide
range of new and complex products have been synthesised, attracting major industries in a diverse field
of applications. Key innovations in FSP reactor engineering and precursor chemistry have enabled
flexible designs of nanostructured loosely-agglomerated powders and particulate films of pure or mixed
oxides and even pure metals and alloys. Unique material morphologies such as core–shell structures
and nanorods are possible using this essentially one step and continuous FSP process. Finally, research
challenges are discussed and an outlook on the next generation of engineered combustion-made
materials is given.
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1. Introduction before the ‘‘Nano’’ buzz, but has since rapidly evolved. Industry
leaders such as Cabot, Cristal (formerly SCM and Millenium
The large scale production of nanoparticles by flame aerosol Chemicals), DuPont, Evonik (formerly Degussa) and Ishihara,
technology is a critical aspect contributing to the progress of manufacture flame-made materials in millions of tons, valued at
a wider Nanotechnology. In fact, the technology existed long more than $15 billion/yr.1 This includes most notably, carbon
blacks, fumed SiO2, TiO2, Al2O3 as well as other ceramic nano-
a
ARC Centre of Excellence for Functional Nanomaterials, School of particles. While many of these nanoparticles are used in
Chemical Engineering, The University of New South Wales, Sydney, commodity applications such as reinforcing agents (carbon
NSW, 2052, Australia blacks, SiO2, carbon-coated SiO2), pigments (TiO2) and flowing
b
Foundation Institute of Materials Science (IWT), Department of aids (SiO2), emerging niche markets requiring more complex and
Production Engineering, University of Bremen, 28359 Bremen, Germany.
E-mail: lmaedler@iwt.uni-bremen.de; Fax: +49-421-218-5378; Tel: +49- functional materials are expected to spearhead the next phase of
421-218-7737 growth. This includes for example, polishing agents in
Wey Yang Teoh is an ARC Rose Amal is an ARC Austra-

Australia Postdoctoral Fellow lian Professorial Fellow (APF)
(APD). He obtained his and University of New South
doctorate from the School of Wales (UNSW) Scientia
Chemical Engineering, Univer- Professor. She heads a group of
sity of New South Wales in 2007 over 30 research members at the
and spent a brief attachment at Particles and Catalysis
the Swiss Federal Institute of Research Group, School of
Technology (ETH) Z€ urich in Chemical Engineering, UNSW.
2003. He continued his post- She is the Director of the ARC
doctoral work at the laboratory Centre of Excellence for Func-
of Prof. Rose Amal, where he is tional Nanomaterials, a multi-
a Program Leader in flame institution research centre. She
Wey Yang Teoh spray pyrolysis with focusing on Rose Amal is also the inaugural Director of
energy, environmental and bio- the Centre for Energy Research
applications. He will assume the and Policy Analysis (CERPA),
role of Assistant Professor at the School of Energy and Environ- the new Energy Research Institute at UNSW. Her research
ment, City University of Hong Kong. interests are in particle technology and nanomaterials, spreading
over a wide range of applications from energy, environmental to
bioapplications.
1324 | Nanoscale, 2010, 2, 1324–1347 This journal is ª The Royal Society of Chemistry 2010
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microelectronics (doped CeO2), catalysts (Pt/Al2O3, V2O5/TiO2, the precursor is also in liquid form, but with significantly higher
Ru/Co3O4–ZrO2), dental fillers (Ta2O5–SiO2) and other specialty combustion enthalpy (>50% of total energy of combustion),
applications – see ref. 2 and references therein, many of which are usually in an organic solvent.10 FSP (the focus of this review),
multielements in nature. Given their complexities and the variety which is the youngest of the three processes, has important
of available permutations, the design of sophisticated and func- technological elements such as self-sustaining flame, usage of
tional flame materials is far from trivial and in fact system liquid feeds and less volatile precursors, proven scalability, high
specific. Nevertheless, their importance and lucrativeness temperature flames and large temperature gradients. It is also the
continue to drive the evolution of flame synthesis. most heavily explored in recent years for the production of
Much is to be learned from the evolution of flame aerosol complex and functional nanomaterials. Some of the most notable
technology, developed through years of industrial significance: applications are in the areas of catalysis (as reviewed by Strobel
from reactor design to process sophistication and versatility. A et al.7 on general flame aerosols), optics and photonics,11–15
classic example is the industrial manufacture of carbon blacks sensors,16–18 health care,19–21 magnetic materials,22–25 electro-
which evolved from the ‘‘smouldering’’ process to the current ceramics for fuel cells26,27 and composite materials.28–33 A key
norm of jet-like flame aerosol reactors.3 Formed via the pyrolysis feature in the use of FSP as a convenient tool in synthesising
of hydrocarbon sprays, the carbon black syntheses take place these nanomaterials is the ability to upscale its production, while
under fuel rich conditions where about half the hydrocarbons are closely preserving its tailored properties.
burnt to supply the energy that pyrolyses the other half to carbon Despite being only at the dawn of FSP research, the applica-
black.4 Modern aerosol reactors for the production of ceramic tions and markets for these nanoparticles are so encouraging that
oxides bear a strong resemblance to carbon black jet furnaces.5 pioneer start-ups based on the FSP process are already in oper-
The fundamental differences between the two, besides the choice ation. Quite recently, Johnson Matthey Co., a major manufac-
of metal elements present in the precursors, lies in the combus- turer of catalysts, announced their systematic exploration of
tion regime in which they operate: fuel rich to obtain carbon
particles and lean oxidising conditions to obtain metal oxides. In
some cases, combination of the two is also possible (e.g. C/TiO2,

C/SiO2), but this is governed by the combustion engineering in
tandem with the corresponding particle formation, materials
chemistry and thermodynamics of the system.
Depending on the precursor state (aqueous-based, solvent-
based, vapour) and combustion conditions, flame aerosol
syntheses fall into three general categories:6,7 (a) vapour-fed
aerosol flame synthesis (VAFS) where a metal precursor is
supplied in the form of vapour like SiCl4 and TiCl4 to make most
of today’s ceramic commodities;8 (b) flame-assisted spray
pyrolysis (FASP) where precursor is supplied in the state of low
combustion enthalpy solution (<50% of total combustion
energy) usually in aqueous solvent, and because of this, its
combustion needs to be assisted by an external hydrogen or
hydrocarbon flame;9 and (c) flame spray pyrolysis (FSP) where
Lutz M€ adler (Dr -Ing. Univ.

Freiberg/Sa., Germany in 1999)
was born in Zwickau, Germany.
He received his Habilitation in
2003 at Swiss Federal Institute
of Technology (ETH Zurich).
He was Senior Lecturer at the
Department of Chemical Engi-
neering, University of Cal-
ifornia, before he joined the
Department of Production
Engineering at the University of
Bremen leading the Particle and
Lutz M€ adler Process Technology division in
2008. He is also Director at the Fig. 1 General paradigm and strategy for the synthesis of functional
Foundation Institute of Mate- nanoparticles by FSP, from conceptual design to targeted end applica-
rials Science. His research focuses on integrated aerosol processes tions, taking into account the tunable synthesis parameters and their
for nanomaterials and surface films for sensors, catalysts, and respective boundary conditions in achieving the product particles with
optical devices, and on nano-bio-interactions. desirable characteristics.
This journal is ª The Royal Society of Chemistry 2010 Nanoscale, 2010, 2, 1324–1347 | 1325
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FSP-made catalysts at its Research Center in UK.34 Many natural gas, were combusted within a closed furnace, followed by
opportunities await discovery, both in particles design as well as control-quenching of the oxygen-starved flames by water sprays
their applications. The key element lies in the continuous inte- to yield ‘‘furnace blacks’’4 (Fig. 2, III).
gration and bridging of knowledge between combustion engi- At about the same time, the production of fumed SiO2 by
neering, aerosol technology and materials science. An inevitable VAFS was conceived where the vapour phase SiCl4 was hydro-
complexity lies in the specificity of every new materials system. lysed in an oxy-hydrogen flame yielding pristine silica aerosols
Hence this review presents up-to-date knowhow in FSP, (Fig. 2, II).35 This patented process is known as the Aerosil
highlighting the many innovations in this area, from reactor process, after its commercial product name. Within 10 years after
design (Section 2) to particles design and synthesis (Section 4). the first fumed SiO2 was produced, the manufacture of fumed
Through this, it aims to provide a clearer, and more importantly, Al2O3 (from AlCl3) and TiO2 (from TiCl4, chloride process) by
a holistic view on the relationship between synthesis properties VAFS followed, demonstrating the versatility of the flame
and the resultant particle properties (see Fig. 1). Intrinsic prop- process for product ceramic particles.36 A very important inno-
erties specific to the precursor formulation (covered in Section 3) vation of the Aerosil-like process is the commercial manufacture
such as enthalpy of combustion, solvent–metal precursor speci- of lightguides for telecommunications, where SiO2–GeO2 parti-
ficity and combustion environment (excess or restrictive oxygen) cles (from SiCl4 and GeCl4) were flame deposited directly onto
are some of the governing factors, while externally tunable and into substrate rods and subsequently extruded into contin-
parameters such as the rate of enthalpy of combustion, uous thin optical fibers of extremely high purity.37 Synthesis of
quenching rate as mediated by natural heat loss or through other ceramic oxide particulates by VAFS e.g. UO2, SnO2,
external quenching unit, thermophoretic gradient, mixing stages Fe2O3, ZrO2, ZnO and its composites,3,38 carbon-coated
of precursors etc. define the extrinsic properties. Understanding oxides39,40 and noble metal/metal oxides41 have also been repor-
the intricate inter-relationship between synthesis properties and ted from their respective halide, carbonyl or acetylacetonate
the limiting boundaries of flame profile, particle formation, vapours.
materials chemistry and thermodynamics is critical towards the Despite its early industrial significance, very little was under-
fabrication of functional nanomaterials with specific character- stood regarding particle formation within VAFS. It was only in
istics. These include the product particles size, homogeneity, the late 80s that Dobbins and Megaridis42 introduced the concept
morphologies, configurations and crystallite properties. of thermophoretic sampling and essentially opened up the ‘‘black
It should be reiterated here that the current manuscript reviews box’’ of particle formation in vapour-fed flames. The rapid
exclusively FSP, with only brief accounts of VAFS and FASP insertion and retraction of a TEM (transmission electron
that will be provided in Section 2, in view of their relevance to microscopy) copper grid into the particle-laden flame allows
FSP. Readers interested in further information on other flame direct sampling of the evolution of particle morphology along the
aerosol techniques are referred to reviews by Pratsinis5 which flame axis, from spherical particles to fractal-like aggregates.
covered extensively the fundamentals and the then state-of-the- From there, quantitative description of the flame particles
art in VAFS of ceramics nanoparticles, and M€adler6 on the spray growth by coagulation and sintering, including population
aerosol techniques (with and without flame). Since the general balance and coalescence models43 contributed decisively to the
applications of flame-made materials have been reviewed earlier development of computational tools for the design of VAFS
by Strobel et al.,2,7 they shall not be repeated here. Rather, this reactors – to the point that particle sizes could be predicted from
review focuses on the general ‘‘art and science’’ of nanoparticle first principles without any adjustable parameters in premixed
fabrication by FSP based on the most current knowledge in the flames.44 Further accounting for the detailed particle residence
area. time distribution by interfacing computational fluid mechanics
with particle dynamics in diffusion flames45 allowed for quanti-
tative understanding of a number of experimental observations:
2. Flame aerosol reactors and flame spray pyrolysis
The effect of process variables (flame temperature, reactant
The origin of flame aerosols for useful materials can be traced as concentration, mixing or flowrate) on product particle size
far back to ancient lampblacks production by which vegetable distributions (example see ref. 46).
oils were combusted in oxygen-starved flames, yielding carbon While VAFS was undoubtedly a milestone achievement in
soot fume.3 For centuries, this was the dominant form of carbon terms of flame aerosol synthesis, its usage of metal vapours is
black, a rather coarse material probably due to prolonged and rather demanding. The continuous demands for process versa-
uneven residence times5 in these rather primitive pyrolysis reac- tility require the replacement of metal vapour precursor, which
tors. Much later, the discovery of natural gas in US and gasifi- can often be costly, difficult to handle or in many cases, simply
cation of tars in Europe enabled the production of carbon blacks not available. This prompted the spraying of liquid precursors
with much finer texture to meet the demand as tire reinforcing directly into the flame i.e. flame-assisted spray pyrolysis (FASP).
agents.4 The so-called gas black or channel black was made by The strategy uses less volatile and economical precursors,
a VAFS process whereby gaseous hydrocarbons (natural gas) particularly those of aqueous metal salts (e.g. nitrates and
were combusted in gas jets and soot collected on water-cooled acetates). Since the precursor exists as liquid, an additional
channel surfaces – justifying the name of ‘‘channel blacks’’ dispersion nozzle feature by ultrasonication or pressure-assis-
(Fig. 2, I). The high demand for carbon blacks driven by the tance, is necessary prior to combustion. Many of these precur-
growing tire market before and during World War II further sors, especially aqueous nitrates have low combustion enthalpy
motivated the development and scale-up of today’s FSP ‘‘furnace or endothermic in nature and as such do not form self-sustaining
process’’. Here, liquid hydrocarbon fuel sprays, rather than flames. Hence an external flame source, usually oxy-hydrogen or
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Fig. 2 Evolution of aerosol flame reactors, including FSP reactor and its modifications. (I) 1940s: Early industrial-scale production of carbon blacks as
commodity particles – ‘‘channel black process’’. (II) 1940–50s: Production of fumed SiO2 (1943) from the flame hydrolysis of metal halide vapours
(picture showing the first Aerosil production plant,36 source: courtesy of Evonik Degussa GmbH). The process further led to the manufacture of other
commodity oxide ceramics such as Al2O3 (1953) and TiO2 (1954) using the same vapour-type flame technique. (III) 1970s: Furnace black process using
a modern ‘‘jet-type’’ flame reactor. Figure adapted from ref. 36. (IV) 1977: First reported development of ultrasonic-assisted Flame Spray Pyrolysis by
Sokolowski et al.,10 where metal acetylacetonate in organic solvent was used as the liquid precursor. (V) 1996/97: Gas-assisted atomiser FSP reported by
Bickmore et al.28 and Karthikeyan et al.64 mark the pioneering of systematic studies in FSP. Figure adapted with permission from ref. 28. (VI) 2002:
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oxy-hydrocarbon, is required to support the combustion.5 One of direct control over primary particle size by controlling the
the disadvantages of FASP is the yield of submicron particles combustion enthalpy rate and metal concentration of the
with inhomogeneous morphology and size especially when precursor alone.65,66 More details on particle formation will be
operating at low rates of combustion enthalpy (defined as the presented in Section 3, considering also the possibilities of
ratio of combustion rate (kJ min1) to total gas flow (ggas min1), different types of particle configurations.
<4.7 kJ g1gas),
47
where there is insufficient energy for the formation Because of the highly exothermic nature of FSP liquid
of metal vapour (see Section 3). In such cases, dense particles are precursors, flame temperatures of up to 2600 K65,70 or 2800 K71
formed as a result of drying and solid-state densification48 while have been measured. At the same time, the high gas velocities of
hollow particles are due to precipitation on surface droplets prior the FSP induce radial entrainment of surrounding gas.72 Coupled
to evaporation of the carrier liquids.49–52 The many types of with the radiation heat loss, this gives rise to extremely short
FASP-synthesised particles include simple metal oxides – TiO2,53 residence times (milliseconds) with high temperature gradients
ZnO,54 perovskites – SrMnO3, NiMn2O4,55 La1xCexCoO3,56 (170 K cm1) along the flame axis.70 The interplay between high
La(Co, Mn, Fe)O357,58 and doped-metal oxides temperature and large temperature gradient is one of the most
3+ 14,50,52,59–61
Y2O3 : Eu , BaMgAl10O17 : Eu2+.62,63 important features in FSP: the high local temperature promotes
In an FSP process, the exclusive use of highly exothermic the formation of homogeneous and highly crystalline materials
liquid precursors (hereby referred to the mixture of metal and also promotes particle growth by sintering and coalescence,65
precursor and solvent), particularly those based on organic while the large temperature gradient (and short residence time)
solvents gives rise to self-sustaining flames. First introduced by preserves the nanoscale feature of the particles. In fact, the rapid
Sokolowski et al.10 (Fig. 2, IV) who reported the synthesis of thermal quenching during FSP has resulted in the formation of
Al2O3 nanoparticles by combusting an ultrasonically-dispersed many metastable materials such as amorphous Ta2O5 up to 45
spray of aluminium acetylacetonate in benzene–ethanol. The wt.% in silica composites,20 Y3Al5O12,73 monoclinic BaCO3,74
concept was only further developed two decades later by Bick- cubic and tetragonal g-Fe2O3.22,23 On an industrial scale,
more et al.28 who used a single pilot-scale FSP to synthesise spinel although the FSP process for ceramic materials is yet to see an
MgAl2O4, while Karthikeyan et al.64 reported the synthesis of equally large-scale implementation as VAFS with productions of
Al2O3, Mn2O3, ZrO2 and Y2O3–ZrO2 using a multiple diffusion- tons h1, it is making its way into the market. Scalability and
flamelet spray gun (Fig. 2, V). Pressure-assisted FSP ignited by reproducibility have been demonstrated at pilot scale production
six surrounding oxy-methane flamelets was introduced by rates of 300 to 1100 g h1 (SiO2,69 ZrO271,75,76), although FSP
M€ adler et al.65 and was very quickly superseded by an oxy- industrial units might already run at higher rates.
methane ring.66 A variant of the more general FSP (or FASP, Among the extensions to the basic FSP synthesis of ceramic
depending on its combustion enthalpy criteria), the emulsion oxide nanoparticles, direct deposition of particulate films is
combustion (ECM) utilises an organic solvent–water metal perhaps one of the most extensively explored. This technique was
precursor stabilised in an emulsion phase.6,67 The presence of demonstrated by Karthikeyan et al.64 by the natural deposition
incombustible water phase in the ECM precursor not only lowers of flame aerosols (i.e. absence of phoresis) onto grit-blasted
the combustion enthalpy density, but may also result in poorer stainless steel substrate. Thermophoretic deposition was later
gas-phase mixing and reaction as compared to a homogenous developed for the direct fabrication of functional porous layers
solvent-based only precursor, thereby affecting the particles as Au/TiO2 catalytic microreactors77 and SnO2-based gas
homogeneity.67 sensors17 (Fig. 2, VII). Here, deposition is driven by the
An integral part of the FSP reactor design is the aerosols temperature difference between the cooled masked substrate78
collection, which can be accomplished either by electrostatic and the gas temperature at which the preformed open aerosol
precipitation or vacuum-assisted filtration. In the latter case, agglomerates are suspended. One of the processing advantages of
fume nanoparticles are collected on a range of high temperature this in situ technique is the independent nanoparticle synthesis
resistant porous media, ranging from glass fiber65 or PTFE and the film thickness control, where the former depends on the
membrane68 sheet filters, to Gore-Tex67 or PTFE-coated fiber69 flame synthesis properties while the latter is a function of depo-
bag type filters. sition time. Strictly speaking, this is different conceptually from
While the design of FASP and FSP reactors bear many simi- the combustion chemical vapour deposition (CCVD) where
larities (and in fact may be inter-transferable), the core difference particles are formed upon nucleation of metal vapour onto
between the two classifications does not exactly lie in the reactor a temperature-controlled substrate, much alike a conventional
design, but more essentially in the origin of majority combustion CVD process, except the metal vapour was generated through
enthalpy content of the system. The bulk of flame enthalpy in the combustion of liquid or gaseous precursors.79 In CCVD, the
FSP originates from the combustion of liquid precursor, whereby substrate properties i.e. temperature and material affect strongly
the external flame serves only as an ignition source. This provides the nucleation and subsequent particle growth, while particles
Pressure-assisted FSP reported by M€adler et al.65 that further led to systematic studies of various simple to complex metal oxides and metal/metal oxide
systems using similar type reactor. (VII) 2004: A one-step film deposition technique by thermophoretic coating that further led to a series of supported
catalysts and gas-sensor fabrications.77 (VIII) 2005: A flame height-selective rapid-quenching technique to control precisely the metal deposit size on
metal oxide support.70 (IX) 2006: Reducing FSP by limiting the ambient O2 in flame reactor that allows production of metallic and carbon-coated
nanoparticles.24 (X) 2006: A multi-nozzle FSP to synthesise multi-component particles with controllable phase segregation.89 (XI) 2008: In situ sequential
coating of preformed FSP nanoparticles by introducing secondary metal vapour via a torus pipe ring with multiple hollow openings.94 Note: Figures are
adapted with permissions from the respective references unless otherwise stated.
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are preformed in the in situ FSP deposition. Typically, the FSP- oxide or carbonaceous layer against further oxidations, such as
deposited particulate films consist of agglomerates with Df C/Co,24,25 C/Cu,87 Co3O4/Co24 or even Ni/Mo alloy with oxide
1.7–1.8 (as a result of Brownian coagulation) and are highly shell.88
porous (>95% porosity). It has been shown theoretically that it is Flame spraying of multicomponent elements in a single nozzle
possible to manipulate the film profile, which is an interdepen- FSP configuration often limits the flexibility in obtaining
dency of film thickness and porosity, by varying primary particle a certain desirable particle configuration. For instance,
size, aggregate size, morphology and thermophoretic tempera- uniformly dispersed Ba species within an Al2O3 matrix, rather
ture difference.80 The reasons are the depth of penetration into than discrete oxide particles, were obtained when spraying both
the film of newly arriving particles during deposition, which is elements simultaneously in a single nozzle.89 To achieve phase
a function of the migration velocity and the particle diffusion separation (i.e. reduced solubility), these aerosol particles (e.g.
coefficient as well as the particle/aggregate structure. Ba and Al) have to be co-precipitated in separate flames and
Sequential deposition of different aerosol materials gives rise interfaced only at a certain angle for even interparticle aerosol
to multilayer films,81,82 each of which can be in principle designed mixing (Fig. 2, X). The flame temperature and remaining resi-
with controlled thickness and morphologies (Fig. 3). The direct dence time at the point of mixing is critical to either induce
immobilisation technique has also been extended to vacuum- delayed solid-state reactions or suppress any reactions between
assisted flame coating of aerosols onto the external and internal these discrete phases altogether. A key advantage of the concept
surfaces of porous substrates e.g. ceramic foams.83 Impinging is the independent control over particle synthesis (in terms of
flame-annealing is a film modification technique. Depending on elements as well as their physical characteristics) at each nozzle.
the thermal stability of the inter-particulate bridge, direct Particle systems that have been synthesised using the multi-
annealing by the flame sinters the morphology of the lacy-like nozzle, besides BaCO3/Al2O3,89 include Pt/Ba/CexZr1xO290 and
porous film to one consisting of dense cauliflower-like aggregates carbon-supported Pt nanoparticles.91
(porosity 62%).78 The wider gaps between cauliflowers were In other circumstances, induced delay and sequential precipi-
especially beneficial for the enhancement of analyte diffusion in tation (rather than co-precipitation) of one of the metal
gas sensor devices.78 Similar films morphology could also be components is required, which in this sense would render the
achieved using high temperature CCVD84 and impinging VAFS multi-nozzle unsuitable. To do so, it is required that the
techniques,85 with similar theoretical concepts. secondary metal component be introduced into the flame, for
While most of FSP particles are synthesised in the form of example as vapour phase precursor – similar to VAFS, only after
metal oxides, the synthesis of metallic nanoparticles is possible the precipitation of the primary phase particles (Fig. 2, XI).92–94
under restrictive oxygen flame conditions.24,86 To achieve this, the The technique circumvents the high temperature solid-state
amount of O2 present must be kept minimal (in inert gas-filled reaction dependencies of multiple components in a co-oxidation
glove box), but sufficient for the complete combustion of configuration. More importantly, it allows the design of thin
hydrocarbon fuels (Fig. 2, IX). Further restricting the O2 partial coating and even encapsulation by the secondary metal oxides
pressure can result in the formation of carbonaceous coating.25 phase, e.g. SiO2-coated TiO292 and SiO2-coated g-Fe2O3.95 As in
To date, the synthesis of metallic nanoparticles have only been the case of multi-nozzle configuration, the flame temperature and
restricted to highly electronegative metallic particles such as Bi remaining residence time at which mixing of secondary compo-
(but unstable in air)86 or particles which are protected by surface nent (i.e. coating precursor) is introduced determines the fate of
this phase. Point of mixing at excessively high temperature and
long residence time may induce solid-state reaction and uneven
segregation of the two components,94 while an excessively low
temperature and insufficient residence time may result in
incomplete formation of the oxide coating layer. In principle, the
technique could also be applied to multi-layer coating by intro-
ducing more sequential stages.
3. Designing of liquid precursors

Formulation of liquid precursors is one of the more important
steps to FSP particle synthesis. Selection of metal precursors and
solvents with suitable combustion enthalpies, melting/decom-
position temperatures, miscibility and chemical stability are
intrinsic to the overall particles formation in the flame which in
turn determine the resultant particle properties. Early formula-
tions of FSP precursors were based on solid nitrates,64,96,97
acetates64,66 and acetylacetonates98,99 as these were natural
choices in direct extensions of FASP. While many of these
Fig. 3 Directly fabricated single- (A,C) and multi-layer sensing films precursors were economical and readily available commercially,
(B,D) on ceramic substrate by FSP. The technique offers high flexibility they do not always yield the homogeneous morphology
in terms of layers composition as well as film thickness. Figure adapted comprising of fine and dense particles. The low combustion
with permission from ref. 82. enthalpy of some of these precursors coupled with their high
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environment necessary. Very recently, a facile conversion of

metal chloride (as WCl4 and WCl6) to moisture tolerant alkoxide
was demonstrated by reacting with benzyl alcohol at room
temperature and pressure.179 Gaseous hydrogen chloride evolves
during the alkoxylation reaction, thereby removing the chloride
content.
Low cost chemical conversion of metal oxides and hydroxides
to soluble ‘‘trane’’ complexes is a robust alternative to preparing
moisture insensitive metal precursors. Introduced by Laine and
co-workers, the procedure involves moderate heating-distillation
of solid metal oxides and/or hydroxides in triethanolamine
(trane)/ethylene glycol under inert environment.28 In the past,
a range of trane complexes ranging from Ti,149 Li, Na,105 Ca, Ba,
Sr,183 Si,29 Ce, Zr, Y, Yb, Er, Tm to Pr,11,118 or even multi-metal
tranes such as Sr–Si–Al, Ba–Si–Al and Al–Mg28 were syn-

thesised. A similar polymerisable complex or Pechini method is
Fig. 4 Morphology map of particles made by spray flames adapted and
another promising technique for the conversions of metal oxide,
modified from ref. 47. The hollow symbols, within the broken line box,
represent inhomogeneous and hollow particles: (a) CeO2;73 (b) Bi2O3,96 carbonates or salts to liquid precursors.184–188 It involves dis-
while solid symbols represent solid and homogeneous particles: (c,f) solving of single or multi-metal components in an acetic acid (as
SiO2,47 (d) CeO2,73 (e) Bi2O3.96 All images are adapted with permissions chelating agent)–ethylene glycol–methanol mixture followed by
from the respective references. heating to polymerise the acetic acid and ethylene glycol. Both
the trane and polymerised complex can be readily dissolved in
alcohols.
melting/decomposition points can be disadvantageous, but as Metal carboxylates189 are another group of metal precursors
discussed below, some of these disadvantages can be circum- with proven versatility and ease in handling (hydrolytically
vented by implementing the right processing conditions. insensitive). The simplicity of carboxylic acids in forming
The combination of low combustion enthalpy density (<4.7 kJ favourable ligand exchange, especially with metal nitrates, is
g1
gas) and higher metal precursor melting/decomposition attractive.96 Although short chain carboxylates such as acetates
point relative to the solvent boiling point i.e. Tbp (solvent)/ have low combustion enthalpy, its calorific value can generally be
Td/mp(precursor) < 1 during FSP results in the formation of increased by increasing the carbon chain length. This prompted
inhomogeneous particles (Fig. 4).54 Under these conditions, both the synthesis of Co, Cu, Ni,167 Y122 propionates or Y12,13,75 and
micron- and nanoparticles co-exist (Fig. 4a,b) due to particle Yb141 2-ethylhexanoates by reaction of the long chain alkanoic
formation through the droplet-to-particle100 and gas-to-particle acids with metal nitrates (Table 1). Heating or refluxing of the
routes,5,101–104 respectively. The former arises from incompletely metal nitrate–alkanoic acid mixture promotes ligand exchange.
evaporated droplets as in classic spray pyrolysis,48 while the latter Besides reacting with metal nitrates, the reaction with 2-ethyl-
from the supersaturation of metal vapour.96 Hollow particles can hexanoic acid can also be extended to the conversion of other low
even be formed if the metal precursor precipitates at the droplet cost materials such as acetates (Na, Ba, Sr, Bi),111 oxides (Ca,19,147
surface during solvent evaporation. In the case where an Mg,19 Ho111), hydroxides (Ca,110,148 Al76,124) and even carbonates
impermeable shell is formed, internal pressure build-up during (Na,111 Zr76). The higher viscosity of 2-ethylhexanoic acid
the evaporation of trapped solvent leads to fragmentation of the compared to water or ethanol has to be accounted for in nozzle
spherical shells.96 Subsequent solid-state reactions and densifi- design and liquid pump selection or dilution with e.g. xylene.
cation take place forming micron-sized metal oxides. In the case
when FSP is operated at high combustion enthalpy densities,
4. Particles formation and configurations by FSP
sufficient heat is provided to evaporate the precursor interme-
diate products to yield homogeneous fine particles, even at Tbp In the previous section, we identified the relevance of liquid
(solvent)/Td/mp(precursor) < 1 (Fig. 4d). precursor design to the formation of particles through the
By definition, the criteria for obtaining dense and homogenous droplet-to-particle or gas-to-particle routes, the latter ensures
fine particles can be achieved as long as the metal precursor, in its homogeneous morphologies and sizes. In this section, we further
pure form i.e. not dissolved in solvent, exists in liquid phase at review the different categories of particle configurations that may
ambient temperature i.e. Tmp(precursor) < Tbp(solvent) form in the gas-to-particle route in FSP. These particles form in
(Fig. 4c,f). Most metal alkoxides fall in this category, with the sequential stages of: (1) precursor spray evaporation/decompo-
exception of some precursors e.g. aluminium propoxide, which sition forming metal vapour; (2) nucleation as a result of
exists as solid crystals. In general, metal alkoxides in the form of supersaturation; (3) growth by coalescence and sintering; and (4)
methoxides to pentoxides, are commonly used in FSP for particles aggregation (forming hard agglomerates by chemical
a number of reasons: high volatilities, high combustion bonds) and agglomeration (forming soft agglomerates by mainly
enthalpies, miscibility in many organic solvents, low viscosity physical bonds) (Fig. 5). Since the general gas-to-particle mech-
and commercial availability (see Table 1). One drawback, besides anism has been well-studied and reviewed in the past, it will not
price, is the general moisture sensitivity of metal alkoxides, be repeated here, but readers are referred to previous literature
rendering their handling and preparation in a humidity-free for a more detailed understanding.5,101–103 Despite the common
Table 1 Selection of metal precursors reported for the FSP preparation of various oxide and non-oxide ceramic particles
Element Metal precursor Solvent Particles Additional remark Reference
Li Lithium–sodium– Ethanol Li-doped Na2O$xAl2O3 Refluxing of alumatrane + Sutorik et al.105

alumatrane–glycolate sodium hydroxide +
lithium hydroxide
hydrate (1 h), followed by
N2 distillation to remove
water and excess ethylene
glycol
Lithium tert-butoxide Tetrahydrofuran–toluene Li–ZnO Height et al.106
Tetrahydrofuran–xylene LiMn2O4, Li4Ti5O12, Ernst et al.26
LiFe5PO8
B Tributyl boride 2-Ethylhexanoic acid Borosilicate glass Brunner et al.107
Vollenweider et al.26
C Organic solvent Ethanol BaCO3 Strobel et al.74
Mineral spirit– C–Co Restricted oxygen flame, Grass et al.25
tetrahydrofuran C2H2
Tetrahydrofuran C–Cu Restricted oxygen flame Athanassiou et al.87,88
Tetrahydrofuran C–Cu Restricted oxygen flame, Athanassiou et al.109
This journal is ª The Royal Society of Chemistry 2010

C2H2
Xylene Pt/C and C/Pt Twin nozzles Ernst et al.91
Xylene–2-ethylhexanoic CaCO3 Osterwalder et al.110
acid
F Trifluoroacetic acid Xylene Ca10(PO4)6(OH)2xFx Loher et al.19
Hexafluorobenzene 2-Ethylhexanoic acid Bioglass Brunner et al.107
Xylene CaF2, SrF2, BaF2 Grass et al.111
Xylene F-MOx (MOx ¼ TiO2, Teoh et al.,112 Emeline
ZrO2) et al.113
Na Lithium–sodium– Ethanol Li-doped Na2O$xAl2O3 See Li Sutorik et al.105
alumatrane–glycolate
Sodium 2-ethylhexanoate 2-Ethylhexanoic acid– NaCl Sodium hydrogencarbonate Grass and Stark111
xylene + ethylhexanoic acid
Acetonitrile, HMDSO, Soda-lime glass Brunner et al.,107
tributyl phosphate, Vollenweider et al.108
tributyl borate,
fluorobenzene
Mg Magnesium 2- 2-Ethylhexanoic acid Mg–Ca3(PO4)2 Magnesium oxide + 2- Loher et al.19
ethylhexanoate ethylhexanoic acid
magnesium acetate Methanol Ni:MgO–SiO2 Suzuki et al.114
tetrahydrate Methanol–butanol Mg2SiO4 : Cr Tani et al.115
Methanol–water MgO Large and inhomogeneous Tani et al.116
MgO at high water
content
Magnesium acetylacetonate Tetrahydrofuran–ethanol MgO–Al2O3 Dissolve metal precursor in Hinklin and Laine33
solvent followed by
filtration to remove 0.5
wt% of residual solids
Magnesium pentanedionato Tetrahydrofuran–ethanol MgO–Fe2O3, MgO–Al2O3 Hinklin et al.117
Al Alumatrane Ethanol 3Al2O3.2SiO2 (mullite) Aluminium hydroxide Baranwal et al.29
hydrate +
triethanolamine +
ehtylene glycol (N2
distillation, 3–4 h to
remove water and
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Table 1 (Contd. )
ethylene glycol). Product

was recovered by vacuum
filtration
Al2O3:(Ce,Pr) Williams et al.118
CoOx–Al2O3 Azurdia et al.31
NiO–Al2O3 Azurdia et al.32
ZrO2–Al2O3 Kim and Laine119
(CeOx)x(Al2O3)1x Kim et al.120
Ethanol–tetrahydrofuran Al2O3 Hinklin et al.121
MgO–Al2O3 Hinklin and Laine33
Ethanol, tetrahydrofuran– Y3Al5O12 Marchal et al.122
1332 | Nanoscale, 2010, 2, 1324–1347

ethanol, aqueous ethanol
Methanol, butanol TiO2/Al2O3 Kim et al.123
Aluminium 2- 2-Ethylhexanoate–toluene Al2O3/ZrO2 Aluminium 2- Jossen et al.76
ethylhexanoate ethylhexanoate basic + 2-
ethylhexanoic acid
followed by N2
distillation to remove
water
Acetic acid anhydride–2- Al2O3/CexZr1xO2 Aluminium 2- Schulz et al.124
ethylhexanoic acid ethylhexanoate (16.5%
Al2O3) + acetic acid/2-
ethylhexanoic acid (N2
reflux, 2 h) followed by
acetic acid
Tetrahydrofuran Hastelloy Athanassiou et al.88
Aluminium acetylacetonate Ethanol–benzene Al2O3 Sokolowski et al.10,98
Ethanol–tetrahydrofuran Al2O3 Heating to 50 C for 1 h, Hinklin et al.121
and kept at 50 C
Methanol–acetic acid CuaMgbAlcOx Haider and Baiker125
M/Al2O3 (M ¼ Rh, Pt–Rh– Hannemann et al.,126 van
Ru, Rh–Ru or Pt–Rh) Vegten et al.127
Aluminium chloride Tetrahydrofuran–ethanol Al2O3 Hinklin et al.121
Aluminium sec-butoxide Butanol–2-propanol Al2O3 Tani et al.97
Diethylene glycol Pt–Ba/Al2O3 Strobel et al.,89 Piacentini
monobutyl ether/acetic et al.128
anhydride
Xylene Pd/Al2O3 Strobel et al.129
Pd/Al2O3 (film) In situ deposition Sahm et al.81,82
Pd/La2O3/Al2O3 Strobel et al.130
Pt–Rh–Ru/Al2O3 Hannemann et al.126
SiO2-coated Al–TiO2, SiO2/ In situ sequential flame Teleki et al.92–94
Al2O3/TiO2 coating
Xylene–acetonitrile Pt–Pd/Al2O3 Strobel et al.131
Aluminium isopropoxide Isopropanol Al2O3
Xylene–ethylacetate Pt/Al2O3 Maintained at 50 C to Strobel et al.132
prevent precipitation
Aluminium nitrate 2-propanol–methanol Al2O3 Tani et al.97
nanohydrate Deionised water–kerosene– Al2O3 Emulsion precursor Tani et al.97
surfactant (hexa(2-

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Table 1 (Contd. )
hydroxy-1,3-propylene
glycol) diricinoleate)
Ethanol, butanol Y3Al5O12 Marchal et al.122
Isopropanol Al2O3 Karthikeyan et al.,64
Tikkanen et al.133
Tetrahydrofuran–ethanol Al2O3 Hinklin et al.121
Lithium–sodium– Ethanol Li-doped Na2O$xAl2O3 see Li Sutorik et al.105
alumatrane–glycolate
Magna-alumatrane Ethanol MgO–Al2O3 Aluminium hydroxide Bickmore et al.28
glycolate hydrate + Magnesium
hydroxide hydrate +
triethanolamine +
ehtylene glycol (200 C
ethylene glycol and
water).
Al2O3 (predominantly Ethanol alpha-Al2O3 Flame spraying of slurries Laine et al.134

sigma, gamma, theta-
phase)
Si Hexamathyldisiloxane 2-Ethylhexanoic acid Bioglass Brunner et al.,107
(HMDSO) Vollenweider et al.108
Acetic acid–methanol SiO2, SiO2/ZnO M€adler et al.,135 Tani
et al.136,137
Deionised water–kerosene– SiO2, SiO2/ZnO Emulsion combustion Tani et al.67
hexa(2-hydroxy-1,3- (ECM), mixing at 10 000
propylene-gricol) rpm for 10 min
diricinoleate
Ethanol SiO2 Pilot-scale FSP Mueller et al.71
Ethanol, iso-octane, SiO2 M€adler et al.65
methanol
Methanol Ni:MgO–SiO2 Suzuki et al.114
Methanol–butanol Mg2SiO4 : Cr Tani et al.115
Methanol–hydrogen SiO2, SiO2/ZnO Tani et al.67
peroxide
Toluene–2-ethylhexanoic Ag/SiO2 Loher et al.138
acid
Xylene SiO2/Al2O3/TiO2 Teleki et al.92–94
SiO2/SnO2 In situ flame deposition- Tricoli et al.139
annealing
Xylene, pentane, hexane, SiO2 Jossen et al.47
octane, decane,dodecane,
tetradecane, hexadecane
SiO2 sol Deionised water–kerosene– SiO2, SiO2/ZnO Emulsion combustion Tani et al.67
hexa(2-hydroxy-1,3- (ECM), mixing at 10 000
propylene-gricol) rpm for 10 min
diricinoleate
TEA–Si–egH Ethanol 3Al2O3.2SiO2 (mullite) Silica + triethanolamine + Baranwal et al.29
ethylene glycol (N2
distillation, 3–4 h). TEA–
Si–egH is filtered and
washed with acetone. The
product is mixed with
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Table 1 (Contd. )
alumatrane and further

distilled (N2, 3–4 h) to
remove excess ethylene
glycol
Tetraethyl siloxane (TEOS) 2-Ethylhexanoic acid– SiO2/CexZr1xO2 Schulz et al.124
toluene
2-Ethylhexanoic acid– SiO2/BiVO4 Strobel et al.140
toluene
Acetonitrile–acetic Yb2O3/SiO2 M€adler et al.141
anhydride, xylene–acetic
anhydride/2-
1334 | Nanoscale, 2010, 2, 1324–1347

ethylhexanoic acid
Ethanol Y2SiO5 : Eu3+ Qin et al.142
Methanol–AcOH ZnO–SiO2 Ramin et al.143
Pentane, hexane, dodecane, Ta2O5/SiO2 Schulz et al.20
xylene, 2-ethylhexanoic
acid–toluene (all under
N2)
Toluene SiO2–V2O5–WO3–TiO2 Jossen et al.144
SiO2/ZrO2 Jossen et al.83
Xylene M/SiO2(M ¼ Au, Ag or Au– Hannemann et al.145
Ag)
Xylene–acetonitrile SiO2/Fe2O3 Li et al.22,146
Tetramethylsilane (TMS), Xylene SiO2 Jossen et al.54
HMDSO, tetramethyl
orthosilicate (TEMOS),
tetrepropyl orthosilicate
(TEPOS)
P Tributyl phosphate 2-Ethylhexanoic acid Ca10(PO4)6(OH)2xFx, Loher et al.19,147
Ca3(PO4)2, M–Ca3(PO4)2
(M ¼ Mg, Zn)
2-Ethylhexanoic acid– Ag/Ca3(PO4)2 Loher et al.138
toluene
Xylene FePO4 Rohner et al.21
S Dimethyl sulfoxide Xylene CaSO4 Osterwalder et al.110
Cl Hexachlorobenzene 2-Ethylhexanoic acid NaCl Grass and Stark111
Ca Calcium 2-ethylhexanoate 2-Ethylhexanoic acid Ca10(PO4)6(OH)2xFx, Calcium oxide + 2- Loher et al.19,146
Ca3(PO4)2, M–Ca3(PO4)2 ethylhexanoic acid
(M ¼ Mg, Zn)
Calcium hydroxide + 2- Brunner et al.147
ethylhexanoic acid
2-Ethylhexanoic acid– Ag/Ca3(PO4)2 Calcium hydroxide + 2- Loher et al.138
toluene ethylhexanoic acid
2-Ethylhexanoic acid– CaO, CaCO3, CaSO4 Calcium hydroxide + 2- Osterwalder et al.110
xylene ethylhexanoic acid (140

C, 3 h)
Glass and bioglass Brunner et al.,107
Vollenweider et al.108
Ti Titanatrane TiO2 TiO2 in ethylene glycol (EG) Bickmore et al.149
+ triethanolamine (200

C, 8 h) followed by

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Table 1 (Contd. )
EG. Resultant precursor

is hydrolytically stable
Methanol, butanol TiO2/Al2O3 Kim et al.123
Titanium tetraisopropoxide Propionic acid, 2- Au/TiO2 Chiarello et al.150
(TTIP) ethylhexanoic acid,
methanol, xylene,
pyridine
Toluene SiO2–V2O5–WO3–TiO2 Jossen et al.144
Xylene Nb–TiO2, Cu–TiO2 Teleki et al.151
M/TiO2 (M ¼ Au, Ag or Hannemann et al.145
Au–Ag)
SiO2-coated Al–TiO2, SiO2/ In situ sequential flame Teleki et al.92–94
Al2O3/TiO2 coating
Xylene–acetonitrile TiO2 Teoh et al.,151–154 Teleki
et al.155
Pt/TiO2 Schulz et al.,70 Teoh
et al.152,154

Fe–TiO2 Teoh et al.156
V2O5/TiO2 Schimmoeller et al.83
Ag/TiO2 Gunawan et al.157
Xylene–tetrahydrofuran Li4Ti5O12 Ernst et al.26
V Vanadium oxo- Toluene SiO2–V2O5–WO3–TiO2 Jossen et al.144
triisopropoxide Xylene–acetonitrile V2O5/TiO2 Schimmoeller et al.83
Vanadyl naphthenate Toluene–2-ethylhexanoic BiVO4 and SiO2/BiVO4 Strobel et al.140
acid
Cr Chromium 2- Mineral spirit– Hastelloy Restricted oxygen flame Athanassiou et al.88
ethylhexanoate tetrahydrofuran
Chromium acetate Methanol/butanol Mg2SiO4 : Cr Tani et al.115
Chromium acetylacetonate Diethylene glycol monbutyl Cr–WO3 Wang et al.158
ether/ethanol
Mn Manganese 2- Mineral spirit– Hastelloy Restricted oxygen flame Athanassiou et al.88
Xylene–tetrahydrofuran LiMn2O4 Ernst et al.26
Manganese acetylacetonate Xylene–tetrahydrofuran LiMn2O4 Ernst et al.26
Manganese nitrate Isopropanol Mn2O3 Karthikeyan et al.,64
Tikkanen et al.133
Fe Iron 2-ethylhexanoate Tetrahydrofuran Hastelloy Restricted oxygen flame Athanassiou et al.88
Iron acetylacetonate Xylene FePO4 Rohner et al.21
Xylene–acetonitrile Fe2O3, SiO2/Fe2O3 Li et al.22,23,146
Iron naphthenate Mineral spirit–xylene M/Fe2O3/Fe3O4 (M ¼ Au, Hannemann et al.145
Ag or Au–Ag)
Mineral sprit–xylene/ Fe–TiO2 Teoh et al.156
acetonitrile
Mineral sprit–xylene– LiFe5PO8 Ernst et al.26
tetrahydrofuran
Iron(III) nitrate Ethanol Nd : Co : Fe2O3 Dosev et al.159
Iron propionate Ethanol (MgO)x(Fe2O3)1x Hinklin et al.117
Co Cobalt 2-ethylhexanoate 2-Ethylhexanoic acid Co-soda lime glass Brunner et al.107
Mineral spirit– Co3O4, CoO, fcc–Co Restricted oxygen flame Grass and Stark24
tetrahydrofuran C–Co Restricted oxygen flame, Grass et al.25
C2H2
Co nanowire External magnetic field Athanassiou et al.109
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Table 1 (Contd. )
Xylene Co3O4, Co3O4–ZrO2, Ru– Teoh et al.160

Co3O4–ZrO2
Cobalt acetate tetrahydrate Carboxylic acids (acetic LaCoO3 Chiarello et al.161–163
acid, propionic acid,
butyric acid, hexanoic
acid, octanoic acid or 2-
ethylhexanoic acid)
Propionic acid–propanol– Pd/LaCoO3 Vigorous stirring at 60 C Chiarello et al.164,165
water
Cobalt nitrate tetrahydrate Ethanol Nd : Co : Fe2O3 Dosev et al.159
Propionic acid + alcohol LaCoO3 Chiarello et al.166
1336 | Nanoscale, 2010, 2, 1324–1347

(methanol, ethanol, 1-
propanol)
Cobalt propionate Ethanol Co3O4, NiO–Co3O4 Reactive distillation of Azurdia et al.167
cobalt nitrate
hexahydrate + propionic
acid under N2 sparging
(150 C, 6 h) to remove
water, propionic acid and
NOx
Ethanol–propionic acid CoOx–Al2O3 Cobalt nitrate hydrate + Azurdia et al.31
propionic acid under N2
sparging followed by
distillation (150 C, 6 h)
to remove water and NOx
Ni Nickel 2-ethylhexanoate Tetrahydrofuran Ni/Mo alloy Athanassiou et al.88
Nickel acetate Methanol Ni:MgO–SiO2 Suzuki et al.114
Nickel propionate Ethanol NiO, NiO–MOx (Mox ¼ Nickel nitrate hexahydrate Azurdia et al.167
Co3O4, MoO3, CuO) + propionic acid under
N2 sparging and
distillation (150 C, 4h) to
remove water, propionic
acid and NOx
Ethanol, ethanol–methanol, NiO–Al2O3 Reactive distillation of Azurdia et al.32
ethanol–butanol nickel nitrate
hexahydrate + propionic
acid under N2 sparging
water, propionic acid and
NOx
Cu Copper 2-ethylhexanoate Tetrahydrofuran C–Cu Restricted oxygen flame Athanassiou et al.87
Xylene Cu–TiO2 Teleki et al.151
Cu–SiO2 Height and Pratsinis168
Xylene, xylene–2- CuO, Cu–MOx (MOx ¼ Kydd et al.169,170
ethylhexanoic acid SiO2, Al2O3, TiO2,
CeO2,ZrO2)
Copper nitrate trihydrate Acetic acid–methanol CuaMgbAlcOx Haider and Baiker125
Copper propionate Ethanol CuO, NiO–CuO Reactive distillation of Azurdia et al.167
copper nitrate hydrate +
propionic acid under N2
sparging (150 C, 6 h) to

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Table 1 (Contd. )
remove water, propionic

acid and NOx
Zn Zinc acetate dihydrate Methanol–water ZnO Large and inhomogeneous Tani et al.116
ZnO at high water
content
Zinc acetylacetonate Methanol–AcOH ZnO–SiO2 Ramin et al.143
Colloidal SiO2 (Ludox)– ZnO–SiO2 Flame spraying of slurries Ramin et al.143
Methanol–AcOH
Zinc acrylate Acetic acid–methanol SiO2/ZnO M€adler et al.,135 Tani
et al.136,137
ZnO Tani et al.171
Zinc napthenate 2-Ethylhexanoic acid Zn–Ca3(PO4)2 Loher et al.19
Mineral spirit–ethanol ZnO, Ag/ZnO Height et al.172
Mineral spirit–toluene ZnO, M–ZnO (M ¼ In, Sn, Height et al.106
Li)
Y Yttrium 2-ethylhexanoate 2-Ethylhexanoic acid– Y2O3/ZrO2 Yttrium nitrate hexahydrate Jossen et al.76
ethanol + ethanol + 2-

ethylhexanoic acid (N2
distilled to remove
ethanol, water, NO)
2-Ethylhexanoic acid– Y2O3/ZrO2 Yttrium nitrate hexahydrate Jossen et al.75
toluene + ethanol + 2-
ethylhexanoic acid (120

C distillation to remove
ethanol, water, NO)
Toluene Y2O3 : Eu3+ Yttrium nitrate hexahydrate Camenzind et al.12,13
+ aqueous ammonia to
form Y(OH)3 followed by
refluxing with 2-
ethylhexanoic acid +
acetic acid (65 C, 4 h)
Tetrahydrofuran–ethanol Y3Al5O12 Marchal et al.122
Yttrium acetate Aqeuous acetic acid Y2O3/ZrO2 Karthikeyan et al.64
Yttrium acetylacetonate Ethanol Y3Al5O12 Marchal et al.122
Yttrium butoxide Toluene Y2O3/ZrO2 Jossen et al.76
Yttrium methoxyacetate Aqueous ethanol Y3Al5O12 Yttrium trichloride + Marchal et al.122
methoxyacetic acid
(reflux under N2,135 C,
2 h)
Yttrium nitrate hexahydrate Ethanol Y2O3/ZrO2 Inhomogeneous and Jossen et al.76
segregated Y2O3
Y2O3 : Eu3+ Dosev et al.14
Y2SiO5 : Eu3+ Qin et al.142
Ethanol, butanol Y3Al5O12 Marchal et al.122
Ethanol–acetic anhydride Y2O3/ZrO2 Slow addition of acetic Jossen et al.76
anhydride under N2.
Resulting NOx is bubbled
through NaOH.
Inhomogeneous and
segregated Y2O3
Yttrium propionate Ethanol, tetrahydrofuran Y3Al5O12 Marchal et al.122
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Table 1 (Contd. )
Yttrium nitrate hexahydrate

+ propionic acid (N2,145

C)
Zr Zirconyl 2-ethylhexanoate 2-Ethylhexanoic acid Pt/CexZr1x Stark et al.173
2-Ethylhexanoic acid– MOx/CexZr1xO2(MOx ¼ Acetic acid digested Schulz et al.124
toluene SiO2, Al2O3) zirconium carbonate + 2-
cerium acetate hydrate
(N2 distilled to remove
water and acetic acid)
Pt/Ba/CexZr1xO2 Twin nozzles Strobel et al.131
1338 | Nanoscale, 2010, 2, 1324–1347

Ethanol Y2O3/ZrO2 Zirconium carbonate Jossen et al.76
hydroxide oxide
dissolved in acetic acid
(50 C) + 2-ethylhexanoic
acid followed by
distillation (120 C) to
remove water and acetic
acid
Xylene Rh/CexZr1xO2 Hotz et al.174
Zirconium acetate Aqueous acetic acid Y2O3/ZrO2 Karthikeyan et al.64
Zirconium butoxide n-Butanol ZrO2 Karthikeyan et al.64
Zirconium propionate Ethanol ZrO2–Al2O3 Zirconium carbonate + 2- KimandLaine119
ethylhexanoic acid
followed by distillation
water and propionic acid
Zirconium propoxide Isopropanol–ethanol Y2O3/ZrO2 Jossen et al.76
Isopropanol–toluene MOx/ZrO2 (MOx ¼ SiO2, Jossen et al.75
La2O3, CeO2, Y2O3,
Al2O3)
Isopropanol–xylene ZrO2, Co3O4–ZrO2,Ru– Teoh et al.160
Co3O4–ZrO2
Zirconium Isooctane/acetic acid/ CeO2/ZrO2 Low boiling point solvent Stark et al.175
tetraacetylacetonate butanol resulting in segregated
ZrO2 and CeO2 phase
lauric acid/acetic acid CexZr1xO2 Heating to full dissolution Stark et al.175
Nb Niobium 2-ethylhexanoate Xylene Nb–TiO2 Teleki et al.151
Mo Ammonium molybdate Lactic acid MoO3, NiO–MoO3 Dissolve ammonium Azurdia et al.167
molybdate in aquoeus
lactic acid (heating >100

C, 2h) followed by
removal of excess water
and acid in rotary
evaporator
Molybdenum 2- Mineral spirit– Ni/Mo alloy Athanassiou et al.88
Ru Ruthenium acetylacetonate Xylene Ru–Co3O4–ZrO2 Teoh et al.160
Ruthenocen Xylene, methanol–acetic Pt–Rh–Ru/Al2O3, Rh–Ru/ Hannemann et al.126
acid Al2O3
Rh Rhodium 2-ethylhexanoate Xylene Rh/CexZr1xO2 Hotz et al.174

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Table 1 (Contd. )
Rhodium acetylacetonate Xylene, methanol–acetic M/Al2O3 (M ¼ Rh, Pt–Rh– Hannemann et al.,126 van
acid Ru, Rh–Ru or Pt–Rh) Vegten et al.127
Pd Palladium acetate Propionic acid–propanol– Pd/LaCoO3 Vigorous stirring at 60 C Chiarello et al.164,165
water
Palladium acetylacetonate Xylene M/Al2O3 (M ¼ Pd, Pt–Pd) Strobel et al.,129,131 Sahm
et al.81,82
Pd/La2O3/Al2O3 Strobel et al.130
Ag Silver acetate 2-Ethylhexanoate–toluene Ag/Ca3(PO4)2, Ag/SiO2 Loher et al.138
Silver benzoate Pyridine Ag/MOx (MOx ¼ SiO2, Hannemann et al.145
TiO2, Fe2O3/Fe3O4)
Xylene–TTIP Ag/TiO2 Gunawan et al.157
Silver nitrate Ethanol Ag/ZnO Height et al.172
Ag/TiO2 Keskinen et al.176,177
In Indium acetylacetonate Toluene In–ZnO Height et al.106
Sn Tin 2-ethylhexanoate Ethanol SnO2 (film) Sahm et al.16
Toluene SnO2, Pd/SnO2, Pt/SnO2 In situ flame deposition M€adler et al.,17,18 Sahm
(films) et al.81,82

Sn–ZnO Height et al.106
Xylene SnO2, SiO2/SnO2 In situ flame deposition- Kuhne et al.,178 Tricoli
annealing et al.78,139
Ba Barium(II) 2-ethylhexanoate Ethanol BaCO3 Strobel et al.74
Pt–Ba/Al2O3 Twin nozzles Strobel et al.,89 Piacentini
et al.128
2-Ethylhexanoic acid– Pt/Ba/CexZr1xO2 Twin nozzles Strobel et al.90
toluene
La Lanthanum 2- 2-Ethylhexanoic acid– La2O3/ZrO2 Lanthanum(III) Jossen et al.75
ethylhexanoate toluene acetylacetonate hydrate +
acetic anhydride + 2-
ethylhexanoic acid
(distilled under N2 to
remove acetic acid,
acetylacetonate, water)
Lanthanum acetate Carboxylic acids (Acetic LaCoO3 Chiarello et al.161–163
dihydrate acid, propionic acid,
butyric acid, hexanoic
acid, octanoic acid, 2-
ethylhexanoic acid)
Propionic acid–propanol– Pd/LaCoO3 Vigorous stirring at 60 C Chiarello et al.164,165
water
Lanthanum isopropoxide Xylene Pd/La2O3/Al2O3 Strobel et al.130
Ta Tantalum ethoxide, Pentane, hexane, dodecane, Ta2O5/SiO2 Schulz et al.20
tantalum butoxide, xylene, 2-ethylhexanoic
tantalum acid–toluene (all under
tetraethylacetonate N2)
W Ammonium tungstate Diethylene glycol monbutyl WO3, Cr–WO3 Wang et al.158
hydrate ether–ethanol
Tungsten benzyl alkoxide Benzyl alcohol WO3 Vigorous stirring of WCl4 or Pokhrel et al.179
WCl6 in benzyl alcohol
for 8 h at 20 C until pH
4.5. Gaseous HCl is
liberated.
Tungsten carbonyl Tetrahydrofuran WO3 Pokhrel et al.179
Nanoscale, 2010, 2, 1324–1347 | 1339

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Table 1 (Contd. )
Tungsten ethoxide Toluene SiO2–V2O5–WO3–TiO2 Jossen et al.144

Pt Platinum acetylacetonate 2-Ethylhexanoic acid Pt/CexZr1xO2 Stark et al.173
toluene
Ethanol Pt–Ba/Al2O3 Twin nozzles Strobel et al.,89 Piacentini
et al.128
Toluene Pt/SnO2 (films) M€adler et al.17,18
Xylene Pt/C and C/Pt Twin nozzles Ernst et al.91
Xylene–acetonitrile Pt/TiO2 Teoh et al.152,154
Xylene–ethyl acetate Pt/Al2O3 Strobel et al.132
Xylene, methanol/acetic M/Al2O3 (M ¼ Pt–Rh–Ru, Hannemann et al.126
1340 | Nanoscale, 2010, 2, 1324–1347

acid Pt–Rh)
Au Dimethyl gold(III)- Xylene Au/MOx, Au–Ag/MOx Extremely moisture- and Hannemann et al.145
acetylacetonate (MOx ¼ TiO2, SiO2, thermal-sensitive
Fe2O3/Fe3O4) precursor
Xylene–pyridine Au/TiO2 Chiarello et al.150
Gold chloride Acetonitrile–2- Au-soda lime glass Brunner et al.107
ethylhexanoic acid
Xylene–acetonitrile Au/MOx (MOx ¼ TiO2, M€adler et al.180
SiO2)
Gold-triphenylphosphine- Tetrahydrofuran/isooctane Au/TiO2 (film) Thybo et al.77
nitrate
Bi Bismuth 2-ethylhaxanoate 2-Ethylhexanoic acid– BiVO4 and SiO2/BiVO4 Strobel et al.140
toluene
Mineral spirit– Bi Restricted oxygen flame Grass and Stark86
tetrahydrofuran CeO2/Bi Grass et al.181
Bismuth acetate Acetic acid, nitric acid and Bi2O3 Bismuth trinitrate M€adler and Pratsinis96
ethanol pentahydrate + acetic
acid in an ethanol/nitric
acid medium
Bismuth trinitrate Nitric acid–alcohol (alcohol Bi2O3 M€adler and Pratsinis,96
pentahydrate ¼ methanol, ethanol, Jossen et al.47
methoxy propanol,
ethoxy ethanol,
propylene glycol
propylether, diethylene
glycol-monoethylether
Ce Cerium 2-ethylhexanoate 2-Ethylhexanoic acid Pt/CexZr1xO2 Stark et al.173
toluene
Xylene Rh/CexZr1xO2 Hotz et al.174
Cerium acetate hydrate 2-Ethylhexanoic acid– MOx/CexZr1xO2 (MOx ¼ Acetic acid digested Schulz et al.124
toluene SiO2, Al2O3) zirconium carbonate + 2-
cerium acetate hydrate
(N2 distilled to remove
water and acetic acid)
Acetic acid CeO2 Inhomogeneous particle size M€adler et al.66
Acetic acid–isooctane– CeO2 Homogeneous particle size M€adler et al.66
butanol CeO2/ZrO2 Low boiling point solvent Stark et al.175
resulting in segregated
ZrO2 and CeO2 phase

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Table 1 (Contd. )
Lauric acid–acetic acid CexZr1xO2 Heating to full dissolution Stark et al.175

Cerium(III) nitrate Ethanol Al2O3 : Ce Williams et al.118
Cerium(III) octoate 2-Ethylhexanoic acid– CexZr1xO2 Jossen et al.75
toluene
Tetrahydrofuran CeO2/Bi Restricted oxygen flame Grass et al.181
Cerium propionate Ethanol (CeOx)x(Al2O3)1x Reaction distillation of Kim et al.120
cerium carbonate with
propionic acid (120 C, 2
h, flowing N2)
Pr Praseodymium(III) nitrate Ethanol Al2O3 : Pr Williams et al.118
Nd Neodymium(III) nitrate Ethanol Nd : Co : Fe2O3 Dosev et al.159
Eu Europium 2-ethylhexanoate Toluene Y2O3 : Eu3+ Camenzind et al.12,13
Europium(III) nitrate Ethanol Y2O3 : Eu3+ Dosev et al.14
Eu : Gd2O3 Goldys et al.182
Y2SiO5 : Eu3+ Qin et al.142
Nd : Co : Fe2O3 in ethanol Eu : Gd2O3/ Flame spraying of slurry Dosev et al.159
slurry Nd : Co : Fe2O3

Gd Gadolinium(III) nitrate Ethanol Eu : Gd2O3 Goldys et al.182
Nd : Co : Fe2O3 in ethanol Eu : Gd2O3/ Flame spraying of slurry Dosev et al.159
slurry Nd : Co : Fe2O3
Ho Holmium 2-ethylhexanoate 2-Ethylhexanoic acid Ho–BaF2 Holmium oxide in 2- Grass and Stark111
ethylhexanoic acid
Yb Ytterbium 2-ethylhexanoate Xylene Yb2O3/SiO2 Reactive distillation of M€adler et al.141
yttrium nitrate + 2-
ethylhexanoic acid (N2,
107 C)
Ytterbium nitrate Acetonitrile–acetic Yb2O3/SiO2 M€adler et al.141
pentahydrate anhydride–acetic acid
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Fig. 5 The formation of different particle configurations via the gas-to-

particle mechanism for single and multicomponent systems. Please refer to
the text for details. Although not shown in the Figure, the stage of droplet
Fig. 6 Examples of as-prepared metal oxides of different morphologies
spray should in the context of FSP, precede the metal vapour stage.
made by FSP, varying from: (a) hexagonal/octagonal platelet g-Fe2O3;

(b) slightly oblonged ZnO; (c) spherical TiO2; and (d) rhomboid-shaped
route to particle formation under the classification of gas-to- CeO2 with sharp edges.
particle, the uniqueness of every material system prohibits
generalisation of each particle configuration predictably. Prior
insights of the materials properties and thermodynamic need to formation and growth takes place. Besides obtaining larger
be taken into account in relevance to the flame conditions. Fig. 5 particle sizes, the technique is unique in the reduction of crystal
summarises all the particle configurations (and combinations) defects such as those achieved in enhanced magnetic moment of
obtained by FSP to date. It must be mentioned that the details of g-Fe2O323,146 as well as the decreased electron capacitance of
particles formation on most of these routes were based only on TiO2 nanoparticles in dye-sensitised solar cells due to elimination
the most current conceptual understanding, rather than proven of charge trapping sites.191
experimentally. Oxygen containing anions such as phosphates19,21 and sulfates
Flame spraying of single metal component precursors in open (currently limited only to group II metal i.e. Ca2+)110 can also
ambient (air) condition produces of simple oxides or carbonates form in the presence of P and S, respectively. The high reactivity
in the case of alkaline metals through reaction with the CO2- of group II metals is particularly interesting as it allows the
laden flame (Fig. 5, Route I). A wide range of elements across the formation of fluorides (BaF2, CaF2, SrF2) even in the presence of
periodic table, from MgO to Yb2O3, have been synthesised via air,111 due to the higher affinity of F towards this group of
this route (see Fig. 6 and Table 1). The high entrainment of metals compared to oxygen anionic species (i.e. oxides and
ambient air72 during particle synthesis provides a continuous and carbonates). Likewise, NaCl salts can be synthesised in the
excess supply of O2 to the flame (oxidizing). Coupled with high presence of Cl.111
flame temperatures, these are the reasons that minimal amount Enclosure of FSP in an inert environment in practice
of carbon soot formed on the metal oxide surfaces in this process. suppresses the amount of external O2 being entrained (limiting
The high temperature formation in the flame renders high O2 solely from internally delivered sources i.e. dispersant and
thermal stability of the as-prepared particles as compared to sheath gases), and depending on the oxidising affinity of the
other lower temperature wet techniques.66,190,191 carbon precursor and that of the metal compound, could yield
Additionally, highly crystalline nanoparticles are often metallic nanoparticles (Fig. 2 IX).24 To date however, only the
produced by FSP, as induced by the high flame temperature FSP synthesis of metallic Co,24,109 Bi86 and Cu87,193 have been
crystallisation. The polymorphic structures of some oxides, such reported, where metallic Bi must be kept under anaerobic
as TiO2,152,192 Y2O312 and WO3,158,179 can be designed by capi- conditions to prevent rapid oxidation to Bi2O3, while metallic Co
talising the inter-relationship of flame synthesis and materials and Cu nanoparticles are protected either by a surface oxide or
characteristics. Only in a few instances are amorphous materials carbon layer (Fig. 5, Route II). The latter is formed when the
such as that in SiO265,135 and C91 obtained due to insufficient total amount of O2 provided is less than needed for total
residence time and/or flame temperatures. Extension of the high combustion of all carbon sources, allowing deposition of
temperature flame regime is achievable by enclosing the FSP carbonaceous layers in the form of soot, graphene or graphite. In
flame in a quartz tube, where external entrainment of ambient air some cases C2H2, CO or H2 can be provided externally to the
is prevented while conserving the convection heat within the spray flame to induce higher degree of reduction and yield highly
tube.155 Doing so extends the residence time at which aerosol ordered carbonaceous deposition layers.25,193
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The particle formation paths in multicomponent systems are

far more complex than single components. A wide range of
particle configurations and their permutations are possible,
dictated by the kinetics and thermodynamics of the component
mixture. Hereby, we present the most general classes of particle
configurations for multicomponents (Fig. 5, Route II–VI). In
highly complex systems, particularly those comprising a large
number of elements with different properties, combinations of
two or more configurations from Route I–IV are indeed possible.
Direct encapsulation of a secondary component metal or metal
oxide shell or even carbonaceous coating is a demanding process
due to the difficult entropic requirements. The possibilities exist
for the formation of composite materials (e.g. complex oxides,
solid solutions) as well as interparticle phase segregations. To
maintain an even coating morphology, favourable and strong

interfacial interaction between the two components, besides
higher amount of the coating component than the solid-state
solubility limit, are required at the stage where the secondary
component is precipitated. Phase segregation could result if the
temperature-dependent interfacial interaction is weaker than
that required to maintain homogeneous coating. To date, only
a small number of such systems prepared by direct flame Fig. 7 Examples of FSP-made supported noble metals on various metal
spraying of the components mixture have been achieved i.e.
oxide supports prepared in a single step, as illustrated in Route III – (a)

SiO2124 and Al2O3124,194 coatings on CexZr1xO2, as well as TiO2 Au/CeO2, (b) Pt/TiO2, (c) Au/SiO2/g-Fe2O3 and (d) Ag/TiO2.
on CeO2.195 In situ sequential coating technique (Fig. 2, XI and
Section 2) capitalizes on the introduction of the secondary
component at a stage where the primary component is fully miscibility of deposit-support materials should also be taken into
formed, and which temperature and remaining residence time is consideration. This is particularly important when the deposits
sufficiently low to avoid segregation of the homogeneous are nucleated at high temperature where solid-state reaction, e.g.
encapsulation layer.92–95 phase miscibility, formation of complex oxides, with support
In the case where full encapsulation is not attainable, either materials is non-negligible. To circumvent this limitation, the
due to insufficient amount of the secondary component or support and deposit materials can be precipitated separately in
occurrence of phase segregation (as small deposits), a supported a twin-nozzle configuration (Fig. 2 X), interfacing both flames at
metal/metal oxide on another metal oxide component can result a point with desirable extent of solid-state reactions.91 Rapid
(Fig. 5, Route III). Most notably, deposition of the secondary quenching of the flame at the stage of post-precipitation of noble
component as fine noble metals (Ru, Rh, Pd, Ag, Pt to Au) or metal deposits is another effective technique in limiting the
even alloys on various metal oxide supports such as Al2O3, TiO2, deposit/support sintering70 (Fig. 2, VIII).
ZnO, SiO2, CexZr1xO2, etc. have been reported by FSP (see Because the deposit/support particles are formed at high
Fig. 7, Table 1). Such morphologies have been largely explored temperature, they (i.e. dispersion of metal deposits, Fig. 5, Route
for catalytic applications,7,196 while others such as gas III) are often presumed to exhibit high thermal stability. While
sensors18,81,82,197 and antimicrobial138,168,157 applications also this may be true,132 but depending on the metal-support inter-
exist. In many cases, the low boiling/sublimation points of the actions, they may be subjected to significant loss in metal
noble metals relative to that of the oxide supports allow dispersion when overly exposed to very high temperatures. For
sequential nucleation and growth along the concentration instance, the initially highly-dispersed Pd deposits (on Al2O3)
gradient of the spray flame.70,129,132,152 The support metal oxide is sinter significantly from 5 nm to 50–150 nm when exposed to
first nucleated at high temperature followed by that of noble 1000 C,130 rendering them indifferent from other lower
metals at cooler downstream gas temperature. The rapid temperature preparations. Besides surface dispersion, the
quenching and short residence time of the spray flame is oxidation state of the as-prepared metal deposits is an important
advantageous here as it prevents significant sintering of the noble characteristic that should not be overlooked. It has direct influ-
metals upon deposition on support and therefore maintains high ence on some targeted end applications, including, catalytic
surface dispersion of deposits (Fig. 7). Strong metal (or deposit)– hydrogenation,132 photocatalysis154 and antimicrobial.157 Other
support interaction is another factor governing its dispersion, as non-precious metals deposit/support structures that have been
the strong interaction limits the mobility (and hence sintering) of synthesised via Route III are V2O5/TiO283,197 and CuO/
the deposits at high flame temperatures. See for example ref. 130– CeO2.169,198
132 on the effect of Pt–Pd alloy deposits on Al2O3, as compared In some multicomponent systems, the different particle phases
to deposits in their pure forms. tend to segregate completely with little miscibility allowing only
Despite the elegance of Route III synthesis, it is somewhat physical inter-particle mixing (Fig. 5, Route IV). Achieving such
limited by the thermodynamic properties of the deposit-support, configuration during co-precipitation in a single flame is usually
where besides the difference in boiling points, solid-state phase rare as multicomponent solid state reaction or mixing at an
View Online
Fig. 8 Examples of embedded core particle systems prepared by a single-step FSP as depicted in Route V – (a) single core and (b) multicore g-Fe2O3 in
a single SiO2 matrix and (c) ZnO cores in amorphous SiO2 matrix. Figure (c) adapted with permission from ref. 136.
atomic level is usually inevitable at high temperature. CeO2/Bi Y3Al5O12,122 LaCoO3,161–163 CoOx–Al2O3,31 NiO–Al2O3,32
prepared in a restrictive oxygen flame is the only such system LiMn2O4, Li4Ti5O12, LiFe5O8,26 BiVO4.140,200,201 In the event of
reported so far.181 By adopting a more engineering approach multicomponent synthesis in restrictive oxygen flames, even
such as that in the twin nozzle synthesis of Pt/Ba/Al2O3, the alloys such as Ni/Mo could be achieved.88
interaction of Pt/BaCO3 and Al2O3 was deliberately kept apart
by separate precipitations in independent spray flames and only
5. Concluding remarks and perspectives
mixed at a point where the flame temperature was low enough to
avoid solid-state reactions between the two phases.89 Formation The advancement of FSP currently lies at the intersection of
of BaAl2O4 is detrimental to the NOx storage capacity during combustion science, aerosols technology and materials chem-
catalytic deNOx applications.89,128 The same concept was adop- istry. As such, the interdisciplinary knowledge of all intersecting
ted for the flame mixing of Pt/BaCO3 and CexZr1xO2.90 fields is not only inevitable but is becoming increasingly impor-
Segregation of phases could also take place within a single tant in the design of flame-made nanoparticles. As in the past
particle host matrix (Fig. 5, Route V) such as that of SiO2/ decade, innovations in FSP technology, in terms of reactor
ZnO135–137 and SiO2/g-Fe2O322,146 (Fig. 8). In these systems, engineering and particles design, will continue to be applications-
molten SiO2 is thought to envelope the precipitated particles i.e. driven. In terms of industrial applications, FSP is a proven
ZnO or g-Fe2O3 producing a multicore structure (see Fig. 8b,c), scalable and high throughput process unmatched by other wet
while the encapsulation layer acts as diffusion barrier, retarding chemical techniques.67,71,75 Formulation of liquid precursors,
the agglomeration and sintering of the core particles.22,199 One of which was previously perceived to be a ‘‘stumbling block’’
the features of such configuration is the phase immiscibility or requiring expensive and moisture-sensitive chemicals, is now
limited solid-state reactions between the core particles and the reasonably well-understood. In fact, high quality metal precur-
encapsulation layer, despite being in intimate contact. This could sors can now be synthesised from cheap raw materials through
possibly arise from the limited thermodynamic miscibility of the various routes, even though more work is still required in the
two phases at the encapsulation temperature, or the formation of area of precious metals.
mixed oxide layers at the phase boundary that further suppressed In terms of particle homogeneity, it is often limited by the so-
the miscibility. called self preserving size distributions (SPSD), which forms the
For systems where general homogeneous mixing between asymptotic limit of polydispersity for particles growth by
multicomponents at intra-particle level are preferred and Brownian coagulation, giving number geometric standard devi-
depending on the states as well as their nature of mixing, a wide ation of 1.46.5 However, there is increasing demand especially
variety of configurations could result, ranging from substitu- in bioapplications for particles with much narrower size distri-
tionally-doped systems, solid solutions, dispersed mixed oxides, bution (high monodispersity), whilst maintaining high particle
complex metal oxides (perovskite, spinel, etc.) to metal alloys. purity and crystallinity. Exclusive particle growth by surface
Such particle configuration in route VI (Fig. 5) is exclusive to condensation rather than coagulation is one possibility102 but the
highly miscible multi-elements. The bottom-up synthesis and implementation of such restrictive system is highly challenging,
high synthesis temperature in FSP can be advantageous in especially within the harsh spray flame conditions. Manipula-
enhancing substitutional dopant concentrations, while its steep tions of flame combustion, fluid and aerosol dynamics is neces-
temperature gradient and short residence time prevent segrega- sary to achieve this task.
tion of the dopants.156 A classic example of perfect solid solutions As for the production of non-oxygen containing ceramics,
by FSP is that of CexZr1xO2, which was obtainable when using only group II metal fluorides have been reported by FSP to
high boiling point solvents (i.e. gas-to-particle route) to ensure date.111 The synthesis of metal carbides, nitrides, phosphides and
good distribution of precursor in the flame.175 Unlike solid sulfides are still elusive in FSP, while the synthesis of SiC and
solutions, Ta2O5/SiO220 and Co3O4/ZrO2160 retain the individual Si3N4 has been shown to be possible by VAFS, using SiH4
crystallite structures, while still achieving physical dispersity precursors.202,203 A requirement for such systems would be to
within a single particle matrix. A large family of complex metal restrict the presence of O2 which would otherwise result in the
oxides involving the oxide of two or more metals also fall in this formation of metal oxides, carbonates, phosphates or sulfates.
route VI configuration: MgAl2O4,28,33 3Al2O3 $ 2SiO2,29 Creation of anisotropic materials or particle shape control by
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FSP is also lacking. Besides CeO2 rhomboids,66 BaF2 cubes,111 15 T. R. Hinklin, J. Azurdia, M. Kim, J. C. Marchal, S. Kumar and
(In, Sn)-doped ZnO nanorods106 and g-Fe2O3 hexagonal/octag- R. M. Laine, Adv. Mater., 2008, 20, 1270.
16 T. Sahm, L. M€adler, A. Gurlo, N. Bârsan, S. E. Pratsinis and
onal platelets,22,23 most other FSP-derived particles are spherical. U. Weimar, Sens. Actuators, B, 2004, 98, 148.
Moreover, most of these non-spherical shapes are naturally 17 L. M€adler, A. Roessler, S. E. Pratsinis, T. Sahm, A. Gurlo,
occurring in the flame thereby providing little flexibility in terms N. Barsan and U. Weimar, Sens. Actuators, B, 2006, 114, 283.
of shape manipulation. Magnetically-assisted formation of 18 L. M€adler, T. Sahm, A. Gurlo, J. D. Grunwaldt, N. Barsan,
U. Weimar and S. E. Pratsinis, J. Nanopart. Res., 2006, 8, 783.
metallic Co nanowires by FSP reported recently marks the 19 S. Loher, W. J. Stark, M. Maciejewski, A. Baiker, S. E. Pratsinis,
beginning of externally-induced shape control by FSP.109 More D. Reichardt, F. Maspero, F. Krumeich and D. Gunther, Chem.
work in this direction is required, for example, template-assisted, Mater., 2005, 17, 36.
20 H. Schulz, L. M€adler, S. E. Pratsinis, Burtscher and N. Moszner,
thermophoretically- or electrophoretically-induced flame aero- Adv. Funct. Mater., 2005, 15, 830.
sols alignment and assemblies. 21 F. Rohner, F. O. Ernst, M. Arnold, M. Hilbe, R. Biebinger,
In the last few years, we have seen successful combinations of F. Ehrensperger, S. E. Pratsinis, W. Langhans, R. F. Hurrell and
FSP-derived inorganic particles with organic materials particu- M. B. Zimmermann, J. Nutr., 2007, 137, 614.
22 D. Li, W. Y. Teoh, C. Selomulya, R. C. Woodward, R. Amal and
larly for bioapplications, namely dental fillers,20,141 bioactive
B. Rosche, Chem. Mater., 2006, 18, 6403.

polymer films147 and magnetic particles with drug delivery204,205 23 D. Li, W. Y. Teoh, C. Selomulya, R. C. Woodward, P. Munroe and
as well as magnetic resonance imaging205,206 functions. This R. Amal, J. Mater. Chem., 2007, 17, 4876.
24 R. N. Grass and W. J. Stark, J. Mater. Chem., 2006, 16, 1825.
requires the coupling of predesigned flame particles with func-
25 R. N. Grass, E. K. Athanassiou and W. J. Stark, Angew. Chem., Int.
tional organic molecules such as DNA, protein, polymers and Ed., 2007, 46, 4909.
surfactants. More developments in this regard, encompassing 26 F. O. Ernst, H. K. Kammler, A. Roessler, S. E. Pratsinis,
various areas of applications from functional pigments, sensors W. J. Stark, U. Ufheil and P. Novak, Mater. Chem. Phys., 2007,
101, 372.
to bioelectronics are expected to take place in the near future. Of 27 T. J. Patey, R. B€ uchel, S. H. Ng, F. Krumeich, S. E. Pratsinis and
equal importance is the fabrication of flame particles-based P. Novak, J. Power Sources, 2009, 189, 149.
devices as readily demonstrated for gas sensors.17,85,178 Other 28 C. R. Bickmore, K. F. Waldner, D. R. Treadwell and R. M. Laine, J.
potential devices such as solar cells, fuel cells, batteries, lab-on-a- Am. Ceram. Soc., 1996, 79, 1419.
29 R. Baranwal, M. P. Villar, R. Garcia and R. M. Laine, J. Am.
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long-range ordering of these particles as-prepared via FSP, with 30 A. C. Sutorik and M. S. Baliat, Mater. Sci. Forum, 2002, 386–388,
or without templating, and their further assemblies in devices 371.
31 J. Azurdia, J. Marchal and R. M. Laine, J. Am. Ceram. Soc., 2006,
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32 J. A. Azurdia, J. Marchal, P. Shea, H. Sun, X. Q. Pan and
Acknowledgements R. M. Laine, Chem. Mater., 2006, 18, 731.
33 T. R. Hinklin and R. M. Laine, Chem. Mater., 2008, 20, 553.
The authors gratefully acknowledge Prof. Sotiris E. Pratsinis 34 Nanomaterials08, http://www.nanomaterials08.com/sponsor_exhibit.
php, accessed 20 October 2008.
(ETH Z€ urich) and Prof. Jan-Dierk Grunwaldt (Technical 35 F. Klopfer German Patent DE 762,723, 1942.
University of Denmark) for their insightful comments and 36 Degussa, Aerosil brochure, 2004.
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38 M. Formenti, F. Juiliet, P. Meriaudeau, S. J. Teichner and
Dr Richard Kydd and Yung Kent Kho (UNSW) and Dr Frank
P. Vergnon, J. Colloid Interface Sci., 1972, 39, 79.
Krumeich (ETH Z€ urich) for many of the electron microscopy 39 P. T. Spicer, C. Artelt, S. Sanders and S. E. Pratsinis, J. Aerosol Sci.,
images presented in this review. W. Y. T. and R. A. thank the 1998, 29, 647.
Australian Research Council (ARC) for financial support on 40 H. K. Kammler and S. E. Pratsinis, J. Mater. Res., 2003, 18, 2670.
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REVIEW www.rsc.org/nanoscale | Nanoscale

Flame spray pyrolysis: An enabling technology for nanoparticles design and

Wey Yang Teoh is an ARC Rose Amal is an ARC Austra-

some cases, combination of the two is also possible (e.g. C/TiO2,

Lutz M€ adler (Dr -Ing. Univ.

3. Designing of liquid precursors

environment necessary. Very recently, a facile conversion of

tranes such as Sr–Si–Al, Ba–Si–Al and Al–Mg28 were syn-

Element Metal precursor Solvent Particles Additional remark Reference

Li Lithium–sodium– Ethanol Li-doped Na2O$xAl2O3 Refluxing of alumatrane + Sutorik et al.105

This journal is ª The Royal Society of Chemistry 2010

Nanoscale, 2010, 2, 1324–1347 | 1331

Element Metal precursor Solvent Particles Additional remark Reference

ethylene glycol). Product

1332 | Nanoscale, 2010, 2, 1324–1347

This journal is ª The Royal Society of Chemistry 2010

Element Metal precursor Solvent Particles Additional remark Reference

This journal is ª The Royal Society of Chemistry 2010

Nanoscale, 2010, 2, 1324–1347 | 1333

Element Metal precursor Solvent Particles Additional remark Reference

alumatrane and further

1334 | Nanoscale, 2010, 2, 1324–1347

This journal is ª The Royal Society of Chemistry 2010

Element Metal precursor Solvent Particles Additional remark Reference

EG. Resultant precursor

This journal is ª The Royal Society of Chemistry 2010

Nanoscale, 2010, 2, 1324–1347 | 1335

Element Metal precursor Solvent Particles Additional remark Reference

Xylene Co3O4, Co3O4–ZrO2, Ru– Teoh et al.160

1336 | Nanoscale, 2010, 2, 1324–1347

This journal is ª The Royal Society of Chemistry 2010

Element Metal precursor Solvent Particles Additional remark Reference

remove water, propionic

This journal is ª The Royal Society of Chemistry 2010

Nanoscale, 2010, 2, 1324–1347 | 1337

Element Metal precursor Solvent Particles Additional remark Reference

Yttrium nitrate hexahydrate

1338 | Nanoscale, 2010, 2, 1324–1347

This journal is ª The Royal Society of Chemistry 2010

Element Metal precursor Solvent Particles Additional remark Reference

This journal is ª The Royal Society of Chemistry 2010

Nanoscale, 2010, 2, 1324–1347 | 1339

Element Metal precursor Solvent Particles Additional remark Reference

Tungsten ethoxide Toluene SiO2–V2O5–WO3–TiO2 Jossen et al.144

1340 | Nanoscale, 2010, 2, 1324–1347

This journal is ª The Royal Society of Chemistry 2010

Element Metal precursor Solvent Particles Additional remark Reference

Lauric acid–acetic acid CexZr1xO2 Heating to full dissolution Stark et al.175

This journal is ª The Royal Society of Chemistry 2010

Nanoscale, 2010, 2, 1324–1347 | 1341

Fig. 5 The formation of different particle configurations via the gas-to-

made by FSP, varying from: (a) hexagonal/octagonal platelet g-Fe2O3;

The particle formation paths in multicomponent systems are

maintain an even coating morphology, favourable and strong

oxide supports prepared in a single step, as illustrated in Route III – (a)

B. Rosche, Chem. Mater., 2006, 18, 6403.

1356. 107 T. J. Brunner, R. N. Grass and W. J. Stark, Chem. Commun., 2006,

Flame, 2006, 144, 809. 113 A. V. Emeline, N. V. Sheremetyeva, N. V. Khomchenko,

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