Smirnova 2016

CH08CH14-Smirnova ARI 23 March 2017 17:17
V I E W Review in Advance first posted online

E on April 3, 2017. (Changes may
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still occur before final publication
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online and in print.)
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D V A
Aerogels in Chemical
Engineering: Strategies
Toward Tailor-Made Aerogels
Annu. Rev. Chem. Biomol. Eng. 2017.8. Downloaded from www.annualreviews.org
Access provided by University of Sherbrooke on 04/04/17. For personal use only.
Irina Smirnova and Pavel Gurikov

Institute of Thermal Separation Processes, Hamburg University of Technology,
21073 Hamburg, Germany; email: irina.smirnova@tuhh.de
Annu. Rev. Chem. Biomol. Eng. 2017. Keywords

8:14.1–14.28
supercritical drying, coating, surface modification, sol-gel, biopolymers,
The Annual Review of Chemical and Biomolecular
Engineering is online at chembioeng.annualreviews.org carbon dioxide
https://doi.org/10.1146/annurev-chembioeng- Abstract
060816-101458
The present review deals with recent advances in the rapidly growing field
Copyright c 2017 by Annual Reviews.
All rights reserved of aerogel research and technology. The major focus of the review lies in
approaches that allow tailoring of aerogel properties to meet application-
driven requirements. The decisive properties of aerogels are discussed with
regard to existing and potential application areas. Various tailoring strate-
gies, such as modulation of the pore structure, coating, surface modification,
and post-treatment, are illustrated by results of the last decade. In view of
commercialization of aerogel-based products, a panorama of current indus-
trial aerogel suppliers is given, along with a discussion of possible alternative
sources for raw materials and precursors. Finally, growing points and per-
spectives of the aerogel field are summarized.
14.1
Changes may still occur before final publication online and in print
1. INTRODUCTION AND MOTIVATION

Aerogels are the lightest solid materials known and produced nowadays at an industrial scale. They
Gel: a nonfluid have fascinated generations of researchers since their invention in the 1930s (1). Generally, they
colloidal network or are low-density (typically <0.2 g cm−3 ), high-porosity (>90% v/v) nanostructured solids obtained
polymer network that by drying almost any kind of wet gel under conditions that preserve their volume (2). Thereby
is expanded
the gels can be formed as monoliths or particles of different shapes and sizes. Depending on the
throughout its whole
volume by a fluid type and mechanical stability of the gels, different drying processes can be applied. Usually the
solvent filling the pores is converted or exchanged by supercritical fluid and subsequently vented
Supercritical fluid:
the defined state of a out (Figure 1), eliminating the capillary forces that would collapse the nanostructure during a
compound or mixture simple evaporative drying. However, in some cases, this effect can also be achieved by freeze drying
above its critical or even evaporative drying, if the gel structure is strong enough to withstand ice crystal growth
pressure and critical or capillary forces. Additionally, gels with modified surfaces may exhibit a spring-back that allows
temperature
for evaporative drying without significant pore collapse.
The initial gel can be produced from any organic or inorganic precursor or their combinations
capable of forming a stable 3D network in a suitable solvent. Therefore, we have at least two degrees
of freedom in aerogels production: the starting material and its processing after gel formation.
Perhaps owing to this enormous variability in possible combinations, there is still no common
consensus on how to define the term aerogel. Several definitions are suggested in the literature.
IUPAC defines an aerogel as “a gel comprised of a microporous solid in which the dispersed
phase is a gas” (3). However, zeolites and microporous glass fall within this definition, making
it too general and inconvenient for the aerogel community. Two recently suggested definitions
seem to be rather comprehensive and satisfying. The first one is based on the aerogel production
process: An aerogel is an open, nonfluid colloidal network or polymer network that is expanded
throughout its whole volume by a gas and is formed by the removal of all swelling agents from
a gel without substantial volume reduction or network compaction (see supporting information
in Reference 4). The second one highlights mainly the final properties: Aerogels are solids that
feature very low density and high specific surface area and consist of a coherent open porous
network of loosely packed, bonded particles or fibers (5). The combination of both statements
Drying
Gelation
Precursors + aging
Gel Monolithic
aerogel
Chemical reaction
or phase Particle (spheres)
transformation formation/gelation Drying
(Spherical)
aerogel particles
Gel particles
(e.g., in a solvent)
Casting/
gelation
Thin aerogel layer
Figure 1
Main steps of aerogel synthesis.
14.2 Smirnova · Gurikov
gives rather a full description of the material and means of its production: [An] aerogel is an open
nonfluid colloidal or polymeric network consisting of loosely packed, bonded particles or fibers
that is expanded throughout its volume by a gas and therefore exhibits very low density and high
specific surface area. Aerogels are usually formed by removing all swelling agents from an initial
gel without substantial volume reduction or network compaction.
Following this definition, aerogels clearly can be prepared from a virtually unlimited number of
starting materials and their combinations. Because the amount of publications related to aerogels
increased to approximately 300–400 per year in the last decade, it is virtually impossible to provide
a comprehensive and meaningful review of all existing aerogel types. Therefore, in our opinion, it
is more worthwhile to ask what drives aerogel development. One possible answer is that it is driven
by applications and stringent performance criteria, which would be impossible or inefficient when
using materials other than aerogels. In this case, the production costs are no longer a bottleneck
because they are justified by a significant improvement or enabling of the final product. Following
this approach, we attempt here to identify the most crucial and unique aerogel properties that
inspire or limit certain applications and to summarize the general strategies of aerogel preparation,
focusing on application-driven requirements.
Therefore, we first review both existing and potential aerogel applications and subsequently
analyze the processes that allow us to (a) adjust pore structure and size, (b) perform the surface
modification or coating, and (c) obtain hybrid aerogels derived from two or more raw materials and
their sources. For readers with a broader interest or wish to acquire deeper insights into certain
aerogel classes, we also recommend the most recent reviews on the corresponding topics, which
are highlighted below and in Table 1.
2. EXISTING AND POTENTIAL APPLICATIONS OF AEROGELS

As the lightest solid materials known, and given the great variety of possible chemistries yielding
wet-gels, aerogels have tremendous potential in a wide range of applications in which high pore
volume and high surface area play major roles. Currently, the industrial production of aerogels
is mainly limited to silica-based systems, carbon, and some small amounts of organic aerogels. At
present, the following producers and sellers are known:
Cabot Aerogel, Aspen Aerogels, Aerogel Composites Ltd., American Aerogel Corp., Aerogel Compos-
ites Inc., Marketech International Inc., Aerogel Technologies, CDT Systems Inc., CF Technologies,
NanoPore Inc., and TAASI in the United States; Airglass in Sweden; Separex and Enersens SAS in
France; Active Aerogel in Portugal; BASF SE in Lemfoerde, Germany; NanoHigh-Tech Co. Ltd.
in China; Okalux in Germany; and JIOS Aerogel Corp. in Korea. Flexible blankets produced by
Aspen Aerogels and pipe-insulation materials produced by Cabot are well-established in the market.
A lot of effort has been devoted toward production of monolithic aerogels for glazing applications
(Airglass). However, for many other applications, aerogels in the particulate form are beneficial. One
important producer of aerogel particles, mainly for the cosmetic industry, is Dow Corning. Organic
aerogels are not well commercialized so far; only small amounts can be ordered, mainly for academic
purposes (e.g., via http://www.buyaerogel.com). The aerogel market has high growth potential, as
lab-scale process breakthroughs described in the scientific literature show potential for translation to
industrial-scale processes. A recent market survey estimated global aerogel production to be worth
$115.7 million in 2011. This value is expected to increase to $1,379.6 million by 2017, at a compound
annual growth rate of 51.2 % (6).
Currently, the main market application of aerogels is thermal insulation, because aerogels
are the best thermal insulating material besides vacuum insulation panels (7, 8). Most recently,
www.annualreviews.org • Aerogels in Chemical Engineering 14.3
Table 1 Existing and potential applications of aerogels

Application Types of aerogels involved Decisive aerogel properties References
Thermal insulation in form Silica, polyurethane, biopolymers Thermal conductivity: main 7, 8, 13, 19–23
of monoliths, blankets, and (cellulose, alginate, pectin), importance to the homogeneity of
panels for insulation of carbon aerogels the pore size distribution to
buildings, pipelines, Composites: interpenetrated ensure Knudsen diffusion,
packaging, winter apparel aerogel networks, granulate + macropores should be avoided;
products, textiles aerogel network, nonporous high mechanical stability;
material + aerogel granulate; hydrophobicity
textile + aerogel granulate;
clay-containing aerogels
Drug delivery Native silica; biopolymers: alginate, High surface area, accessibility of 9, 10, 24
pectin, starch, chitosan, cellulose, the pores for the drugs
and hybrids thereof (micropores may be a hindrance),
affinity to specific drugs (surface

modification may be needed)
Tissue engineering Mainly biopolymers: alginate, PE, Combination of meso- and 10, 25, 26
starch, chitosan, cellulose, and macroporosity in the same
hybrids thereof material, biocompatibility
Medical implants Polyurea crosslinked aerogels, Pore structure suitable to 10, 27–29
natural biopolymers: alginate, applications (usually micropores
alginate-starch, gellan gum, to be avoided), biocompatibility,
hybrids with gelatin stability in liquids,
biodegradability
Cosmetics Silica particles Amorphous aerogel backbone, 30; http://www.
potential to adsorb liquid, cabotcorp.com/
flowability solutions/products-
plus/aerogel
Catalysts and carrier SiO2 , various metal oxides (TiO2 , High surface area, stability in 14, 18, 31–39
materials for catalysis Al2 O3 , CuO-CoO-MnO/SiO2 , corresponding gaseous or liquid
and electrocatalysis Fe2 O3 , ZrO2 ), graphene oxide, phases, transport through large
Ru/graphene, gold, chalcogenides meso- and macropores
and their mixtures, carbon (fuel
cells), polysaccharides, (chitosan,
alginate), noble metals and
bimetals, Pt-Ni, hybrids of metal
and semiconductor nanoparticles,
photovoltaics
Biocatalysis Mainly silica Compatibility with enzymes, 40–42
absence of toxic gelation
by-products, pore sizes adjusted
to molecular size of reaction
products/adducts
Energy/hydrogen storage Carbon, graphene-oxide, Large surface area, electrical 13, 35
devices combinations thereof, including conductivity
those with functionalized pores
(Continued )
Table 1 (Continued )
Application Types of aerogels involved Decisive aerogel properties References
Sorbents for liquids, Carbon, graphene-oxide, Surface functionalization to ensure 16, 35, 43
hazardous ions (heavy combinations thereof, including the selectivity to target molecules,
metal ions) (e.g., water those with functionalized pores; open porosity, hydrophobicity, or
treatment), oil spills functionalized/hydrophobized oleophobicity
silica aerogels; magnetic cellulose
aerogel, titania, clay aerogels
(Bio)sensors AuNPs-carbon aerogel, graphene, Surface functionalization to ensure 18, 36, 44–47
silica, zirconium phosphate– the selectivity to target molecules,
carbon, carbon/metal hybrids, open porosity
N-doped graphene,
graphene/alginate, tungsten
oxide, graphene-ZnO, RF
aerogels, MoS2 /graphene, boron

nitride aerogel
Sorbents for gases (CO2 , Silica, amino-modified silica, Surface functionalization to ensure 16, 48
hazardous gases, VOC) carbon, graphene-oxide, the selectivity to target molecules,
combinations thereof including open porosity
functionalization (e.g., N-doping)
Cherenkov detectors Silica Refractive index 18
Ballistic protection Crosslinked silica aerogels Mechanical strength 18
Fillers (paints) Silica particles Hydrophobicity, particle size http://www.
cabotcorp.com/
solutions/products-
plus/aerogel
Separation technologies Carbon, fiber-aerogel hybrids, Selectivity to target molecules, 16, 49, 50
(membranes) graphene, graphene oxide, pore size tuning, hydrophobicity
chitosan
Miniaturized gas Hydrophobized silica aerogel Low skeletal and gas thermal 51
(μ-Knudsen) pump conductivities, open-porous
structure (rarefied air flow)
Foundry RF, carbon Pore structure, open porosity 18
Construction material Silica aerogels in high performance Mechanical properties and density 52
aerogel concrete of composites
Space applications Mainly silica and hybrids Transparency, thermal 18
conductivity
Abbreviations: PE, polyethylene; RF, resorcinol-formaldehyde; VOC, volatile organic compound.
BASF took the first steps toward commercialization of organic (polyurethane) aerogels. Their
product, Slentite, is a strong monolithic product available for insulation purposes, primarily for
the construction industry. The growing interest in biopolymer aerogels enables applications in
the life science, such as drug delivery (9), tissue engineering, cosmetics/personal care (10), and
food (11). Carbon-based aerogels (12), being conductive, open up numerous opportunities for
electrochemical applications, such as in batteries and supercapacitors (13). Noble metal–based
aerogels as well as chalcogenide aerogels and related hybrids are widely studied for electrochemical
applications (14, 15). The latest achievements in surface modification that allow tailoring of aerogel
hydrophobicity/oleophobicity give rise to environmental applications (16). The ability to change

aerogel hydrophobicity enables promising applications in separation technologies. He et al. (17)
proposed using reduced graphene oxide aerogels as membranes to remove oil from water surfaces.
In contrast to previous works, they proved that floating oil can be continuously absorbed and
pumped out of the aerogel with a simple peristaltic pump.
Table 1 summarizes the main existing and potential applications of aerogels and highlights
the representative literature for each of them. Other recent reviews on the corresponding topics
are available (7–14, 16). For the state of the art and common knowledge up to 2010, we highly
recommend the Aerogels Handbook (18). As identified in Table 1, for many applications the fol-
lowing properties are decisive: pore structure and size and functional surface groups. Therefore,
these aspects are discussed in detail below.
3. PORE ENGINEERING
The vast majority of aerogels described in the literature have statistically distributed pores with
sizes ranging from a few to tens of nanometers. Three quantities that characterize the porous
system are routinely reported: specific surface area, specific pore volume, and density. The first
two are determined from nitrogen adsorption/desorption isotherms. In most cases, the nitrogen
porosimetry allows for the reconstruction of the pore size distribution (PSD). A typical PSD is
unimodal with a maximum radius between 5 and 20 nm. This set of characteristics portrays an
ordinary metal oxide or (bio)polymer aerogel. Clearly, many process parameters influence these
quantities. As observed from Table 1, most applications heavily rely on an extremely high surface
area of aerogels in combination with a certain pore structure and especially with a desired PSD. In
this section, we review various approaches that allow manipulation of pore architecture, referred
as to pore engineering. We start from solution-based processes (sol-gel transition), followed by
the impact of drying on the porous network, and finally pore modulation in dried aerogels.
3.1. Pore Engineering in the Wet State

Most of the aerogels described in the literature so far have been derived from wet gels produced
by the sol-gel process. According to IUPAC, the sol-gel process is defined as a process through
which a network is formed from solution by a progressive change of liquid precursors into a fluid
colloidal system (sol), to a nonfluid colloidal network or polymer network (gel), and in most cases
finally to a dry network. Although the definition does not specify the nature of the precursors, it
is referred mainly to inorganic and inorganic-organic networks. For the sake of simplicity, in the
following discussion we refer to any process that results in a gel as a sol-gel process, being fully
aware that other terms, such as polymerization, coagulation, or crosslinking, may be preferred in
some cases.
Although literally thousands of papers have been published on gelation of water glass and
organosilanes, an empirical approach still dominates when it comes to the precise control of pore
size and textural properties at a microscopic level. This fact emphasizes the lack of rules that
are general and accurate enough to predict experimental outcomes at various process parameters
reasonably well and conveniently enough for experimentalists. The situation is even less clear
for other gelation processes, such as crosslinking and precipitation of (bio)polymers. Although
at first glance the use of additives and templates appears impractical because it adds an extra
degree of freedom to the process, this approach has in fact proven to be very efficient for pore
engineering.
Nearly countless resources are available on the preparation of templated silica gels. Here we
review only those recent works in which all steps from gelation to aerogel are presented. We refer
interested readers to the recent comprehensive reviews by Feinle et al. (53, 54) and Kanamori &
Templating
Nakanishi (55). (structure-directing)
Examples of suitable templating (structure-directing) agents include low–molecular weight and agent: a compound
block copolymer surfactants, emulsions, and solid particles. Hüsing and colleagues (53, 56) have added during gelation
compiled a substantial body of research on templated metal oxide aerogels. In a typical protocol, an to aid in manipulating
the pore size, the pore
organometallic precursor is subjected to hydrolysis and condensation in the presence of a polymeric
topology, and
template, such as poly(ethylene oxide), poly(acrylic acid), amphiphilic block copolymers, industrial morphology
surfactants, and others. Ethylene glycol–modified silanes are used in the sol-gel process because
Macropores: pores
releasing ethylene glycol is compatible with amphiphilic block copolymers that act as templating with widths exceeding
agents. The use of ethylene glycol–modified silanes is justified by their solubility in water, the ∼50 nm
catalyst-free character of the sol-gel transition, and the fact that they are not detrimental for most Low
liquid crystal surfactant mesophases (53, 56). Numerous hierarchically organized aerogels with molecular–weight
macropores in the range of 0.1–80 µm and well-developed uniform mesoporosity (2–60 nm) have gelator (LMWG): a
been reported. monomer or oligomer
that strongly
Formation of a target gel within a template gel is another attractive technique. Owing to slow
physically interacts in
diffusion in gels, it is often inefficient to preform the template and then impregnate it with a solution, leading to the
reactive mixture for the target gel formation. At the same time, template gels must be easy to formation of a gel
remove once the target gel is formed. For this purpose, low–molecular weight gelators (LMWGs)
would be best suited, as they form physical gels and can be extracted during solvent exchange.
This technique has been exemplified by the gelation of silica and silica-zirconia sols infiltrated
into an organogel with fibrillar structure (70-nm fibers) (57).
Liu et al. (58) have presented an interesting template-free method of narrowing the PSD
wherein aerogels are derived from a mixed sol that consists of two populations of silica particles,
3–5 and 10–12 nm in size. Near-uniform distribution of pore diameters could be achieved in
the range of 5–60 nm. Aerogels derived from the mixed sols also possess larger storage moduli,
indicating that even PSD reflects in a stronger skeletal framework. We anticipate that this method
may be effective for those catalytic applications for which transport pores should be combined
with appreciable mesoporosity.
Oil in oil-in-water emulsions can also act as a porogen when the sol-gel process takes place
in the continuous phase. Although emulsions as templating agents mostly lead to closed-cell
macroporous structures, mesoporosity is automatically generated in the continuous phase or can
be developed by the addition of other structure-directing agents. Although the droplet size can
principally be adjusted by changing the emulsification conditions (oil-to-water ratio, energy in-
put, surfactant concentration), one should expect a certain span of droplet sizes. This approach
has been proved for both metal oxide and biopolymer aerogels (59). It is very advantageous
if the oil phase can immediately be extracted by supercritical carbon dioxide (sc-CO2 ) during
drying.
Phenomena at gas-liquid interfaces can sometimes be used to comprise multiple levels of
pore sizes. Recently our group demonstrated that several biopolymers and their blends can be
gelled with the help of pressurized CO2 (60, 61). Once the gelation was completed, we used fast
depressurization to introduce macropores of a few hundred micrometers into purely mesoporous
gel (26). The resulting dual porous aerogels were suggested for applications in tissue engineering
and regenerative medicine.
Combinations of the above-mentioned templating strategies are also known; however, they are
not straightforward because corresponding chemistries are not orthogonal. Because the wet gel is
subjected to the solvent exchange (62), drying, and often a postprocessing, there are attempts to
modulate pore structure at these subsequent steps.
Cryogel: an open
network formed by the
3.2. Evolution of the Porous Network During Drying
removal of all swelling
agents from a gel by Even if the gel with the desired pore structure is already formed, the drying has a significant
freeze drying influence on the final pore structure of an aerogel. Because recently more and more researchers
Hydrogel: a gel in use the term aerogels for gels dried by freeze drying (more clearly referred to as cryogels), or
which the swelling even evaporative drying, it is worth discussing whether the same pore structure can be achieved
agent is water
by these drying processes.
Mesopores: pores Prior to or during freeze drying, hydrogels are subjected to freezing followed by vacuum or
with widths between 2
ambient pressure sublimation. This process may result in materials with well-developed meso-
and 50 nm
porosity; however, they are often accompanied by larger pores, reducing the overall surface area.
Supercritical drying:
This may be advantageous for applications in which transport pores are required to not hinder
a drying process
during which the mass transport (catalysis, sensors, tissue engineering). Essential process parameters that control
swelling agent of a gel the ratio between meso- and macroporosity in the ice templating (freeze-casting) process are
is in its supercritical (a) freezing rate and temperature gradient and (b) composition of the liquid phase, especially if
state nonvolatile liquid compounds are presented.
Although porous bodies obtained via freeze drying are often referred as to aerogels (not con-
flicting with the above-given definition), it is often not explicitly articulated to what extent the
mesopores contribute to the overall porosity of such materials. Borisova et al. (63) reported on a
very promising method for mesoporous aerogels, including biopolymer ones, that relies on the
partial solvent exchange of water by t-butanol with subsequent freeze drying. Larger mesopore
volume is observed when the solvent composition is close to one of two eutectic points (23 and
90 wt% t-butanol), whereas freeze-casting leading to macropores was found to dominate for
noneutectic crystals (63). Owing to volumetric contraction upon freezing, nonaqueous systems
with appropriate melting points and vapor pressures (e.g., t-butanol, cyclohexane, acetic acid)
allow preservation of a larger fraction of mesopores and physical integrity of monolithic samples
(64).
When hydrogels are subjected to freeze drying, clear differences in the structure are seen. Just
recently, supercritical drying and freeze drying were compared for cellulose hydrogels (65, 66).
Supercritically dried samples exhibited hierarchical structure, with pore size varying from a few
tens of nanometers between the fibrils to a few micrometers between the hairy beads, whereas
cryogel morphology turned out to be a sheetlike cellulose network with large interconnected
pores of several micrometers. Even more clear differences can be seen for protein-based aerogels,
for which it was not possible to preserve porosity by freeze drying (surface area dropped almost
to zero), whereas supercritical drying allowed for a surface area of ∼450 m2 g−1 (67). Obviously,
supercritical drying better preserves the inner porosity of the gels, whereas the growth of ice crystals
during freezing leads to compact pore walls and large pores (65). One attractive feature, however,
is that it is possible to vary the pore size within one cryogel sample by applying a unidirectional
freezing before freeze drying. This allows us to decrease the pore size in the direction of the
temperature gradient, from lower to higher temperatures (65).
As mentioned before, certain types of aerogels can be dried by evaporative drying without
significant collapse of the porous network. This is possible for two reasons: (a) a decrease of the
surface energy via surface modification of the pores (e.g., with trimethylchlorosilane) along with
the use of nonpolar solvents (e.g., hexane) and (b) the use of wet gels with a reinforced backbone.
In the former scenario, the capillary pressure is greatly lowered so the shrinkage can be almost
completely by-passed; however, the process is primarily limited to silica systems and requires
reactivation of the surface (heat or plasma induced if native silica surface is desired). The latter
scenario is often realized for resorcinol-formaldehyde or silica-based crosslinked aerogels that are
strong enough to withstand the capillary forces developed during direct solvent evaporation (68).
Thermal
Recent achievements in the optimization of evaporative drying and solvent exchange allowed for superinsulator: a
preparation of granulated silica and even silica-biopolymer hybrid aerogels with superinsulating material with thermal
properties (thermal conductivity as low as 17.4 mW m−1 K−1 ), indicating that the porous structure conductivity below
remains largely unaffected during solvent evaporation (69). that of air in ambient
conditions (25–26 mW
m–1 K–1 )
3.3. Pore Engineering in Dry State Xerogel: an open
network formed by the
Once drying is completed, the porous structure can still be modulated in two key ways: (a) by removal of all swelling
removing the remaining template using heat or plasma treatment or (b) by partial etching of agents from a gel;
the bulk aerogel backbone. Because in the former case the porous structure has to be preserved, often refers to partially
shrunk gels and/or the
a nondestructive treatment is generally preferred. In the latter case, porosity can be developed
gels dried by
even in initially nonporous materials. In fact, these processes border between ceramic and aerogel
evaporative drying
technologies. Processing of porous ceramics has been exhaustively reviewed recently (70, 71).
Heat treatment is a common method for removing templating agents used for pore engineering
in the wet state. The process is typically performed under inert or oxidative atmosphere at a
temperature of a few hundred degrees Celsius. Ideally, complete transformation of the template
into volatile products is expected, whereas the backbone remains intact. In practice, however,
various transformations may happen, such as crystallization of the initially amorphous backbone,
polymorphic transformations, reaction between surface groups, or formation of carbides (reaction
with pyrolyzed template) or nitrides (reaction with carrier nitrogen gas).
In the context of aerogel processing the most important outcome is that the heat treatment may
greatly reduce the pore volume and affects the macroscopic appearance, resulting, for instance,
in crumbling. Hence, the calcination process should be considered as a process in its own right
and is subject to optimization (precalcination, etching with reactive gases and others). Making no
claims of completeness, we give a brief overview of relevant examples published in the last decade.
Casula et al. (72) undertook optimization of the calcination temperature and were able to
completely remove organics and convert initially amorphous CoFe2 O4 –SiO2 aerogels into ho-
mogeneous and highly porous products without significant changes in either surface area or pore
volume. In another example, low crystallization temperatures of 350–450◦ C allowed transforma-
tion of amorphous template-free Cu(II) and mixed Cu–Ni oxide aerogels into a crystalline one,
with a moderate reduction in both pore volume and surface area (73, 74).
In fact, backbones of polysaccharide aerogels can serve as sacrificial templates. Porous Co–
Mn mixed oxide was prepared starting from alginate hydrogels crosslinked by Co2+ and Mn2+ .
Aerogels obtained after solvent exchange and sc-drying were calcined at 450◦ C, resulting in mixed
oxide phases with a porous structure that resembled the original alginate aerogel (75). Quignard
and coworkers (see 76 and later works) pioneered this method, which can be seen as an extension
of the well-known Pechini method, in which the porous structure of the final oxide phase is shaped
at the gelation step and preserved through sc-drying. Taking into account that biopolymers have
been increasingly studied as precursors for oxide phases (77), we believe that aerogel technology
can enter catalytic applications with these achievements.
Template removal can be realized in milder conditions using plasma technology. An original
approach by Loy et al. (78) consists of the sol-gel transformation of bis(triethoxysilyl)arylene and
bis(triethoxysilyl)alkane monomers followed by supercritical or air drying. Resulting aerogels or
xerogels are subjected to template oxidation by an inductively coupled radiofrequency plasma. Pore
diameter can be modulated depending on the size of the bridging group to be sacrificed, similar
to methods described in Section 3.1. This approach has been taken further for the preparation of
thin-film silica aerogels using polyethylene glycol as a sacrificial template (79). Besides the porous
structure, the functionality of aerogels can be further modified by varying the surface chemistry
in the wet or dry state, as discussed in the following section.
4. COATING AND SURFACE MODIFICATION

One powerful possibility to alter the functional properties of the aerogel without substantial
change in the structural properties of the material is to coat aerogels with a layer consisting of
a material with the desired properties, for instance, with a polymer. Here the main issue is to
complete the coating in such a way that only a thin homogeneous layer is formed, covering the
whole aerogel surface without blocking the pores or leading to an unnecessary increase in bulk
density. Generally, this approach leads to different final states of the modified aerogels: (a) Either
only the outer surface of the sample is coated with a thin layer of a polymer, whereas the structure
and the chemical composition of the pristine aerogel are preserved, or (b) the whole internal
structure, including the surfaces of the pores and the junctions between them, is covered with a
homogeneous layer of coating material, mainly a few nanometers thick.
Depending on the application, both final products can be aimed for. From the molecular point
of view, one can differentiate several types of interactions between the coating and the aerogel
surface. The coating material either can be attached to the surface through noncovalent inter-
actions (van der Waals forces or hydrogen bonding) or can chemically react with the selected
functional/active groups of the aerogel providing covalent bonds between both materials. Obvi-
ously, in case of chemical reaction, the thickness and homogeneity of the layer depend on the
number of functional groups available on the aerogel surface and the ability of the coating ma-
terial to self-polymerize, whereas nonspecific interactions lead rather to a total surface coverage
depending mostly on the process parameter, like the amount of the coating material, number of
deposition cycles, and coating time.
Therefore, we suggest differentiating between these two cases and using the terms coating and
coated aerogel for nonspecific noncovalent interactions and the terms surface modification and
modified aerogel for chemically grafted layers. Both the coating and surface modification can take
place in a gas or liquid or supercritical phase when in contact with a wet gel or dried aerogel
correspondingly. This suggested convention with possible variations is illustrated in Figure 2. In
the following sections, we discuss each route in Figure 2 in detail. Some representative examples
are summarized in Table 2 and discussed in detail in Sections 4.1–4.6.
4.1. Wet Coating

Layer formation on the wet gel with subsequent preparation of aerogels was realized by an exter-
nally induced polymerization/crosslinking on the surface of the aerogel samples. Erkey’s group
(80) suggested the formation of a polyethylene glycol (PEG)-based hydrogel layer on the sur-
face of dry hydrophobic aerogel particles via immersion into a monomer solution and subsequent
photopolymerization using visible light. Nakayama et al. (81) demonstrated a somewhat similar
process, wherein trimethyl-modified wet silica gel was dispersed in an ultraviolet-curable resin
solution, which in turn was deposited on solid surfaces and polymerized.
The group of Knez and Novak (82) produced layered aerogels by conducting a Ca2+ -induced
gelation of Ca-alginate on previously formed alginate hydrogel beads via their subsequent im-
mersion in alginate solutions. Subsequent supercritical drying led to the layered aerogels (82). A
similar procedure was used to prepare an alginate layer around the silica aerogel core (83). Much
Gel (wet) or
aerogel (dry)
Coating Surface modification
4.1 4.2, 4.3 4.4 4.5, 4.6
Liquid Gas/vapor, sc-fluid Liquid Gas/vapor, plasma, sc-fluid
(Supercritical) drying (Supercritical) drying

Coated aerogel Surface-modified aerogel
Figure 2
Possible processes of aerogel coating or surface modification, including liquid or gas phases. Numbers next
to the arrows point to the corresponding section. Abbreviation: sc, supercritical.
high throughput has been demonstrated for pectin particles coated with alginate via the prilling
technique. The resulting hydrogel was solvent exchanged, drug loaded, and supercritically dried
for use in wound dressing applications (84). Principally, formation of multiple layers of different
organic polymers on both organic and inorganic aerogel cores can be achieved in this way. Obvi-
ously, the coating materials should not penetrate into the pores (for instance, owing to the large
size of the polymer/oligomer molecules), which would otherwise lead to the coating of not only
the external but also the internal aerogel structure, as discussed in the following section.
The group of Ratke and Milow (85) has presented a modified electroless plaiting process for the
deposition of metals onto an inner aerogel structure. A 10–30-nm-thick layer of silver nanoparticles
has been successfully prepared on cellulose aerogels and shown to be catalytically active with
good aging stability as a facile and sustainable route to functionalize open-porous fibrillar aerogel
structures with a homogeneous layer of Ag nanoparticles (NPs). The combination of cellulose
aerogel supports and electroless plaiting is strikingly fitting: The polar surface chemistry of the
cellulose promotes a dense nucleation and an efficient metal particle attachment, whereas the
conformal deposition is able to use the complex aerogel structure. As it was shown in a catalytic
model reaction that the hybrid biopolymer-metal material combines the functionality of the metal
NPs with the benefits of the CA support.
4.2. Coating in sc-CO2

In principle, the coating in sc-CO2 could be realized by (a) precipitation of the coating material
around the gel upon contact with sc-CO2 or (b) deposition of sc-CO2 -soluble material upon drying.
Although if realized any process would represent a significant achievement in process integration,
published results are very scarce.
Following the first route (a), the wet gel particles are dispersed in a polymer solution. This
mixture is sprayed into a chamber with sc-CO2 in a semicontinuous or batch mode. Owing to
Table 2 Examples of aerogel modification by coatings and surface modification: properties and applications
Coating/surface Way of
Type of aerogel modification material modification Improved properties Application area Reference
Silica PEG/Eudragit Coating pH sensitivity Drug delivery 92
Silica Different polymer Coating Mechanical properties, Space 91
suspensions moisture sensitivity applications
Alginate Eudragit Coating Mechanical properties, Drug delivery 94
pH sensitivity
Alginate Ca-alginate Sol-gel Permeability, diffusion Drug delivery 82
Silica Ca-alginate Sol-gel Permeability, diffusion Drug delivery 9
Silica PEG-based hydrogel layer Sol-gel Permeability, diffusion Drug delivery 80
Silica Cyanoacrylate polymer CVD Mechanical strength – 112
Silica Silylation agents CVD Mechanical strength – 113
Carbon nanotube Graphene – Elastic mechanical Fatigue 102

properties resistance
Sulfur-impregnated Polypyrrole Surface poly- Electron conductivity Lithium–sulfur 122
graphene merization battery
Polydopamine- Polyethylenimine – Affinity to heavy metals Adsorption 43, 103
graphene (environmental
oxide applications)
Cellulose PFOTS CVD Oleophobicity Oil adsorption 111
from water
Cellulose Trimethylchlorosilane, Plasma Hydrophobicity – 117–119
tetrachloromethane
Silica Polyurea, polystyrene, Postgelation Mechanical properties, Thermal 18
polymethylmethacrylate, (gas or liquid hydrophobicity insulation,
polyacrylonitrile phase) ballistic
protection
Different metal Polyurea Postgelation Mechanical properties, Thermal 18
oxides (Sc, Ti, V, hydrophobicity insulation,
Cr, Mn, Fe, Co, Y, ballistic
Zr, Nb, Hf, Ta, protection
W, Re, Al, Ge, In)
Abbreviations: CVD, chemical vapor deposition; PFOTS, 1H,1H,2H,2H-perfluorodecyltrichlorosilane.
hindered diffusion of the polymer into the gel, the deposition of the polymer can be achieved
mainly on the outer surface of the particles. Eudragits (RL 100, RS 100, L 100) and PEGs of
various molecular weights have been used as coating materials (86, 87). Liebner and colleagues
(88, 89) have demonstrated that cellulose aerogels can be reinforced by immersing wet gels in
a polymer solution prior to drying. Polylactic acid, poly-caprolactone, cellulose acetate, and
poly(methyl methacrylate) have been shown to form layers, individual spheres, or interpenetrating
networks.
Although interactions between aerogel backbones may be strong, this method leads to phys-
ically deposited layers. Hydroxyl-terminated poly(dimethylsiloxane) dissolved in sc-CO2 was
shown to form ∼1-mm layers on silica aerogel surfaces (90). This work, to our knowledge, is
the sole example of the second route (b) in application to aerogels.
4.3. Coating of Dry Aerogels

Three main methods were suggested for dry coating: (a) by liquid solutions/suspensions or melts
through the direct physical solidification of polymers on the surface of the aerogel samples (91– Chemical vapor
94); (b) by the formation of a layer owing to externally induced polymerization or gelation on the deposition (CVD):
dried aerogel particles (80); and (c) by deposition of a layer from the gaseous phase (95, 96). a process in which a
volatile precursor
The coating process was realized mainly in a fluidized bed apparatus, allowing fast solidification
reacts and/or
owing to intensive heat transfer between the liquid layer on the aerogel surface and the gaseous decomposes on the
bulk phase. This method was first suggested by Plawsky et al. (91) and realized in a draft tube spout substrate surface,
fluid bed coating system for silica aerogel particles (subcritically dried Cabot aerogels/xerogels) of yielding the desired
irregular shape and 0.1–2 mm in size. Mainly aqueous polymer suspensions, partly with additives layers
(carbon black and silica nanoparticles), were used. Depending on the coating duration, nozzle
type, and flow regime, a relatively homogeneous coating was achieved, although no evidence
for the integrity of the internal structure was provided. It remains unclear whether the water
penetration in the pores had partly influenced their structure. However, taking into account the
general hydrophobicity of the Cabot aerogels and the fact that mainly conventional drying is
used for their production, one could suggest that these samples are not as sensitive to the liquid
evaporation as the supercritically dried hydrophilic aerogels. Later, Alnaief et al. (92) suggested
using coating with a polymer melt to avoid this problem because the thin layer of polymer melt
solidifies much faster than a (diluted) polymer solution. PEG melt was used to create a protection
layer on spherical silica aerogel particles, which were subsequently coated by an aqueous solution
of pH-sensitive polymer Eudragit. The whole process took place in a specially constructed spouted
bed apparatus, allowing the stable fluidization of the extremely small and light aerogel particles.
The uniformity of the coating was proven by pH-dependent release of ketoprofen loaded into
aerogel prior to coating. Recently, Antonyuk et al. (94) have extended this method to organic
aerogels. Relatively large cylindrical aerogel samples (alginate-starch hybrids) were coated by an
aqueous suspension of Eudragit L 30 D-55. No protecting layer was needed for this aerogel type,
contrary to the case of hydrophilic silica aerogels, because a closed layer with uniform thickness
was produced, and no penetration of the coating liquid into the porous aerogel structure was
observed (Figure 3).
Chemical vapor deposition (CVD) has been proved to be applicable for the formation of
nanometer-scale layers on aerogel films. Much thinner layers, down to a few nanometers, can be
achieved with this technique. The thickness of the layer is controlled by the number of deposition
Mag = 100×
100 μm 100 µm WD = 8.1 mm
Figure 3
Cross-section of the coated aerogel showing the coating layer. (Left) Digital light microscopy image and
(right) scanning electron microscopy image. Reproduced from Reference 94 with permission.
cycles. The CVD technique has been exemplified by deposition of a 2.4–12-nm-thick TiO2 layer
on 30-µm-thick silica aerogel film for applications in dye-sensitized solar cells (95). In this case,
water adsorbed on aerogel hydrolyzes a precursor that is fed into a gaseous phase. In fact, many
precursors used in CVD can diffuse into the aerogel pores and cover or modify the inner surface of
the aerogel. However, this relates more to surface modification, and the corresponding examples
are discussed in Section 4.6.
Coating of dried aerogels with 2–3 mm of hard crust can also be realized at high-
temperature conditions in magnesium vapors, as exemplified by Franzel et al. (96). Hybrid
silica/polyacrylonitrile aerogels were oxidized at 225◦ C in air, wrapped in magnesium turnings,
and processed at 850◦ C for 12 h. Upon reaction with magnesium, the resulting aerogel mono-
liths were found to be covered by a mechanically strong crust composed of magnesium silicates,
cristobalite, and magnesium oxide. A remarkable feature of the obtained material is that the core
maintained chemical and physical characteristics close to those of pristine aerogel (hardness of
0.81 MPa), whereas the crust was mechanically strong, with a hardness of 28 MPa, but still porous
(with a surface area of 169 m2 g−1 ).
4.4. Surface Modification in Wet State

Reactions between OH-groups on the oxide aerogel surfaces and various silanes are widely used
and result in mono- or multimolecular layers chemically bonded to the parent surface. Such mod-
ification may take several days and sometimes requires higher temperatures and solvent exchange.
Hydrophobization (69) and grafting of amino (97) and carboxylic (98) groups are typical exam-
ples. Other classes of aerogels can also be modified in the wet condition. As an example, we refer
to the study by Lin et al. (99) in which graphene oxide aerogels were fluorinated using perflu-
orodecyltrichlorosilane. The achieved contact angle was as large as 160◦ , suggesting potential
applications in, e.g., lightweight self-cleaning and anticorrosive materials. More information on
surface-modified carbon aerogels can be found in an excellent review by Nardecchia et al. (100).
Extensive research pioneered by the Leventis group (2, 101) was done on surface modification
and subsequent crosslinking of different functional groups on silica and organic aerogels, leading
to a large variety of hybrid materials (crosslinked aerogels). Different polymers, such as polyurea,
polystyrene, polymethylmethacrylate, and polyacrylonitrile, were used for the crosslinking of
metal oxide aerogels, starting with silica aerogels and further expanding to other oxide aerogels
(18). This approach is based on the introduction of a monomer after gelation by washing wet gels
with its solutions followed by chemical reaction with the aerogel surface and self-polymerization.
Such a modification results in a dramatic improvement in mechanical properties, enabling, for
instance, the use of aerogels in armor applications, ballistic protection, and aerogel-based thermal
insulation materials that can be machined (18).
Surface modification from polymer solutions turned carbon nanotube aerogels elastic and
therefore resistant to fatigue (102). A nanolayer of poly(iminoethylene) on the polydopamine–
graphene oxide aerogels is reported to improve the hydrophilicity of graphene oxide aerogels and
to provide additional active sites for adsorption of heavy metal ions (43, 103).
4.5. Surface Modification in sc-CO2

Pore modification directly in sc-CO2 can be realized as a subsequent one-pot process right after
supercritical drying. Subra-Paternault & Domingo (104) have extensively studied and recently
summarized chemical modification of various surfaces in sc-CO2 as reaction media. The process
is usually realized by the exposure of the porous material to solutions of silanes, polysilanes, or
aminosilanes in sc-CO2 at pressures typical of sc-drying (∼10 MPa) but higher temperatures
(≥60◦ C). Sanli & Erkey (105) presented a review with a special emphasis on the modification of
aerogels and potential applications, including microelectronics, membranes, and catalysis.
Murillo-Cremaes et al. (106) developed an elegant ship-in-a-bottle method. A single precur-
Lyogel: a gel in which
sor (1,3,5-triphenyl-2-pentene-1,5-dione) and a mixture of two precursors (benzaldehyde and the swelling agent is an
anisole) were loaded at a lower temperature into silica aerogel from sc-CO2 as a successive step organic solvent
after sc-drying. By heating up the sc-solution, adsorbed precursors were converted into 2,4,6- Superhydrophobic
triphenylpyrylium and dimethoxytrityl cations immobilized in aerogel pores. Owing to the absence surface: a surface for
of light diffusion restrictions, these transparent silica aerogels can be used as recoverable carriers which the contact
in heterogeneous photocatalysis, with excellent stability and lower mass transfer limitations as angles of a water
droplet exceed 150◦
compared with identically treated zeolites.
Micropores: pores
with widths not
4.6. Surface Modification in Dry State exceeding ∼2 nm
Aerogels with hydrophilic skeletons imbibe liquids with partial or complete collapse of the porous
structure (most of inorganic aerogels), whereas (bio)polymer aerogels can be reswollen to original
hydrogel (lyogel). Thus, development of gas- and plasma-phase modification methods is of high
importance. Moreover, gas-phase modification of dried aerogels allows avoidance of diffusion-
limiting and thus time-consuming impregnation of the wet gel with a monomer and successive
washing to remove the unreacted monomer.
Silanol groups on the silica surface are reactive and can be nucleophilically attacked in the
gas phase. Hence, up to one covalently bonded molecular layer can be obtained. In reaction with
alcohols, only water is formed as a by-product; however, typical operating conditions are relatively
harsh (220–240◦ C, 10–40 h, reflux conditions) (107). Obtained aerogels are superhydrophobic
(4–9% CH3 groups) with minimal loss of transparency (108). The latter fact is important for
transparent insulation materials for which high water resistivity and transparency are decisive (109).
Apart from alcohols, trimethylethoxysilane and other silanes can be used (108, 110). Although this
method is mainly employed to obtain hydrophobic oxide aerogels owing to the presence of reactive
OH-groups, examples for biopolymer aerogels are also known. Cellulose aerogels were modified
with gaseous perfluorodecyltrichlorosilane at 140◦ C for 1 h. Low-density aerogels turned up with
superoleophobic properties, whereas less porous aerogels exhibited much higher wetting with oil
(Wenzel state) (see Reference 111).
The CVD method can also be applied for surface modification. It relies on the same principle
as the above-described surface modification by volatile alcohols and silanes; however, it results
in much thicker layers owing to self-polymerization of monomers on the aerogel surface. The
polymer form can be either physically deposited or covalently bonded to the aerogel surface (mainly
via reaction with previously grafted amino, vinyl, and other groups). Boday et al. (114) reported a
CVD process of anionic polymerization of methylcyanoacrylate on the amino-functionalized silica
aerogel pores, yielding poly(methyl cyanoacrylate) layers with a molecular weight of approximately
10 kDa. The flexural strength of the resulting aerogel was found to be enhanced by a factor of
31 compared with the pristine aerogel (for a 2.5-fold increase in density) attributed to capillary
filling of micropores early in the CVD process. Aside from enhanced mechanical properties, the
obtained aerogels possessed excellent stability in liquid water.
Examples of inorganic layers prepared by CVD are as follows. Silica multilayers were deposited
on the hydrophilic silica aerogels using hexachlorodisilane vapor and resulted in aerogel reinforce-
ment (113). Deposition of a tungsten layer (∼2 nm) on alumina and germania aerogels using WF6
has also been reported (114). Metal oxide hollow tube aerogels were prepared by CVD on nanofib-
rillated cellulose aerogels subsequently removed by calcination. This material was suggested as a
humidity sensor with a fast response (115).
Cold plasma treatment is another promising postprocessing approach toward preparing hy-
drophobic aerogels, especially biopolymer ones. Here dried aerogels are exposed to cold plasma
generated by glow discharging of a gaseous hydrophobizing agent in moderate vacuum. The ap-
proach has been exemplified by turning intrinsically hydrophilic aerogels from alginate (116),
cellulose, and cellulose/silica hybrids (117, 118) into hydrophobic materials with average water
contact angles between 100◦ and 150◦ (117–119). Another advantage of the approach is short con-
tact times (15–25 min). Two hydrophobizing agents have been employed: trimethylchlorosilane
(silylation) and tetrachloromethane (chlorination). Although for such a short time a modification
depth in the nanometer range is expected, partial hydrophobization of the bulk of aerogels has
also been reported (119).
Plasma treatment can also be used to eliminate grafted groups from the aerogel surface: As
Ghosal et al. (120) reported, reactivation of protective trimethylsilyl groups on a silica aerogel
surface by oxidative degradation has been achieved in a much shorter time compared with heat-
induced reactivation at 325◦ C. Extra hydrophilization of a silica surface has also been reported
using radiofrequency plasma (121). This methodology may find its use in electrical devices and
(bio)sensor applications, as well as for aerogel regeneration after adsorption.
Further, electropolymerization of polypyrrole on the sulfur-impregnated graphene aerogel
results in improved electron conductivity, and the use of sulfur enhances the cycle stability of
the lithium–sulfur battery (122). To sum up, both coating and surface modification represent an
additional, quite flexible degree of freedom to tune the aerogel properties for desired applications.
5. HYBRID AEROGELS: INFLUENCE OF THE SOL-GEL PROCESS

ON FINAL PROPERTIES
The general term hybrid aerogel indicates that at least two precursors are employed in the gelation
step. Possible scenarios embrace situations ranging from those where precursors retain their in-
dividuality in the final aerogel (interpenetrating networks) to perfect chemical homogeneity with
a wide range of intermediate cases. Additionally, aerogel backbones can be either crystalline or
amorphous, being composed of amorphous and crystalline domains.
Regardless of the level of chemical homogeneity, hybrid aerogels represent an attractive and
novel class of materials that inherit from the individual components and often demonstrate a
synergy allowing for applications that would hardly be possible with single components only.
Several aspects of this topic were partially covered by excellent reviews (9, 11, 20, 35, 54, 123).
The sol-gel process of mixed systems is a fundamentally more complex process than that of
single aerogels: Aiming at a synergy in the aerogel properties, the reactivities of the precursors used
are so distinct that without careful control over hydrolysis and homo- and hetero-condensation
rates, only ill-defined structures can be obtained (54). Hence, chemical reactivity strongly deter-
mines the end properties of aerogels, especially catalytic and mechanical ones. Below we outline
only existing approaches toward metal oxide aerogels. For an in-depth discussion, the readers are
referred to Feinle & Hüsing’s (54) recent review on the topic.
One approach to improve chemical homogeneity is to spatially separate precursors at the
hydrolysis step followed by condensation in a merged mixture (124). This approach is shown
to increase the catalytic activity of TiO2 /SiO2 aerogels by a factor of three as compared with
nonprehydrolyzed samples in 1-butene isomerization. Based on higher cis/trans isomerization
product ratios for the nonprehydrolyzed aerogels, the authors concluded that in this case silica
and titania domains are segregated (124).
However, the segregation in the mixed aerogels should not necessarily be seen negatively.
Brodzik et al. (125) reported a series of TiO2 /SiO2 aerogels with photocatalytic activities toward
degradation of salicylic acid in water. Prehydrolyzed, i.e., more chemically homogeneous, aerogels
showed lower catalytic activity, whereas the presence of separate and easily reachable anatase
particles resulted in higher activity (125).
Another approach to control chemical homogeneity of mixed oxide aerogels is to inhibit the
reaction rate, for example, by complexation with chelating ligands or sol-gel processes in highly
viscous media, or by employing so-called single-source precursors, i.e., hydrolyzable molecules
with two or more metal centers. All of these approaches have been exploited in aerogel prepa-
ration (54). The use of tailor-made single-source precursors, though limited by inherently fixed
stoichiometry between the metal centers and at industrial scale by availability, offer ultimate con-
trol over chemical homogeneity and potentially carry functional groups, precluding the need for
further surface functionalization. Aerogels aimed at catalytic properties generally have to be heat
treated (400–800◦ C) to crystallize amorphous species into a catalytically active crystalline phase
(e.g., titania into anatase). Similar to the sol-gel process in the presence of structure-directing
agents (Section 3), ethylene glycol–modified single-source precursors can be used in the produc-
tion of mixed oxide hierarchically porous aerogels (126).

Analogous to the oxide aerogels, two or more (bio)polymer networks can be either covalently
crosslinked to each other or bound by noncovalent bonds (interpenetrating networks). Moreover,
similar to the oxide aerogels, two polymer networks can form domains of various sizes or be sta-
tistically distributed around each other. Unfortunately, in most cases only limited information
on crosslinking degree and chemical homogeneity is available. Many polymers, such as alginate,
pectin, starch, cellulose, lignin, gelatin, and chitosan, can be blended with one another and with
inorganic precursors to form hybrid aerogels (60, 88, 123, 127). Because even more hybrid hy-
drogels are known in food science, we expect this area to grow substantially over the next few
years.
Thanks to the mild conditions of sc-drying and the inertness of sc-CO2 , a wide range of insolu-
ble materials can be admixed at the gelation step. Selected examples include active calcium silicate
(wollastonite) in silica aerogel (128), zeolites encapsulated in chitosan aerogels (129), hydrophobic
silica aerogel, and oxides in alginate aerogels (60). Besides their functionality, such additives often
act as reinforcing materials. Many examples are reported to date, including silicate, textile fibers,
clay, carbon nanotubes (130, 131), and even macroscopic aramid honeycombs (132). Incorporation
of functional materials such as quantum dots into transparent aerogels adds another dimension to
the use of hybrid aerogels as 3D display applications (133, 134).
6. STARTING MATERIALS FOR AEROGELS: THE SEARCH

FOR ALTERNATIVE SOURCES
One of the major obstacles in further commercialization of aerogels is generally higher production
costs in comparison to existing materials for a given application. The two main contributors to
the overall cost are (a) the cost of the raw materials and (b) processing costs. Although processing
costs have been gradually decreasing with further understanding of the drying procedure and
experience with accumulation in the scale-up of both drying and wet gel generation in various
forms (monoliths, particles, films), the question of inexpensive raw materials remains unclear.
Concerning silica aerogels, organic silicates and water glass are established precursors. How-
ever, silica can be found in different types of biomass, being mainly considered as a part of inorganic
ash (135). Recently, ashes of various (industrial) biowastes containing silica species (mainly silicon
dioxide), such as rice husk (136, 137), bagasse (138), oil shale (139), fly (140), and wheat husk
(141), have been used as a silica source for aerogel production. Typically, acidic hydrolysis of
the biomass followed by dissolution of SiO2 in NaOH was applied for isolation of silica species.
Hydrophobic aerogels were obtained after gelation combined with the corresponding chemical
modification with subsequent ambient pressure drying. Most probably this approach alone would
not be economically feasible, but when integrated in a biorefinery concept for lignocellulosic
biomass, it could bring additional value. However, silicon content in different biomasses (135)
should be carefully considered to draw up cost and process management strategies.
Tremendous interest in LMWGs (142) as precursors for stimuli-responsive, self-healing, and
chiral materials in life sciences, electronics, photonics, and other areas has expanded into aero-
gel science (143, 144). We anticipate that LMWGs will promote cross-fertilization between
supramolecular chemistry and aerogel science. In this context, we also expect that studies in metal-
organic frameworks and related materials will recognize the importance of sc-drying as the most
powerful tool for porosity preservation. Studies on the sc-drying of metal-organic frameworks
have started to appear, showing great possibilities for synergy (145–147).
Along with widely used metal alkoxides, various salts are now the subject of keen interest as
low-cost commercially available precursors. An epoxide-based approach toward oxide aerogels,

pioneered by Gash et al. (148), makes use of the reaction between propylene oxide and salts such as
metal chlorides, sodium silicate, or mixtures thereof. In the last decade, this attractive approach has
been studied extensively (18); so far, however, it has been only scarcely applied for the preparation
of inorganic/(bio)polymer hybrid aerogels (149).
In the case of organic aerogels, biopolymers from various sources, such as alginate, cellulose,
lignin, pectin, chitosan, and proteins, have been tested as precursors. Owing to their biological
nature, these materials are mainly produced from renewable sources, e.g., chitosan being obtained
by deacetylation of chitin, which is itself extracted from shells of crustacean and mollusks such as
shrimps, crabs, and squids (123), or pectin being produced from the fruit shells in the food industry.
Lignocellulosic biomasses that are another source of “green gold” have recently attracted a great
deal of attention as starting materials for aerogel preparation [see, e.g., work by Mikkonen and
colleagues (150)].
Obviously, all these biopolymers can also be a source for carbon aerogels produced by pyrolysis
(151). Antonietti’s group generalized hydrothermal carbonization of biomass (HTC) and use of
glucose to achieve highly porous carbon aerogels (e.g., 152, 153). They introduced the term
carbogels with regard to this specific product. The role of hydrothermal conditions and specific
additives [e.g., templating by salts or functionalization by proteins (154)] during the HTC process
was studied extensively, and a large variety of aerogels, mainly in the form of small spheres and
monoliths, were produced (153). Several biomasses seem to be convertible into carbon aerogels
via a hydrothermal carbonization and postpyrolysis process, as shown for watermelon (155) and
winter melon (156). Sugar cane was converted to carbon aerogels by HTC, freeze drying, and
pyrolysis, resulting in porous monoliths (157). However, the ethical issues of the conversion of
foodstuffs into non-food-related materials should be taken into account. These issues could be
partly addressed by using waste streams of the corresponding biomasses or a thorough life cycle
assessment of the foodstuffs.
An alternative way to find new raw materials for organic aerogels is based on recycling of used
materials, for instance, using ideas established in paper recycling; the use of waste newspaper (158,
159) and waste cotton fabrics (160) to prepare cellulosic aerogels was described recently. This
approach could also be extended to various waste plastics. Synthesis of porous carbon nanosheets
from mixed waste plastics for CO2 and hydrogen uptake can serve as an example (161). For sure,
further synthesis routes are possible, even taking into account that waste materials are always a
mixed fraction of different polymers.
The variable quality of the waste materials most likely would play an important role and should
be addressed appropriately. Nevertheless, to prove the real applicability of these new types of
aerogels in real industrial settings, significant amounts of material are required. Therefore, not
only the materials but also the production process aspects should be significantly revised, with
special attention to process scalability at least up to the pilot scale.
The use of pressurized and supercritical CO2 other than drying media is another line of research
at the interface of unconventional starting materials and novel processes. Gelation in pressurized
or sc-CO2 has been demonstrated for several precursors, such as metal alkoxides (162, 163),
sodium silicate and aluminate (164, 165), and biopolymers (alginate, pectin, cellulose, and chitosan)
and their blends (60, 61). Recently, the feasibility of performing the solvent-exchange step in
pressurized/sc-CO2 has also been demonstrated (61, 166). Hence, all essential components for
the integration have recently been developed at the laboratory scale. We hope that further scale-up
will open up new vistas for aerogel technology.
7. SCALE UP OF AEROGEL PRODUCTION PROCESSES

Currently, a variety of different aerogels are being developed at the laboratory scale, and some of
them have been taken to pilot production. However, to significantly increase the market, much
larger production should be enabled, scaling up existing processes. Here, supercritical drying is the
most challenging step. Two principal methods for upscaling this process are (a) constructing larger
autoclaves that work in parallel for batchwise or semi-batchwise drying of monoliths or powders
and (b) continuous drying, allowing the usage of smaller apparatus. The first method is currently
being applied to produce all types of monoliths. Here, no real alternatives likely exist, because
the depressurization step for taking the monoliths out of the autoclave is needed. However, in
the case of particle production more options are available. The production of aerogels directly
in the form of particles has a tremendous advantage: The solvent exchange and extraction time
for small particles is much shorter than that for monoliths by a factor of 10 to 100, allowing for
significant reductions in process costs. In this case, the numbering-up strategy using relatively
small autoclaves with fixed beds is possible. Further, microfluidic approaches at high pressure
could also be promising. In our opinion, drying aerogels in the form of particles is currently the
most emergent topic in terms of scaling up aerogel production. Currently, this topic has received
much attention from the European Union and other countries (see, e.g., http://nanohybrids.eu/).
8. CONCLUDING REMARKS AND PERSPECTIVES

There is no doubt that the aerogel field will continue its rapid development in the coming years.
The key factor, however, is the simultaneous development of the material aspects and correspond-
ing production process to decrease aerogel prices and enable practical applications apart from pure
academic research.
Because a large number of individual aerogel materials are principally available, further devel-
opment should be application driven: Crucial product properties and restrictions should be known
at the outset of development. This can be realized only by close cooperation between academic
groups and industrial partners, which should be further encouraged. From our point of view, the
following topics could receive attention in the near future.
8.1. Hybrid Aerogels

We are convinced that from the material point of view the future development of aerogel-related
products is mainly associated with hybrid materials. Combinations of different polymer matrices,
modification of inorganic ones, and combinations with nonaerogel materials (fibers, particles,
textiles) are the most promising ways to fulfill the requirements of specific applications and to
make a real product out of chemically promising aerogels. Thereby both the post-treatment of
the corresponding primary matrix and simultaneous gel formation of different materials will be in
focus.
8.2. Carbon Aerogels

In the last five years, carbon-based aerogels, including carbon nanotubes, graphene, and graphene
oxide, have received a lot of attention. The main advantage of this aerogel type is that it can be
produced from several different organic gels via pyrolysis. The structure of the initial gel mainly
predetermines the structure of the final carbon aerogels, enabling significant variations in pore
size. Further, the unique feature of this aerogel type is the electrical conductivity, which can
be increased via appropriate additives/coatings. We expect that the application of carbon-based
aerogels as (electro)catalysts, materials for hydrogen storage, and supercapacitors will further
advance in the near future. In general, conductive aerogels based on carbon, different metals, and
their hybrids provide a large variety of promising catalytic materials for application in fuel cells
and different chemical and biochemical sensors. Here an emerging area in the cross-pollination
of electrochemistry, biochemistry, and renewable energies exists and could grow further.
8.3. Surface Modification Perspectives of Plasma

Because hydrophilic aerogels are often sensitive to direct contact with liquids, nondestructive gas
and plasma treatment can be performed in the dry state, so no wetting and redrying of the aerogels
is needed. Taking into account that substantial data have been accumulated and reviewed on the
modification of polysaccharides, synthetic polymers, and inorganic materials, we expect this area
to expand in importance in the upcoming years.
8.4. Aerogels for Separation Processes

In the last three years, several groups have highlighted the practical application of aerogels for
separation of gas and liquid mixtures. Environmental applications, especially for the separation
of oil-water emulsions and oil recovery from aqueous systems, seem to have great potential for
further development.
8.5. Alternative Raw Materials

The search for suitable raw materials with better sustainability and lower prices must continue,
especially for commodity applications, such as thermal insulation or foodstuffs. The use of both by-
products (e.g., lignin) and well-known food components (starch, cellulose) represents significant
opportunities.
8.6. Process Development

Further commercialization of aerogels does heavily depend upon the cost structure of the pro-
duction process. The transition from batch to (semi)continuous processes for solvent exchange
and drying, as well as the overall decrease in aerogel production time, are especially decisive for
further price development in this sector. Generally, more pilot production facilities are needed to
produce enough material for prototyping and to engage with large enterprises.
DISCLOSURE STATEMENT
The authors are not aware of any affiliations, memberships, funding, or financial holdings that
might be perceived as affecting the objectivity of this review.
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CH08CH14-Smirnova ARI 23 March 2017 17:17

V I E W Review in Advance first posted online

still occur before final publication

Irina Smirnova and Pavel Gurikov

Annu. Rev. Chem. Biomol. Eng. 2017. Keywords

1. INTRODUCTION AND MOTIVATION

14.2 Smirnova · Gurikov

2. EXISTING AND POTENTIAL APPLICATIONS OF AEROGELS

www.annualreviews.org • Aerogels in Chemical Engineering 14.3

Table 1 Existing and potential applications of aerogels

affinity to specific drugs (surface

14.4 Smirnova · Gurikov

aerogels, MoS2 /graphene, boron

Abbreviations: PE, polyethylene; RF, resorcinol-formaldehyde; VOC, volatile organic compound.

www.annualreviews.org • Aerogels in Chemical Engineering 14.5

hydrophobicity/oleophobicity give rise to environmental applications (16). The ability to change

3.1. Pore Engineering in the Wet State

14.6 Smirnova · Gurikov

www.annualreviews.org • Aerogels in Chemical Engineering 14.7

14.8 Smirnova · Gurikov

www.annualreviews.org • Aerogels in Chemical Engineering 14.9

4. COATING AND SURFACE MODIFICATION

4.1. Wet Coating

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Coating Surface modification

4.1 4.2, 4.3 4.4 4.5, 4.6

Liquid Gas/vapor, sc-fluid Liquid Gas/vapor, plasma, sc-fluid

(Supercritical) drying (Supercritical) drying

Coated aerogel Surface-modified aerogel

4.2. Coating in sc-CO2

www.annualreviews.org • Aerogels in Chemical Engineering 14.11

Carbon nanotube Graphene – Elastic mechanical Fatigue 102

Abbreviations: CVD, chemical vapor deposition; PFOTS, 1H,1H,2H,2H-perfluorodecyltrichlorosilane.

14.12 Smirnova · Gurikov

4.3. Coating of Dry Aerogels

www.annualreviews.org • Aerogels in Chemical Engineering 14.13

(with a surface area of 169 m2 g−1 ).

4.4. Surface Modification in Wet State

4.5. Surface Modification in sc-CO2

14.14 Smirnova · Gurikov

www.annualreviews.org • Aerogels in Chemical Engineering 14.15

5. HYBRID AEROGELS: INFLUENCE OF THE SOL-GEL PROCESS

14.16 Smirnova · Gurikov

tion of mixed oxide hierarchically porous aerogels (126).

6. STARTING MATERIALS FOR AEROGELS: THE SEARCH

www.annualreviews.org • Aerogels in Chemical Engineering 14.17

low-cost commercially available precursors. An epoxide-based approach toward oxide aerogels,

14.18 Smirnova · Gurikov

7. SCALE UP OF AEROGEL PRODUCTION PROCESSES

8. CONCLUDING REMARKS AND PERSPECTIVES

8.1. Hybrid Aerogels

www.annualreviews.org • Aerogels in Chemical Engineering 14.19

8.2. Carbon Aerogels

8.3. Surface Modification Perspectives of Plasma

8.4. Aerogels for Separation Processes

8.5. Alternative Raw Materials

8.6. Process Development

14.20 Smirnova · Gurikov

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14.22 Smirnova · Gurikov

porosity. Chem. Soc. Rev. 45(12):3377–99

www.annualreviews.org • Aerogels in Chemical Engineering 14.23

14.24 Smirnova · Gurikov

by a co-condensation approach. J. Sol-Gel Sci. Technol. 2016:1–9