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Molecular Schizophrenics: Switchable Materials with Multiple Functions
Chapter 21 Bioinspired Block Copolymer-Based Hybrid Materials
Although the precise cutoff may vary depending on enthalpic considerations and NP
concentration, this heuristic provides a guideline for NP size.
Casting a ﬁlm of a macroscopically homogeneous solution of aged NPs and block
copolymer resulted in a homogeneous, shiny black solid, which was weak and brittle
(Fig. 21.24a). Analysis of samples by TEM (Fig. 21.24b) revealed that a mesostructure
had formed. The order could be improved, however, by annealing at 1308C for 2 days
under vacuum, as conﬁrmed by TEM (Fig. 21.24c). The representative TEM image in
Figure 21.24c revealed an inverse hexagonal mesostructure with grain sizes on the
Figure 21.24 Photograph (a) and bright-ﬁeld TEM images (b) to (g) of materials produced after each
stage of the synthesis. (a) Pieces of unannealed inverse hexagonal hybrid ﬁlm. The grid paper has 5 mm
markings. (b) Unannealed inverse hexagonal hybrid. (c) An annealed inverse hexagonal hybrid. (d)
Examination of the hybrid from (c) at higher magniﬁcation resolved individual PtNPs, seen as dark spots in
the bright-ﬁeld image. (Inset) A typical convergent-beam electron diffraction pattern (seen with an
ultra-high-vacuum scanning transmission electron microscope) from a single PtNP, demonstrating its
crystallinity. (e) An annealed lamellar hybrid. (f) Pyrolysis of an annealed inverse hexagonal hybrid yields a
mesoporous Pt-C composite. (Inset) Selected area electron diffraction, showing Pt expected face-centered
cubic scattering proﬁle. (g) Removal of carbon with an Ar-O plasma yielded mesoporous inverse hexagonal
Pt.86 (Reprinted with permission from S. C. Warren et al., Science 2008, 320, 1748–1752. Copyright AAAS.)
21.3 Nanostructured Polycrystalline Hybrid Materials
order of a few micrometers. Examination of the mesostructure at higher magniﬁcation
(Fig. 21.24d) revealed that individual PtNPs composed the walls of the mesostructure,
with three to ﬁve NPs spanning the thickness of the wall. Besides inverse hexagonal
mesostructures, samples with lamellar morphology were produced. Annealing at
1308C led to a well-developed mesostructure as conﬁrmed by TEM (Fig. 21.24e).
These results suggest that as in the cases discussed earlier of oxide structures, metal
NP –block copolymer hybrid morphologies can be tailored by simply adjusting the
NP volume fraction.14
A rapid pyrolysis process75,90 was used to convert inverse hexagonal hybrids to
ordered mesoporous Pt-carbon composites. Samples were heated at 108C min21
under N2 or Ar to at least 4108C, followed by immediate cooling. Under these conditions, the sp 2-hybridized carbons of the PI block decompose into an amorphous
carbon-rich material with slight graphitic character.75 Characterization of the resulting
materials by TEM (Fig. 21.24f) indicated that the inverse hexagonal structure was preserved. Analysis of a particular sample by PXRD and application of the Scherrer
equation indicated that the Pt nanocrystals’ domain size was 4.1 + 0.4 nm, representing a substantial increase from the parent aged NPs. Nitrogen physisorption (data not
shown) on this sample indicated that the mesopores were open and that 26% of the
sample’s volume (micropores and mesopores) was open space, as expected for an
inverse hexagonal nanocomposite that has pores lined with carbon. The BET surface
area was 18 m2 g21, and the pore diameter 17 nm.
For many applications, such as fuel cells, it is desirable for the metal surface to be
completely exposed. The carbon was removed from microtomed thin ﬁlms ($50 nm
thick) of the nanocomposites using an Ar-oxygen plasma. The mesoporous Pt was
structurally similar to the Pt-carbon nanocomposites, as determined by TEM
(Fig. 21.24g). Close inspection of the pores in TEM images revealed that the grainy
texture indicative of the carbon had disappeared. Alternatively, for thicker ﬁlms (10
to 100 mm thick), a sulfuric acid:nitric acid 3 : 1 (v/v) etch at 708C91 successfully
removed most carbon. Electrochemical data from acid-etched samples indeed conﬁrmed that the metal surface was exposed, showing current densities nearly identical
to that of bulk Pt (Fig. 21.25a). Energy-dispersive spectroscopy (EDS) on the metalcarbon nanocomposites (Fig. 21.25b) showed a composition of 74 wt% Pt, 18 wt%
C, 7 wt% O, and 1 wt% S. In contrast, after the plasma treatment, EDS revealed
that .98 wt% of the sample was Pt, with only trace contributions from carbon and
oxygen (Fig. 21.25c).
We measured the electrical conductivity of Pt-C nanocomposites using two-point
measurements. In a representative example the NP-polymer hybrid had a conductivity
of 2.5 mS cm21, which increased to 400 S cm21 upon pyrolysis. Despite the presence
of carbon, to the best of our knowledge this value represented the highest electrical
conductivity yet measured for ordered mesoporous materials derived from block
copolymers. This discovery creates a potential pathway to a new class of ordered
mesoporous metals made from nanoparticles of different elements and/or distinct
compositions. Such nano-heterogeneous mesoporous metals may have a range of
exceptional electrical, optical, and catalytic properties.
Chapter 21 Bioinspired Block Copolymer-Based Hybrid Materials
Figure 21.25 (a) Polarization curves of the H2 oxidation reaction in H2-saturated 0.1 M H2SO4 solution
(at 2000 rpm and 10 mV s21). Dashed line, mesoporous Pt-C nanocomposite; grey curve, mesoporous
Pt; black curve, planar Pt electrode. E, potential; sat., saturated. (b) EDS of pyrolized sample. The pie
chart displays elemental weight fractions. The sample was on a Si substrate and the primary energy
was 10 keV. Pt ¼ 74 wt%, C ¼ 18 wt%, O ¼ 7 wt%, and S ¼ 1 wt%. (c) EDS of acid-treated sample.
Pt ¼ 98 wt%, C ¼ 1 wt%, and O ¼ 0.5 wt%.86 (Reprinted with permission from S. C. Warren et al.,
Science 2008, 320, 1748– 1752. Copyright AAAS.)
Copying strategies used in nature to structure organic (polymer) – inorganic hybrids is
a rich and fascinating area. In this chapter we have only discussed entirely synthetic
material approaches that did not include any bio(macro)molecules. In particular, we
have focused on the ﬁeld of nanoparticle – block copolymer hybrid systems, which
has tremendous scientiﬁc as well as technological promise. Since the start of the
use of block copolymers to structure direct amorphous silica-type materials, we
have gained a lot of fundamental understanding about these systems and their formation mechanisms. In the meantime, the concept has been successfully generalized
towards other macromolecular architectures of the structure-directing agents, for
example, dendritic blocks and ABC triblock copolymers elevating the complexity
of the resulting structures signiﬁcantly. Moreover, on the inorganic side, beyond amorphous materials powerful approaches towards building mesoporous polycrystalline
structures have been developed.
Through the choice of the appropriate synthetic block copolymer systems as well
as nanoparticles, unprecedented morphological control on the nano- and mesoscales is
obtained in the block copolymer-directed synthesis of hybrid materials. For systems
with favorable enthalpic interactions between one block of the copolymer and the inorganic, that is, with a negative interaction parameter, x, experiments suggest a critical
size of the nanoparticles where the self-assembly behavior of polymers and particles
changes fundamentally. This critical size is the result of competing entropic effects
(translation versus conformation). Competing interactions is a feature also found in
complex biological systems. Below the critical size, the nanoparticles can be regarded
as small molecular weight additives or solvents that are selectively added to one of the
blocks, thereby swelling it, resulting in rational design criteria for controlled hybrid
The potential of this approach for new materials, with multiple nanoscale functional features for applications in nanotechnology and beyond, lies in the versatility
of the polymer chemistry as well as that of the nanoparticle chemistry that can be
exploited in the materials synthesis. Experiments described in this chapter and work
of many others in the ﬁeld so far probably only scratch the surface of things to come.
In the long run, such powerful bottom-up strategies will develop into alternatives to,
or converge with, various top-down approaches, thereby revolutionizing the precision
with which materials will be fabricated over length scales from the molecular all the
way to the macroscopic length scales. This may lead to the design of entirely new
classes of materials with properties that have no analog in the natural world.
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Emerging Concepts in
Interfacial Chemistry of
DMITRY G. SHCHUKIN, DARIA V. ANDREEVA,
KATJA SKORB, AND HELMUTH MO
22.2 SELF-HEALING MULTICOMPONENT COATINGS WITH
PH-TRIGGERED INHIBITOR RELEASE
22.2.1 MESOPOROUS PARTICLES WITH POLYELECTROLYTE
SHELL AS NANOCONTAINERS FOR INHIBITORS
22.2.2 SOLID PARTICLES WITH POLYELECTROLYTE SHELL
AS NANOCONTAINERS FOR INHIBITORS
22.2.3 HALLOYSITE NANOTUBES AS NANOCONTAINERS
22.3 SELF-HEALING MULTICOMPONENT COATINGS WITH
LIGHT-INDUCED INHIBITOR RELEASE
22.3.1 ACTIVATION OF THE INHIBITOR RELEASE BY UV LIGHT
22.3.2 ACTIVATION OF THE INHIBITOR RELEASE BY IR LIGHT
The Supramolecular Chemistry of Organic–Inorganic Hybrid Materials. Edited by Knut Rurack and
Copyright # 2010 John Wiley & Sons, Inc.
Chapter 22 Emerging Concepts in Interfacial Chemistry of Hybrid Materials
The development of a new generation of hybrid coatings, which act at the same time as
passive matrix material and can actively respond to changes in the local environment
of functional inclusions inside the matrix, is attracting a great deal of interest in
the ﬁeld of materials sciences nowadays. Among other types of coatings, hybrid
self-healing anticorrosion coatings are extremely important for the aerospace, maritime, and automotive industries. Active corrosion protection aims to restore material
properties (functionality) if the passive coating matrix is penetrated and corrosive
species come into contact with the substrate. In addition, the partial recovery of the
main functionality of a material can also be considered as self-healing ability. The
main function of anticorrosion coatings is protection of an underlying metallic substrate against environmentally induced corrosion attacks. Thus, it is not obligatory
to recuperate all properties of the ﬁlm; only the protection of the substrate has to be
guaranteed. Consequently, the coatings have to release the active and repairing
material within a short time after changes in the coating’s integrity.
Recent developments in surface science and technology offer several general
approaches to fabricate hybrid self-healing coatings. In the following section, selfhealing coatings with pH-triggered inhibitor release are discussed. In Section 22.3,
we report examples where light is used for annealing/repairing. These systems are
self-annealing/repairing if the light acts only at defect sites because of their peculiar
properties, not if, for example, the light is merely focused. The container-based coating employed for photoinduced autorepairing of polymers and polymer coatings consist of micrometer-scale containers incorporated into the polymer body.1 These
containers are ﬁlled with monomers that can be used for repairing of the coating
and with appropriate catalysts or UV-sensitive agents to initiate the polymerization
of the monomer released at the damaged spot of the polymer coating. In general,
mechanical stress exerted on the coating leads to mechanical deformation of the
microcontainers embedded therein and starts the release of the monomer from the
latter, leading to a sealing of the defects.2 Furthermore, repair of macroscopic adhesion
defects formed throughout the service life of composites can be carried out by
hollow ﬁbers that are ﬁlled with a polymer resin; the ﬁbers then fracture under excessive service life of the composites.3 In a related sense, Lee et al. developed a protective
ceramic composite coating based on sodium-clay and silica multilayers and epoxyamine microcapsules containing MgSO4.4 Self-repairing is achieved here by the sealing of defects with magnesium hydroxide formed after release of magnesium ions
from the capsules. Moreover, electroactive conductive polymers were found to be
effective coating systems for corrosion control due to their ability to trap oxygen
reduction that follows the corrosion process at a remote site with respect to the
Another approach for hybrid self-healing coatings is based on the use of chemical
inhibitors that can be released from the coating system. However, the direct introduction of inhibitor components to the protective coatings very often leads to deactivation
of a corrosion inhibitor and degradation of the polymer matrix.6 To avoid this drawback, research activities have been shifted to the development of containers that can