MNano 06

Preparation and properties of nanomaterials
A. Credi
Nanotecnologia Molecolare
LS-FCM Universit di Bologna
A nanostructured material (or nanomaterial) is defined as a solid material characterized by at least one dimension in the nanometer range MOLECULES
Size (approx.) Nanocrystals and clusters (quantum dots) Other nanoparticles Nanowires Nanotubes Nanoporous solids 2-D arrays (of nanoparticles) Surfaces and thin films 3-D structures (superlattices) 1 10 nm (diam.) 1 100 nm (diam.) 1 100 nm (diam.) 1 100 nm (diam.) 0.5 10 nm (pore diam.) Several nm2 m2 1 1000 nm (thickness) Several nm in the three dimensions Materials Metals, semiconductors, magnetic materials Ceramic oxides Metals, semiconductors, oxides, sulfides, nitrides Carbon, layered metal chalcogenides Zeolites, phosphates, etc. Metals, semiconductors, magnetic mater. A variety of materials Metals, semiconductors, magnetic materials
BULK MATERIALS
A. Credi Nanotecnologia Molecolare LS-FCM Universit di Bologna
Size effects
Size effects constitute a peculiar and fascinating aspect of nanomaterials. The effects determined by size pertain to the evolution of structural, thermodynamic, electronic, spectroscopic, electromagnetic and chemical features of these finite systems with changing size.
The properties of a material depend on the type of motion its electrons can execute, which depends on the space available for them. Thus, the properties of a material are characterized by a specific length scale, usually on the nm dimension. If the physical size of the material is reduced below this length scale, its properties change and become sensitive to size and shape.
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Size effects
Figure 4. Melting temperature versus size for CdS nanocrystals.
Figure 6. Size dependence of the wurtzite to rock salt pressureinduced structural transformation in CdSe nanocrystals.
Figure 48. Observation of discrete electronic transitions in optical absorption for a series of sizes of monodisperse CdSe.
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Quantum confinement
In any material, substantial variation of fundamental electrical and optical properties with reduced size will be observed when the energy spacing between the electronic levels exceeds the thermal energy (kT). In small nanocrystals, the electronic energy levels are not continuous as in the bulk but are discrete (finite density of states), because of the confinement of the electronic wavefunction to the physical dimensions of the particles. This phenomenon is called quantum confinement and therefore nanocrystals are also referred to as quantum dots (QDs).
Moreover, nanocrystals possess a high surface are and a large fraction of the atoms in a nanocrystal are on its surface. Since this fraction depends largely on the size of the particle (30% for a 1-nm crystal, 15% for a 10-nm crystal), it can give rise to size effects in chemical and physical properties of the nanocrystal.
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Quantum confinement
108
NANOSCALE MICROSCALE
100% 10% 1% Fraction of atoms on surface

Kubo gap (K)
104
0.1% 0.01%
10-4 0.001% 0.1 1 10 100 1000
Particle diameter (nm)

Fig. 1.3. A plot of the average electronic energy level spacing (Kubo gap, ) of sodium as a function of the particle diameter. Also shown is the percentage of Na atoms at the surface as a function of particle diameter
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Electronic band theory

* * * 2 *1
Energy
2Li
2s1
3Li 2s1
4Li
2s1
2
1
Biatomic molecule Li2
Triatomic molecule Li3
Tetratomic molecule Li4
MO for metallic Lithium NA Li
NA MO unoccupied
NA Li 2s1
NA MO occupied
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3s Band
MO unoccup.
Energy FERMI LEVEL
MO occupied
Fermi level: in an orbital band electronic structure, it is the highest occupied electronic level
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Electronic bands in metallic lithium CONDUCTION BAND
3NA equivalent 2p AO NA equivalent 2s AO
Band of 3NA 2p orbitals delocalized and unoccupied Overlap between bands of orbitals 2s and 2p Band of NA 2s orbitals delocalized and half-occupied
Energy
VALENCE BAND NA equivalent 1s AO Band of NA 1s orbitals delocalized and occupied
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Conduction band (empty)
band gap
band gap
Valence band (full)
Metal (conductor)
Insulator
Semiconductor
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Energy levels in metallic and semiconductor nanoparticles
Density of states in metal (A) and semiconductor (B) nanocrystals. In each case, the density of states is discrete at the band edges. The Fermi level is in the center of a band in a metal, and so kT will exceed the level spacing even at low temperatures and small sizes. Nevertheless, metal nanoparticles of very small size can exhibit insulating properties. In contrast, in semiconductors the Fermi level lies between two bands, so that the relevant level spacing remains large even at large sizes. The band gap increases in smaller semiconductor nanocrystals.
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Gold nanoparticles
Gold nanoparticles are the most stable and widely used metal nanoparticles
5th Millennium B.C.: start of extraction of gold metal Ca. 400 B.C.: appearance of soluble gold
Gold colloids were used for aesthetic (decoration) and curative purposes
Colloidal gold is still used for colouring and decoration purposes

the Lycurgus Cup (4th Century B.C) is ruby red in transmitted light and green in reflected light, due to the presence of gold colloids
1857: Faraday reported formation of deep-red solutions of colloidal Au by reduction of an aqueous solution of AuCl4 by phosphorus in CS2 (two phase system) Thin films prepared from dried colloidal solutions showed reversible colour changes upon mechanical compression.
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Preparation of Au NP
All chemical methods for the preparation of gold nanoparticles are based on reduction of Au(III) derivatives. However, in general it is difficult to control the size of the nanoparticles, and in absence of stabilizing agents the particles tend to aggregate (collapse).
Alkylammonium salts can be used to stabilize nanoparticles, as they form a sort of electrical double layer on the surface. Such an interaction is weak and the gold surface remains reactive. For this reason, these nanoparticles are not very stable and cannot be separated from the solution from which they have been prepared.
The synthesis is usually performed in a two phase (water/organic solvent) system. Alkylammonium salts like TOAB (tetraoctylammonium bromide), besides passivating the gold surface, perform the task of phase transfer agents towards the Au(III) species to the organic phase.
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Procedure for preparation of Au nanoparticles in a biphasic system. A phase-transfer agent which also acts as a surface stabilizer is employed.
TOAB Toluene
TOAB Toluene HAuCl4 Water HAuCl4 Water
Stirring
TOA+ [AuCl4] Toluene Water
Separation
Stirring
Au NP Toluene Water
TOA+ [AuCl4] Toluene NaBH4 Water
NaBH4 Water
TOA+ [AuCl4] Toluene
_
TOAB=tetraoctylammonium bromide
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Au nanoparticles, as well as other metal and metal oxide nanoparticles, can be prepared inside a suitable block copolymer micelle. Reduction of the metal salt is performed with usual reagents (H2, NaBH4, hydrazine)
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Preparation of Au NP: the Brust-Schiffrin method

Formation of Au NP coated with organic shells by reduction of Au(III) compounds in the presence of thiols
TOAB=tetraoctylammonium bromide
TOAB Toluene
TOAB Toluene HAuCl4 Water HAuCl4 Water
Stirring
TOA+ [AuCl4] Toluene Water
Separation
R
R
R
S S
Au
S S
S
NaBH4
R
R(CH2)nSH
TOA+ [AuCl4] Toluene
_
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S S R
R
S S
Stirring
R
M. Brust et al., J. Chem. Soc. Chem. Commun. 1994, 801; 1995, 1655.
Au clusters and NP
Gold clusters are made up of a defined number of Au atoms. Such a number is based on the dense packing of atoms taken as spheres, each atom being surrounded by 12 nearest neighbors. Thus, the smallest cluster contains 13 atoms, and the following layers contain 10n2+2 atoms (n = layer number). Clusters containing 55, 147, 309, 561, 923, 1415 and up to 2057 atoms (n=28) have been isolated. Larger aggregates constitute the fuzzy frontier between clusters and colloids (Au NP), the latter being objects with some dispersity described by a histogram of size distribution determined using TEM data.
The size of the NP can be controlled from the stoichiometric ratio of the reactants employed in the synthesis. For example, the following ratios HAuCl4 : TOAB : thiol : NaBH4 = 1 : 3 : 2 : 10 afford NP of diameter around 5 nm.
TEM images and size distributions of Au NP capped with dodecanethiol: (b) as prepared and after heating at (c) 150C, (d) 190C, (e) 230C. (f): octadecanethiol Au NP heat-treated at 250C
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Optical properties of metal NP

The optical properties of metallic NP are determined by the surface plasmon resonance phenomenon. The SPR is caused by the coherent motion of the conduction band electrons from one surface of the particle to the other, upon interaction with an electromagnetic field. The decrease in size below the electron mean free path (distance the electron travels between scattering collisions with the lattice centers) gives rise to intense absorption in the UV-vis range. Optical excitation of the SPR gives rise to the surface plasmon absorption
max of SPA for Au NP in water
d (nm) <2 9 15 22 48 99 SPA max (nm) no SPA band 517 520 521 533 575
Figure 59. Illustration of the excitation of the dipole surface plasmon oscillation. A dipolar oscillation of the electrons is created with period T
UV-vis absorption spectra of (a) AuCl4, and Au NP capped with dodecanethiol with the following mean size: (b) 1.5, (c) 3.4, (d) 5.4, (e) 6.8 nm.
Figure 60. Optical absorption spectra of 22, 48, and 99 nm spherical gold nanoparticles. The broad absorption band corresponds to the surface plasmon resonance.
For Ag NP, the SPR band peaks around 370 nm
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The surface plasmon absorption depends on the size and the shape of the particles, and on the dielectric constant of the matrix. For small particles it depends also on the nature of the molecules adsorbed on the NP surface.
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Noble metals exhibit extremely weak photoluminescence ( ca. 1010) in the bulk, assigned to recombination of the excited electrons with the holes within the d band. In metal NP the luminescence yield increases by as much as 6 orders of magnitude because of the so-called lightning rod effect: the incoming (exciting) and outcoming (emitted) electric fields are amplified by the plasmon resonances around the particles. Hence, the luminescence energy and efficiency are subjected to the size effect.
Figure 62. Luminescence spectra of colloidal gold nanorods with aspect ratios of 2.6, 3.3, and 5.4 (480-nm excitation). The inset shows the linear dependence of the luminescence maximum on the aspect ratio.
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Electrical properties of metal NP

Electrical conductivity of bulk metals is based on their electronic band structures, and the mobility of electrons is related to their mean free path between two collisions with the lattice. The collective motion of electrons in a bulk metal obeys Ohms law, V = RI, where V is the applied voltage, R is the resistance of the material and I is the current. As the electronic band structure changes into discrete energy levels, Ohms law is no longer valid. If one electron is transferred to a small particle, the Coulomb energy of the latter increases by EC = e2/2C, where C is the capacitance of the particle. If the temperature is low such that kT < e2/2C, single electron tunneling processes are observed.* Hence, the I-V characteristic of a quantum dot is not linear, but staircase-like. No current flows up to VC = e/2C. If this value is reached, an electron can be transferred. Following this, an electron tunnelling process occurs if the Coulomb energy of the particle is compensated by an external voltage of V = ne/2C. This behaviour is called Coulomb blockade. The charging energy increases with decreasing the size of the quantum dot.
Figure 66. I-U characteristic of ideal single electron transport, where Coulomb blockade is shown as the step function.
* Thermal motion of the atoms in the particle can initiate a change in the charge and the Coulomb energy so that further electrons may tunnel uncontrolled

Experimental approaches to measure the Coulomb blockade.
Two metallic leads with spacing of a few nm are fabricated. An organic monolayer is then used to bind nanocrystals to the leads. When a nanocrystal bridges the gap between the leads, it can be electrically investigated.
a)
Figure 67. (a) Field emission scanning electron micrograph of a lead structure before the nanocrystals are introduced. The light gray region is formed by the angle evaporation and is 10 nm thick. The darker region is from a normal angle evaporation and is 70 nm thick. (b) Schematic cross section of nanocrystals bound via a bifunctional linker molecule to the leads. Transport between the leads occurs through the mottled nanocrystal bridging the gap.
b)
Fig. 1. Schematic illustration of a single-electron tunnel junction formed by a nanocrystal held between the STM tip and the substrate.
Fig. 1.7. (a) IV characteristic of an isolated 3.3 nm Pd nanocrystal (dotted line) and the theoretical fit (solid line) obtained at 300 K using a semiclassical model. (b) The size dependence of the charging energy. (Experimental setup as in Fig. 1)
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In voltammetric experiments in solution, metal nanoparticles behave as redox active molecules, showing redox cascades that are well known in inorganic and organometallic electrochemistry.
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Preparation of semiconductor nanoparticles

The chemical growth of bulk or nanometer-sized materials involves the process of precipitation of a solid phase from solution. The challenge in nanoparticles synthesis is to control the size and shape of the crystals such that their properties can be tailored. This requires the understanding and control of the key processes of nucleation, growth and termination. Many strategies are available: sol processes, micelles, sol-gel, hydrothermal syntheses, etc. Among the most common and widely studied semiconductor nanoparticles are those of the II-VI type (ZnS, ZnSe, CdS, CdSe, CdTe and HgS) and of the III-V type (e.g., GaAs, InP and InAs) Semiconductor NP can be prepared in aqueous media using stabilizing agents, with procedures similar to those employed for the synthesis of gold NP. These approaches, however, lead to highly defective and polydisperse nanocrystals. More recently, procedures have been reported for the synthesis of highly crystalline and nearly monodisperse NP. E.g., for CdE (E=S, Se or Te):
Cd precursor (dimethyl Cd, Cd oxide, carbonate or acetate) + chalcogen (elemental S, Se or Te) in a hot coordinating solvent (e.g., TOPO, tri-n-octylphosphine oxide)
High temperature (fast particle nucleation)
Low temperature (slow particle growth)
Nanoparticles
Washing
Reaction quenching
YES
Desired size reached?
NO
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Optical properties of semiconductor NP

In semiconductors, optical excitation causes the promotion of a valence band electron into the conduction band, leaving behind a valence band hole. Once promotion has occurred, the CB electron quickly relaxes into the lowest energy CB state, while the hole moves to the top of the VB (VB electrons cascade down into lower energy valence states). The coupled electron-hole pair is often referred to as a single entity called exciton, since one cannot exist without the other.
electron-hole pair (exciton)
CB
Energy
CB
CB _
Band gap
h > b.g.
thermal relaxation
h'
Band edge luminescence
+ VB VB + VB
Photoluminescence arises from recombination of the CB electron with the VB hole and is called band edge luminescence. Such a luminescence is characterized by a very small Stokes shift relative to band edge absorption.
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Since the promoted electron and the VB hole have opposite charges, a strong electrostatic attraction causes them to remain relatively localized within a nanometer-sized region. The exciton volume can be calculated for a given material, and the corresponding radius is known as the Bohr radius. For a semiconductor particle, quantum confinement occurs when the nanocrystal radius becomes comparable to the Bohr radius. For CdSe the Bohr radius amounts to ca. 5.6 nm.
D (nm) 4.4 4.2 4.1 3.9 3.3 2.9 2.5 2.4
Size tunable fluorescence emission from CdSe/ZnS core shell nanocrystals synthesized by Quantum Dot Corporation (www.qdots.com). The size of the CdSe core dictates the emission wavelength through quantum confinement. Vials of CdSe nanocrystals from NN-labs (www.nn-labs.com)
Emission and absorption spectra of CdSe nanocrystals of different sizes. The change in the emission width is due to the decrease in the nanocrystal diameter distribution with increase in diameter.
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The presence of dangling orbitals at the surface of the NP, or any defect states in the bulk, provide traps for the excited electrons and holes prior to recombination. Therefore, an electron excited to the CB, or a VB hole, can transfer itself non-radiatively to one of these surface or defect states before undergoing a (radiative or non-radiative) transition to a lower energy state. The net result is that either band edge luminescence is quenched, or emission is shifted to much lower energies compared to those of band edge recombination (redshifted emission of NP)
Band edge emission: small stokes shift, sharp, controllable by size Defect (redshifted) emission: large stokes shift, broad, controllable by chemical means (doping)
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Since defect emission is difficult to fine tune, for many applications it is important to preserve band edge emission. To this aim, the surface of the NP can be passivated by chemically binding a capping agent. Another approach consists in overcoating a nanocrystal of a given semiconductor with a thin layer of a semiconductor with higher band gap (core-shell particles).
All semiconductors undergo absorption processes, but because of selection rules (conservation of momentum) only direct gap semiconductors (e.g. CdSe) exhibit intense band edge luminescence, with yields close to 100%. Indirect gap semiconductors (e.g. Si) show luminescence with yields that are 3 to 4 orders of magnitude smaller than direct gap materials.
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Engineered semiconductor NP for NIR LEDs

Core: InAs (2.4 nm diameter) Shell: ZnSe (1.5 monolayers)
Science 2002, 295, 1506-1508
MEHPPV/NC composites Spin-casted films on glass or ITO Thickness ca. 100 nm
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Metal and semiconductor NP: a summary

Metal NP: Synthesis with a sol method by using capping agents to prevent aggregation and control the size Quantum confinement occurs when the electrons motion is limited by the size of the NP The electronic energy levels of the particle around the Fermi level are affected only for very small sizes The UV-visible absorption is determined by the surface plasmon resonance, which is size and shape dependent Exhibit a very weak luminescence The I-V behaviour is characterized by the Coulomb blockade Show valuable catalytic properties, owing to the large surface to mass ratio Semiconductor NP: Synthesis with a variety of chemical methods to produce NP with desired size, shape and structure Quantum confinement occurs when the radius of the NP is comparable to the excitons Bohr radius The electronic energy levels of the particle around the Fermi level are strongly affected for sizes in the 10-100 nm range The UV-visible absorption is determined by the band edge transition, which is strongly size and shape dependent (bandgap energy increases as the size decreases) and hence highly tunable Can exhibit band edge or defect (redshifted) luminescence; in both cases luminescence can be very intense and can be tuned The I-V behaviour is characterized by the Coulomb blockade Show valuable catalytic properties, owing to the large surface to mass ratio
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Chemically functionalized nanoparticles

R
R
S S S
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S S S
R S
Au
S S
R
R
S S
Chemically functionalized nanoparticles: Heterosupramolecular Chemistry

When one (of more) component(s) of a supramolecular system is a condensed-phase component (referred to as a heterocomponent), a heterosupermolecule is formed. The heterocomponent is usually a metal or metal oxide nanoparticle, and it is linked to the other molecular components by exploiting the same type of interactions used to prepare SAMs.
self-assembly
molecular components heterocomponent (nanoparticle)
heterosupramolecular system
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Chemically controlled aggregation of nanoparticles
SH O O O O O
+
O O O O O SH
N H2
H2 N
+
Ag
Ag
Ag
Aggregate
Ag
D. Fitzmaurice et al., J. Am. Chem. Soc., 2000, 122, 6253
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Dye-sensitized solar cells

O
O OH
eh dye
O
HO N N HO N NCS
HO O O OH O HO N N N NCS RuII N NCS
NCS RuII NCS
TiO2
HO O
black dye
N3
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M. Gratzel, Nature, 2001, 414, 338
Carbon nanoparticles and nanowires

C60 (Buckminsterfullerene)
Discovered in 1985 Diameter: ca. 0.7 nm
Kroto, Curl, Smalley et al., Nature, 1985, 318, 162
Carbon Nanotubes
Discovered in 1991 (MWNT) and 1993 (SWNT) Diameter: 0.4 nm (SW) 100 nm (MW) Length: up to 20 cm!
S. Iijima, Nature, 1991, 354, 56
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The fullerene family

C60 (Buckminsterfullerene)
Higher fullerenes
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Preparation of fullerenes
Graphite vaporization under high energy laser pulse in inert atmosphere, followed by ionization and mass spectrometry (Kroto, Smalley, Curl 1985)
Electrical discharge between graphite electrodes in an atmosphere of He at 100 torr. The resulting soot is scraped from the evaporation chamber and dissolved in benzene. Further separation and purification leads to C60 in gram scale (Kratshcmer, Huffman 1990)
Cost: ~ 800 /g (Aldrich)
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Structural features of C60
Structure: 20 hexagons and 12 pentagons, truncated icosahedron 60 atoms C sp2, perfectly equivalent, a kind of huge atom Diameter of the inner cavity: 3.6 5,6 1.45 6,6 1.38
Examples of endohedral fullerenes: N@C60, Li@C60, He@C60, Ln@C60, Ln@C70, Ln@C82
Different reactivity!
(6,6 > 5,6)
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Properties of C60 and its derivatives

Black crystalline solid, thermally stable up to 400 C Doped with alkali metals: conductor and superconductor Only (sparingly) soluble in organic apolar solvents (CS2, benzene, toluene, CH2Cl2) Very difficult to oxidize Easy to reduce, six reversible stepwise reductions Broad UV-vis absorption Fluorescence Long lived triplet excited state with high absorption coefficient Potent singlet oxygen sensitizers Acceptors of electrons and electronic energy Photostable
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Change of electronic structure, change in colour
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Chemical functionalization of C60

Performed by addition reactions on the C=C bonds
sp2 carbon atoms are highly pyramidalized: the driving force of addition is relief of strain of the fullerene cage
R R
Pyrrolidino-C60
(or fulleropyrriolidine)
Methano-C60
Cyclohexyl-C60
NO2 N
Dihydro-C60
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Isoxazolino-C60
Pyrazoline-C60
Carbon nanotubes
Carbon nanotubes (CNTs) are cylinder-shaped macromolecules made by carbon atoms. The walls are made up of a hexagonal lattice of atoms (like a graphite sheet) and are capped at their ends by one half of a fullerene-like moiety
single-walled nanotube (SWNT) 0.4-3 nm diameter
multi-walled nanotube (MWNT) 2-100 nm diameter
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Carbon nanotubes
Chiral indices m, n m = 0 zig-zag NTs m = n armchair NTs non chiral
m n chiral NTs (two enantiomers)
chiral vector
zig-zag
armchair
Small 2005, 1, 180
Preparation of carbon nanotubes
Cost: ~ 100 /g (but purity is very low)
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Properties of carbon nanotubes

ELECTRICAL PROPERTIES The main interest around CNTs arises from their electrical properties. Calculations, verified by single-molecule experiments, show that they are expected to be metallic or semiconducting depending on their structure, i.e. on their chiral vector Armchair NTs show metallic properties Zig-zag and chiral NTs can be either metallic or semiconducting
n m = 3k (with k integer): metallic NTs n m 3k: semiconducting NTs (Ebandgap diameter1)
Similarly shaped molecules consisting of only one element (carbon) may have very different electronic behaviour! At present, no synthetic method ensures a reliable control of the electrical properties of the NTs. The raw nanotube material thus consists of a mixture of metallic and semiconducting NTs (usually in ratio of 1:2). Separation of the metallic NTs from semiconductor ones is extremely difficult MECHANICAL PROPERTIES CNTs possess highly valuable mechanical properties: Tensile strength 10 times larger than a steel wire of corresponding diameter Huge aspect ratio (length/diameter) Low density (6 times smaller than that of steel)
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Chemical functionalization of CNTs

CHEMICAL PROPERTIES CNTs are extremely stable molecules Chemical functionalization of CNTs is difficult! CNTs possess two distinct region of different reactivity: At the caps: the presence of 5-membered rings leads to a higher reactivity at these points, comparable to that of fullerenes On the walls: more difficult to accomplish
Addition reactions to the C=C bonds involve the transformation of trigonalplanar sp2 into tetrahedral sp3 carbon centers The process is energetically favoured by a convex curvature of the carbon lattice The caps are more reactive than the walls, which are in turn more reactive than a graphene sheet
The inner surface of NTs is very unreactive towards addition owing to its concavity. CNTs have been proposed as nanocontainers for reactive gas atoms, e.g. N, like N@C60)
NTs of smaller diameter are more reactive than larger NTs
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Chemical functionalization of CNTs

CNTs are not ideal structures: they contain defects formed during synthesis Typically 13% of the C atoms are located at a defect site The Stone-Wales defect (two pairs of 5-membered and 7-membered rings, also known as 7-5-5-7) is one of the most common defects. It leads to a local deformation of the graphene sidewall, introducing an increased curvature ( higher reactivity). The strongest curvature is at the border between the two 5-membered rings
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Possible applications of CNTs

Nanowires (metallic NTs) Field-effect transistors (semiconductor NTs) Chemical sensors (all atoms are on surface!) Electrochemical sensors (high electron transfer rates for many redox couples and size comparable to biomolecules NTs as nanoelectrodes) Heterogeneous catalysis (defined morphology, covalent attachment of catalyst units) Mechanically reinforced composites (e.g. with polymeric materials)
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Supramolecular templating of inorganic nanowires

Molecule 1 self-assembles into a network of ribbons 10x2 nm in cross section and up to 10 m in length. These ribbons, whose cross section is made up of two hydrogen-bonded 1 species packed head-to-head, can be either flat or twisted depending on the solvent. In ethyl methacrylate, addition of Cd(II) nitrate in THF to suspensions of twisted ribbons creates a supersaturation of Cd2+ ions on the surface of the ribbon because the Cd2+ ions prefer the relatively hydrophilic phenolic groups of 1 over the hydrophobic solvent. Upon exposure to gaseous H2S as a source of S2 ions, nucleation and growth of CdS localized to the ribbon occurs, leading to a templating effect.
If mineralization occurs on one face only, single helices of CdS nanowires are obtained. In the case of mineralization on both faces, a double helix is expected. (Note that if the ribbon is straight, the two faces are fully equivalent)
Small 2005, 1, 694
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Supramolecular templating of inorganic nanowires
Formation of double vs single helices does not depend on mineralization time. Single helices are normally obtained with freshly prepared ribbons, whereas double helices are formed by using aged ribbons the different templating ability must reside in structural differences between ribbons
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Viruses as templates for nanomaterials

Viral capsids (the self-assembled protein cage structures) offer robust and monodisperse structures and exist in a large variety of sizes and shapes The protein surface can be used as a synthetic platform for synthetic modification, or simply aminoacid residues can be exploited as nucleation sites Many viruses can be genetically modified, offering a virtually unlimited range of templates
Some of the routes followed to synthesize biohybrid materials using rod-shaped (TMV, M13) and cage-structured (CCMV, CPMV) viruses.
Chem. Rev. 2005, 105, 1445
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TMV template-directed synthesis of metallic nanowires
The metal crystals can be deposited by electrochemical methods. Depending on the metallization conditions, it is possible selectively target the outer or inner surface of the tubelike Tobacco Mosaic Virus
Chem. Rev. 2005, 105, 1445
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M13 template-directed synthesis of nanowires

The M13 bacteriophage is a rod-shaped virus which infects bacteria. This virus contains a single stranded DNA and three different types of coat proteins. 2700 copies of the major coat protein are arranged in a repeating helical array, forming a flexible cylinder in which the DNA is encased. Five copies of the two minor coat proteins are situated at each end of the virus. The wild-type virus is approximately 860 nm long and 6.5 nm wide. The viral coat proteins can be easily modified by genetic engineering to insert nucleation centers on the virus surface or to specifically functionalize viruses with different binding motifs.
Chem. Rev. 2005, 105, 1445

Nanoporous materials
Nanoporous materials are solid materials showing channels, pores or cavities with at least one dimension in the nanometer range
The most common and prototypical nanoporous materials are represented by the zeolites. Zeolites are crystalline solids with well-defined structures that generally contain silicon, aluminium and oxygen in their framework and cations, water and/or other molecules wthin their pores. Many occur naturally as minerals, and are extensively mined in many parts of the world. Others are synthetic, and are made commercially for specific uses, or produced by research scientists trying to understand more about their chemistry. Because of their unique porous properties, zeolites are used in a variety of applications with a global market of several million tonnes per annum. Major uses are in petrochemical cracking, ion-exchange (water softening and purification), and in the separation and removal of gases and solvents. They are often also referred to as molecular sieves.
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The framework structure of zeolites

A defining feature of zeolites is that their frameworks are made up of 4-connected networks of atoms. One way of thinking about this is in terms of tetrahedra, with a silicon atom in the middle and oxygen atoms at the corners. These tetrahedra can then link together by their corners (see illustration below) to from a rich variety of beautiful structures. The framework structure may contain linked cages, cavities or channels, which are of the right size to allow small molecules to enter - i.e. the limiting pore sizes are roughly between 3 and 10 in diameter.
In all, over 130 different framework structures are now known. In addition to having silicon or aluminium as the tetrahedral atom, other compositions have also been synthesised, including the growing category of microporous aluminophosphates, known as ALPOs.
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Applications of zeolites
Catalysis
Zeolites have the ability to act as catalysts for chemical reactions which take place within the internal cavities. An important class of reactions is that catalysed by hydrogen-exchanged zeolites, whose framework-bound protons give rise to very high acidity. This is exploited in many organic reactions, including crude oil cracking, isomerisation and fuel synthesis. Zeolites can also serve as oxidation or reduction catalysts, often after metals have been introduced into the framework. Examples are the use of titanium ZSM-5 in the production of caprolactam, and copper zeolites in NOx decomposition. Underpinning all these types of reaction is the unique microporous nature of zeolites, where the shape and size of a particular pore system exerts a steric influence on the reaction, controlling the access of reactants and products. Thus zeolites are often said to act as shape-selective catalysts. Increasingly, attention has focused on fine-tuning the properties of zeolite catalysts in order to carry out very specific syntheses of high-value chemicals e.g. pharmaceuticals and cosmetics. Adsorption and Separation The shape-selective properties of zeolites are also the basis for their use in molecular adsorption. The ability preferentially to adsorb certain molecules, while excluding others, has opened up a wide range of molecular sieving applications. Sometimes it is simply a matter of the size and shape of pores controlling access into the zeolite. In other cases different types of molecule enter the zeolite, but some diffuse through the channels more quickly, leaving others stuck behind, as in the purification of para-xylene by silicalite. Cation-containing zeolites are extensively used as desiccants due to their high affinity for water, and also find application in gas separation, where molecules are differentiated on the basis of their electrostatic interactions with the metal ions. Conversely, hydrophobic silica zeolites preferentially absorb organic solvents. Zeolites can thus separate molecules based on differences of size, shape and polarity. Ion Exchange The loosely-bound nature of extra-framework metal ions (such as in zeolite NaA) means that they are often readily exchanged for other types of metal when in aqueous solution. This is exploited in a major way in water softening, where alkali metals such as sodium or potassium prefer to exchange out of the zeolite, being replaced by the "hard" calcium and magnesium ions from the water. Many commercial washing powders thus contain substantial amounts of zeolite. Commercial waste water containing heavy metals, and nuclear effluents containing radioactive isotopes can also be cleaned up using such zeolites.
A. Credi
Guests entrapment in zeolites

Zeolites can be easily loaded with molecular guests that can enter the pores. Interesting types of guests in this regard are catalysts and dyes. Guests that are larger than the pores can also be incorporated Inside the cavities of zeolites (ship-in-a-bottle complexes). Most often, the entrapped guests are catalytically active metal compounds.
Ship-in-a-bottle complexes can be prepared in two different ways: (i) synthesis of the guest (e.g., assembly of the metal complex) within the cavity by externally adding the reactants (i.e. metal ions and ligands) (ii) synthesis of the zeolite around the preformed guest, also referred to as the build-bottle-around-ship approach.
A. Credi
Design of new crystalline porous materials

The chemistry of metal-organic frameworks (MOFs) has provided an extensive class of crystalline materials with high stability, tunable metrics, organic functionality, and porosity. Owing to modern design strategies (crystal engineering) it is possible to obtain materials with predetermined structures, composition and properties. Crystalline materials with extremely high surface area (up to 3000 m2/g) and very low density (down to 0.2 g/cm3) have been produced. These species, which overperform zeolites as far as porosity is concerned, are promising for applications in gas storage, catalysis, structural materials, delivery systems.
O. Yaghi et al., Nature 2003, 423, 705
Examples of MOFs based on metalcarboxylate motifs. The yellow shperes indicate the internal cavities of the materials
A. Credi

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Preparation and properties of nanomaterials

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Figure 4. Melting temperature versus size for CdS nanocrystals.

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100% 10% 1% Fraction of atoms on surface

Kubo gap (K)

10-4 0.001% 0.1 1 10 100 1000

Particle diameter (nm)

Electronic band theory

Biatomic molecule Li2

Triatomic molecule Li3

Tetratomic molecule Li4

MO for metallic Lithium NA Li

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Electronic band theory

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Electronic band theory

3NA equivalent 2p AO NA equivalent 2s AO

VALENCE BAND NA equivalent 1s AO Band of NA 1s orbitals delocalized and occupied

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Electronic band theory

Conduction band (empty)

Valence band (full)

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Energy levels in metallic and semiconductor nanoparticles

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Colloidal gold is still used for colouring and decoration purposes

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TOA+ [AuCl4] Toluene Water

TOA+ [AuCl4] Toluene NaBH4 Water

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Optical properties of metal NP

For Ag NP, the SPR band peaks around 370 nm

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Optical properties of metal NP

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Optical properties of metal NP

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Electrical properties of metal NP

Electrical properties of metal NP

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Electrical properties of metal NP

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Preparation of semiconductor nanoparticles

High temperature (fast particle nucleation)

Low temperature (slow particle growth)

Desired size reached?

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Optical properties of semiconductor NP

Band edge luminescence

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Optical properties of semiconductor NP

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Optical properties of semiconductor NP

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