CHEM 1270H: TOPICS IN

INORGANIC CHEMISTRY

MESOCHEMISTRY
SYNTHESIS IN “INTERMEDIATE” DIMENSIONS

Geoffrey A. Ozin
Materials Chemistry Research Group
University of Toronto

Tel: 416 978 2082, Fax: 416 971 2011

E-mail: gozin@chem.utoronto.ca
Group web-page: www.chem.toronto.edu/staff/GAO/group.html
 MESOCHEMISTRY
SYNTHESIS IN “INTERMEDIATE” DIMENSIONS

• Purpose of the four lectures

• Introduce key physicochemical design principles that

underpin the template directed synthesis of inorganic
mesoporous materials

• Focus on synthetic control of structure, composition and

form

• Appreciate how the properties of materials fashioned at

this intermediate length scale can be orchestrated to create
a purposeful function directed to a specific field of use.
Angew Chem 2006, 45, 3216
 ZEOLITES
CRYSTALLINE MICROPOROUS ALUMINOSILICATES
WITH PORES AND CHANNELS IN SIZE RANGE 0.3-1NM
ESCAPE FROM THE 1NM ZEOLITE PRISON

ISI Citations
6386
(scopus2019:14230)
ESCAPE FROM 10 Å PRISON
• Discovery by Mobil
researchers that an assembly
of surfactant molecules could
function as a supramolecular
template for organizing and
polymerizing silicates
• Produced the first fully
characterized examples of
periodic hexagonal and cubic
forms of mesoporous silica
with pore diameters 2-10 nm
• Integration of surfactant and
sol-gel chemistry
 Air drying
SOL-GEL CHEMISTRY

SC CO2 drying
SOL-GEL CHEMISTRY

From molecular size to micrometer

Air drying
 SOL-GEL CHEMISTRY
Base catalyzed hydrolytic poly-condensation of silicon alkoxides to silica
 SOL-GEL CHEMISTRY
Acid catalyzed hydrolytic poly-condensation of silicon alkoxides to silica

• HYDROLYSIS

• (RO)3SiOR + H3O+  (RO)3SiORH+ + H2O

• 2H2O + (RO)3SiORH+ (RO)3SiOH + ROH + H3O+   

• CONDENSATION

• (HO)3SiOH + H3O+  (HO)3SiOH2+ + H2O

• (HO)3SiOH + (HO)3SiOH2+  (HO)3SiOSi(OH)3 + H3O+   

SOL-GEL CHEMISTRY
 Lyotropics
Kraft T
 CO-ASSEMBLY
SURFACTANT AND SOL-GEL CHEMISTRY
 MILESTONES IN MESOPOROUS MATERIALS

• Escape from the 1 nm prison (surfactant templated synthesis)

• Diagnostics (structure, property)
• Structure control (H, C, L, WH)
• Template removal (calcination, ion exchange, solvent extraction,
photocalcination, ozonolysis, microwave, lizard fragmentation)
• Pore size control (surfactant, block copolymer, swelling additive)
• Templating mechanism (micelle, liquid crystal)
• Smart mesostructure (pore size expansion, metamorphic channels)
• Free-standing and supported film (mesoepitaxy, pore orientation)
• Topological defects (nucleation, growth, origin of curved pores and form)
• Morphogenesis of curved shapes (fiber, discoid, gyroid, spiral, sphere)
 MILESTONES IN MESOPOROUS MATERIALS

• Nanomeso (nanoscale particles, nanocrystalline texture)

• Biomimetics (biomineralization connection, hierarchy (nm-micron length
scales), complexity, organic-inorganic nanocomposites or hybrids)
• Panoscopic materials (global self-assembly over “all” scales, surfactants,
block copolymers, opals)
• Patterning (microcontact printing, micromolding in capillaries,
microtransfer printing, ink jet printing, photolithography)
• Smart guests (SC, M, OM, C, P)
• Smart channels (terminal and bridging organofunctionality)
• Beyond silica (metals, oxides, sulfides, phosphates, coordination, polymers)
• Mesoreplication (carbons, metal oxides)
• Function and utility (fuel cell, solar cell, battery, laser, low-k, controlled
chemical and drug release, chemical/biosensor, electrochromic display, 1D
Bragg photonic crystals, low refractive index optical cladding )
 pH, pH, pH

EFFECT ON SELF-
ASSEMBLY MECHANISM

Surfactant
Catalyst Temperature

Concentration
pH
Precursor Template removal

Ageing conditions
HYDROLYSIS, CONDENSATION, SELF-ASSEMBLY
 ESCAPE FROM 10 Å PRISON
100

110

200

210

HEXAGONAL MESOPOROUS SILICA

Small angle X-ray diffraction Nitrogen gas adsorption isotherms

hexagonal Mesoporous 2 -50 nm

Macroporous > 50 nm

cubic

Microporous < 2 nm

lamellar IUPAC CONVENTION

FOR PORE SIZES
 CUBIC BICONTINUOUS MESOPOROUS SILICA
Equipotential minimal energy surface TEM image cubic mesoporous structure

Mesocrystalline glass –
crystalline mesoporosity
- periodic arrangement
of mesopores – glassy
walls - long range order
Cubooctahedral morphology at mesoscale – short
range order at
microscale
 WHAT CAN WE DO WITH PMS MATERIALS?
HOST-GUEST INCLUSION WITH LARGE GUESTS !!!
ORGANICALLY FUNCTIONALIZED
PMS - GRAFTING
CLEVER USE OF GRAFTING CONTROLLED
RELEASE OF ACTIVE COMPOUNDS
 NANO-PMS
SMART DRUG
DELIVERY
AFM 2007
ORGANICALLY FUNCTIONALIZED
PMS - COCONDENSATION
 PHOTOCHEMICAL SWITCH
PORE SIZE CONTROL

Synthesis of films bearing photosensitive azobenzene units: 4-(3-triethoxysilyl-

propylureido) azobenzene by the coupling of triethoxysilylpropylisocyanate with 4-
phenylazoaniline used as organosilane precursor in co-condensation reaction
 HEAVY METAL SPONGE

Periodic mesoporous silica with channel walls functionalized with terminally bound
alkanethiol groups that chelate and sequester toxic heavy metals.
PERIODIC MESOPOROUSN
ORGANOSILICAS PMOs
ZOO OF PMO PRECURSORS
 Acc. Chem. Res. 2005, 38, 305-312.

https://www.nature.com/articles/am201413
MATERIALS CHEMISTRY SOLUTION
TO THE LOW k CHALLENGE

Periodic mesoporous
organosilicates PMOs with
organic cross-links!!!

Hatton, B.D., Landskron, K., Hunks, W.J., Bennett, M.R., Shukaris, D., Perovic, D.D., Ozin, G.A., New Materials Chemistry
Approaches for Low Dielectric Constant Materials as Interlayer Dielectrics, Materials Today 2006, 9, 22.
METAMORPHIC CHANNEL WALLS – PMO BRIDGE
TERMINAL EXCHANGE
PMO WITH ORDERED BRIDGING AROMATIC
GROUPS IN THE CHANNEL WALLS
MOLECULAR MODEL OF THE ORDERING OF BRIDGING BENZENE
GROUPS IN THE CHANNEL WALL OF BENZENE PMO
MOLECULAR MODEL OF THE ORDERING OF BRIDGING THIOPHENE
GROUPS IN THE CHANNEL WALL OF THIOPHENE PMO
BIFUNCTIONAL PMOs
 The Idea – PMO to MIPMO

IMPRINT IMPRINT
 IMPRINT
the idea

imprint
molecule

imprint
removal
 collaboration
Jean-Christophe Leroux (CRC in Drug Delivery)

Nature Nanotechnology. 2007, 2, 679-684.

 MIPMOs

Schematic of the synthesis of molecular

imprinted periodic mesoporous
organosilica MIPMO materials
 Drug-PMOs
commercially available drugs
↳silsesquioxane PMO precursors
↳assemble MIPMO structures
↳remove the drug imprints
↳detoxification

calcium channel blockers

Diltiazem Verapamil
Drug Silsesquioxanes
MESOPOROUS MATERIALS
GRAND CHALLENGES – UTILITY

• Large (bio)molecule catalysis

• Polymerization nanoreactor
• Membrane separation
• Chromatography stationary phase
• Fuel cell anode
• Lithium battery electrolytes
• Electrochromic display
• Solar cell photo-cathode
• (Bio)chemical sensor
• Drug storage and release vehicle
• Heavy metal sponge
• Low dielectric constant film
• Low refractive index optical cladding
• Lithographic masks
• Nanofluidic ion channels
• Nanocomposites