Mesoporous materials: Synthesis Mesoporous materials: Synthesis and characterizationand characterization
Dr. Roberto Hanoi Labrador,
Project manager
• Nanoporous materials classification
• :Mesoporous materials Synthesis and characterization• Nanologica AB, company profile
Outline Outline
Pore Size (Å)
40
60
5
10
20
Mesoporousporous
Microporousporous
80
500
100
600Macroporousporous
Classification of Nanoporous MaterialsClassification of Nanoporous Materials
>Surface area increases contact area between reactants and products, increases contact area between reactants and products,
>Pore size / / / /allows to exclude include separate adsorb absorb/ / / /allows to exclude include separate adsorb absorb……
>Composition and surface properties mechanical, conductive, magnetic mechanical, conductive, magnetic hydrophobichydrophobic--hydrophilic properties, create interactionshydrophilic properties, create interactions……
1-D 2-D 3-D
>Connectivity and pore structure allows to fine tune allows to fine tune /selectivity diffusion/selectivity diffusion……
Important parameters of Nanoporous MaterialsImportant parameters of Nanoporous Materials
MESOPOROUS
2nm<Pore size<50nm Surface area 400-1500m2/g
MCM-41 in 1992 Novel drug vehicle systems
SYNTHESIS OF MESOPOROUS SILICA
Typical Sol-gel route
Template agents•Anionic surfactants•Cationic surfactants•Geminal surfactants•Polymers•Other molecules (FA)
Silica precursors•Tetramethyl ortosolicato (TMOS)•Tetraethyl ortosilicato (TEOS)•Sodium silicate
In situ functionalisation
Template removal bysolvent extraction
Post-synthetic functionalisation
SiOEt
OEtEtO
EtO RSiEtO
EtOEtO
OH
O
OSi
O
SiO
SiO
O
R
O
O
SiO
Si
O
OO
O
OH+
Si OH
Si OH
Si OH
Siliceous surface
(EtO)3SiPrCl
(EtO)3SiPh
(EtO)3SiPrSH
(EtO)3SiPrNH2
Si O
Si O
Si O
Si SH
Si O
Si O
Si O
Si NH2
Si O
Si O
Si O
Si Cl
Si O
Si O
Si O
Si
Si O
Si O
Si O
Si CN
(EtO)3SiPrCN
Si O
Si O
Si O
SiOH
O
H+/H2O
R R RR R
SiO2
SiO2
R R RR R
SiO2
SiO2
R R RR R
SiO2
SiO2EtOH
EtOH
Surfactant template
Silica wall
Surface ChemistrySurface Chemistry
SYNTHESIS OF MESOPOROUS SILICA NFM-1*
Folic acidas TA
Schematic representation of self-assembled hexagonal columnar phase
* Nanologica´s patent WO2009/101110A9
TUNNING THE NFM-1: Concentration of FA
Sample
FA-x
d100
(Å)
Surface Area(BET)(m²/g)
Avrg. Pore Size
(DFT)(Å)
Pore Volume
(cm³/g)
FA-1.02 39.4 563 30.7 0.39FA-0.85 39.7 721 30.9 0.45FA-0.68 38.4 847 30.9 0.45FA-0.51 39.1 851 30.8 0.45
TUNNING THE NFM-1: Concentration of TEOS
TUNNING THE NFM-1: Stirring speed
SampleSR –‘‘R’’
(rpm)
d100
(Å)
BET Surface
Area
(m²/g)
Pore Size
(DFT)
(Å)
Pore Volume
(cm³/g)
R – 250 38.0 571 23 0.29
R – 500 39.7 583 23 0.29
R – 750 39.0 596 26 0.30
R – 1000 37.7 769 26 0.39
R – 1400 37.3 941 23 0.47
Physico-Chemical Characterization of Nanomaterials
*OECD Guidance Manual for the testing of manufactured nanomaterials. ENV/JM/MONO(2009)20/REV
Characterizing mesoporous silica: Surface area and porosity
Surface area: Brunauer-Emmett-Teller (BET)
Pore size and pore volume:Barret-Joyner-Hallenda (BJH)
Characterizing mesoporous silica: Morphology
Scanning Electron Microscopy (SEM)
Different morphologies in NFM-1 (templated by FA): Spheres, roid type and spherical shell
Different morphologies for silica particles templated with different polimeric agents: P123 (b) and F127(d)
Characterizing mesoporous silica: Particle size
Dynamic light scattering (DLS)Particle size in disperssion
Transmission Electron Microscopy (TEM)Particle size and information on pore structure
Characterizing mesoporous silica: Identifying the mesophase
Powder X-Ray Diffraxion Analysis (XRD)
Transmission Electron Microscopy (TEM)
Characterizing loaded/functionalized mesoporous silica: Loading %
Thermo Gravimetric Analysis (TGA) of a mesoporous silica loaded with Vitamin A (Retinol)
TGA
0
2
4
6
8
10
12
14
16
18
20
22
25
73.7
122
171
220
268
317
366
414
463
512
560
609
658
706
755
804
852
901
950
998
T(deg)
m(m
g)
NPF-Si/Retinol
49%
51%
Making Space for InnovationInterdisciplinary Solutions for
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• The Business concept of Nanologica is to develop and sell products based on our material innovation
• Nanologica AB is producing cutting edge nanostructured materials with properties tailored for specific applications
• Spin-off company founded in August 2004, emerging from the Structural Chemistry Department at the University of Stockholm• Nanologica has the ability to create nanoporous structures with novel properties and functions because of their size, shape or composition
Nanologica AB Nanologica AB
NANOPOROUSNANOPOROUSMATERIALSMATERIALS
Diagnostics
Drug Delivery
Water Purification
Insulators
Clean Tech
Catalysis
Gas-Separation
Separation
Sensors
Fuel Cells
Nanologica AB area of ApplicationsNanologica AB area of Applications
Innovative Oral DrugDelivery SolutionsStable and amorphous APIs inside the pores of silica particles
Dissolution curves of free Atazanavir (ATV) and three different porous silica particles loaded with ATV in simulated Intestine fluid* (SIF, pH 6.8)
In-vitro enhancement of solubility
* Nanologica´s patent WO2012/03507A1
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