Materials for Environmental Applications Laboratory Institute of Physical Chemistry

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Network of Excellence IN SItu study and
DEvelopment of processes involving nano-PORous
Solids
Priority 3 NMP research area 3.4.1.1-1
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• The most important parameter in applications is
  the ability of materials to retain their
  properties.
• In the nano pore scale, materials are prone to
  "deactivation" (pore blocking, coking, poisoning,
  thermal degradation etc.)
• Changes are highly relevant for many applications
  e.g. catalysis and separation processes.
• The kinetics of deactivation have enormous impact
  on process economics.

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Proposal

• The solution is the application of combination of
  process based, in-situ experimental techniques
• INSIDE_POReS. Development of combination
  methodologies for the "in situ" application of
  characterization techniques to probe the
  evolution of properties of the nanoporous
  structure
• Applications synthesis (particle size control,
  crystallization kinetics) to processes
  (catalytic, separations, etc.)

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Important success tips for integration If you
want to integrate you have to know each
other Existence of Previous Cooperation among
the partners
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Core Group
National Center for Scientific Research
"Demokritos" (HL) number of common
projects Centre Nationale de la Researche
Scientifique (F) 3 University of Leipzig,
Department of Interface Physics (D)
3 University of Antwerp (B) Imperial College
(UK) 6 Universität Stuttgart, Institut für
Technische Chemie (D) Institute for Energy and
Technology (NO) TU Delft (DelftChemTech)
(NL)1 Universidad de Alicante- Departamento de
Quimica Inorgánica (E)1 Consiglio Nazionale
delle Ricerca, Istituto di Chimica dei Materiali
(I 2 Chemical Process Engineering Research
Institute-Centre for Research and Technology
(HL)3 University of Hannover-Institut fuer
Physikalische Chemie Elektrochemie (D) SINTEF
(NO) 2 TNO Industrial Tech. Materials
Technology Division (NL) 6
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Important success tips Expansion of cooperation
from small FP5 projects, by combining more
complementary characterization techniques
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Characterisation of Porous Materials Modeling
of Gas Separation Applications

• Validation of the nanoPore Structure Model by
  analysing reference material data

• Equilibrium Methods
• Sorption
• SANS (HMI-Berlin)
• Mercury Porosimetry

Pore Structure Model
Pore Size Distribution

• Dynamic Methods
• Gas Relative Permeability
• Liquid Relative Permeability
• Differential Desorption

Predictive Equation for Permeability and
Selectivity
Connectivity of the Pores
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Maximum at 30 bar of CO2 Permeability through a
carbon membrane at supercritical temperature(308
and 333 K)
CO2 presents a behaviour shown only in mesoporous
membranes at 308K
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Theoretical approach -
Monte Carlo Simulation

• CO2 Molecules
• L-J interaction sites on the atoms
• Point charges (quadrupole)

Atom-atom Lennard-Jones
2q
-q
-q

• Interactions cut-off at 2.0 nm.
• No long-range corrections

Murthy, et al Mol. Phys. 50, 531 (1983).

• Graphitic surface
• Stacked planes of L-J atoms.

H?
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Monte Carlo simulation of CO2 sorption in
activated carbon nanopores pores
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Radial Distribution function from Neutron
diffraction of adsorbed CO2 at 308 K
C-O, O-O
C-C
Orientational interactions
Shoulder at 0.5 nm
Orientational transition at 308 K
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Orientational transition at 308 K Fraction of
flat molecules is decreasing
40 bar
35 bar
30 bar
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Important success tips Integration of
complementary the partners, Not coordination of
similar labs
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• Two modes of operation
• (1) traditional coordination of consecutive
  application characterization techniques on the
  same sample
• (2) integration,simultaneous on-line operation of
  the virtual laboratory setting.

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Consecutive characterization of the same sample
by different methods
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Membrane and Filter Testing Rigs
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Q-Sense D300 System
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Coordinators Lab continuously receives data
from the satellite labs operating at the same
pressure, temp. and composition.
Optimal control of the common experimental
conditions at each participating lab.
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• Optimal remote control of scientific
  instrumentation scattered in 10 European
  countries in a revolutionary dynamic way of
  experimenting.
• replacing blind experiments at predetermined
  conditions and selecting the optimum one
  afterwards with dynamic experiment in which the
  experimental conditions will be changed
  continuously, based on the analysis of incoming
  data from the different sites.

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Develop a virtual center Expand of
complementary characterization techniques from 5
to 45
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Characterization of nanopore reference materials

• Modeling Tools
• Single and network nanopore model (Monte Carlo,
  molecular simulation)
• Reconstruction models

• Experimental Techniques
• Neutron Scattering (SANS)
• X-Rays Scattering
• NMR
• Sorption
• Raman Spectroscopy
• Permeability
• SEM, TEM, AFM
• Magnetic measurements
• Gas volumetric reaction kinetics
• Liquid/gas microcalorimetry
• Frequency Response
• Electrical Conductivity
• Oxidation (TPD, TRP, TPO)
• Thermal Transport

Analysis of refernce material data
Validated nanostructure model
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Characterization Nanopore Ceramic membranes and
Sorbents

• Experimental Techniques
• Neutron Scattering (SANS)
• X-Rays Scattering
• NMR
• Sorption
• Raman Spectroscopy
• Permeability
• SEM, TEM, AFM
• Magnetic measurements
• Gas volumetric reaction kinetics
• Liquid/gas microcalorimetry

• Analysis of Combined measurements data

Development of realistic membrane model
(nanopore layer inluding cracks) for the
predictiion of permeability and selectivity

• Modeling Tools
• Validated nanopore model
• Reconstruction models predicted transport in
  cracks

Validated realistic nanopore-crack model
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In Situ Experimental Monitoring of Changes in
Nanopore Structure (or Synthesis)

• Experiments performed on the same nanoporous
  material, under the same pressure, temperature
  and composition conditions
• Monitoring at the changes by combining different
  ïn situ techniques

• Prediction of the nanostructure changes (or the
  structure of the prepared materials)

Optimal Control of the separation process (or
synthesis process)
Application of the realistic nanopore-crack
model
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Adaptation of the in situto on site
methodology In situ monitoring and simultaneous
process adjustment real time interactive
engineering super-nano-tool 45
complementary characterization techniques
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Optimal control of the common experimental
conditions at each participating lab.
Coordinators Lab continuously receives data
from the satellite labs. This data is analyzed
with the aid of modeling software.
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Taking into account the nanostructure changes
leads to the development of high economic value
innovative, processes, ensuring sustainability of
the network
SustainabilityGeneric applications of the
supr-nano-pore-toolto nonporous application,
like the skin applications
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High temperature hydrogen Separation
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Room temperature CO2 sorption separation
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CO2 Permeability through a carbon membrane (308
and 333 K)
CO2 presents a behaviour shown only in mesoporous
membranes at 308K
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Important success tips Sustainability Generic
applications of the super-nano-pore-toolto
nanoporous systems (catalysts,membranes,sorbents)
and to nonporous ( skin)
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Skin structure
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Structure of stratum corneum
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Combination of in situ Water Vapour Sorption
Very-Small Angle Neutron Scattering (V-SANS)
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MESL Academic Partnerships
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Thank you and Good luck!!!
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SustainabilityGeneric applications of the
supr-nano-pore-toolto nonporous application,
like the skin applications
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SustainabilityGeneric applications of the
supr-nano-pore-toolto nonporous application,
like the skin applications
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Membrane and Filter Testing Rigs
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2-D Reconstruction of VYCOR Glass
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MESL Academic Partnerships