Advanced materials for catalysis UMR 5253 - Institut de Chimie … · 2014. 10. 14. · jet fuel or...

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anté Advanced materials for catalysis

Francesco Di RenzoInstitut Charles Gerhardt Montpellier

Advanced Materials for Catalysis and Healthcare

1st SINCHEM School Bologna, 17-20 February 2014

Control of structure, porosity and size of zeolite catalysts for

refinery and petrochemistry

Anastas P. T. et Warner J. C Green Chemistry: Theory and Practice. Oxford University Press 1998

Green chemistry's twelve principles

Francesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014

what chemists think about the principles of green chemistry?

the application of a process engineering basic principle

whole-of-system approach to optimisation

increased accountability, complete cycle analysis, think globally

nothing newchemists always did it

Molière (1622-1673)“there are more than forty years that I speak prose and I didn’t know it”

a public relation need in a world of increasing public awareness

Coluche (1944-1986) “ça va sans dire, mais il vaut

mieux en le disant”


what a catalyst is for?

to make a reaction possibleobtain a product from cheaper or renewable reagents

to improve productivityreduce time-on-stream, plant volume, energy costs

to improve selectivityavoid side-reactions or consecutive reactionatom efficiency means no need for separation (hence energy efficiency, less capital investment)

better catalysts: the key for better processes


Giuseppe Bellussi

1992 Breck Award for the Ti-silicalite

current president of the IZA

isomorphous substitution in zeolite networks

Ti-silicalite

a redox site in a hydrophobic environment

SzigmundCsicsery

the theoretician of the shape selctivity in

zeolites Zeolites, 4 (1984) 202

M. Taramasso, G. Perego, B. Notari, US 4,410,501, 1983.G. Bellussi, A. Carati, M.G. Clerici, G. Maddinelli, R.Millini, J. Catal. 133 (1992) 220.


environment-friendly propylene oxide synthesis

made possible by TS-1 catalyst


environment-friendly propylene oxide synthesis

made possible by TS-1 catalyst


M. Clerici, G. Bellussi, EP 526945A1 (1993).

HClHCl

anthraquinone to be reduced to hydroxyanthraquinone by H2

7.4 Å

network of aluminosilicate tetrahedra in zeolite Y (faujasite with Si/Al 2.5)

Control of structure, porosity and size of zeolite catalysts for refinery

and petrochemistry

active site (acid or redox) : where the reaction takes place

micropore: shape selectivity by

molecular sieving

mesopores and micropores improve the diffusion of reagents and products

the size of crystals controls the diffusion

time


Distillation fractions of different crude oils

-46

boiling point

the hydrogen deficit crude oil has lower H/C than most oil products (except gasoline = light naphtha)


HC hydrocracking

purposes: decrease boiling range (molecular mass), increase H/C ratiodifferences with FCC: hydrogen prevents the formation of olefins (sources

of gumming and coke), less deep cracking, less gas formedbifunctional catalyst: metal for hydrogenation, acid site for crackingNi/silica-alumina or Pt/zeolite catalysts, 300-370 °C, 10-20 bar H 2

HDT hydrotreatments

purpose: remove undesirable heteroatoms (sulfur, nitrogen), secondary effect: reduction of alkenes (gumming), aromatics

HDN denitrogenation

analog to desulfurisation butrequires higher T and more H2, as N can be removed only by hydrogenation of the aromatic ring:

HDS desulfurisation

RSH + H2 → RH + H2S

CoMoS/alumina catalyst300-420 °C, 10-50 bar H 2


0

0,5

1

1,5

2

300 350 400 450 500 550

Re

lati

ve

fir

st o

rde

r h

yd

rocr

ack

ing

ra

te c

on

sta

nt

Final boiling point of the feed

NiW/ SiO2-Al2O3(395°C)

NiW/ Y(355°C)

I.E. Maxwell, Catal. Today 1(1987)385

Zeolites vs ASA:

-Higher activity (Strong acid sites)

-Diffusion limitations(Micropores) prevent treatment of heavy molecules

- Lower middle distillate selectivitiy(Secondary cracking due to high residence time)

Hydrocracking catalystszeolites vs. amorphous silica-alumina (ASA)

Adequate (meso)porosity

Adequate acidity

need for Micro-Mesoporous zeolites: hierarchical porosityFrancesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014

P. O’Connor, A.P. HumphiesAccessibility of functional sites in FCCPrep. ACS Div. Petrol. Chem. 38 (1993) 598-603


15-45 %

10-60 %

silica-alumina 15-30 %

FCC catalyst

a hierarchical pore system

distribution of cracking products

J. Weitkamp, S. Ernst, in Guidelines for mastering the properties of molecular sieves(D. Barthomeuf, E.G. Derouane, W. Holderich Eds), Plenum Press, New York 1990, 343

n-hexadecane feed hydrogen stabilizes the products of primary crackin gless secondary cracking = less gas, more liquid


Micro-Mesoporous zeolites: hierarchical porosity to retain activity and decrease secondary reactions

R. Chal, C. Gerardin, M. Bulut, S. Van Donk. Overview and Industrial Assessment of Synthesis Strategies towards Zeolites with Mesopores. ChemCatChem, 3, 2011, 67-8


TEM image of a hierarchical TS-1 zeolite sample prepared using Carbon Black Pearls as hard-template

I. Schmidt, A. Krogh, K. Wienberg, A. Carlsson, M. Brorson and C. J. H. Jacobsen, Chem. Commun., 2000, 2157–2158.

hard templating

solid porogens in the zeolte

synthesis


TEM image of a hierarchical TS-1 zeolite sample prepared using Carbon Black Pearls as hard-template


yield ratios between classical and mesoporous TS-1 in epoxidation of 1-octene and cyclohexene

I.I. Ivanova, E.E. Knyazeva, Chem. Soc. Rev. 2013, 42,.3671-3688


D. P. Serrano, J. M. Escola, P. Pizarro, Synthesis strategies in the search for hierarchical zeolites, Chem. Soc. Rev. 2013, 42, 4004-4035

C. Gerardin, J. Reboul, M. Bonne, B. Lebeau, Ecodesign of ordered mesoporous silica materials, Chem. Soc. Rev. 2013, 42, 4217-4255

the aluminium content of zeolites increases with the alkalinity of the synthesis system

S.P. Zhdanov, in Molecular Sieves, R.M. Barrer Ed.,

Society of Chemical Industry, London 1968

at high alkalinity, silicates have less tendency to oligomerize and the spacing among aluminates decreases

selective solubility of silicate and aluminate in acid ans basic conditions


Creation of a zeolite Y material with crystals comprising Trimodal intra-crystalline porosity:

K.P. de Jong, J. Zecevic, H. Friedrich, P.E. de Jongh, M. Bulut,, S. van Donk, R. Kenmogne, A. Finiels, V. Hulea, F. Fajula,

Angew. Chem.49 (2010) 10074

SteamingAcid leaching

Micropores +”Large”mesopores

Micropores

Al-removal Base leaching

Si-removal

CBV 760 from Zeolyst

HY-30

Dealumination :a classical method to

increase the Si/Al ratio of zeolite network

Desilication :a method to decrease the

Si/Al ratio of zeolite networkR. Le Van Mao, S.T. Le, D. Ohayon, F. Caillebot, L. Gelebart, G. Denes.

Zeolites 19 (1997) 270


Secondary porosity is formed by both destructive methods

bifunctional catalysisthe effect of temperature

J. Weitkamp, S. Ernst, in Guidelines for mastering the properties of molecular sieves(D. Barthomeuf, E.G. Derouane, W. Holderich Eds), Plenum Press, New York 1990, 343

shifts from isomerisation to cracking with the incr ease of temperature


Catalysts with hierarchical porosity

to combine the high selectivity of shape-selective microporous zeolites with the high diffusivity in

mesoporous channels

Angew. Chemie Int. Ed. 49 (2010) 10074WO 2010/072976

Chem. Commun. 46 (2010) 7840

Electron tomography and pore size distribution of a zeolite Y with trimodal porosity obtained by consecutive dealumination and desilication treatments. A first acid leachingallows to connect the structural micropores (0.7 nm) by 3 nm mesopores. A consecutive basic leaching further improves the accessibility of reagents by opening 30 nm mesopores.

The addition of surfactants to the leaching solution allows to obtain monodispersed mesopores

Due to better accessibility of reagents, a zeolite Y with hierarchical porosity (green triangles) requires lower temperature than the parent dealuminated zeolite (black crosses) to reach high conversion in hexadecane hydrocracking.

catalysts with 0.3 % Pt, 20 bar H2

Hydroconversion of n-hexadecaneWHSV = 1-3 h-1, PH2 = 20 Atm., H2/hc = 4 (mol.), 220-280°C

Hydroisomerisation and hydrocracking yields vs total conversion

0

10

20

30

40

50

60

70

0 20 40 60 80 100

Rendem

ent en p

roduits

(%)

Conversion totale (%)

Pt/HY-30 ♦ HC ◊ HIPt/HY-30A ● HC ○ HIPt/HY-30B ▲ HC ∆ HI

Total conversion (%)

Yie

ld (

%)

cracking

Desilication Towards ideal hydroconversion behaviour

Isomerization

Cracking


Pt/HY-30

Pt/HY30-A Pt/HY30-B

Pt/HY-30: Conv. : 68 %; Cracking yield. 25.2 %; C6/C10 = 1.79Pt/HY-30A: Conv. : 85,6 %; Cracking yield. 44.7 %; C6/C10 = 1.21Pt/HY-30B: Conv. : 72,6 cracking yield. 15.6 %; C6/C10 = 0.92

Hydroconversion of n-hexadecaneDistribution of hydrocracking products

Classical DealuminatedY zeolite

Dealuminated & Desilicated


better accessibilityno secondary crackingsymmetrical product distribution

Hydroconversion of n-hexadecane

Symmetry index (C 6/C10 ratio) of the distribution in cracking products as a function of conversion

Desilicated zeolites primary cracking

Dealuminated

Dealuminated & desilicated


@ 75% conversion

For hydrocracking of squalane (i-C30) the product s ymmetry is largely improved:

• Limit residence time of reactants in micropores

• Decrease in the contribution of secondary cracking (gas production)

• Enhanced selectivity and yield of middle distillate s.

gasolinejet fuel or diesel oil

Pt/Dealuminated Y zeolite

Pt/Dealuminated & Desilcated Y zeolite

hydrocracking of squalane

Pt/HY-30 Pt/HY30-A


why squalane?


bacteria-produced C15 sesquiterpene

squalenea triperpene extracted from some plants

(cosmetics) and actively studied for industrial production from microalgae (biofuel)

T.G. Tornabene, Formation of hydrocarbons by bacteria and algae, US Dpt Energy SER I /TP-621 -999 (1980)

Makazawa et al. Biores. Technol. 109 (2012) 287–291


can micelle-templated mesoporous silicas

find useful applications in catalysis?

Towards ideal hydrocracking catalysts

Mesoporous Silica (MCM-48)

Nitrogen sorption isotherms of parent and aluminated mesoporous silic a

0 100 200 300 400 500 6000,000

0,004

0,008

0,012

0,016

Vite

sse

de d

esor

ptio

n de

NH

3 (u

a)

Temperature oC

Pt/MCM-48B sites forts sites faibles

Acidity profile (Ammonia TPD) of MSA(Total : 0.7 mmol/g, Strong : 0.22 mmol/g)

Post-synthesis alumination of a mesoporous silica (MCM-48)

No microporesNo large mesopores

M. Bulut, R. Kenmogne-GatchuissiF. Fajula, J.P. Dath, S. van Donk, A. Finiels, V. Hulea WO 2012/085289

Mesoporous Silica Alumina (MCM-48, 13 wt% Al2O3)



Comparison of the activity of hydrocracking catalysts based on dealuminated Y (HY-30), dealuminated & desilicated Y

(Pt/HY-30A) and Mesoporous Silica Alumina (Pt/MSA)

Pt/MSA (MCM-48)

Hydroconversion of n-hexadecaneWHSV = 1-3 h-1, PH2 = 20 Atm., H2/hc = 4 (mol.)

Pt/MSA (MCM-48) same activity & higher selectivity than desilicated HY

0

20

40

60

80

100

0 20 40 60 80 100

Re

nd

em

en

t en

pro

du

its (%

)


Hydroisomerisation and hydrocracking yields vs total conversion

Pt/MSA(MCM-48)

(Pt/HY-30A)

M. Bulut, R. Kenmogne-GatchuissiF. Fajula, J.P. Dath,

S. van Donk, A. Finiels, V. Hulea WO 2012/085289



Comparison of the activity of hydrocracking catalysts based on dealuminated Y (HY-30), dealuminated & desilicated Y

(Pt/HY-30A) and Mesoporous Silica Alumina (Pt/MSA)

Pt/MSA (MCM-48)

Hydroconversion of n-hexadecaneWHSV = 1-3 h-1, PH2 = 20 Atm., H2/hc = 4 (mol.)

Pt/MSA (MCM-48) same activity & higher selectivity than desilicated HY


0

1

2

0 20 40 60 80 100

C6

/C1

0


Pt/HY-30

Pt/HY-30A

Pt/MCM-48Pt/MSA (MCM-48)

Symmetry (C6/C10 ratio) of the distribution of cracking products as a function of

conversion

a: Reaction rate slower than reagent diffusion (k i < kd), CS = C – Chemical controlb: Reaction faster than reagent diffusion (k i > kd), CS > C – Physical control

⇒ If (b): not worth looking for a more active catalys t!⇒ same rationale for thermal conduction as for reagen t diffusion

physical or chemical control?

catalyst particleC reagent concentrationK i reaction rateKd diffusion rate


E.A. Swabb, B.C. Gates, Ind. Eng. Chem. Fund. 11 (1972) 540

the effectiveness of a porous catalyst can be affected by diffusional constraints related to the length of the pores

size matters

mordenite : unidirectional pores

along the c axis


F. Hamidi, F. Boukli-Hacène, A. Bengueddach, F. Di Renzo, Microp. Mesop. Mater. 153 (2012) 59

1.E+14

1.E+15

1.E+16

1.E+17

1.E+18

0 1 2 3 4 5

OH- (moles L-1)

germ

s pe

r m

ole

Ag

The number of zeolite crystals nucleated by silver seeding does not depend on the type of zeolite formed (A, LSX, X, Y, L, Beta), nor on the Si/Al

ratio and decreases only at high alkalinity, due to partial Ag2O dissolution)

Nucleation promotion of zeolite crystals by in-situ formation of silver-based heterogeneous nuclei

The addition of silver nitrate to the synthesis gel of zeolites allows to form heterogeneous silver oxide seeds on which zeolite crystals can grow.

The enhanced nucleation brings to the formation of smaller zeolite crystals, with improved diffusional and kinetic properties.

2Ag+ + 2OH → 2AgOH↓→ Ag2O↓ + H2O

0 2 4 6grain size D (µm)

fre

que

ncy

M/(Σ

M*∆

D)


fre

que

ncy

M/(Σ

M*∆

D) LSX X


fre

que

ncy

M/(Σ

M*∆

D)


fre

que

ncy

M/(Σ

M*∆

D) LSX X

Size distribution of crystals of zeolites LSX and X formed in the absence (dashed lines) and in the presence (full line) of silver nucleation promoter


why pore geometry is important ?

SAPO-34 (CHA)SAPO-17 (ERI)SAPO-18 (AEI)

ZSM-5 (MFI)

UOP/Hydro LurgiExxonMobil

J.Q. Chen et al. Catal. Today 106 (2005) 103


methanol to olefinsMTO

SAPO-34:

light olefins highly favoured,

C2=/C3= higher than equilibrium distribution

C2=-C5= olefin equilibria

ZSM-5:

near to the equilibrium distribution


addition of Ethylene Glycol led to the formation of SAPO-18

instead than SAPO-34

not completely unexpected: the earliest synthesis of SAPO-18 were in the presence of EtOH

and isopropanol can also be used

SAPO-34 (CHA)

D6R in parallel rows

SAPO-18 (AEI)

D6R in alternate rows

very similar structures with 8R channels formed by connected D6R (hexagonal prisms)

[110]

Cmcm[001]

R3m


36-tetrahedra cages of SAPO-34 and SAPO-18 : same volume, different shapes

[001] windows of CHA (left) and AEI (right)

similar MTO behaviour of SAPO-18 and SAPO-34

J. Chen, J.M. Thomas, P.A. Wright, R.P. Townsend, Catal. Lett. 28 (1994) 241.

R. Wendelbo, D. Akporiaye, A. Andersen, I.M. Dahl, H.B. Mostad, Appl. Catal. A 142 (1996) L197


common morphologies of SAPO-34

common morphologies of SAPO-18

J. Chen et al., J. Phys. Chem. 98 (1994) 10216

R. Wendelbo et al., Appl. Catal. A 142 (1996) 197

1 µm 1 µm

1 µm1 µm

D. Chen et al., Microp. Mesop. Mater. 29 (1999) 191 commercial calcined SAPO-34

1 µm CHAR3m

AEICmcm

typical pseudocubic rombohedra of chabazite (Parrsboro, Nova Scotia)

rombohedra of trigonal crystals are formed by slow growth of apical faces


Synthesis of EthGly SAPO-18

Synthesis formulation (molar basis)

1.0 TEAOH ⋅ xSiO2 ⋅ Al2O3 ⋅ P2O5 ⋅ zH2O ⋅ yEThGlyx = 0.025 ÷ 0.1 y = 1 ÷ 12 z = 0 ÷ 45 150 °C

possible to form SAPO-18 with Si/tet ratio in the range 0.01-0.08

peculiar morphology

50 nm-thick lamellae

orientation (h00)

EthGly/TEA ratio in crystals ≤ 0.05

1 µm


W. Vermeiren, N. Nesterenko, C. Petitto, F. Di Renzo, F. Fajula, WO 2008/110526

Catalytic testsTemperature: 450 °C MeOH WHSV: 2h -1

C2/C3 olefin ratio on thick SAPO-34 crystals (500 nm) and thin SAPO-18 crystals (50 nm)

0

0.5

1

1.5

2

0 1 2 3 4 5 6 7

lamellar EthGly SAPO-18

time on stream (Hours)

70% MeOH 30%H2O

100% MeOH

C2/

C3

olef

inra

tio

0

0.5

1

1.5

2

0 1 2 3 4 5 6

pseudocubic SAPO-34

time on stream (Hours)

70% MeOH 30%H2O

100% MeOH

C2/

C3

olef

inra

tio

the ethylene/propylene ratio does depend on the crystal size


TON = 340 TON = 317

0

10

20

30

40

50

60

0 1 2 3 4 5 6 7

SAPO-18 Si/(Si + Al + P) = 0.031

Time on stream (Hours)

C2H4

C3H6

C4 =

CH4C5=

MeOH

DME

wt

(%)

0

10

20

30

40

50

60

0 1 2 3 4 5 6 7Time on stream (Hours)

SAPO-34 Si/(Si + Al + P) = 0.041

DME

MeOH

C3H6

C2H4

C4 =

CH4C5=

wt

(%)

MTO test450 °C MeOH WHSV: 2h-1Feed : 70 % MeOH 30 % H2O

isometric morphology

C2=/C3= ratio 1.3 C2=/C3= ratio 1.3

the ethylene/propylene ratio does not depend on the structure difference between SAPO-18 and SAPO-34

MTO test450 °C MeOH WHSV: 2h -1

Feed : 100 % MeOH

EthGly SAPO-18 TON = 100

SAPO-34 TON = 60


1 µm

lamellar SAPO-18 crystals formed in the presence of 'EG

thickness ~ 50 nmorientation (h00) (postdoc Rossella Arletti)

control of the ratio Si/(Si+P+Al) in the range 0.01-0.08

a better dispersion of heat shifts the equilibria towards higher olefins

S.W. Kaiser, US 4,499,327 (1985), US 4,613,721 (1986), D.M. Ruthven, in Karge, Weitkamp, Molecular Sieves Adsorption and Diffusion, Springer 2008, 1

historical mechanism of MTO reaction ∆H° STP

-23.4 KJ/mol

5.4 KJ/mol

-66.5 KJ/mol


historique AIE, CCFA

40

90

140

190

240

290

1998 2000 2002 2004 2006 2008 2010 2012 2015

FOD

Gasoline

Diesel

Heavy Fuel

Jet/kero

Mto

n/y

Evolution of demand in Europe-27 dieselisation

In the coming years:

� GOM and JET demands are foreseen to increase in the next year

� Gasoline demand will continue to decrease

Traditionally, gasoline excesses are exported to th e USA; however, gasoline importation in the USA is decreasing due to:

� The use of cars with a better fuel-economy

� The generalization of bio ethanol use


Olefins oligomerisationOverview of existing technologies


Company Cuts Purpose Catalyst Process

UOP Olefins ex FT Gasoline SPA CATPOLY

IFP C3-C4 Gasoline IP501 (ASA) Polynaphta

IFP C3-C4 Gasoline Ion Liquid Dimersol

ExxonMobil Olefins ex MTO Gasoline/Jet/Diesel ZSM-5 or ZSM-22 MOGD

Shell C2-C6 Gasoline/Jet/Diesel Ni/MOR SPGK

Süd-Chemie/Lurgi Olefins ex MTO Gasoline/Jet/Diesel ZSM-5 MTS

Süd-Chemie FT naphtha Jet/Diesel CODZSM-5

Süd-Chemie Olefins ex FT Gasoline SPA

Gasoline

Jet/Diesel

valorisation of excess ethylene

formation of hydrocarbons in the jetfuel-diesel rangea double challenge

Ni-exchanged porous catalysts(~ 1.5 %Ni, Si/Al = 15-20, 150 °C, 35 bar, 1 h)

ethylene oligomerisation

120

140

Ni-MCM-48interconnected mesopores(3.5 nm)

Ni-SBA-15interconnected mesopores(8.5 nm)


M. Lallemand, A. Finiels, F. Fajula, V. Hulea, Chem. Eng. J. 172 (2011) 1078

Distillate-Range Products from Non-Oil-Based Sources by Catalytic Cascade ReactionsA. Lacarrière, J. Robin, D. Swierczynski, A. Finiels, F. Fajula, F. Luck, V. Hulea, ChemSusChem. 5 (2012) 1787


Activity of Ni-MCM-41(3.5) catalysts in ethylene oligomerization as a function of nickel loading (150 8C, 3.5 MPa, reaction time 1 h).

TPR profiles of Ni-MCM-41(3.5) for various nickel loadings. a) Ni1.4-MCM-41(3.5), b) Ni2.0-MCM-41(3.5), and c) Ni7.5-MCM-41(3.5).

15.8 kmol ethylene /mol Ni/h 25 kmol ethylene /mol Ni/h

1 catalyst (Ni-MCM-41) 2 catalysts (Ni-MCM-41 + H-MCM- 41)

Single-site Ni catalystC4 olefins

Bifunctional catalystJetfuel

oligomerisation catalyst

condensation catalyst


A. Lacarrière et al. ChemSusChem. 5 (2012) 1787

Self-assembly of surfactant aggregates and inorganic precursors to form an orderedmesophase in which the micelles are separated by amorphous silica walls

+ silicates

∆T

An ordered pore system is formedby extraction or calcination of the micellar template


Design of new mesostructure directing agents

Previously : Sacrificial porogens to be removed

Use smart micelles : responsive to stimuli in aqueous medium� Dissociable in water for recovery under soft conditions

� Able to confer functionalities to the mesoporous material

Double-hydrophilic block copolymers (DHBC)

Two hydrosoluble blocks : - different affinities for a substrate or a molecule- different sensitivities to a change of parameter- neutral or charged, with variable functions

stimuluspH, ionic strength,

T, radiationhydrophilichydrophilic

Reversible micellizationin waterDHBC


N. Anik, M. Airiau, M.P. Labeau, C.T. Vuong, J. Reboul, P. Lacroix-Desmazes, C. Gérardin, H. Cottet, Macromolecules 2009, 42, 2767

PolyIon electrostaticComplex (PIC) Micelle

pH-sensitive electrostatic complex micelles of DHBC

DHBC : weak acid – neutral

- - - - - - - - - - - - - -neutral

pKaacid

pH

DHBC micellization induced by complexation of an oppositely charged polymer :

+ + + + + + + + + + + + + + +

pKabase

Weak base : polyamine neutral

pH

AUXILIARY OF MICELLISATION

PAA-b-PEO(CH2-CH(COOH))m-b-(CH2-CH2-O)n

ChitosanFrancesco Di Renzo (Institut Charles Gerhardt Montpellier) 1st SINCHEM School Bologna, 17-20 February 2014

N. Anik, M. Airiau, M.P. Labeau, C.T. Vuong, J. Reboul, P. Lacroix-Desmazes, C. Gérardin, H. Cottet, Macromolecules 2009, 42, 2767

Micelle dissociation Washing

Inorganicpolycondensation

Micelle arrangement

Hybrid material

PAA b PEO and chitosane in

solution, without TEOS.

+

+TEOS

TEOS hydrolysis

0

100

200

300

400

500

600

700

800

2 4 6 8 10 12pH

Inte

nsité

(Kcp

s/s)

Inte

nsity

(kc

ps/s

)

PAA b PEO and chitosane with

TEOS :

silica structuring

MATERIAL SYNTHESIS

Templating of mesoporous silica by pH-switchable mic ellar assemblies


N. Baccile, J. Reboul, B. Blanc, B. Coq, P. Lacroix-Desmazes, M. In, C. Gérardin, Angew. Chem. Int. Ed. 2008, 42, 3681

H20

Electrostatic complex

Environment-friendly process

Versatile/functional micelle system Controlled reversible micellization

Controlledmesostructures

lamellar, hexagonal…

Polymer- functionalized mesoporous silica

H20

PIC

pH=2

pH=5.5

pH=7.7

pH=5.5


N. Baccile, J. Reboul, B. Blanc, B. Coq, P. Lacroix-Desmazes, M. In, C. Gérardin, Angew. Chem. Int. Ed. 2008, 42, 3681

Elemental analyses :N/COO=1 in the solid

Silica based hybrid material templated with PEO5000-b-PAA1580/chitosan

100

1000

104

105

0 0,05 0,1 0,15 0,2

q en A -1

Inte

nsité

(K

cps/

s)

JRS4

d(100)=13.9 nm

SAXS

3 µµµµm3 µµµµm

Polyion electrostatic complex micelles can adopt a c ylindrical morphology in long-range ordered mesophases: lyotropic behaviour / silicates

2D hexagonal structure.

1 2 √7(100) (200) (210)

0

50

100

150

200

250

0 0,2 0,4 0,6 0,8 1p/p

0

Va

ds (

cm3 /

g)

TEM SEM

N2 adsorption

WO2009/081000


POE(113)-b-PAA(4)

100 nm100 nm100 nm

100 nm100 nm100 nm

POE(113)-b-PAA(15)

AA/OE = 0.03

AA/OE = 0.13

POE(113)-b-PAA(33)

AA/OE = 0.3

Non mesostructuredmaterial

2D hexagonal structure

Lamellarmesostructure

AA/OE

++

++

+-

--

--

-++

+

++

++

++

++

++

--

--

--+

++

Tuning mesostructures by varying the volume fraction of polymer blocks

--

--

-+

++

++

--

--

--

++

++

++

++

++

-


Micelle dissociation

Template removal


Micelle arrangement

+

+TEOS

TEOS hydrolysis

0

100

200

300

400

500

600

700

800

2 4 6 8 10pH

Inte

nsi

té(K

cps/

s)

Inte

nsi

ty (

kcp

s/s)


Template removal


Template removal


Template removal


Micelle arrangement


Micelle arrangement

+

+TEOS

TEOS hydrolysis

+

+TEOS

TEOS hydrolysis

+

+TEOS

TEOS hydrolysis

0

100

200

300

400

500

600

700

800

2 4 6 8 10pH

Inte

nsi

té(K

cps/

s)

Inte

nsi

ty (

kcp

s/s)

0

100

200

300

400

500

600

700

800

2 4 6 8 10pH

Inte

nsi

té(K

cps/

s)

Inte

nsi

ty (

kcp

s/s)

Silica structuring and template removalAfter material washing in water at pH 7.7

100 nm

(100

)

(110

)(2

00)

(210

)

10

100

1000

104

105

106

0.04 0.08 0.12 0.16 0.2

matériau hybridematériau lavématériau calciné

Inte

nsité

(u

.a.)

q (A-1)

(100

)

(110

)(2

00)

(210

)

10

100

1000

104

105

106

0.04 0.08 0.12 0.16 0.2

matériau hybridematériau lavématériau calciné

Inte

nsité

(u

.a.)

q (A-1)

Calcined materialWashed materialHybrid material

0

100

200

300

400

0 0,2 0,4 0,6 0,8 1

Vad

s (cm

3 /g

)

p/p0

10

6,5

Pore diameter

(BJH) (nm)

15,513,5Washed

13,511,5Calcined

15,513,5Hybrid

dc-c (nm)

d100 (nm)

Matérial

Angewandte Chemie, 2008, 47, 8433.


thank you for your attention

Advanced materials for catalysis UMR 5253 - Institut de Chimie … · 2014. 10. 14. · jet fuel or...

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