Dr. Christian SERRE
Directeur de Recherches (DR),
Institut Lavoisier, Université de Versailles-St-Quentin
Depuis Janvier 2001, Chargé
de Recherches (CR), Institut Lavoisier, Université
Postdoctoral Research Assistant,
Unité mixte CNRS-RHODIA, Université de Princeton.
Janvier 2000 à Décembre 2000.
Doctorat de l'Université
de Versailles, Spécialité Chimie Inorganique, Décembre
1999, Mention très honorable.
Diplôme d'ingénieur de l'Ecole
Supérieure de Physique et de Chimie Industrielle de Paris
(ESPCI), Juin 1994.
à la liste de publications
Thèmes de recherche développés
Synthesis and structure of porous
and characterization of porous hybrid solids based on transition metals
(Fe, Cr, V)
(collaboration P. Horcajada (Fe), T. Devic (V) (Versailles);
N. Stock (Kiel, Germany))
This concerns the development of new synthetic routes of MOFs based on
trivalent transition metals with a particular interest for iron, a non
toxic, cheap and redox active cation. A route based on trimeric oxocentered
SBUs has been set-up,  leading either to very large pores rigid solids
MIL-100 and -101 [2 3] with huge pore volumes and surface areas or the
highly flexible MIL-88A-D compounds  with breathing amplitudes between
85 and 230 % (figure 1).
Figure 1: (left) view of the crystal structures of MIL-100/101(left);
(right) the breathing phenomena in MIL-88.
and characterization of porous hybrid solids based on tetravalent transition
metals (Ti, Zr)
(collaboration T. Devic (Zr) (Versailles), S. Gross (Zr) (Padova, Italy),
K.P. Lillerud (Zr) (Oslo, Norway); C. Sanchez, L. Rozes (Ti) (Paris))
There is still a high interest in the development of new porous hybrid
solids based on titanium(IV) or zirconium, which are non toxic elements
interesting for many applications. A higher chemical stability of the
resulting MOFs is also expected with these higher valence metals. A nice
example concerns the porous titanium diphosphonate MIL-91(Ti) built up
from corner sharing chains of titanium octahedral and piperazinediphosphonate
moieties (figure 2). Its structure exhibits a small permanent porosity
(4 Angst.) and an accessible pore volume for gases (SBET=350 m2.g-1).
Current work concerns the discovery of new Ti or Zr based MOFs, using
new SBU approaches, with increased porosity.
Figure 2 : view of the crystal structures of MIL-91(Ti) along
the c axis.
Functionalization of MOFs
(Collaboration: T. Devic, P. Horcajada, O. David and E. Magnier (Versailles);
N. Stock (Kiel, Germany); J. S. Chang (Korea))
In order to modulate the adsorption or catalytic properties, we have
started to implement new strategies to functionalize our porous solids.[6,
7] Two approaches have been followed: either introducing prior to the
synthesis an organic functional group directly by replacement of a proton
of the aromatic ring by a polar or apolar group (Cl, NH2, CH3…)
to produce an isostructural MOF with functionality within its framework,
or post-synthesis grafting of amino groups on the accessible Lewis Metal
sites (figure 3).
Figure 3: (top) organically modified carboxylate linkers; (down)
schematic view of the post-synthesis grafting of amines on a supertetrahedron
To determine the structures of new solids, computer simulation (G. Maurin
(Montpellier)) is used in order to decrease the time consuming process
of the structure determination. X-Ray powder diffraction data on the dried
solids are collected by Dr. N. Audebrand (Rennes) while high resolution
X-Ray diffractions patterns are often collected at the ESRF (SNBL (Y.
Filinchuk), ID31 (I. Margiolaki)) or Soleil (Cristal, E. Elkaim). The
physical properties of the MOFs are often analyzed by spectroscopy (IR,
Raman, UV) by A. Vimont and M. Daturi (Caen) or by Solid State NMR (F.
Taulelle). The iron solids are also analyzed on a regular basis by Mossbauer
spectroscopy (J.M. Grenèche, Le Mans).
Applications of MOFs
(Collaboration : P. Horcajada (Versailles); R. Gref, P. Couvreur (Chatenay);
R. Morris (St Andrews, UK); G. Maurin (Montpellier); R. Denoyel and O.
We were the first to use porous hybrid solids for drug delivery, with
the controlled release of Ibuprofen using the large pores hybrid solids
MIL-100 and MIL-101 or the flexible compound MIL-53, leading either to
a record drug loading capacity of 1.4g of drug per g of dried solid or
a very slow release up to three weeks (figure 4). [8, 9] This was the
starting point of a new field of research, i.e. the use of porous cristallized
hybrid solids for several bioapplications including drug delivery, adsorption
of toxins, biological gases and so on… The European community has
considered this approach as highly valuable since a European Research
Council FP7 starting researcher grant has been awarded for 2008-2013 to
develop the understanding of biomolecules-MOFs interactions.
Figure 4: kinetics of Ibuprofen release (SBF, 37°C)
of different porous materials.
separation of fluids
(Collaboration: T. Devic, P. Horcajada and F. Millange (Versailles); S.
Bourrelly, P.L. Llewellyn (Marseille); M. Latroche (Thiais); G. de Weireld
(Mons); J.S. Chang (Korea); A. Rodrigues (Porto); P. Trens and G. Maurin
(Montpellier); H. Jobic (Lyon); A. Vimont and M. Daturi (Caen))
MOFs are promising candidates for gas storage (hydrogen, methane) or
the capture of gases (or vapors) such as CO2. [10, 11] Three types of
solids have been evaluated: flexible MOFs which exhibit steps in their
adsorption isotherms, MOFs with metal sites that possess a high affinity
useful to increase the selectivity and finally large pore hybrid solids
which have huge sorption capacity. Our work consists in making purified
samples for adsorption or separation tests as well as studying the influence
of the breathing character upon adsorption of guests. [12, 13]
Figure 5: left : hydrogen adsorption isotherms of MIL-101a
(as-synthesised; b : activated) (77 K and 298 K); right : CO2 adsorption
isotherm of MIL-53(Cr) (303 K).
(collaboration: P. Horcajada and O. David (Versailles); R. Gref and P.
Couvreur (Chatenay) ; J.S. Chang (Korea); D. Grosso, C. Boissière,
C. Sanchez (Paris))
The use of MOFs for some practical applications (drug delivery, thin
films) requires the synthesis of nanoparticles with a controlled particle
size as well as a narrow pore size distribution. In addition, the surface
of the particles has to be modified with surface agents (polymers…)
in order both to control the growth and avoid agglomeration but also to
provide furtivity and addressing properties to the particles. The synthesis
of nanoMOFs is currently done either by traditional solvothermal synthesis
or by the use of microwave irradiation (figure 6). [14, 15]
Figure 6: nanoparticles obtained by microwave synthesis (left
: MIL-101(Fe); right : MIL-101(Cr)).
The catalytic properties of our MOFs have been to date analyzed by the
group of Dr. J.S. Chang (Krict, Korea). MOFs with Lewis acidity have been
tested for oxidation reactions or for basic catalysis through the grafting
of amines.[16, 6] Insertion of polyanionic species (Keggin…) within
the large pores MIL-100 and MIL-101 solids, performed by Dr. C. Roch (Versailles),
will also lead soon to new catalytic properties.
The lithium insertion properties of iron MOFs are currently evaluated
by the group of J.M. Tarascon and M. Morcrette (Amiens). The proof of
principle of the use of MOFs as new battery materials has been demonstrated
with the porous flexible iron carboxylate MIL-53(Fe). 
 A route to the synthesis of trivalent transition metals porous carboxylates
with trimeric secondary building units.., Serre, C.; Millange, F.; Surblé,
S.; Férey, G., Angew. Chem. Int. Ed 2004, 43, 6286-6289
 A hybrid solid with giant pores prepared by combination of targeted
chemistry, simulation and powder diffraction. Férey, G.; Serre,
C.; Mellot-Draznieks, C.; Millange, F.; Surblé, S.; Dutour, J.;
Margiolaki, I., Angew. Chem. Int. Ed., 2004, 43, 6296-6301
 A chromium terephthalate-based solid with unusually large pore volumes
and surface area. Férey, G.; Mellot-Draznieks, C.; Serre, C.; Millange,
F.; Dutour, J.; Surblé, S.; Margiolaki, I. Science, 2005, 309,
 The role of solvent-host interactions that lead to very large swelling
of hybrid frameworks. C. SERRE C. MELLOT-DRAZNIEKS, S. SURBLE, N. AUDEBRAND,
Y. FILINCHUK & G. FEREY, Science. 2007, 315, 1828-1831
 Synthesis, structure and properties of related microporous N,N’-piperazinebismethylenephosphonates
of aluminium and titanium; C. Serre, J. A. Groves, P. Lightfoot, A. M.
Z. Slawin, P. A. Wright, N. Stock, T. Bein, M. Haouas, F. Taulelle, and
G. Férey: Chem. Mater. 2006 18, 1451-1457:
 High-throughput rationalization of the formation of metal organic
frameworks in the iron(III) aminoterephtalate solvothermal system. S.
BAUER, C. SERRE, T. DEVIC, P. HORCAJADA, J. MARROT, G. FEREY & N.
STOCK. Inorg. Chem. 2008, 47, 7568-7676
 Y. K. Hwang, D.-Y. Hong, J. S. Chang, S. H. Jhung, Y.-K. Seo, J. Kim,
A. Vimont, M. Daturi, C. Serre, and G. Férey, Angew. Chem. Int.
Ed, 47, 2008, 4144
 Metal-organic frameworks as new materials for drug delivery. Horcajada,
P.; Serre, C.; Vallet-Regi, M.; Sebban, M.; Taulelle, F.; Férey,
G., Angew. Chem. Int. Ed., 2006, 45, 5974-5978
 P. Horcajada, C. Serre, G. Maurin, N. A. Ramsahye, M. Vallet-Regí,
M. Sebban, F. Taulelle, and G. Férey J. Am. Chem. Soc., 130, 2008,
 Hydrogen storage in the giant pores of Metal-organic frameworks MIL-100
and MIL-101. M. LATROCHE, S. SURBLE, C. SERRE, C. MELLOT-DRAZNIEKS, P.L.
LLEWELLYN, J.S. CHANG, S.H. JHUNG & G. FEREY, Angew. Chem. Int. Ed..
2006, 45, 8227-8231
 An explanation for the very large breathing effect of a metal-organic
framework during CO2 adsorption. C. SERRE, S. BOURRELLY, A. VIMONT, N.
A. RAMSAHYE, G. MAURIN, P. LLEWELLYN, M. DATURI, Y. FILINCHUK, O. LEYNAUD,
P. BARNES & G. FÉREY, Adv. Mater. 2007, 19, 2246-2251
 Structural effects of the nature of solvents on the breathing of
MOFs : an in situ diffraction study. F. MILLANGE, C. SERRE, N. GUILLOU,
G. FEREY & R.I. WALTON. Angew. Chem. Int. Ed. 2008, 47, 4100-4105
 Experimental evidence supported by simulations of the hydrogen super-mobility
in metal-organic frameworks materials.
F. SALLES, H. JOBIC, G. MAURIN, M.M. KOZA, T. DEVIC, C. SERRE, G. FEREY.
Phys. Rev. Lett. 2008, 100, 245901, 1-4
 Facile Synthesis of the Chromium Terephthalate MIL-101 with Giant
Pores and Its Sorption Ability for Benzene; Sung Hwa Jhung, Jin-Ho Lee,
Ji Woong Yoon, Christian Serre, Gérard Férey and Jong-San
Chang Adv. Mater (2006), 19(1), 121-124.
 Colloidal route towards Optical thin films of Nanoporous Metal-Organic-Frameworks;
P. Horcajada, C. Serre, D. Grosso, C. Boissière, S. Perruchas,
C. Sanchez and G. Férey Adv. Mater., 2008, in press
 Synthesis and catalytic properties of MIL-100(Fe), an iron(III) carboxylate
with large pores. P. HORCAJADA, S. SURBLE, C. SERRE, D-Y HONG, Y-K SEO,
J-S CHANG, J-M GRENECHE, I. MARGIOLAKI & G. FEREY, Chem. Comm. 2007,
 Mixed valence Li/Fe-based MOFs with both reversible redox and sorption
properties. G. FEREY, F. MILLANGE, M. MORCRETTE, C. SERRE, M.L. DOUBLET,
J.M. GRENECHE & J.M. TARASCON, Angew. Chem. Int. Ed.. 2007, 46, 3259-3263