Development of Metal Organic Framework (MOFs) for
artificial photosynthesis
With the increasing global energy demand and the depletion of fossil fuels, the conversion
and storage of solar energy into chemical potentials has become one of main challenges of
today’s chemistry. Chemists have developed a variety of artificial photosynthetic systems
which mostly rely on collisional electron transfers between components operating in solution.
There is, however, a considerable potential in hierarchically organizing these components
because the efficiency of the light collection, the electron transfer and catalysis chain can be
optimized if they can be energetically and spatially assembled in a controlled manner. Metalorganic frameworks (MOFs) represent a unique class hybrid materials assembled from metal
ions or clusters and organic ligands as building units. The versatility in terms of porosity,
topology and combination of functional ligands offered by these highly ordered threedimensional structures makes them appealing platforms to design and study artificial
photosynthetic systems, which is indeed a burgeoning field. However, despite the very recent
reports of MOFs for energy transfer and photocatalysis, the integration of all the key
components (light harvesting, electron relay, and catalyst) within the same MOF architecture
has not been realized yet.1
Figure 1. Structure of a MOF recently prepared in our team (left) and general structure of one MOF
envisioned in this program (right).
In this program, we will specifically design novel photoactive MOFs by integrating multiple
components into a single architecture in order to generate a cooperative and synergetic effect
(Figure 1). Different photo/redox active ligands based on organic dyes1 or polypyridine
transition metal complexes2 will be prepared and implemented as MOF4 building blocks in
order to investigate the photoinduced charge-separation between the randomly organized
components in the structure. Consecutively, a higher degree of hierarchical organization of
the components will be achieved through the preparation of lamellar MOF by the layer-bylayer synthetic methodology in collaboration with the group of Prof. Wöll in Karlsruhe.5
Another goal is to perform highly directional multi-step charge transfers to achieve long-lived
charge separation and ultimately use the generated redox equivalents to produce solar fuels
when combined with suitable electrocatalysts.
This multidisciplinary project spans from molecular synthesis of sophisticated organic dyes
and coordination complexes, to the preparation and the characterization of MOFs and to the
elucidation of ultrafast energy/electron transfer dynamics as well as the investigation of their
photocatalytic properties.
References:
1. (a) X. Zhang, W. Wang, Z. Hu, G. Wang and K. Uvdal, Coord. Chem. Rev., 2015, 284, 206-235; (b) M.
C. So, J. E. Mondloch, J. T. Hupp and O. K. Farha, Chem. Commun., 2015, 51, 3501-3510.
2. (a) J. Warnan, L. Favereau, E. Blart, Y. Pellegrin, D. Jacquemin and F. Odobel, ChemSusChem, 2012,
5, 1568-1577; (b) J. Warnan, Y. Pellegrin, E. Blart and F. Odobel, Org. Lett. 2011, 13, 3944-3947.
3. (a) T. Stoll, M. Gennari, I. Serrano, J. Fortage, J. Chauvin, F. Odobel, A. Deronzier and M.-N. Collomb,
Chem.-Eur. J., 2013, 19, 782-792; (b) S. Karlsson, J. Boixel, Y. Pellegrin, E. Blart, H.-C. Becker, F. Odobel
and L. Hammarström, J. Am. Chem. Soc., 2010, 132, 17977-17979.
4. (a) S. Diring, D. O. Wang, C. Kim, , S. Kitagawa, K.-i. Kamei and S. Furukawa, Nature Commun., 2013,
4; (b) O. Shekhah, K. Hirai, H. Wang, H. Uehara, M. Kondo, S. Diring, D. Zacher, R. A. Fischer, O. Sakata,
S. Kitagawa, S. Furukawa and C. Woll, Dalton Trans., 2011, 40, 4954-4958.
5. (a) R. A. Fischer and C. Wöll, Angew. Chem. Int. Ed., 2009, 48, 6205-6208; (b) M. Tsotsalas, J. Liu, B.
Tettmann, S. Grosjean, A. C. Azucena, M. Addicoat, T. Heine, J. Lahann, J. Overhage, S. Bräse, H.
Gliemann and C. Wöll, J. Am. Chem. Soc., 2014, 136, 8-11; (c) D. Zacher, O. Shekhah, C. Woll and R. A.
Fischer, Chem. Soc. Rev., 2009, 38, 1418-1429.
6. (a) D. Y. Lee, E.-K. Kim, C. Y. Shin, D. V. Shinde, , J. K. Lee and S.-H. Han, RSC Adv., 2014, 4, 1203712042; (b) D. Y. Lee, D. V. Shinde, W. Lee, N. K. Shrestha and S.-H. Han, J.Phys. Chem. C, 2014, 118,
16328-16334.
We are looking for a talented, dynamic and motivated candidate (M.Sc or equivalent) with an
excellent background in synthetic and physical chemistry. Experience with porous and/or
crystalline materials is considered to be a plus. The multidisciplinary project will cover organic,
coordination and solid-state chemistry. The successful candidate will have strong synthetic
skills, essential to the conception of sophisticated organic and organometallic ligands.
The PhD student will work at CEISAM laboratory in collaboration with IMN (Material Institute
at Nantes) which are both mixed CNRS-Nantes University organizations with a staff of about
100 researchers working in different chemistry areas spanning from organic and coordination
chemistry physical-chemistry, and solid state chemistry. There are a large number and
diversity of research projects currently being developed with funds from research agencies
and industry. The building is very recent (one year old) and was designed to provide a flexible
and interactive research environment capable of supporting the widest possible range of
research. It provides excellent facilities for research including extensive NMR and Mass
Spectrometry services, glove boxes, fluorimeter, X-ray diffraction technique, TEM, SEM, UVvis and FTIR spectrometers, solar simulator, electrochemical setups for cyclic voltammetry and
impedance electrochemistry. The team of Dr. Fabrice ODOBEL is specialized in solar energy
conversion projects including dye-sensitized solar cells and artificial photosynthesis.
Applicants are invited to send a covering letter with CV and the names and addresses of two
referees to both Dr. Fabrice ODOBEL (E-mail: [email protected]) and Dr.
Stéphane DIRING (E-mail: [email protected]).
Address of the laboratory :
Chimie et Interdisciplinarité, Synthèse, Analyse, Modélisation UMR 6230 - CEISAM
Faculté des Sciences et des Techniques de Nantes, BP 92208
2, rue de la Houssinière
44322 NANTES Cedex 3 FRANCE