1. 2D Hybrid materials: a tremendous potential for application in modern technology P. Rabu IPCMS UMR7504 (CNRS-UNISTRA), 23, rue du Loess, F67034 Strasbourg, France; pierre.rabu@ipcms.unistra.fr Black Sea Horizon International Workshop “Applied research in chemistry: Smart materials for a smart future” Identifying perspective areas of STI Cooperation between the European Union and the Black Sea region in the field of smart materials 31 MARCH 2016, SOFIA, BULGARIA

2. Organic component: Molecules, polymers Templating Connecting Functionnalizing Hybrid Organic/Inorganic Materials Inorganic component : Networks of oxides, chalcogenides, hydroxides, oxalates… Physical properties Hybrid O/I Materials : Multiproperty Coexistence of properties classe II Materials : strong bonds For real synergy (Multi)functional/ Adaptable Materials

3. INTRODUCTION montmorillonite [AlMn 2 (OH) 6 ] 3 (SO 4 ) 2 Na(H 2 O) 6 LDH tobermorite, calcium silicate hydrate V2O5V2O5 Co 3 (2-OOCC 6 H 4 PO 3 ) 2 (H 2 O) 3 · H 2 O layered zinc phosphate MPS3 Bi 2 MnTe 4 Fernandes, F.M., et al., Appl. Clay Sci. (2014), http://dx.doi.org/10.1016/j.clay.2014.05.013

4. Seeking for new materials with improved functionalities Fernandes, F.M., et al., Appl. Clay Sci. (2014), http://dx.doi.org/10.1016/j.clay.2014.05.013

5. Controlling properties by assembling hybrid organic – inorganic networks PR & coworkers: Adv. Eng. Mater. 5(4) 2003; Chem. Mater. 16 2004; Chem. Mater. 18 2006; J. Mater. Chem. 19 2009; J. Mater. Chem. 20 2010; Dalton Trans. 39 2010; Chem. Soc. Rev. 40 (2) 2011; Chem. Sciences 3 2012; NJC, 38(5), 2014; Inorg. Chem., 53(2), 2014; Nanotechnol. Rev., 4, 2015; Magnetism Photoluminescence Non-linear optics Chirality Electrochemistry … Multifunctionality c = 6.9 Å - > 40 Å + P + Solvent M 2 (OH) 3 (A),xH 2 O Magnetic Exchange Photo-magnetism Magneto-Chiral Magnetic Dipolar Connection,  system Films & exfoliation Bio-inorganic OH - Functional bricks Chemically compatible Physically compatible Synergy <> Interfaces chemistry

6. Thomas T. M. Palstra et al. Chem. Mater. 2012, 24, 133−139 Hydrogen bond network and multiferroicity CuCl 4 (C 6 H 5 CH 2 CH 2 NH 3 ) 2 at 100 K

7. Topochemical Manipulation ion exchange, intercalation, layer extraction, reductive deintercalation, grafting, exfoliation, layer construction, pillaring, substitution reactions J. Wiley et al. Adv. Mater. 2011, 23, 442–460 PR & coworkers Eur. J. Inorg. Chem. 2016.

8. Functionalized Nanosheets as Ultimate 2D Functional Bricks (a) Ma, et al. Adv. Mater. 2010, 22 (45), 5082–5104; (b) Geim, Science 2009, 324 (5934), 1530-1534; (c) Nicolosi, et al. Science 2013, 340 (6139); (d) Coronado, et al. Nat Chem 2010, 2 (12), 1031–1036; (e) Britnell, et al. Science 2013, 340, 1311–1314; Osada, et al. ACS Nano, 2011, 5 (9), pp 6871–6879 a MoX 2, WX 2, … Semiconducting 2D materials c graphene b [Ni 0.66 Fe 0.66 (OH) 2 +0.33 ] [TaS 2 -0.33 ] supraconductivity and magnetism d multilayered two-dimensional heterostructures in interaction with environment e

9. Hybrid multi-component compounds : a powerful approach to multifunctional and smart materials Modifying layers with different kind of ligands can influence the properties Templating : size, chemical pressure, anisotropy Connecting : electronic polarisation (  systems) Multi-function: chemical bond between sub-networks Photo – actives or Photo-sensitive systems Luminescence + magnetism Optical Activity + magnetism (ferroelectrics?) Photo-induced Transitions Tuning properties by assembling bio molecules into magnetic layered structures Realisation of adaptable films and nanostructures

10. Transdisciplinary Solid-state /coordination /supramolecular /bio chemistries + interaction with other disciplines (physics, biology, engineering, … Interactions & interfaces component – environment / component - component Understanding Materials computering, multiscale-multiprobe Exploratory research no need of « x, 1-x » chemistry Need to re-fill the shields in the R&D offices Smart materials for a smart future

11. Current topics FET Area 3: Disruptive information technologies c. Hybrid opto-electro-mechanical devices at the nano-scale Area 4: New technologies for energy and functional materials b. Complex bottom-up construction LEIT (high TRL) H2020-NMBP-2016-2017 Advanced materials and technologies for high added values and processes in industries NMBP-01-2016: Novel hybrid materials for heterogeneous catalysis NMBP-04-2017: Architectured /Advanced material concepts for intelligent bulk material structures (composites and nanocomposites) NMBP-07-2017: Systems of materials characterization for model, product and process optimisation NMBP-17-2016: Advanced materials solutions and architectures for high efficiency solar energy harvesting NMBP-19-2017: Cost-effective materials for “power-to-chemical” technologies Suggestions for sub-topics (in FET) 2D hybrid structures and nanostructures … …for multi-adressable devices in electronic, environmental sensors, bio-sensors, … with controlled storage/release, Multiprobe-multiscale characterization and modelling of “hybrid” interfaces Exploratory chemistry & materials science