2D Hybrid materials: a tremendous potential for application in modern technology P. Rabu IPCMS UMR7504 (CNRS-UNISTRA), 23, rue du Loess, F67034 Strasbourg, France; 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

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

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),

Seeking for new materials with improved functionalities Fernandes, F.M., et al., Appl. Clay Sci. (2014),

Controlling properties by assembling hybrid organic – inorganic networks PR & coworkers: Adv. Eng. Mater. 5(4) 2003; Chem. Mater ; Chem. Mater ; J. Mater. Chem ; J. Mater. Chem ; Dalton Trans ; Chem. Soc. Rev. 40 (2) 2011; Chem. Sciences ; 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

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

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

Functionalized Nanosheets as Ultimate 2D Functional Bricks (a) Ma, et al. Adv. Mater. 2010, 22 (45), 5082–5104; (b) Geim, Science 2009, 324 (5934), ; (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) ] [TaS ] supraconductivity and magnetism d multilayered two-dimensional heterostructures in interaction with environment e

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

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

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 Advanced materials and technologies for high added values and processes in industries NMBP : Novel hybrid materials for heterogeneous catalysis NMBP : Architectured /Advanced material concepts for intelligent bulk material structures (composites and nanocomposites) NMBP : Systems of materials characterization for model, product and process optimisation NMBP : Advanced materials solutions and architectures for high efficiency solar energy harvesting NMBP : 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