In In sit itu u po poly lymeriza merization tion in in 3D 3D - PowerPoint PPT Presentation

Department of Materials Science University of Milano-Bicocca In In sit itu u po poly lymeriza merization tion in in 3D 3D po porou ous ma mate teri rials als PIERO SOZZANI Milano MIPOL - February 16th 2017

Porous Materials and Polymer Science • High surface area and Large accessible room for gas storage and monomer sorption. • In-situ Polymerization. • Nanometric control at the hierarchical levels of pores and particle morphology: • Replica of both shape and porosity

Angew. Chem. Int. Ed. 2015 , 54, Angew. Chemie Int. Ed. 2010 , 49 Nature Chem. 2015 , 7, 634 J. Am. Chem. Soc. 2014 , 136, 618 Angew. Chem. Int. Ed. 2014 , 53 , 1043 Angew. Chem. Int. Ed. 2012 , 51 , 10136 Nature Chem. 2013 , 5, 335 J. Am. Chem. Soc . 2015 , 137, 5231 Angew. Chem. Int. Ed. 2015 , 54 ,15684 Angew. Chem. Int. Ed. 2012 , 51 , 9258

The “biozeolite” L -Valyl-L-Alanine (VA) • permanent porosity • right-handed helical channels L -valyl- L -alanine (VA)

Nanoporous hydrophobic dipeptides L-valyl-L-valine (VV) L-valyl-L-isoleucine (VI) L-alanyl-L-valine (AV) L-alanyl-L-isoleucine (AI) Ø = 4.0 Å Ø = 5.1 Å Ø = 5.4 Å Ø = 3.4 Å Ø = 3.0 Å Ø = 3.6 Å Ø = 4.3 Å r helix = 0.6 Å r helix = 1.1 Å r helix = 0.6 Å r helix = 0.9 Å r helix = 0.3 Å r helix = 1.0 Å r helix = 0.6 Å L-valyl-L-alanine (VA) L-isoleucyl-L-valine (IV) L-isoleucyl-L-alanine (IA)

CO 2 Adsorption Measurements at 298K 35 30 amount adsorbed / cm 3 g -1 25 20 15 10 5 0 0 2 4 6 8 10 Pressure / atm ALA-VAL - Adsorption, CO2 VAL-ALA - Adsorption, CO2 ILE-VAL - Adsorption, CO2 VAL-ILE - Adsorption, CO2 ALA-ILE - Adsorption, CO2 ILE-ALA - Adsorption, CO2 VAL-VAL - Adsorption, CO2 LS - Adsorption, CO2

2D 1 H- 13 C Heteronuclear Correlated NMR spectroscopy Ile-Val/CO 2 13 C 1 H Gas Matrix

In-situ Reactions & Transformations akin to enzymatic processes Polymerization 1. in biological nanovessels 2. in synthetic nanoreactors Shape-replica and pore-replica • Retention of order from the crystal state and stereochemical control • Unusual architectures • Polymer chain alignment

Polymerization in the dipeptide crystals

Thermal transformation of PAN 2D Cyclization Crosslinking 200-300 ° C 400-600 ° C Carbonization > 600-1300 ° C

Thermal modification of PAN in dipeptide crystals G. Distefano, A. Comotti, S. Bracco, M. Beretta, P. Sozzani Angew. Chem. Int. Ed. (Hot paper) 2012, 51 , 9258

Morphological replica and production of stretched graphitic carbon fibrils 20 m m Ala-Val crystal Ala-Val/PAN ladder-polymer graphitized carbon

Polymerization in ultra-high surface area porous organic frameworks PAF1 monomer AIBN BET surface area > 5000 m 2 /g

N 2 adsorption isotherm 13 C MAS NMR A. Comotti, S. Bracco, M. Mauri, S. Mottadelli, T. Ben, S. Qiu, P. Sozzani Angew. Chem. Int. Ed. 2012, 51 , 10136

2D 1 H- 13 C HETCOR PMLG MAS NMR 2 ms 0.1 ms HOST GUEST extended interfaces

Thermal transformation to ladder polymer 2.5 eV

PAN chains encapsulated in the framework: interpenetration at the molecular level intimate interactions A robust texture made of a 1D polymer interwoven with a regularly spaced 3D polymer

Angew. Chem. Int. Ed. 2015 , 54, 4773; Angew. Chem. Int. Ed. 2010 , 54, 4773; J. Phys. Chem. B 2012 , 116, 1623; Chem. Commun. 2008 , 4798

Metal-Organic Frameworks Cu +2 [Cu(terephthalate)triethylenediamine 0.5 ] n

Metal Organic Framework Cu +2 [Cu(terephthalate)triethylenediamine 0.5 ] n

PARTICIPATION OF THE MATRIX IN THE POLYMERIZATION A. Comotti, S. Bracco, P. Sozzani, T. Uemura, S. Kitagawa, Nature Chem. 2013, 5, 582

Powder XRD of the extracted polymer

Acknowledgments • Susumu Kitagawa and Takashi Uemura (Kyoto University) • Teng Ben and Shilun Qiu (Jilin University) • Josef Michl (Colorado State University) University of Milano Bicocca: • Angiolina Comotti • Silvia Bracco • Mario Beretta • Irene Bassanetti • Gaetano Distefano • Patrizia Valsesia • Giovanni Alberini • Donata Asnaghi • Irene Campana • Elkid Cobani • Francesca Denaro • Giacomo Sormani