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

In In sit itu u po poly lymeriza merization tion in in 3D 3D po porou

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Department of Materials Science University of Milano-Bicocca

Milano MIPOL - February 16th 2017

PIERO SOZZANI

• 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

Porous Materials and Polymer Science

Nature Chem. 2015, 7, 634

• J. Am. Chem. Soc. 2014, 136, 618
• Angew. Chem. Int. Ed. 2015, 54,
• Angew. Chemie Int. Ed. 2010, 49
• Angew. Chem. Int. Ed. 2015, 54,15684
• Angew. Chem. Int. Ed. 2012, 51, 9258

Nature Chem. 2013, 5, 335

• J. Am. Chem. Soc. 2015, 137, 5231
• Angew. Chem. Int. Ed. 2014, 53, 1043
• Angew. Chem. Int. Ed. 2012, 51, 10136

• permanent porosity
• right-handed helical channels

The “biozeolite” L-Valyl-L-Alanine (VA)

L-valyl-L-alanine (VA)

Nanoporous hydrophobic dipeptides

Ø = 5.1 Å Ø = 5.4 Å Ø = 3.4 Å Ø = 3.0 Å Ø = 3.6 Å Ø = 4.3 Å Ø = 4.0 Å rhelix= 0.6 Å rhelix= 1.1 Å rhelix= 0.6 Å rhelix= 0.9 Å rhelix= 0.3 Å rhelix= 1.0 Å rhelix= 0.6 Å

L-valyl-L-valine (VV) L-alanyl-L-valine (AV) L-valyl-L-alanine (VA) L-isoleucyl-L-valine (IV) L-valyl-L-isoleucine (VI) L-isoleucyl-L-alanine (IA) L-alanyl-L-isoleucine (AI)

CO2 Adsorption Measurements at 298K

5 10 15 20 25 30 35

2 4 6 8 10

amount adsorbed / cm3 g-1 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

Gas Matrix

13C 1H

2D 1H-13C Heteronuclear Correlated NMR spectroscopy Ile-Val/CO2

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

200-300°C Cyclization 2D Crosslinking Carbonization > 600-1300°C 400-600°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

Ala-Val crystal Ala-Val/PAN ladder-polymer graphitized carbon

20 mm

Morphological replica and production of stretched graphitic carbon fibrils

Polymerization in ultra-high surface area porous organic frameworks

monomer AIBN

BET surface area > 5000 m2/g

PAF1

N2 adsorption isotherm 13C MAS NMR

• A. Comotti, S. Bracco, M. Mauri, S. Mottadelli, T. Ben, S. Qiu, P. Sozzani Angew. Chem. Int. Ed. 2012, 51, 10136

HOST GUEST

2 ms 0.1 ms

2D 1H-13C HETCOR PMLG MAS NMR 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(terephthalate)triethylenediamine0.5]n Cu+2

Metal Organic Framework

[Cu(terephthalate)triethylenediamine0.5]n Cu+2

PARTICIPATION OF THE MATRIX IN THE POLYMERIZATION

• A. Comotti, S. Bracco, P. Sozzani, T. Uemura, S. Kitagawa, Nature Chem. 2013, 5, 582

Powder XRD

• f 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