Domino reaction for the controlled functionalization of sp2 carbon allotropes

Domino Reaction for the Controlled Functionalization

of sp

2

_{Carbon Allotropes}

Politecnico di Milano, Department of Chemistry, Materials and Chemical Engineering “G. Natta”

Innovative Sustainable Chemistry and Materials and Proteomics Group

Vincenzina Barbera

Alberto Milani, Luigi Brambilla, Chiara Castiglioni, Maurizio Galimberti

vincenzina.barbera@polimi.it

Yield: at least 96%

Atom efficiency: 85%

Easy procedure

No solvent

By product: H

O

Chemistry from biobased C-3 platform

INTERACTION WITH

GRAPHITIC CARBONS

INTERACTION

WITH POLAR

SURROUNDING

graphene

stacked graphene layers

CNT

stacked

randomly

arranged

wrapped

with different

shape anisotropy

carbon black

graphite,

nano-graphite,

graphene

CNT

CB

FEW LAYERS

GRAPHENE

CNT

CB

FEW LAYERS

GRAPHENE

TGA, Elemental Analysis:

carbon purity

BET:

surface area, activity

Infrared, XPS:

functional groups

Raman, X-ray:

bulk structure

TEM, HRTEM:

morphology

Oxygenated functional groups

on carbon allotrope surface

Bulk structure

substantially unaltered

Carbon

allotrope

Mixing, energy, air

Facile functionalization of carbon materials

Oxygenated functional groups

on carbon allotrope surface

Bulk structure

substantially unaltered

Carbon

allotrope

Mixing, energy, air

Facile functionalization of carbon materials

86 %

97 %

98 %

Yield:

77 m

_/g

_{275 m}

_/g

_{300 m}

_/g

BET

Surface area:

86 %

97 %

98 %

Yield:

77 m

_/g

_{275 m}

_/g

_{300 m}

_/g

BET

Surface area:

High yield functionalization!

High surface area graphite

HSAG

HSAG water suspensions from 1 to 0.01 mg/mL

N CH3

H₃C

H₃C

Model compound

Mechanistic investigation

Model compound

Thermal energy

+

HSAG

Thermal energy

In air

In air

Mechanistic investigation

25°C A b so rb a n ce ( a .u .) 800 1000 1200 1400 1600 1800 2000 Wavenumbers (cm-1₎

1,2,5-Trimethylpyrrole (TMP)

out of plane

C-H bending

25°C 150°C 130°C 80°C A b so rb a n ce ( a .u .) 800 1000 1200 1400 1600 1800 2000 Wavenumbers (cm-1₎

out of plane

C-H bending

C=C stretching cyclic alkene

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

Δ

TMP from 25 to 150

_°

C

800 1000 1200 1400 1600 1800 2000 TMP+HSAG 1% 80°_C TMP A b so rb a n ce ( a .u .) Wavenumbers (cm-1₎

Δ

_{, Air}

TMP + HSAG cat. - from 25 to 150

_°

C

out of plane

C-H bending

C=C stretching cyclic alkene

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

Wavenumbers (cm-1₎

TMP + HSAG cat. - from 25 to 150

_°

C

800 1000 1200 1400 1600 1800 2000 TMP+HSAG 1% 100°_C TMP+HSAG 1% 80°C TMP+HSAG 1% 130°C TMP

Oxidation

out of plane

C-H bending

C=C stretching cyclic alkene

Δ

_{, Air}

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

800 1000 1200 1400 1600 1800 2000 TMP+HSAG 1% 100°_C TMP+HSAG 1% 80°_C TMP+HSAG 1% 130°C TMP TMP+HSAG 1% 150°C A b so rb a n ce ( a .u .) Wavenumbers (cm-1₎

TMP + HSAG cat. - from 25 to 150

_°

C

800 1000 1200 1400 1600 1800 2000 TMP+HSAG 1% 100°_C TMP+HSAG 1% 80°C TMP+HSAG 1% 130°C TMP

Oxidation

out of plane

C-H bending

C=C stretching cyclic alkene

Δ

_{, Air}

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

800 1000 1200 1400 1600 1800 Wavenumbers (cm-1₎ A b so rb a n ce ( a .u .) TMP

Δ

TMP + HSAG 1/1 - from 25 to 150

_°

C

out of plane

C-H bending

C=C stretching cyclic alkene

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

800 1000 1200 1400 1600 1800 Wavenumbers (cm-1₎ A b so rb a n ce ( a .u .) TMP+HSAG 1/1 100°C TMP+HSAG 1/1 80°C TMP TMP+HSAG 1/1 130°C

Oxidation

TMP + HSAG 1/1 - from 25 to 150

_°

C

out of plane

C-H bending

C=C stretching cyclic alkene

Δ

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

800 1000 1200 1400 1600 1800 Wavenumbers (cm-1₎ A b so rb a n ce ( a .u .) TMP+HSAG 1/1 100°C TMP+HSAG 1/1 80°C TMP TMP+HSAG 1/1 150°C TMP+HSAG 1/1 130°C

Oxidation

TMP + HSAG 1/1 - from 25 to 150

_°

C

out of plane

C-H bending

C=C stretching cyclic alkene

Δ

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

Paal-Knorr reaction

1

Paal – Knorr Reaction

HSAG

Carbocatalyzed benzyl oxidation

1

2

Paal – Knorr Reaction

Carbocatalyzed Oxidation

Mechanistic path

Mechanistic path

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

Mechanistic path

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

Mechanistic path

In

c

re

a

s

in

g

te

m

p

e

ra

tu

re

Model reaction and DFT calculation

OHC

DFT (B3LYP/6-311++G(d,p))

TMP + Anthracene 150°C * A b s TMP + HSAG 130°C * A b s A b s A b s 1250 1300 1350 1400 1450 1500 1550 1600 Wavenumbers (cm-1₎

Model reaction and DFT calculation

OHC

TMP + Anthracene 150°C * A b s TMP + HSAG 130°C * A b s A b s A b s 1250 1300 1350 1400 1450 1500 1550 1600 Wavenumbers (cm-1₎

Model reaction and DFT calculation

OHC

3

1

2

Paal – Knorr Reaction

Carbocatalyzed Oxidation

Diels-Alder reaction

Carbon

allotrope

Facile functionalization of carbon materials

Functional group:

from few % to 20%

Functionalization yield:

from 85% to quantitative

Covalent bond

between functional group

and graphene layer

Bulk structure of graphitic materials:

substantially unaltered

Facile functionalization of carbon materials

V. Barbera, A. Citterio, M. Galimberti, G. Leonardi, R. Sebastiano, S.U. Shisodia, A.M. Valerio. WO/2015/189411 A1 (2015)

M. Galimberti, V. Barbera, R. Sebastiano, A. Citterio, G. Leonardi, A.M. Valerio. WO/2016/050887 A1 (2016)

M. Galimberti, V. Barbera, R. Sebastiano, A. Truscello, A.M. Valerio. WO/2016/023915 A1 (2016)

M. Galimberti, V. Barbera, Italian Patent 102016000113012 (2016)

Monolithic

aerogel

Carbon papers

Rubber

nanocomposites

Latex

dispersions

Polyol

dispersions

Polyurethane

Conductive ink

Conductive

coating

Versatile Technology

Nano-carbon Up

Acknowledgments