Domino Reaction for the Controlled Functionalization of sp 2 Carbon - - PowerPoint PPT Presentation

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Domino Reaction for the Controlled Functionalization of sp 2 Carbon - - PowerPoint PPT Presentation

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Workshop AICIng Milano, 12-13 June, 2017 Domino Reaction for the Controlled Functionalization of sp 2 Carbon Allotropes Vincenzina Barbera Alberto Milani, Luigi Brambilla, Chiara Castiglioni, Maurizio Galimberti vincenzina.barbera@polimi.it

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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

Domino Reaction for the Controlled Functionalization

  • f sp2 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

Workshop AICIng – Milano, 12-13 June, 2017

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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

Chemistry from biobased C-3 platform

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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

Yield: at least 96% Atom efficiency: 85% Easy procedure No solvent By product: H2O

Chemistry from biobased C-3 platform

  • V. Barbera, A. Citterio, M. Galimberti, G. Leonardi, R. Sebastiano, S.U. Shisodia, A.M. Valerio. WO/2015/189411 A1 (2015)
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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

INTERACTION WITH GRAPHITIC CARBONS INTERACTION WITH POLAR SURROUNDING Serinolpyrrole: Janus molecule

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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

graphene

stacked graphene layers CNT stacked randomly arranged wrapped with different shape anisotropy carbon black graphite, nano-graphite, graphene

Carbon fillers from a layer of sp2-bonded carbon atoms

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CNT CB FEW LAYERS GRAPHENE

Characterization of carbon allotropes (CA)

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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

Characterization of carbon allotropes (CA)

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Oxygenated functional groups

  • n carbon allotrope surface

Bulk structure substantially unaltered

Carbon allotrope Mixing, energy, air

Facile functionalization of carbon materials

  • M. Galimberti, V. Barbera, R. Sebastiano, A. Citterio, G. Leonardi, A.M. Valerio. WO/2016/050887 A1 (2016)
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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

Oxygenated functional groups

  • n carbon allotrope surface

Bulk structure substantially unaltered

Carbon allotrope Mixing, energy, air

Facile functionalization of carbon materials

  • M. Galimberti, V. Barbera, R. Sebastiano, A. Citterio, G. Leonardi, A.M. Valerio. WO/2016/050887 A1 (2016)
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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

86 % 98 % 97 %

Yield:

77 m2/g 300 m2/g 275 m2/g

BET Surface area:

High yield functionalization!

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86 % 98 % 97 %

Yield:

77 m2/g 300 m2/g 275 m2/g

BET Surface area:

High yield functionalization!

High surface area graphite HSAG

HSAG water suspensions from 1 to 0.01 mg/mL

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N CH3 H3C H3C

Model compound Mechanistic investigation

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Model compound Thermal energy

+ HSAG

Thermal energy In air In air

N CH3 H3C H3C N CH3 H3C H3C N CH3 H3C H3C

Mechanistic investigation

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25°C

Absorbance (a.u.) 800 1000 1200 1400 1600 1800 2000 Wavenumbers (cm-1)

1,2,5-Trimethylpyrrole (TMP)

  • ut of plane

C-H bending C=C stretching cyclic alkene

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25°C 150°C 130°C 80°C

Absorbance (a.u.) 800 1000 1200 1400 1600 1800 2000 Wavenumbers (cm-1)

  • ut of plane

C-H bending C=C stretching cyclic alkene

Increasing temperature Δ

Air

TMP from 25 to 150°C

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800 1000 1200 1400 1600 1800 2000

TMP+HSAG 1% 80°C TMP

Absorbance (a.u.) Wavenumbers (cm-1)

Δ, Air

HSAG as cat.

TMP + HSAG cat. - from 25 to 150°C

  • ut of plane

C-H bending C=C stretching cyclic alkene

Increasing temperature

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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

Absorbance (a.u.)

  • ut of plane

C-H bending C=C stretching cyclic alkene

Δ, Air

HSAG as cat.

Increasing temperature

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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

Absorbance (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

Absorbance (a.u.)

  • ut of plane

C-H bending C=C stretching cyclic alkene

Δ, Air

HSAG as cat.

Increasing temperature

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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

800 1000 1200 1400 1600 1800 Wavenumbers (cm-1) Absorbance (a.u.)

TMP

Δ

Air

+HSAG

TMP + HSAG 1/1 - from 25 to 150°C

  • ut of plane

C-H bending C=C stretching cyclic alkene

Increasing temperature

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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

800 1000 1200 1400 1600 1800 Wavenumbers (cm-1) Absorbance (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

  • ut of plane

C-H bending C=C stretching cyclic alkene

Δ

Air

+HSAG

Increasing temperature

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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

800 1000 1200 1400 1600 1800 Wavenumbers (cm-1) Absorbance (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

  • ut of plane

C-H bending C=C stretching cyclic alkene

Δ

Air

+HSAG

Increasing temperature

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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

Paal-Knorr reaction

1

Paal – Knorr Reaction HSAG

Mechanistic path

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Carbocatalyzed benzyl oxidation

1 2

Paal – Knorr Reaction Carbocatalyzed Oxidation

Mechanistic path

HSAG

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Mechanistic path

Increasing temperature

* Structure confirmed by means of NMR spectroscopy

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Mechanistic path

Increasing temperature

* Structure confirmed by means of NMR spectroscopy

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  • V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017

Mechanistic path

Increasing temperature

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Model reaction and DFT calculation

OHC

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

* Structure confirmed by means of FT-IR and NMR spectroscopy

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

Model reaction and DFT calculation

OHC

* Structure confirmed by means of FT-IR and NMR spectroscopy

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

Model reaction and DFT calculation

OHC

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

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3 1 2

Paal – Knorr Reaction Carbocatalyzed Oxidation Diels-Alder reaction Carbon allotrope

Facile functionalization of carbon materials Hypothesis for the mechanism

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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)
  • M. Galimberti, V. Barbera, Italian Patent 102016000113070 (2016)
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Monolithic aerogel Carbon papers Rubber nanocomposites Latex dispersions Polyol dispersions Polyurethane Conductive ink Conductive coating Versatile Technology

Nano-carbon Up

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Acknowledgments

Thanks for the Attention