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 Politecnico di Milano, Department of Chemistry, Materials and Chemical Engineering “G. Natta” Innovative Sustainable Chemistry and Materials and Proteomics Group V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 1
Chemistry from biobased C-3 platform V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 2
Chemistry from biobased C-3 platform � Yield: at least 96% � Atom efficiency: 85% � Easy procedure � No solvent � By product: H 2 O V. Barbera, A. Citterio, M. Galimberti, G. Leonardi, R. Sebastiano, S.U. Shisodia, A.M. Valerio. WO/2015/189411 A1 (2015) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 3
Serinolpyrrole: Janus molecule INTERACTION WITH INTERACTION GRAPHITIC CARBONS WITH POLAR SURROUNDING V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 4
Carbon fillers from a layer of sp 2 -bonded carbon atoms graphene wrapped stacked stacked graphene layers CNT randomly with different arranged shape anisotropy graphite, carbon black nano-graphite, graphene V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 5
Characterization of carbon allotropes (CA) CB CNT FEW LAYERS GRAPHENE V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 6
Characterization of carbon allotropes (CA) CB TGA, Elemental Analysis: carbon purity BET: surface area, activity CNT Infrared, XPS: functional groups Raman, X-ray: bulk structure TEM, HRTEM: morphology FEW LAYERS GRAPHENE V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 7
Facile functionalization of carbon materials Carbon allotrope Mixing, energy, air Oxygenated functional groups on carbon allotrope surface Bulk structure substantially unaltered M. Galimberti, V. Barbera, R. Sebastiano, A. Citterio, G. Leonardi, A.M. Valerio. WO/2016/050887 A1 (2016) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 8
Facile functionalization of carbon materials Carbon allotrope Mixing, energy, air Oxygenated functional groups on carbon allotrope surface Bulk structure substantially unaltered M. Galimberti, V. Barbera, R. Sebastiano, A. Citterio, G. Leonardi, A.M. Valerio. WO/2016/050887 A1 (2016) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 9
High yield functionalization! 98 % Yield: 86 % 97 % BET 300 m 2 /g 77 m 2 /g 275 m 2 /g Surface area: V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 10
High yield functionalization! 98 % Yield: 86 % 97 % BET 300 m 2 /g 77 m 2 /g 275 m 2 /g Surface area: High surface area graphite HSAG HSAG water suspensions from 1 to 0.01 mg/mL V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 11
Mechanistic investigation H 3 C CH 3 Model compound N H 3 C V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 12
Mechanistic investigation H 3 C CH 3 Model compound N H 3 C H 3 C H 3 C + HSAG CH 3 CH 3 N N H 3 C H 3 C In air In air Thermal energy Thermal energy V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 13
1,2,5-Trimethylpyrrole (TMP) out of plane C=C stretching cyclic alkene C-H bending Absorbance (a.u.) 25°C 2000 1800 1600 1400 1200 1000 800 Wavenumbers (cm -1 ) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 14
TMP from 25 to 150 ° C Δ Air out of plane C=C stretching cyclic alkene C-H bending Increasing temperature Absorbance (a.u.) 150°C 130°C 80°C 25°C 2000 1800 1600 1400 1200 1000 800 Wavenumbers (cm -1 ) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 15
TMP + HSAG cat. - from 25 to 150 ° C Δ , Air HSAG as cat. out of plane C=C stretching cyclic alkene C-H bending Increasing temperature Absorbance (a.u.) TMP+HSAG 1% 80 ° C TMP 2000 1800 1600 1400 1200 1000 800 Wavenumbers (cm -1 ) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 16
TMP + HSAG cat. - from 25 to 150 ° C Δ , Air HSAG as cat. out of plane C=C stretching cyclic alkene C-H bending Oxidation Increasing temperature Absorbance (a.u.) TMP+HSAG 1% 130 ° C TMP+HSAG 1% 100 ° C TMP+HSAG 1% 80 ° C TMP 2000 1800 1600 1400 1200 1000 800 Wavenumbers (cm -1 ) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 17
TMP + HSAG cat. - from 25 to 150 ° C Δ , Air HSAG as cat. out of plane C=C stretching cyclic alkene C-H bending Oxidation Increasing temperature TMP+HSAG 1% Absorbance (a.u.) Absorbance (a.u.) 150 ° C TMP+HSAG 1% TMP+HSAG 1% 130 ° C 130 ° C TMP+HSAG 1% TMP+HSAG 1% 100 ° C 100 ° C TMP+HSAG 1% TMP+HSAG 1% 80 ° C 80 ° C TMP TMP 2000 2000 1800 1800 1600 1600 1400 1400 1200 1200 1000 1000 800 800 Wavenumbers (cm -1 ) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 18
TMP + HSAG 1/1 - from 25 to 150 ° C Δ + HSAG Air out of plane C-H bending C=C stretching cyclic alkene Increasing temperature Absorbance (a.u.) TMP 1800 1600 1400 1200 1000 800 Wavenumbers (cm -1 ) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 19
TMP + HSAG 1/1 - from 25 to 150 ° C Δ + HSAG Air out of plane C-H bending C=C stretching cyclic alkene Oxidation Increasing temperature TMP+HSAG 1/1 Absorbance (a.u.) 130 ° C TMP+HSAG 1/1 100 ° C TMP+HSAG 1/1 80 ° C TMP 1800 1600 1400 1200 1000 800 Wavenumbers (cm -1 ) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 20
TMP + HSAG 1/1 - from 25 to 150 ° C Δ + HSAG Air out of plane C-H bending C=C stretching cyclic alkene Oxidation TMP+HSAG 1/1 Increasing temperature 150 ° C TMP+HSAG 1/1 Absorbance (a.u.) 130 ° C TMP+HSAG 1/1 100 ° C TMP+HSAG 1/1 80 ° C TMP 1800 1600 1400 1200 1000 800 Wavenumbers (cm -1 ) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 21
Mechanistic path Paal-Knorr reaction HSAG 1 Paal – Knorr Reaction V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 22
Mechanistic path Carbocatalyzed benzyl oxidation 1 2 HSAG Paal – Knorr Reaction Carbocatalyzed Oxidation V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 23
Mechanistic path Increasing temperature * Structure confirmed by means of NMR spectroscopy V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 24
Mechanistic path Increasing temperature * Structure confirmed by means of NMR spectroscopy V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 25
Mechanistic path Increasing temperature V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 26
Model reaction and DFT calculation OHC DFT ( B3LYP/6-311++G(d,p) ) * Structure confirmed by means of FT-IR and NMR spectroscopy V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 27
Model reaction and DFT calculation OHC Abs TMP + Anthracene 150°C * Abs TMP + HSAG 130°C * Abs Abs 1600 1550 1500 1450 1400 1350 1300 1250 Wavenumbers (cm -1 ) * Structure confirmed by means of FT-IR and NMR spectroscopy V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 28
Model reaction and DFT calculation OHC Abs TMP + Anthracene 150°C * Abs TMP + HSAG 130°C * Abs Abs 1600 1550 1500 1450 1400 1350 1300 1250 Wavenumbers (cm -1 ) DFT ( B3LYP/6-311++G(d,p) ) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 29
Facile functionalization of carbon materials Hypothesis for the mechanism 1 3 2 Carbon allotrope Paal – Knorr Reaction Carbocatalyzed Oxidation Diels-Alder reaction V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 30
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 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) V. Barbera – Domino reaction for the controlled… AICIng - Milano – 12-13 June, 2017 31
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