PROJECT TITLE: POLYMER COATED ORDERED MESOPOROUS CARBONS WITH MULTIFUNCTIONAL PROPERTIES CONTRACTOR: "Petru Poni" Institute of Macromolecular Chemistry, Romanian Academy GRANTED BY: Romanian National Authority for Scientific Research, CNCS - UEFISCDI PROJECT LEADER: dr. Maria IGNAT MENTOR: dr. Valeria HARABAGIU PROJECT NUMBER: PROJECT DURATION: 1st May 2013 - 30th April 2015 PN-II-RU-PD-2012-3-0357 Project summary The proposed project entitled “Polymer coated ordered mesoporous carbons with multifunctional properties” will be developed in Institute of excellence of the Romanian Academy by a team formed from the project leader and a tutor with complementarily expertise required for the project development, e.g. mesoporous carbons and polymer science, respectively. The aim of this research project is to prepare polymer-coverd ordered mesoporous carbon materials with high adsorption properties, appropriate for decontamination of industrial water and haemoperfusion. The project is organized in three research phases dealing, respectively, with (a) the preparation of mesoporous nanoparticles; (b) functionalisation of the particle by chemical treatment and polymer coating; (c) characterization of structure, physicochemical and the sorption properties of the functional particles. Expected results: three ISI papers; six conference presentations. Project objectives • - To establish a reproducible method for the synthesis of highly ordered mesoporous carbons with designed architecture and showing high sorption properties; • - To provide a treatment method affording high functionality (surface reactivity and wettability) of the pore surfaces; • - To optimize the preparation conditions of polymer-carbon systems in order to minimize the particle agglomeration and to maintain appropriate porosity; • - To establish preparation-structure-properties correlations and to check the end use properties of the optimized materials. Project activities • 2013 A1.1. Synthesis and characterization of ordered mesoporous carbon materials with high sorption properties. A1.2. Providing a treatment method affording high functionality of mesoporous carbon surface. • 2014 A2.1. Synthesis and characterization of polymer-carbon composites. A2.2. Optimizing the synthetic conditions of the propozed composites in order to maintain appropriate porosity. A3.3. Establishing the preparation-structure-properties correlations of the optimized composites. • 2015 A3.1. Study of the polymer coated-ordered mesoporous carbon for the prevention particles agglomerations. A3.2. Verification of end-use properties of the synthesized composites. Project results 1C1000 1C1000 700 0,5 600 1,5 2,5 2 theta degree 500 0,7 0,6 400 0,5 dVd Adsorbed volume, cc/g STP (110) Intensity (counts) 900 800 (100) 2013 – synthesis of ordered mesoporous carbon 300 0,4 0,3 0,2 200 0,1 0 100 2 4 6 8 Pore diameter, nm 10 0 0 0,2 0,4 0,6 0,8 1 Relative pressure, P/P0 Ordered mesoporous carbon materials were obtained by template synthesis using SBA-15 silica template and glycerol as carbon precursor. 3,5 1000 Tratament la MW 900 Adsorbed volume cc/g STP Transmitance, a.u. MC-MW CM 600 CM-St 500 400 300 200 100 4000 3500 3000 2500 2000 1500 1000 500 0 0 0 0.2 0.4 Wavenumber, cm-1 0.6 Relative pressure, P/P0 0.8 1 0.6 0.5 0.4 Transmitance, a.u. CM CMChM dVd CM-St Ch 0.3 CM-COOH CMChL 0.2 0.1 4000 3500 3000 2500 2000 1500 Wavenumber, cm-1 1000 500 0 0 0 5 10 15 Pore diameter, nm 20 25 30 1000 900 St CM CM-St Adsorbed volume, cc/g STP 800 Transmitance, a.u. 700 600 500 400 CM 300 CM-PNiPAM2 200 100 0 0.0 4000 3500 3000 2500 2000 1500 Wavenumbers, cm-1 1000 500 0.2 0.4 0.6 Relative pressure, P/P0 0 0.8 1.0 dV(r) 2014 – polymer-coating ordered mesoporous carbon 700 MC Transmitance, a.u. Project results 800 CM CM-PNiPAM2 PNIPAM 1 CM-COOH CM-PNIPAM 2 CM-PNIPAM 1 4000 3500 3000 2500 2000 1500 Wavenumber, cm-1 1000 500 0 1 3 5 7 9 Pore diameter, nm 11 13 1000 Project results 2014 – preliminary application test PNiPAM/MC-VB2 dV(r) Adsorbed volume, cc/g STP 900 800 700 1 600 3 5 7 9 11 Pore diameter, nm 13 500 400 MC 300 PNiPAM/MC 200 Transmitance, a.u. 100 PNiPAM/MC-VB2 MC-VB2 0 0.0 0.2 0.4 0.6 0.8 1.0 Relative pressure, P/P0 MC-VB2 VB2 0.003 5 Langmuir model 1500 Freundlich model Temkin model 4 0.002 2400 1900 Wavenumber, cm-1 1400 900 400 2 0.001 500 1 y = 0.0003x + 0.0011 R² = 0.9572 0 2 y = 132.67x + 670.38 R² = 0.9997 y = 0.1801x + 1.8861 R² = 0.9957 0 0 -2 0 1/Ce 2 4 0 -2 ln Ce 0 ln Ce 2 4 PNiPAM/MC-VB2 8 Langmuir model 2000 Freundlich model 0.001 Temkin model 7.5 1500 1000 7 q 1/q The obtained results showed that the adsorption capacity obtained for PNiPAM-functionalized mesoporous carbon (80%) is greater than the vitamin B2 adsorption on pristine mesoporous carbon (53%). These results show that the PNiPAM-functionalized mesoporous carbon compare favorably with unfunctionalized mesoporous carbon q 2900 ln q 3400 ln q 1/q 3900 1000 3 6.5 y = 0.0008x + 0.0005 R² = 0.7535 0 6 0 0.2 1/Ce 0.4 500 y = 0.2163x + 6.9134 R² = 0.7002 0 1 2 ln Ce 3 y = 298.46x + 951.25 R² = 0.7263 0 0 1 ln Ce 2 3 Dissemination 2013 ARTICLES „Effect of the synthesis conditions on glycerol-derived mesoporous carbon materials”, M. Ignat E. Popovici, P. Cool, V. Harabagiu, Microporous and Mesoporous Materials, submitted for publication. ORAL PRESENTATIONS AT INTERNATIONAL SCIENTIFIC MEETINGS „Mesoporous materials: synthesis, characterization, applications”, Maria Ignat, STREAM Summer School, 8-13 iulie, Iasi, Romania 2013. “Influence of the Pyrolizing Temperature on the Textural Properties of the Templated Mesoporous Carbon Materials”, M. Ignat, E. Popovici, P. Cool, V. Harabagiu 3rd International Conference Nanomaterials: Applications and Properties 2013 (NAP 2013), 16-21 septembrie, 2013, Golden Kolos Resort, 9, Chervonoarmiiys'ka Str., Alushta, Crimea, Ucraina. Dissemination 2014 ARTICLES „Surface chemistry – the key-property of templated mesoporous carbons for sorption”, Maria IGNAT, Vera MEYNEN, Pegie COOL, Valeria HARABAGIU, Revue Roumaine de Chimie, under review; „Glycerol-derived mesoporous carbon: N2-sorption and SAXS data evaluation”, Maria IGNAT, Liviu SACARESCU, Pegie COOL, Valeria HARABAGIU, Applied Surface Science, under review; "PNiPAM-functionalized mesoporous carbon for adsorption of vitamin B2", Maria IGNAT, Maria Emiliana FORTUNA, Liviu SACARESCU, MirelaFernanda ZALTARIOV, Valeria HARABAGIU, Environmental Engineering and Management Journal, 2015, accepted for publication in 2015; „The effect of heating temperature on glycerol-derived mesoporous carbon porosity”, Maria IGNAT, Liviu SACARESCU, Valeria HARABAGIU. Dissemination 2014 ORAL PRESENTATIONS AT NATIONAL/INTERNATIONAL SIMPOSIA „Polysilanes: organic-inorganic polymers for optoelectronics”, V. Harabagiu, M. Ignat, G. Sacarescu, M. Simionescu, L. Sacarescu, XIème Colloque Franco-Roumain sur les Polymères, Pitești (Cornul Vanatorului), Roumanie, Les 27-29 août 2014 – oral presentation. “Riboflavin uptake by polymer functionalized mesoporous carbon”, M. Ignat, M. Fortuna, L. Sacarescu, V. Harabagiu, XIème Colloque Franco-Roumain sur les Polymères, Pitești (Cornul Vanatorului), Roumanie, Les 27-29 août 2014 - poster. “Glycerol-derived mesoporous carbon: N2-sorption and SAXS data evaluation”, M. Ignat*, M. Fortuna, L. Sacarescu, V. Harabagiu, 10th International Conference on Physics of Advanced Materials – ICPAM-10, Iasi, Romania, 22-28 September 2014 – poster. “The effect of heating temperature on the templated carbon porosity”, Maria Ignat, Liviu Sacarescu, Valeria Harabagiu., 6th Szeged International Workshop on Advances in Nanoscience - SIWAN6, 15–18 October 2014, Szeged, Hungary poster. “PNiPAM-functionalized mesoporous carbon for adsorption of vitamin B2”, Maria Ignat, Maria Fortuna, Liviu Sacarescu, Valeria Harabagiu., 2nd International Conference on Chemical Ingeneering – ICCE 2014, Romania, Iasi, 5-8 Noiembrie, 2014 – poster. “Adsorption study of vitamin B2 on polimer-carbon composite: Freundlich and Langmuir isotherms”, Maria Ignat, Maria Fortuna, Liviu Sacarescu, Valeria Harabagiu, A XXXIII-A Conferinţă Naţională De Chimie, Căciulata, 01-03 Octombrie 2014 poster. Budget Stage 2013 105600 Stage 2014 165600 Stage 2015 28800 Total Budget 300000 Contact Dr. MARIA IGNAT "Petru Poni" Institute of Macromolecular Chemistry Aleea Grigore Ghica Voda 41A, 700487 Iasi, Romania Tel: +40232 260188 Fax: +40232 211299 E-mail: ignat.maria@icmpp.ro