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 DURATION: 1st May 2013 - 31st October 2015 PROJECT LEADER: dr. Maria IGNAT MENTOR: dr. Valeria HARABAGIU PROJECT NUMBER: 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, physico-chemical 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 planed 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 selected results 2013 – synthesis of ordered mesoporous carbon Ordered mesoporous carbon materials were obtained by template synthesis using SBA-15 silica template and glycerol as carbon precursor.

Project selected results 2014 – polymer-coating ordered mesoporous carbon

Project selected results 2014 – preliminary application test 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

Project selected results 2015 – sorption tests of creatinine on PNiPAM-functionalized ordered mesoporous carbon materials The obtained results showed that the adsorption capacity obtained for PNiPAM-functionalized mesoporous carbon (460 mg/g) is greater than that of pristine mesoporous carbon (390 mg/g). These results show that the PNiPAM-functionalized mesoporous carbon are good candidate for haemofiltration

sorption of Pb2+ ions on CMS Project selected results 2015 – sorptive properties tests on mesoporous carbon material coated with polystirene three adsorption isotherm models were studied the sorption data fitted into Langmuir, Freundlich and Temkin isotherms the Langmuir adsorption model was found to be have the highest regression value and hence the best fit sorption of Pb2+ ions on CMS 9

Project selected results 2015 – sorptive properties tests on mesoporous carbon material coated with polystirene Isotherm constants for the adsorption of Pb(II) ion into CM and CMS samples The maximum monolayer coverage The separation factor and the sorption intensity indicate a favourable sorption The heat of sorption process 10

Specific surface area, m2/g Sorption capacity of Cr(III) ions, mg/g Project selected results 2015 – sorptive properties tests on mesoporous carbon material coated with chitosan Specific surface area, m2/g Total pore volume, cc/g Pore diameter, nm Sorption capacity of Cr(III) ions, mg/g CMCh 328 0.44 3.2 56 FerriteCh 18 0.10 6.26 A comparative study have been done, focusing on ordered mesoporous carbon materials coated with chitosan and chitosan-coated ferrite. Due to the greater textural properties of ordered mesoporous carbon materials, the best sorption capacity for Cr(III) ions has been obtained.

Dissemination ARTICLES 1) „Surface chemistry – the key-property of templated mesoporous carbons for sorption”, Maria IGNAT, Vera MEYNEN, Pegie COOL, Valeria HARABAGIU, Rev. Roum. Chim., 59(6-7), 2014, 591-595; 2) „Glycerol-derived mesoporous carbon: N2-sorption and SAXS data evaluation”, Maria IGNAT, Liviu SACARESCU, Pegie COOL, Valeria HARABAGIU, Materials Today: Proceedings 2 ( 2015 ) 3836 – 3845; 3) "PNiPAM-functionalized mesoporous carbon for adsorption of vitamin B2", Maria IGNAT, Maria Emiliana FORTUNA, Liviu SACARESCU, Mirela-Fernanda ZALTARIOV, Valeria HARABAGIU, Environmental Engineering and Management Journal, March 2015, Vol.14, No. 3, 607-613; 4) „Effect of synthesis parameters on sorptive properties of glycerol-derived mesoporous carbon”, Maria IGNAT, Liviu SACARESCU, Maria Emiliana FORTUNA, Pegie COOL, Valeria HARABAGIU, Environmental Engineering and Management Journal, accepted for publication in April, 2015. 5) „Novel chitosan-coated zinc ferrite nanoparticles as sorbents for wastewater treatment”, Maria IGNAT, Petrisor SAMOILA, Corneliu COJOCARU, Liviu SACARESCU, Valeria HARABAGIU, Chemical Engineering Communications, under review.

Dissemination ORAL PRESENTATIONS AT INTERNATIONAL SCIENTIFIC MEETINGS „Mesoporous materials: synthesis, characterization, applications”, M. Ignat, STREAM Summer School, 8-13 iulie, Institutul de Chimie Macromoleculara „Petru Poni”, 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; 3) „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; 4) “Polystyrene/Mesoporous Carbon Sorbents for Heavy Metal Ions Removal”, M. Ignat, L. Sacarescu, V. Harabagiu, 19th Romanian International Conference on Chemistry and Chemical Engineering, RICCCE 19, September 2-5, 2015, Sibiu, Romania.

Dissemination POSTER PRESENTATIONS AT NATIONAL/INTERNATIONAL SIMPOSIA 1) “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;   2) “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 ; “The effect of heating temperature on the templated carbon porosity”, M. Ignat, L. Sacarescu, V. Harabagiu., 6th Szeged International Workshop on Advances in Nanoscience - SIWAN6, 15–18 October 2014, Szeged, Hungary; 4) “PNiPAM-functionalized mesoporous carbon for adsorption of vitamin B2”, M. Ignat, M. Fortuna, L. Sacarescu, V. Harabagiu., 2nd International Conference on Chemical Ingeneering – ICCE 2014, Romania, Iasi, 5-8 Noiembrie, 2014; 5) “Adsorption study of vitamin B2 on polimer-carbon composite: Freundlich and Langmuir isotherms”, M. Ignat, M. Fortuna, L. Sacarescu, V. Harabagiu, A XXXIII-A Conferinţă Naţională De Chimie, Căciulata, 01-03 Octombrie 2014; 6) “Adsorption of Biomolecules on Mesoporous Carbon. Effect of pH”, M. Ignat, L. Sacarescu, V. Harabagiu, Frontiers in Macromolecular and Supramolecular Science, Seventh Cristofor I. Simionescu Symposium, June 4 – 5, 2015; 7) “Novel Chitosan-Coated Zinc Ferrite Nanoparticles as Sorbents for Wastewater Treatment”, M. Ignat, P. Samoila, C. Cojocaru, L. Sacarescu, V. Harabagiu, 19th Romanian International Conference on Chemistry and Chemical Engineering, RICCCE 19, September 2-5, 2015, Sibiu, Romania.

Stage 2013 105600 Stage 2014 124200 Stage 2015 70200 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