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:

1stMay 2013 - 31stOctober 2015PROJECT LEADER:

dr. Maria IGNAT MENTOR:

dr. Valeria HARABAGIU PROJECT NUMBER:

PN-II-RU-PD-2012-3-0357

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Project summaryThe 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.

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- 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 objectives

2013A1.1. 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.

2014A2.1. 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.

2015A3.1. 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 planed activities

Project selected results2013 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 selectedresults2014 polymer-coating ordered mesoporous carbon

Project selected results2014 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 results2015 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

Project selected results2015 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

Project selected results2015 sorptive properties tests on mesoporous carbon material coated with polystirene

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The heat of sorption process

The separation factor and the sorption intensity indicate a favourable sorption

The maximum monolayer coverage

Isotherm constants for the adsorption of Pb(II) ion into CM and CMS samples

Project selected results2015 sorptive properties tests on mesoporous carbon material coated with chitosan

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.

Specific surface area, m2/gTotal pore volume,cc/gPore diameter, nmSorption capacity of Cr(III) ions, mg/gCMCh3280.443.256FerriteCh180.10186.26

DisseminationARTICLES1) 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.

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DisseminationORAL 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, XIme Colloque Franco-Roumain sur les Polymres, Piteti (Cornul Vanatorului), Roumanie, Les 27-29 aot 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.

DisseminationPOSTER PRESENTATIONS AT NATIONAL/INTERNATIONAL SIMPOSIA1) Riboflavin uptake by polymer functionalized mesoporous carbon, M. Ignat, M. Fortuna, L. Sacarescu, V. Harabagiu, XIme Colloque Franco-Roumain sur les Polymres, Piteti (Cornul Vanatorului), Roumanie, Les 27-29 aot 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, 1518 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 Conferin Naional De Chimie, Cciulata, 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.

Budget

Stage 2013105600Stage 2014124200Stage 201570200Total Budget300000

Contact

Dr. MARIA IGNAT

"Petru Poni" Institute of Macromolecular ChemistryAleea Grigore Ghica Voda 41A, 700487 Iasi, RomaniaTel: +40232 260188Fax: +40232 211299E-mail: ignat.maria@icmpp.ro

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*1C1000

0

100

200

300

400

500

600

700

800

900

0

0,2

0,4

0,6

0,8

1

Relative pressure, P/P0

Adsorbed volume, cc/g STP

1C1000

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

2

4

6

8

10

Pore diameter, nm

dVd

1C1000

1C1000

0,5

1,5

2,5

3,5

2 theta degree

Intensity (counts)

1C1000

(100)

(110)

05001000150020002500300035004000Transmitance, a.u.Wavenumber, cm-1Tratament la MWMCMC-MW

05001000150020002500300035004000Transmitance, a.u.Wavenumber, cm-1ChCMChMCM-COOHCMChL

05001000150020002500300035004000Transmitance, a.u.Wavenumbers, cm-1StCMCM-St

05001000150020002500300035004000Transmitance, a.u.Wavenumber, cm-1PNIPAM 1CM-COOHCM-PNIPAM 2CM-PNIPAM 1

0100200300400500600700800900100000.20.40.60.81Adsorbed volume cc/g STPRelative pressure, P/P0CMCM-St

010020030040050060070080090010000.00.20.40.60.81.0Adsorbed volume, cc/g STPRelative pressure, P/P0CMCM-PNiPAM2

135791113dV(r)Pore diameter, nmCMCM-PNiPAM2

00.10.20.30.40.50.6051015202530dVdPore diameter, nmCMCM-St

400900140019002400290034003900Transmitance, a.u.Wavenumber, cm-1VB2MC-VB2PNiPAM/MC-VB2

010020030040050060070080090010000.00.20.40.60.81.0Adsorbed volume, cc/g STPRelative pressure, P/P0MCPNiPAM/MCPNiPAM/MC-VB2135791113dV(r)Pore diameter, nm

y = 0.0003x + 0.0011R = 0.957200.0010.0020.003021/q1/CeLangmuir modely = 0.1801x + 1.8861R = 0.9957012345-2024ln qln CeFreundlich modely = 132.67x + 670.38R = 0.9997050010001500-2024qln CeTemkin modelMC-VB2

y = 0.0008x + 0.0005R = 0.753500.00100.20.41/q1/CeLangmuir modely = 298.46x + 951.25R = 0.726305001000150020000123qln CeTemkin modelPNiPAM/MC-VB2y = 0.2163x + 6.9134R = 0.700266.577.580123ln qln CeFreundlich model

0501001502002503003504004505000100200300400Q

e,

mg/gC

e

, mg/LCM-PNiPAMCM

y = 0,001x + 0,0007R

2

= 0,9992y = 0,0006x + 0,0007R

2

= 0,987100.10.20.30.40.50.60.70.80.910100200300400Ce/qCe

Langmuir model

CMCM-PNiPAM

y = 0.175x + 5.104R = 0.986y = 0.159x + 2.654R = 0.8120123456702468ln qln Ce

Freundlich model

CM-PNiPAMCM

Q

0

(mg/g)

k

L

(L/mg)R

L

R

2

1/nn

k

f

(mg/g)

R

2

A

t

(L/mg)b

T

B

R

2

Pb

2+

on

CM

50.2530.0460.1520.9400.3153.17510.1260.8661.451339.7197.2930.820

Pb

2+

on

CMS

88.5130.0810.0990.9840.4832.07011.7540.9681.133147.47516.8000.916

LANGMUIR ISOTHERM FREUNDLICH ISOTHERM TEMKIN ISOTHERM

Metal

ions