PN-II-ID-PCE-2011-3-0473 ( contract nr. 17/2011)

1. PN-II-ID-PCE-2011-3-0473 (contract nr. 17/2011) Eco-friendly design/synthesis of nano-oxides:control of size, shape, morphology and functionalizationof ZnO by polysaccharides assisted methodologies (2011-2014)

2. Team Project leader: Dr. Oana Carp- Institute de of Physical-Chemistry “IlieMurgulescu”, Bucharest Team’s members: Dr. Greta Socoteanu (Patrinoiu)- Institute de of Physical-Chemistry “IlieMurgulescu”, Bucharest Dr. Diana Visinescu - Institute de of Physical-Chemistry “IlieMurgulescu”, Bucharest, Dr. Jose Maria Calderon-Moreno- Institute de of Physical-Chemistry “IlieMurgulescu”, Bucharest Dr. RalucaVoda (Dumitru) -Universty –University “Politehnica”Faculty for Industrial Chemistry and Environmental Engineering, Timisoara MasterandRalucaNegrea (Damian) - National Institute of Material Physics, Bucharest Dr. RuxandraBirjega-National Institute for Lasers, Plasma and Radiation Physics, Bucharest Dr. Cornel Munteanu- Institute de of Physical-Chemistry “IlieMurgulescu”, Bucharest Dr. Adina Magdalena Musuc-Institute de of Physical-Chemistry “IlieMurgulescu”, Bucharest MasterandAlina Stan- Institute de of Physical-Chemistry “IlieMurgulescu” employed by competition on a free position of the project

3. Abstract Generally, the polysaccharide polymer ability to capture, bind and thus preorganizing metal ions, provides preferred nucleation and crystal growth constrained to nanoscale, allowing morphology control and preventing spontaneous particles agglomeration if the crystalline oxide is formed in solution, or sintering, if heating treatment are required for oxide crystallization. The polysaccharides interference in oxide synthesis occur in various stage of synthesis and depend both on intrinsic features like raw materials nature and extrinsic ones materialized in tunable reaction conditions. Since the project aims to analyze how polysaccharides properties may control the design/synthesis of oxide materials under various extrinsic factors, the synthetic methodology was chosen as methodological criterion. For each synthetic procedure, an in-depth characterization of the precursor, its conversion to oxide (if the reaction proceed via a precursor) and of the obtained oxide will be performed, taking advantage of the complementary scientific competences of the research team. Thus, the precursor will be characterized by elemental analysis and FTIR spectroscopy, the precursor→oxide conversion by thermal analysis, while the obtained oxide by optical (FTIR, UV-Vis, PL, Raman spectroscopy), structural (XRD), morphological (SEM, TEM, HRTEM) and specific surface investigations. The different developed synthetic approaches are focused on the synthesis of ZnO materials of nanomeric sizes and various morphologies and functionalizations using polysaccharides build up from D-glucose units linked either by α-glycosidic bonds (starch and dextran) and β-bonds (methyl-cellulose) as raw materials. The choice of these systems is not accidental. Thus, the chosen methodologies can be developed toward eco-friendly approaches, through improving their atom and energy economical (high-yield with small amounts of by-products, low energy consumption, room or low-temperatures synthesis) and minimizing hazard effect on human health and environmental (nontoxic, low cost and bio-renewable raw materials), permitting also a reliable control of the oxide products (crystallinity, purity, size, shape, morphology, functionalization) without compromising their quality, on the contrary improving it. The selected polysaccharide will allow for the first time to accomplish a comparative study concerning the dependence of oxide characteristics on polysaccharides properties. Thus, the effect of the glycosidic bond position (α and β), the polymerization degree, hydrocarbonate chain branching and distinct rheological properties will be equally analyzed. On the other hand, ZnO plays an outstanding role in many aspects of science and engineering due to its unique optical, semiconducting, catalytic and piezoelectric properties. The oxides remarkable properties, tunable through size, morphology, and functionalization, are the starting point for attractive potential applications.

4. The project implementation plan

5. Used instrumentations Institute of Physical Chemistry“Ilie Murgulescu” FTIR Spectrometer JASCO -4100 400-4000 cm-1 UV-Vis Spectrometer PERKIN-ELMER LAMBDA L35, 200-1100 nm PL spectrometerJASCO FP-8300 200-650 nm TEM Microscope FEI - Tecnai G2-F30 coupled with EDX Memmert Incubator UNB500 SEM Microscope FEI - Quanta 3D FEG Dual Beam Simultaneous thermal analysis STA 449 Jupiter f1 Acquisition of the project

6. The general scientific objective is focused on the developing of innovative environmental friendly strategies polysaccharides-assisted, for the design and synthesis of tailor made oxide-based nanomaterials, exploiting either individually or simultaneously polysaccharides diverse and versatile properties. The project’s specific objectives that constitute also novelty features belonging both to fundamental and applicative research, are as follows: • to establish a relationship with a large degree of generalization between polysaccharide peculiarities - synthesis methodology - oxide features, in order to detect a general trend, forwarding polysaccharide-assisted design and synthesis topic; • to develop environmentally friendly protocols for the synthesis of nanosized (50-300 Å) ZnO materials, functionalized or not with polysaccharides; • to develop environmentally friendly protocols for the synthesis of ZnO spherical structures such as sphere, core/shell, hollow sphere and jingle-bell; • to develop environmentally friendly protocols for the synthesis of ZnO/C composites. • Besides these scientific objectives (original results in areas of interest and perspective), objectives like international visibility increasing (by publication in journal of high impact factor and participation to prestigious international conference), young researchers motivation (by financial advantages) as well as infrastructure improvement and supplies purchase have to be mentioned. • Project obiectives

7. Budget Breakdown

8. Dissemination of project scientifically results

9. Article A green chemical approach to the synthesis of photoluminescent ZnO hollow spheres with enhanced photocatalytic properties Greta Patrinoiu, Madalina Tudose, Jose Maria Calderón-Moreno, Ruxandra Birjega, Petru Budrugeac, Ramona Ene, Oana Carp Journal of Solid State Chemistry, 186, 2012, 17-22 9 citari Abstract ZnO hollow spheres have been synthesized by a simple and environmentally friendly template assisted route. Starch-derived carbonaceous spheres were used as template, impregnated with Zn(CH3COO)2·2H2O to obtain zinc-containing precursor spheres and thermally treatment at 600°C, yielding hollow ZnO spherical shells. The precursor spheres and hollow shells were characterized by X-ray diffraction, FTIR spectroscopy, scanning electron microscopy, thermal analysis and room-temperature photoluminescence measurements. The hollow spherical shells with diameters of ∼150 nm and wall thickness of ∼20 nm, are polycrystalline, with a mean crystallite size of 22 nm, exhibiting interesting emission features, with a wide multi-peak band covering blue and green regions of the visible spectrum. The photocatalytic activities (under UV and visible light irradiations) of the ZnO spherical shells evaluated for the phenol degradation reaction in aqueous solutions are outstanding, a total phenol conversion being registered in the case of UV irradiation experiments. Keywords: Green synthesis; Hollow spheres; Phenol degradation/mineralization; Photoluminescence; ZnO

10. Article Carbonaceous spheres-an unusualtemplate for solid metal oxide mesoscale spheres: Application to ZnO spheres Greta Patrinoiu, Jose Maria Calderón-Moreno, Daniela C. Culita, Ruxandra Birjega, Ramona Ene, Oana Carp Journal of Solid State Chemistry, 202, 2013, 291-299 Abstract A green template route for the synthesis of mesoscale solid ZnO spheres was ascertain. The protocol involves a double coating of the carbonaceous spheres with successive layers of zinc-containing species by alternating a non-ultrasound and ultrasound-assisted deposition, followed by calcination treatments. The composites were characterized by FTIR spectroscopy, thermal analysis, scanning electron microscopy while the obtained ZnO spheres by X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, N2 adsorption-desorption isotherms and photoluminescence investigations. A growth mechanism of the solid spheres is advanced based on these results. While the spheres’ diameters and the mean size values of ZnO are independent on deposition order, the surface area and the external porosity are fairly dependent. The photoluminescence measurements showed interesting emission features, with emission bands in the violet to orange region. The spheres present high photocatalytical activity towards the degradation of phenol under UV irradiation, the main reaction being its mineralization. Keywords: Carbonaceous spheres,ZnO solid spheres, Ultrasound, Green synthesis

11. Article Eco-friendly synthetic route for layered zinc compound and its conversion to ZnO with photocatalytical properties Greta Patrinoiu, Jose Maria Calderón-Moreno, Daniela C. Culita, Ruxandra Birjega, Ramona Ene, Oana Carp Journal of Solid State Science 23, 2013, 58-64. Abstract Layered basic zinc salt (LBZS) that contains both carbonate and acetate as intercalated anions was obtained by a sonochemical procedure, using a non-basic zinc acetate aqueous solution. The compound was characterized by IR spectroscopy, thermal analysis, SEM and XRD investigations. The LBZS consists in a lamellar structure with two interlayer distances (13.70 and 19.34 Ǻ), the XRD pattern and SEM images being characteristic for turbostratic materials. The acetate anions are intercalated as free anions and monodentate ligands, while carbonate anions behave as bidentate ligands. A growth mechanism for the LBZS is advanced. Its calcination at 600oC led to ZnO porous sheets with uniform pores and pore density and a BET surface of 10.9 g/m2. ZnO exhibits interesting photoluminescence features, with two multi-peaks bands covering the visible region. The UV photocatalytical activity tested for phenol degradation shows that ZnO acts as a promising photocatalyst, ~90 % of the phenol being mineralized. Keywords: Green synthesis, Layered compounds, Zinc oxide, Photocatalyst

12. Article Influence of the synthesis parameters on the thermal behaviour of some ZnO-starch composites Bogdan Jurca, Alina Tirsoaga, Adelina Ianculescu, Oana Carp Journal of Thermal Analysis and Calorimetry DOI 10.1007/s10973-013-3290-1 Abstract Ten ZnO-starch composites were synthesized using a simple precipitation methodology. The IR spectroscopy and XRD investigations reveal the presence of amorphous starch and crystalline ZnO. The obtained composites present a spherical morphology, 5-8 spheres being interconnected into aggregates. The thermal analysis demonstrates that starch decomposition and ZnO thermally induced nucleation and crystal growth depend on synthesis parameters such as starch processing (dissolution or gelatinization), reaction temperature (80, 90, 100 oC), reaction time (15 minutes or 6 hours) and applied treatments (heating or ultrasound irradiation). Keywords: ZnO, Starch , Composites , Thermoreactivity

13. Article Carbonaceous spheres: versatile intermediary of metal oxide spherical structures synthesis Greta Patrinoiu, Jose Maria Calderon-Moreno, Simona Somacescu, Nicolae Spataru, Adina M. Musuc, Ramona Ene, Ruxandra Birjega, and Oana Carp European Journal of Inorganic Chemistry ( DOI: 10.1002/ejic.201301263) Abstract A facile, versatile, genuine green route that used starch-derived carbonaceous spheres as template and carbon source for tailor-made ZnO spherical structures is described. A simple adjustment of the thermal treatments permits the generation of either ZnO/C solid microporous spheres or ZnO hollow spheres, the later with controlled diameter and shell morphology. The spherical structures demonstrate a good photocatalytic activity for the visible light degradation of methylene blue dye. Also, ZnO/C has promising electrochemical capacitor applications,revealing a good electrochemical and mechanical stability. Keywords: oxide, semiconductor, precipitation, crystal growth

14. Article Biopolymer starch mediated synthetic route of multi-spheres and donut ZnO structures Oana Carp, Alina Tarsoaga, Ramona Ene, Simona Somancescu, Daniela C. Culita, Adelina Ianculescu Carbohydrate Polymer (submitted) Abstract Multi-spheres ZnO were obtained by a simple precipitation procedure in the presence of the biopolymer starch. The starch removing associated with thermal processing induces a change of the structure to a donut-like one. The ZnO-starch composites and their calcinations products were in depth characterized by UV-Vis and Fourier transform infrared spectroscopy, room-temperature photoluminescence measurements, thermal analysis, X-ray photoelectron spectroscopy, N2 adsorption-desorption isotherms, scanning and transmission electron microscopy and, X-ray diffraction investigations. The photocatalytic activities of the ZnO structures evaluated for phenol degradation in aqueous solutions are significant, a total phenol mineralization being registered using donut-like ZnO and visible irradiation. Such a behavior is attributed to the relatively large specific surface area related to its distinctive donut morphology, high crystallinity and favorable combination of defects for band narrowing that permits an enhanced light utilization rate. A formation mechanism in which starch plays a dual role as soft and hard template for the ZnO-starch composites and corresponding oxides is advanced. Keywords: ZnO; Starch; Multi-spheres and donut structure; Visible-photocatalyst

15. Article Facile ultrasound mediated protocol for ZnO flower-like structures synthesis: formation mechanism, structural, optical and photocatalytic properties Oana Carp, Alina Tirsoaga, Ramona Ene, Adelina Ianculescu, Paul Chesler, Gabriela Ionita, Viorica Pirvulescu, Raluca F. Negrea Applied Surface Science (submitted) Abstract Flowers-like zinc oxide structures have been successfully obtained by a simple and fast ultrasound-assisted method using an ammoniacal aqueous solution of zinc acetate without any surfactant or template. The composition, structure, crystallinity, morphology and optical properties of the obtained oxides were characterized by infrared spectroscopy, X-ray diffraction, scanning and transmission electron microscopy, UV-Vis and photoluminescence investigations. A plausible growth mechanism of the flower structures that implies aggregation via oriented attachment at the initial stages and Ostwald ripening during the last ones is advanced based on these results. The photocatalytic activities of the ZnO flower-like structures evaluated for the phenol degradation reaction in aqueous solutions are significant, a total phenol conversion being registered in the case of visible irradiation experiments. The obtained structures present also a noteworthy catalytic activity, being tested in the same degradative reaction in the absence of any irradiation. Keywords: Carbohydrates, Green chemistry, Semiconductors, Template synthesis, Zinc

16. Book chapter 2012 Polysaccharides route: a new green strategy for metal oxides synthesis Diana Visinescu, Greta Patrinoiu, Alina Tirsoaga, Oana Carp In Environmental Chemistry for Sustainable World, Editor E.Lichtfouse, J.Scharzbauer, D.Roberts, Vol I. Nanotechnology and Health Risk, Springer , 2012, pp.119-172, ISBN 978-94-007-2441-9 Abstract The present paper reviews some of the most important polysaccharide-based synthetic strategies of metal oxides, highlighting the polysaccharides multitasking abilities in the synthesis of nanosized oxide particles. The perspectives but also the unexplored areas of this new and promising green chemistry topic are also examined. Keywords: polysaccharides; starch; cellulose; dextran; alginate; carrageenan; chitosan; metal oxides synthesis 6. Dextran (Co)-precipitation synthesis Gel template synthesis 7.Alginate (Co)-precipitation synthesis Gel-template synthesis Hydrothermal synthesis 8. Chitosan (Co)-precipitation synthesis Hydrothermal synthesisPost synthesis procedures Gel-template methods 9. Carrageenan 10. Perspectives and conclusions References Table of content 1. Introduction 2. Polysaccharides in our world 3.The role of the polysaccharides in metal oxides synthesis 4. Starch (Co)-precipitation synthesis Sol-gel synthesis Combustion synthesisAlternative solution synthesis 5. Cellulose (Co)-precipitation synthesisSurface sol-gel synthesisHydrothermal synthesisCombustion synthesis Alternative synthesis

17. Book: Romanian Publishing House 2013 ISBN 978-973-27-2281-7 THERMAL ANALYSIS. FUNDAMENTS AND APPLICATIONS Kinetic Analysis of Heterogenous Transformation (in romanian) ANALIZA TERMICĂ. FUNDAMENTE ŞI APLICAŢII Analiza cinetică a transformărilor heterogene Authors:Petru Budrugeac, Oana Carp, Nicolae Doca, Crişan Popescu, Titus Vlase, Eugen Segal

18. Patent Procedeu de obtinere a unor oxizi metalici simpli si complecsi Nr.126777/30.07.2013 Authors: Oana Carp, Diana Beatrice Visinescu, Greta Mihaela Socoteanu, Alina Jurca,Madalina Tudose, Bogdan Jurca, Claudiu Octavian Mazilu, Carmen Stefanescu, Andrei Cucos, Petru Budrugeac, Adelina-Carmen Ianculescu

19. Participation to national and international conferences • 2012 • -Greta M. Socoteanu, Madalina Tudose, Jose M. Calderón-Moreno , Ruxandra Birjega, Oana Carp, Old Starch: New Approaches on Synthesis of ZnO with Spherical Structures, 26th International Carbohydrate Symposium (ICS2012) , 22 - 27 iulie 2012, Madrid • -Raluca Dumitru, Jose Calderon-Moreno, Ruxandra Barjega , Oana Carp, Zinc oxide controlled biopolymer assisted synthetic route, 4th EuCheMS Chemistry Congress, 26-30 august, 2012 Praga • - Greta Socoteanu, Madalina Tudose, Jose Maria Calderón-Moreno, Ruxandra Birjega, Oana Carp, From Layered Basic Zinc Salts to ZnO Hollow Spheres by an Eco-Friendly Sonochemical Procedure, 4th EuCheMS Chemistry Congress, 26-30 august, 2012 Praga • -Oana Carp, Greta Patrinoiu, Alina Tarsoaga, Ruxandra Barjega, Jose Calderon Moreno, Adelina Ianculescu , Photoluminescent and photocatalytic properties of different ZnO morphologies controlled by biopolymer assisted routes, Structure-Property Relationships in Solid State Materials Conference, 24-29 iunie, Bordeuax • -Oana Carp, Alina Tirsoaga, Paul Chessler, Viorica Pirvulescu, Adelina Ianculescu, Raluca Damian, Ultrasound assisted synthesis of zno flower-like structures and their photoluminescence and photocatalytic properties, XI International Conference on Nanostructured Materials, 26-31 august, 2012, Rhodos • 2013 • -Adina Magdalena Musuc, Alina Stan, Raluca Dumitru, Adelina Ianculescu, Oana Carp, Synthesis, characterization and thermal behaviour of some ZnO – methylcellulose composites,2-nd Central and European Conference on Thermal Analysis and Calorimetry, 27-30 august, 2013, Vilnius, Lituania • -Oana Carp, Alina Tarsoaga, Adelina Ianculescu, Bogdan Jurca, Ramona Ene, ZnO obtained by a ultrasound-assisted method in the presence of starch, Sustainable Chemical Summit, 5-7 iunie, 2013, Montreal, Canada • Alina Stan, Adina Musuc, Adelina Ianculescu, Oana Carp, Carbohydrates-assisted synthetic routes of ZnO ROMPHYSCHEM 15, Bucuresti, 9-11 septembrie 2013 • Alina Stan, Adelina Ianculescu, Adina Magdalena Musuc, Oana Carp, ZnO obtained by methylcellulose-mediated synthesis, ROMPHYSCHEM 15, Bucuresti, 9-11 septembrie 2013 • Adina Magdalena Musuc, Alina Stan, Adelina C. Ianculescu, Raluca Dumitru, Oana Carp, The thermal reactivity of some ZnO-methylcellulose composites, ROMPHYSCHEM 15, Bucuresti, 9-11 septembrie 2013 • Diana Visinescu, Oana Carp, RalucaDamian,Ruxandra Birjega, Jose Calderon Moreno, Mariana Scurtu, Ioan Balint, ZnO nanocrystal clusters: polyol-assisted synthesis, optical and catalytic properties, ROMPHYSCHEM 15, Bucuresti, 9-11 septembrie 2013 • Greta M. Socoteanu, Jose M. Calderón-Moreno, Ruxandra Birjega, Daniela C. Culita, Simona Somacescu, Adina M. Musuc, Raluca Ene, Oana Carp, Starch-derived Carbonaceous Spheres - Versatile Templates for Spherical Structures, ROMPHYSCHEM 15, Bucuresti, 9-11 septembrie 2013 • Oana Carp, Greta M. Patrinoiu, Alina Stan, Ruxandra Birjega, Jose Calderon Moreno, Nicolae Spataru, Adelina Ianculescu, Sinteze ale materialelor oxidice mediate de zaharide, Zilele Academice iesene, 3-5 octombrie, 2013

20. Training -Dr. Cornel Munteanu : Transmission electron microscopy “Tecnai Basic”, 11-15 june, 2012, Eindhoven, Olanda -Dr. Jose M.Calderon-Moreno: Transmission electron microscopy Tecnai Basic”, 11-15 june, 2012, Eindhoven, Olanda

21. In work- 2013 In present two articles are under preparation. Their titles (provisionally) are: - The thermoreactivity of some MC-Zn2+ composites - A green strategy of oxide synthesis: saccharides-assisted synthetic route of ZnO