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Eco-friendly design/synthesis of nano-oxides: control of size, shape, morphology and functionalization of ZnO by polysaccharides assisted methodologies.

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Presentation on theme: "Eco-friendly design/synthesis of nano-oxides: control of size, shape, morphology and functionalization of ZnO by polysaccharides assisted methodologies."— Presentation transcript:

1 Eco-friendly design/synthesis of nano-oxides: control of size, shape, morphology and functionalization of ZnO by polysaccharides assisted methodologies ( ) Financed: UEFSCDI PN-II-ID-PCE (contract no. 17/2011)

2 Team Project leader: Dr. Oana Carp- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Team’s members: Dr. Greta Socoteanu (Patrinoiu)- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Dr. Diana Visinescu - Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest, Dr. Jose Maria Calderon-Moreno- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Dr. Adina Magdalena Musuc- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Dr. Raluca Voda-Universty –University “Politehnica” Faculty for Industrial Chemistry and Environmental Engineering, Timisoara Masterand Raluca Florentina Negrea- National Institute of Material Physics, Bucharest Dr. Ruxandra Bârjega-National Institute for Lasers, Plasma and Radiation Physics, Bucharest Dr. Cornel Munteanu- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Dr. Adina Magdalena Musuc-Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Masterand Alina Stan- Institute de of Physical-Chemistry “Ilie Murgulescu” employed by competition on a free position of the project Team Project leader: Dr. Oana Carp- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Team’s members: Dr. Greta Socoteanu (Patrinoiu)- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Dr. Diana Visinescu - Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest, Dr. Jose Maria Calderon-Moreno- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Dr. Adina Magdalena Musuc- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Dr. Raluca Voda-Universty –University “Politehnica” Faculty for Industrial Chemistry and Environmental Engineering, Timisoara Masterand Raluca Florentina Negrea- National Institute of Material Physics, Bucharest Dr. Ruxandra Bârjega-National Institute for Lasers, Plasma and Radiation Physics, Bucharest Dr. Cornel Munteanu- Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Dr. Adina Magdalena Musuc-Institute de of Physical-Chemistry “Ilie Murgulescu”, Bucharest Masterand Alina Stan- Institute de of Physical-Chemistry “Ilie Murgulescu” employed by competition on a free position of the project

3 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. Abstract

4 The project implementation plan YearObjectivesActivitiesResults 2011 Design/synthesis of ZnO nanostructures: solvent, surfactants and additives influence The synthesis of different ZnO structures: preliminary results -Raport 2012 Design/synthesis of ZnO nanostructures by precipitative and combustion procedures -The influence of synthesis experimental parameters on ZnO morphological and structural properties -Photoluminescence and photocatalytical properties -Book chapter -article -participation to national and international conferences 2013 Design/synthesis of ZnO nanostructures by hydrothermal procedures using polysaccharides as hard-template - The influence of synthesis experimental parameters on template’s size and shape -The influence of deposition techniques on ZnO structural and morphological properties -The use of template for the synthesis of solid and hollow ZnO structures -Book -articles -participation to national and international conferences ZnO obtained by hydrothermal procedure using polysaccharides as soft-template -ZnO obtained by gel- template procedures using polysaccharides -The influence of synthesis experimental parameters on ZnO morphological and structural properties -Photoluminescence and photocatalytical properties -articles -participation to national and international conferences ZnO obtained by forced hydrolysis procedures -ZnO obtained by gel- template procedures using polysaccharides For all two synthesis protocols will be investigated : -The influence of synthesis experimental parameters on ZnO morphological and structural properties -Photoluminescence and photocatalytical properties -articles -participation to national and international conferences

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

6 Project obiectives 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 ( 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.

7 Budget Breakdown No. Budget chapter (expenses) Total 1.Salaries Inventory Mobility Overhead Total

8 1.The synthetic protocols and used carbohydrates: the building of a green methods 2. Polysaccharides as soft templates for ZnO: precipitation synthetic protocols 2.1 Zn 2+ -starch system: model system 2.2. Zn 2+ -methylcellulose Zn 2+ -dextran systems 3. Polysaccharides as combustion agents for ZnO 4. Polysaccharides as hard templates for ZnO spherical structures: 4.1 Template synthesis 4.2 Synthesis, characterization and applications of ZnO hollow spheres Impregnation deposition method Ultrasound deposition method 4.3 Synthesis, characterization and applications of ZnO solid spheres 4.4. Synthesis, characterization and applications of ZnO/C spherical structures 5. Polysaccharides as soft templates for ZnO: hydrothermal synthetic protocols

9 1.The synthetic protocols and used carbohydrates: the building of a green methods Although some progress regarding the involvement of saccharides in materials synthesis has been already made, the identification, investigation and development of carbohydrates assisted synthetic routes is (unfortunately) an insufficiently explored research topic of the chemistry. Following a small steps approach, we selected for the start polisaccharides having in common the presence of D-glucose units: polysaccharides starch and dextran containing D-glucose units linked by α- glycosidic bonds and, methylcellulose constituted from D-glucose units linked by β- bonds.

10 zinc source precipitation agent 1 precipitation agent 2 starch dextran metyl- cellulose 2. The main precipitation synthetic methodologies developed with posyccharides as soft template

11 Various hierarchical spherical shaped assemblies ZnO structures were successfully synthesized via a simple, low-cost starch-mediated precipitation method. It was proved that starch is the key parameter for the synthesis of pure ZnO material with spherical morphologies. The temperature increase lead to a variation of ZnO stoichiometry and implicit its associated defects that determine an interesting change of the optical properties (band gap, photoluminescence characteristics). While ZnO-starch composites obtained initially after the synthesis reaction performed at 80 o C are of 5-7 spheres aggregates with diameters of 100 to 500 nm, after the calcination (500 o C) their morphologies change into a donut-like ones which centered-located holes shrinks to extinction with further temperature rising (800 o C). The donut morphology is connected with the highest surface area and total pore volume. The oxide obtained after calcinations at 500 o C demonstrated excellent photodegradation ability under visible light irradiation, a total mineralization of phenol being achieved. Such properties is caused by a combination of relatively significant specific surface area due to its donut morphology, high crystallinity and a favorable combination of defects for band narrowing that permit a enhanced light utilization rate. 2.1 Zn 2+ -starch system: model system

12 2.1 Zn 2+ -starch system: characterization and applications (c) (d) (a)(b) (c) (d) (e)(f) SEM images of: (a-b) ZnO_starch; (c-d) ZnO_500 and (e-f) ZnO_800 XRD patterns UV-Vis specta Photoluminescence spectra Phenol conversion XPS results for ZnO_500 and ZnO_800

13 NH 4 (OH) 80 o C 500 o C800 o C AB C D E F =ZnO ZnO-starch ZnO 2.1 Zn 2+ -starch system: ZnO/starch formation and transformation mechanism toward ZnO Biopolymer starch mediated synthetic route of multi-spheres and donut ZnO structures, O. Carp,A. Tirsoaga, B. Jurca, R. Ene, S. Somacescu, A. Ianculescu, Carbohydrate Polymers, 2015, 115 (22),

14 2.1 Zn 2+ -starch system: influence of synthesis parameters (time, temperature, ultrasound irradiation) The thermal behavior of the ZnO-starch composites consists in three decomposition stages, a dehydration assigned to water evolving and a two-step starch degradation, followed by phase transformation processes assigned to ZnO the crystallization and crystal growth. The starch decomposition is different comparative with pure starch. The degradation occurs at lower temperature ranges being associated with an inferior exothermic effect, behavior attributed to the catalytic effect of ZnO. The registered starch content is explained as a result of two processes, starch homogenization in reaction medium, and Zn2+-starch complex thermal stability. The nucleation and crystal growth processes of ZnO that follow the burning of the carbonaceous materials occur at higher temperatures than in bulk oxide. DTA curves of ZnO-starch composites corresponding to starch decomposing : (a) predissolved starch and heated o C (DT); (b) pregelatinezed starch and heated o C (GT); (c) predissolved or pregelatinezed starch 25 min, ultrasound (D/G15U); (d) predissolved or pregelatinezed starch, 6 h ultrasound (D/G6U). DTA curves of ZnO-starch composites corresponding to ZnO nucleation/growth : (a) predissolved starch and heated o C (DT); (b) pregelatinezed starch and heated o C (GT); (c) predissolved or pregelatinezed starch 25 min, ultrasound (D/G15U); (d) predissolved or pregelatinezed starch, 6 h ultrasound (D/G6U). “Influence of the synthesis parameters on the thermal behavior of some ZnO-starch composites”, Jurca, B., Tirsoaga, A., Ianculescu, A., Carp, O, Journal of Thermal Analysis and Calorimetry, 2014, 115 (1),

15 2.2 Zn 2+ -methylcellulose and Zn 2+ -dextran systems The developed green synthetic protocols lead to diverse morphologies: spherical, spindle, rod ones. The influence of the synthesis parameters (time, temperature, raw materials nature and ratio, precipitation agent, initial pH and its evolution during the synthesis, ultrasound irradiation) on the shape, size and porosity of the obtained ZnO-based composites is investigated. The thermoreactivity of the synthesized composites is scrutinized. The possibility of obtaining ZnO/C composites is also analyzed, establishing the parameters of polysaccharide  carbon containing materials conversion, degree of crystallization/graffitization, influence of Zn 2+ amount on final material quality. The optical properties of the ZnO based materials were analyzed by UV-Vis and photoluminescence spectroscopy. A formation mechanism for each system was advanced, evidencing the auto-assembling processes. The composites, either ZnO-saccharide and ZnO/C were tested as photocatalysts and antimicrobian agents, establishing different correlations between the optical properties and the efficiency in these applications. For same composites, electrochemical investigations (linear sweep voltammetry, electrochemical activity analysis) were also performed. One article is in preparation : Methylcellulose based synthesis for ZnO with spindle like morphologies, R.Dumitru, J.M.Calderon-Moreno, R.Birjega, O.Carp.

16 3. Polysaccharides as combustion agents for ZnO SEM images of ZnO: (A) starch-Zn(NO 3 ) 2 ; (B) cellulose-Zn(NO 3 ) 2 ; (C)Sta rch-Zn(CH 3 COO) 2 ; (D)cellulose-Zn(CH 3 COO) 2 In this synthetic procedure the polysaccharides act as high temperature fuels. The obtained ZnO crystallites are larger than those obtained by precipitate method, the specific surface lower (2-4 m 2 /g), but the activity in photocatalytic degradation reactions tested for phenol and resorcinol are particularly good, a 100% mineralization of pollutants being achieved. The obtained data are the subject of an article in preparation.

17 4. Polysaccharides as hard templates for ZnO spherical structures: Hard templates syntheses are generally used for obtaining hollow structures. In principle, regardless of the used methodology, the synthesis procedure should include three stages: - hard-template synthesis; -introduction /deposition on template surface of the metallic cations; - the remove of the hard-template by further processing (usually thermal ones). We utilized several introduction techniques as impregnation, ultrasound irradiation, or a double deposition (impregnation and impregnation). The diameter and the wall thickness of the obtained spherical morphology, its type (solid or hollow) and porosity depend on the synthesis and calcination parameters. Our research showed for the first time that the template generated by polysaccharides can also function as a template in obtaining solid oxide spherical structures (solid spheres) and also for metal oxide / C composites preserving the same morphology. The scheme of hydrothermal processSEM images of carbonaceous sphere templates 4.1 Template synthesis

18 4.2 Polysaccharides as hard templates for ZnO spherical structures: synthesis, characterization and applications of hollow structures Deposition: impregnation method SEM images of Zn 2+ /carbonaceous template and ZnO hollow sphere „A green chemical approach to the synthesis of photoluminescent ZnO hollow spheres with enhanced photocatalytic properties”, G. Patrinoiu, M.Tudose, J.M.Calderon-Moreno, R.Birjega, P.Budrugeac, R.Ene, O.Carp, published in J. Solid State Chem. 2012, 186, citations TOP Most downloaded 25 articles Thermal curves of Zn 2+ /carbonaceous composite XRD of ZnO hollow sphere PL spectra of ZnO hollow sphere Photocatalytical activity in degradation/mineralization of phenol

19 3.2 Polysaccharides as hard templates for ZnO spherical structures: synthesis, characterization and applications of hollow structures Deposition: ultrasound method TEM images of ZnO hollow sphere: (a) 3 o C/min and (b) 20 o C/min BET and PL spectra of ZnO hollow sphere: (a) 3 o C/min and (b) 20 o C/min Thermal curves of the precursor (a) air and (b) argon. XRD of ZnO hollow sphere: (a) 3 o C/min and (b) 20 o C/min Photocatalytical activity in degradation of MB under visible irradiation “Eco-friendly synthetic route for layered zinc compound and its conversion to ZnO with photocatalytical properties”, G.Patrinoiu, J.M. Calderon-Moreno,D.C. Culita, R.Birjega, R.Ene, O.Carp, Solid State Sciences, 2013, 23, citations ” Carbonaceous spheres: versatile intermediary of metal oxide spherical structures synthesis“ autori G.Patrinoiu, J. M. Calderon-Moreno, S. Somacescu, N. Spataru, A. M. Musuc, R. Ene, R. Birjega, O. Carp, Eur.J.Inorg.Chem. 2014,

20 Polysaccharides as hard templates for ZnO spherical structures: synthesis, characterization and applications of solid structures 4.3 Deposition: impregnation and ultrasound methods Mechanism of solid ZnO spheres formation TEM images of ZnO solid spheres: (a-b)impregnation and ultrasound; (c-d) ultrasound and impregnation Raman (A) and PL (B) spectra of the solid spheres (a:U/I and b:I/U) adsorbtion/desorbtion isotherm and pore distribution of (C) U/I and (D) I/U Photocatalytical activity in degradation of phenol under visible irradiation „Carbonaceous spheres-an unusual template for solid metal oxide mesoscale spheres: Application to ZnO spheres” autori: G.Patrinoiu, J. M. Calderón-Moreno, D. C. Culita, R. Birjega, R. Ene, O. Carp, Journal of Solid State Chemistry, 202, 2013,

21 Polysaccharides as hard templates and carbon source for metal oxide/C spherical structures: 4.4 synthesis, characterization and applications of ZnO/C structures XRD, adsorbtion/desorbtion isotherm and pore distribution and Raman spectra of the solid ZnO/C spheres ProbaEnergii de legatura, eV concentratie atomica relativa at% C1sO1sZn2p3/2ZnLMMCOZn ZnO/C 284,8 (C-C) 286.5( OH-C-O) (C=O) (O 2- ) (OH-C-O, C=O) ZnO/C 1 min sputtering 284,8 (C-C) 286.5( OH-C-O) (C=O) (O 2- ) (OH-C-O, C=O) ZnO/C 5 min sputtering 284,8 (C-C) 286.5( OH-C-O) (O 2- ) (OH-C-O, C=O) XPS data: binding energies, chemical species, atomic relative concentrations ” Carbonaceous spheres: versatile intermediary of metal oxide spherical structures synthesis“ autori G.Patrinoiu, J. M. Calderon-Moreno, S. Somacescu, N. Spataru, A. M. Musuc, R. Ene, R. Birjega, O. Carp, Eur.J.Inorg.Chem. 2014, Thermal curves, photocatalytical activy (phenol) and specific capacitance

22 5. Polysaccharides as soft templates for ZnO/saccharide composites The developed one-pot synthetic procedure is green both regarding utilized raw materials [zinc acetate as zinc source, carbohydrates (glucose, fructose, sucrose, dextran, starch and methylcellulose)as growth inhibitors and crystal habit modifiers], and synthetic methodology (mild hydrothermal procedure carried out at low temperature for a short period of time). The general character of the method derives from the possibility of using either mono, di- or polysaccharides that contains D-glucose units. Because the nature of the saccharide rules the construction features of the ZnO structures (rods spindles, hollow and solid spheres), the ability to use various carbohydrates adds to this method a high versatility. The enhanced photocatalytical and antimicrobial performances indicate the great potential of the ZnO based composites in relevant water detoxification and biomedical applications. Correlating the ZnO_SAC antimicrobial activity with the photocatalytical one, and also with their photoluminescence peculiarities we were able to identify that the mechanism of the biocidal action toward the two investigated bacterial strains follows different paths. An article “Green synthesis for green materials: ZnO-saccharide composites for environmental remediation and antimicrobial applications”, A.Stan, C.Munteanu, R.Ene, E.M.Anghel, A.M. Musuc, R.Birjega,A. Ianculescu, I.Raut, L.Jecu, M.Badea Doni, O.Carp, is submitted to Chemistry-An European Journal

23 Polysaccharides as soft templates for ZnO/saccharide composites 30 minutes 1 hour 2 hours 48 hours 30 minutes 1 h2 h48 h 30 minutes1 hour2 hours 48 hours 30 minutes1 hour2 hours 48 hours 2 hour 1 hours 48 hours 30 min glucose fructose starch dextran metylcellolose

24 Grow curves of P. aeruginosa and B. subtilis in the presence of different concentrations of ZnO_SAC composites Decoloration of MO under UV light irradiation in the presence of: (a) ZnO_D, (b) ZnO_S, (c) ZnO_MC, (d) ZnO_ST, (e) ZnO_G, (e) ZnO_F Room-temperature photoluminiscence spectra of: (a) ZnO_G, (b) ZnO_F, (c) ZnO_MC (inset ZnO_MC_500) (d) ZnO_ST, (e) ZnO_S, (f) ZnO_D Absorption spectra of: (a) ZnO_F, (b) ZnO_MC (inset ZnO_MC_500), (c) ZnO_G, (d) ZnO_S, (e) ZnO_ST, (f) ZnO_D Raman spectra of: (a) ZnO_MC_500, (b) ZnO_MC, (c) ZnO_F, (d) ZnO_S, (e) ZnO_ST, (f) ZnO_D, (g) ZnO_G samples within (A) cm -1 and (B) cm -1 spectral ranges 5. Polysaccharides as soft templates for ZnO/saccharide composites

25 5. Polysaccharides as soft templates for ZnO/saccharide composites: thermoreactivity of methylcellulose composites Thermal curves of ZnO_MC_H (a) TG (I), DTG (II), DSC (III) and Gram - Schmidt (IV) curves; (b) 3D-FTIR plot of the evolved gases Thermal curves of ZnO_MC_PP (a) TG (I), DTG (II), DSC (III) and Gram - Schmidt (IV) curves; (b) 3D-FTIR plot of the evolved gases Thermal curves of ZnO_MC (a) TG (I), DTG (II), DSC (III) and Gram - Schmidt (IV) curves; (b) 3D-FTIR plot of the evolved gases FTIR spectra MC (a); ZnO_MC_H (b); ZnO_MC_PP (c); ZnO_MC(d) SEM micrographs of (a) ZnO_MC_H; (b) ZnO_MC_PP and (c) ZnO_MC_500 “Synthesis, characterization and thermoreactivity of some methylcellulose- zinc composites”, A.M.Musuc, R. Dumitru, A.Stan, C.Munteanu, R.Birjega and O.Carp, Journal of Thermal Analysis and Calorimetry, (submitted, minor revisions)

26 Dissemination of project scientifically results

27 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, citations 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(CH 3 COO) 2 ·2H 2 O 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 Article

28 Carbonaceous spheres-an unusual template 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, 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, N 2 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 Article

29 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, 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 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 600 o C led to ZnO porous sheets with uniform pores and pore density and a BET surface of 10.9 g/m 2. 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 Article

30 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, 2014, 115 (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 o C), reaction time (15 minutes or 6 hours) and applied treatments (heating or ultrasound irradiation). Keywords: ZnO, Starch, Composites, Thermoreactivity Article

31 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, 2015, 115 (22), 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, N 2 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 Article

32 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, 2014, Abstract A facile, versatile, genuine green route that uses starch-derived carbonaceous spheres as the templates and carbon source for tailor-made ZnO spherical structures is described. A simple adjustment of the thermal treatment 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 good photocatalytic activity for the visible light degradation of methylene blue. Furthermore, ZnO/C has promising electrochemical capacitor applications and good electrochemical and mechanical stability. Keywords: Carbohydrates, Green chemistry, Semiconductors, Template synthesis, Zinc

33 Article Synthesis, characterization and thermoreactivity of some methylcellulose-zinc composites Adina Magdalena Musuc, Raluca Dumitru, Alina Stan, Cornel Munteanu, Ruxandra Birjega and Oana Carp Journal of Thermal Analysis and Calorimetry, (submitted, minor revisions) Abstract Two methylcellulose-ZnO and one methylcellulose-Zn 2+ composites were obtained by precipitation and hydrothermal procedures. The thermal behavior of the composites was examined by simultaneous TG, DTG, DSC-FTIR thermal method. It was found that the thermal reactivity of the methylcellulose contained by the composites is strongly dependent on the composites’ synthetic procedure, but in all cases its stability is shifted toward lower temperatures. For each type of composites, the causes that lead to a change of methylcellulose thermoreactivity were highlighted. The structural, morphological and optical characteristics of the ZnO_based materials are also demonstrated. Keywords: Methylcellulose, Zinc-methylcellulose composites, Thermoreactivity

34 Green synthesis for green materials: ZnO-saccharide composites for environmental remediation and antimicrobial applications Article Alina Stan, Cornel Munteanu, Ramona Ene, Elena Maria Anghel, Adina Magdalena Musuc, Ruxandra Birjega, Adelina Ianculescu, Iulia Raut, Luiza Jecu, Mihaela Badea Doni, and Oana Carp Chemistry –An European Journal (submitted) Abstract A bioinspired one-pot approach for the synthesis of ZnO - carbohydrate hierarchical architectures was developed. The synergy between a saccharide (mono, di- or polysaccharide) that contains D- glucose units and triethanolamine is the key parameter of the synthetic methodology. The morphology of the ZnO composites is dictated by the used saccharide, and rod, spindle, solid and hollow spherical- like ZnO structures are obtained varying the carbohydrate. The synthesized composites present good photocatalytical and antimicrobial activity.

35 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 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: Carbohydrates, Green chemistry, Semiconductors, Template synthesis, Zinc

36 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 , ISBN Book chapter 2012 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 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 synthesis Alternative solution synthesis 5. Cellulose (Co)-precipitation synthesis Surface sol-gel synthesis Hydrothermal synthesis Combustion synthesis Alternative 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 synthesis Post synthesis procedures Gel-template methods 9. Carrageenan 10. Perspectives and conclusions References

37 Book: Romanian Publishing House 2013 ISBN Book: Romanian Publishing House 2013 ISBN 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

38 Patent Procedeu de obtinere a unor oxzi metalici complecsi si simpli Nr / 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

39 Participation to national and international conferences Greta M. Socoteanu, Madalina Tudose, Jose M. Calderón-Moreno, Ruxandra Birjega, Oana Carp, Old Starch: New Approaches on Synthesis of ZnO with Spherical Structures, 26 th International Carbohydrate Symposium (ICS2012), iulie 2012, Madrid -Raluca Dumitru, Jose Calderon-Moreno, Ruxandra Barjega, Oana Carp, Zinc oxide controlled biopolymer assisted synthetic route, 4th EuCheMS Chemistry Congress, 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, august, 2012 Praga - Oana Carp, Greta Patrinoiu, Adelina 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, 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, august, 2013, Rhodos 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, august, 2013, Vilnius, Lituania -Oana Carp,Alina Tarsoaga, Adelina Ianculescu, Bogdan Jurca, Ramona Ene, ZnO obtaied 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 Alina Stan, Adelina Ianculescu, Adina Musuc, Oana Carp, ZnO obtained by methyl celulose-mediated synthesys, ROMPHYSCHEM 15, Bucuresti, 9-11 septembrie Adina Magdalena Musuc, Alina Stan, Adelina C. Ianculescu, Raluca Dumitru, The thermal reactivity of some ZnO- methylcellulose composites, Oana Carp, ROMPHYSCHEM 15, Bucuresti, 9-11 septembrie Diana Visinescu, Oana Carp, Raluca Negrea, 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 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 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

40 OanaCarp, Greta Patrinoiu, Jose Calderon Moreno, Adina Musuc, Simona Somacescu, Ruxandra Barjega, Nicolae Spataru, Versatile metal spherical structure via carbonaceous templates, “Forth International Congress on Grenn Chemistry”, 7 – 10 aprilie 2014, Sevilia, Spania. - Oana Carp, Spherical metal oxides structures obtained by saccharide-assited synthetic routes, plenary lecture, 7 th Edition of symposium with international participation - New trends and strategies in the chemistry of advanced materials with relevance in biological systems, technique and environmental protection – iunie, 5- 6,Timisoara, Oana Carp, Saccharides-assisted synthetic routes of ZnO nanostructures, plenary lecture, Journée Franco- Roumaine, 15 iunie 2014, Brasov.

41 Training -Dr. Cornel Munteanu : Transmission electron microscopy “Tecnai Basic”, iune, 2012, Eindhoven, Olanda -Dr. Jose M.Calderon-Moreno: Transmission electron microscopy Tecnai Basic”, iune, 2012, Eindhoven, Olanda

42 In work In present four articles are under preparation. Their titles (provisionally) are: - Carbonaceous spheres: versatile templates towards metal oxide spherical structures; - Methylcellulose based synthesis for ZnO with spindle like morphologies; - From hollow toward solid spheres: a saccharide mediated synthesis; - ZnO-strarch: magic spheres for advanced materials


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