Research Projects for Young Independent Teams - 2021 Call

Project code: PN-III-P1-1.1-TE-2021-0963, TE13/2022

Project title: Hybrid electrodes for detection and degradation of the cytostatics from water

Project Acronym: DDCyT

Total Funging: 450.000,00 lei

Project duration: 24 months

Project Leader: CS II Dr.ing. Cornelia BANDAS

https://www.brainmap.ro/cornelia-elena-bandas-ratiu

Contact:

Tel: 0256222119

Fax: 0256201382

e-mail: cornelia.bandas@gmail.com

Financing Authority: Ministry of Research, Innovation and Digitization, CNCS - UEFISCDI

Host Institution: National Institute for Research and Development in Electrochemistry and Condensed Matter Timisoara -INCEMC

Project Abstract

Cytostatic drugs, are a group of pharmaceuticals which are employed in cancer treatment and consumed in large quantities all over the world. These compounds are considered the most hazardous contaminants in the water cycle, because of their cytotoxic, mutagenic/teratogenic properties and are supposed to be harmful for human and wildlife even at very low concentration. The classical detection methods used for eliminating cytostatic drugs present in wastewater presents a several disadvantages, but electrochemical methods present distinctive advantages. Development of electrochemical sensors for the analysis of pharmaceutically compounds with respect to their sensitivity, accuracy and simplicity, has been study lately. Chemically modified electrodes have become an important subject of research and have been used vastly for the electrochemical sensing of biologically important compounds due to their significant advantages.

This project aim is the development of hybrid electrodes based on Ti-TiO₂-rGO/Au/Ag and Zn-ZnO-rGO/Au/Ag with dual function, detection and degradation of cytostatics from water. These hybrid electrodes combine the synergistic properties of the proposed structures, characterized by structural, morphological and electrochemical specific properties suitable for electrochemical detection and photoelectrochemical degradation of cytostatic (doxorubicine-DOX).

Project objectives

OI. Development and characterization of hybrid electrodes based on Ti-TiO₂-rGO/Au/Ag (type I) and Zn-ZnO-rGO/Au/Ag (type II)

OII. Testing and demonstrating the functionality of hybrid electrodes for electrochemical detection and photoelectrochemical degradation of DOX.

OIII. Comparative studies on the performances of the hybrid electrodes in the detection processes, as well as the degradation efficiency of the DOX from simulated water.

OIV. Dissemination of the project results. 4 scientific papers ISI; 6 presentations of international conferences; 2 requested patents application

Project Team

Eng. Cornelia BANDAS, PhD – scientific reasearcher II, project leader - will coordinate research activities according to the established work plan, will ensure the proper management of funds; will plan the acquisition procedures stipulated in this proposal for the optimal supply of the required materials within the project time. She has research expertise in the synthesis of micro/nanonostructured materials based on TiO₂, development of synthesis installations for obtaining new materials with multiple applications.

Eng. Corina ORHA, PhD. – scientific researcher III - her research activity is focused on the synthesis of micro- and nano-materials based on functionalized materials and TiO₂; morpho-structural characterization of materials (SEM/EDX, UV-VIS); synthesis of nanomaterials; electrochemical techniques for pollutants removal.

Eng. Aniela POP, PhD. – lecturer - lecturer at the „Politehnica” University of Timisoara, her scientific research activity focused on the directions: water and wastewater treatment by electrochemical methods; electrochemical and electroanalytical techniques; new sensor development based on carbon structures

Phys. Mihaela-Ionela BIRDEANU, PhD. – scientific researcher II - high expertise in morphological analysis (especially surface topography of various organic and inorganic (nano) materials through AFM), multiple synthesis methods and characterization of pseudo-binary oxide (nano) materials.

Phys. Cristian CASUT –PhD student at the „West” University of Timisoara, as scientific researcher at INCEMC, his research expertise is related to synthesis of semiconductor materials, structural characterization of the samples by XRD and UV-VIS methods.

Chem. Eng. Mina-Ionela POPESCU – PhD student at the „Politehnica” University of Timisoara, as scientific researcher at INCEMC, has research expertise in the synthesis of micro/nanostructured materials; photocatalytic techniques process; inorganic chemistry synthesis.

Eng. Mircea NICOLAESCU – PhD student at the „Politehnica” University of Timisoara, as scientific researcher at INCEMC, his research expertise is focused on the development of laboratory installation; materials synthesis and characterization; films deposition by spin-coating and Dr. Blade; development of the supports for electrodes.

REZULTATE 2022:

In cadrul etapei I „Dezvoltarea si caracterizarea morfo-structurala si electrochimica a electrozilor hibrizi pe baza de Ti-TiO₂-rGO/Au/Ag (tipul I) si Zn-ZnO-rGO/Au/Ag (tipul II)” au fost realizate activitati stiintifice de cercetare care au presupus obtinerea si caracterizarea morfologica, structurala, optica si electrochimica a electrozilor hibrizi pe baza de Ti-TiO₂-rGO si Ti-TiO₂-rGO/Au/Ag (tipul I) precum si a electrozilor hibrizi pe baza de Zn-ZnO-rGO si Zn-ZnO-rGO/Au/Ag (tipul II).

In cadrul acestei etape au fost obtinute urmatoarele rezultate:

ü electrozii hibrizi pe baza de Ti-TiO₂-rGO si Ti-TiO₂-rGO/Au/Ag (tipul I) au fost obtinuti prin mai multe metode de depunere: metoda „spin-coating”, „dip-coating” si metoda „in-situ” in conditii hidrotermale in camp de microunde.

ümetoda de obtinere in-situ in conditii hidrotermale in camp de microunde pentru obtinerea electrozilor de Ti-TiO₂-rGO reprezinta o noutate pe plan national si international fiind brevetata in cadrul proiectului (cerere de brevet depusa OSIM A/00482/09.08.2022).

ü electrozilor hibrizi pe baza de Zn-ZnO-rGO si Zn-ZnO-rGO/Au/Ag (tipul II) s-a realizat prin doua metode de depunere: in-situ in conditii hidrotermale in camp de microunde si metoda „dip-coating”.

ü pe baza rezultatelor morfo-structurale a fost selectata ca si metode de depunere, metoda in-situ in conditii hidrotermale in camp de microunde si metoda „dip-coating”, pentru ambele tipuri de electrozi hibrizi dezvoltati

Diseminare:

Articole publicate in reviste indexate ISI:

1.C. Lazau, M. Nicolaescu, C. Orha, V. Serban, C. Bandas. „Self-powered photodetector based on FTO/n-TiO₂/p-CuMnO₂ transparent thin films”, Materials 2022, 15, 5229. DOI: 10.3390/ma15155229

2.M. Nicolaescu, C. Bandas, C. Orha, V. Purcar, C. Lazau. “Development of the Zn‐ZnO(Nw)@CuMnO2 Heterojunction by Low Temperature Zn Foil Oxidation for Gas Sensor Fabrication”, Coatings 2022, 12, 1630, https://doi.org/10.3390/coatings12111630

3.C.Lazau, M. Nicolaescu, C. Orha, A. Pop, S. Caprarescu, C. Bandas, „In-situ deposition of reduced graphene oxide on Ti foil by a facile microwave-assisted hydrothermal method” Coatings 2022, 12, 1805, https://doi.org/10.3390/coatings12121805

4.C. Lazau, C. Bandas, M. Nicolaescu, C. Orha, A. Pop, "A facile dip-coating process graphene-TiO2 on titanium foil for hybrid electrode fabrication," 2022 International Semiconductor Conference (CAS), 2022, pp. 277-280, DOI: 10.1109/CAS56377.2022.9934754

5.C. Orha, M. Nicolaescu, C. Bandas, C. Lazau, A. Baciu, F. Manea, "Comparative morphostructural and electrochemical characterization of the La and F doped porous Ti/SnO₂ dimensionally stable anodes," 2022 International Semiconductor Conference (CAS), 2022, pp. 285-288, DOI: 10.1109/CAS56377.2022.9934122

Cerere brevet inventie:

Bandas C., Lazau C., Nicolaescu M., Orha C., „Procedeu de depunere “in-situ” a filmelor de rGO pe suport de Ti-TiO₂ prin metoda hidrotermala in camp de microunde”, cerere de brevet inregistrata la OSIM A/00482/09.08.2022.

Participari conferinte:

1.C. Lazau, C. Bandas, M.Nicolaescu, C.Orha, A. Pop, "A facile dip-coating process graphene-TiO₂ on titanium foil for hybrid electrode fabrication," 45^th International Semiconductor Conference CAS 2022, 12-14 Octombrie 2022, Brasov, Romania.

2.C. Bandas, M. Nicolaescu, C. Orha, C. Lazau, „Synthesis of ZnO-reduced graphene oxide hybrid materials via dip-coating method for pollutants removal” 5^th International Conference on Emerging Technologies in Materials Engineering – EmergeMAT, 27-28 Octombrie 2022 – Bucuresti, Romania (conferinta online).

3.C. Orha, M. Nicolaescu, C. Bandas, C. Lazau, A. Baciu, F.Manea, "Comparative morphostructural and electrochemical characterization of the La and F doped porous Ti/SnO₂ dimensionally stable anodes," 45^th International Semiconductor Conference CAS 2022, 12-14 Octombrie 2022, Brasov, Romania.

4.C. Lazau, M. Nicolaescu, C. Orha, V. Şerban, C. Bandas, “TiO₂/CuMnO₂ heterojunction based

Self-powered UV photodetectors” 28^th International Symposium on Analytical and Environmental Problems (ISAEP 2022) 14-15 Noiembrie 2022, Szeged, Hungary (conferinta online)

5.M.I. Popescu, N. Duteanu, C. Orha, C.Lazau, C. Bandas, „Aluminum /iron mixed oxides obtained by co-precipitation method“ 28^th International Symposium on Analytical and Environmental Problems (ISAEP 2022) 14-15 Noiembrie 2022, Szeged, Hungary (conferinta online)

6.M. I. Popescu, A.Pop, C. Orha, A.M.Baciu, F. Manea, “Capecitabine removal from water using commercial granular activated carbon” 28^th International Symposium on Analytical and Environmental Problems (ISAEP 2022) 14-15 Noiembrie 2022, Szeged, Hungary (conferinta online)

7.Bandas C., Lazau C., Nicolaescu M., Orha C. “In-situ deposition process of rGO films on Ti-TiO₂ support by microwave-assisted hydrothermal method”, 3^th International Exhibition INVENTCOR 15-17 Decembrie, Deva, Romania (conferinta online).

REZULTATE 2023:

In cadrul etapei II „Testarea si demonstrarea functionalitatii electrozilor hibrizi in procese de detectie electrochimica si degradarea fotoelectrochimica a doxorubicinei (DOX)” s-au realizat activitati stiintifice de cercetare care au presupus testarea electrozilor hibrizi dezvoltati in procese de detectie electrochimice, procese de electrooxidare si procese de electrooxidare asistate fotocatalitic pentru degradarea doxorubicini din solutii sintetice. Au fost obtinute urmatoarele rezultate:

üA fost aplicat procesul de fotocataliza pentru degradarea doxorubicinei in solutie de electrolit, obtinanduse o eficienta de degradare de aproximativ 20% dupa un timp de iradiere de 90 minute pentru o concentratie de 2.5mg L^-1 DOX.

üMaterialele de electrod de tipul Ti-TiO₂, Ti-TiO₂-rGO, Ti-TiO₂-rGO/Ag si Ti-TiO₂-rGO/Au au fost aplicati in procese de detectie electrochimica in diferite solutii electrolit suport, prin tehnica voltametriei ciclice utilizand o celula cu un sistem de trei electrozi: electrod de Ag/AgCl ca si electrod de referinta, contraelectrod de platina si electrozii de lucru, electrozi hibrizi.

üS-a realizat testarea materialelor de electrod de tipul Ti-TiO₂, Ti-TiO₂-rGO, Ti-TiO₂- rGO/Ag si Ti-TiO₂-rGO/Au in procese de electrooxidare si electrooxidarea asistata fotocatalitic in prezenta diferitelor concentratii de doxorubicina (2.5 si 5 mg mL^-1).

üCele mai bune performante de degradare au fost obtinute prin utilizarea electrodului hibrid de tipul Ti-TiO₂-rGO/Ag in timpul procesului de electrooxidare asistata fotocatalitic pentru o concentratie de 2.5 mg mL^-1 cu un randament degradare de pana la 68 % pentru un curent de 7V, iar pentru procesul de electrooxidare randamentul a fost atins un randament de 30% dupa un timp de iradiere de 90 minute.

Diseminare:

Articole publicate in reviste indexate ISI:

1. C. Bandas, M. I. Popescu, C. Orha, M. Nicolaescu, A. Pop, C. Lazau, „Development of hybrid electrodes based on a Ti/TiO2 mesoporous/reduced graphene oxide structure for enhanced electrochemical applications”, Coatings 2023, 13, 1359, https://doi.org/10.3390/coatings13081359

2. C.Bandas, M. Nicolaescu, M. I. Popescu, C. Orha, S. Caprarescu, C. Lazau, “One-Step Microwave-Assisted Hydrothermal Preparation of Zn-ZnO(Nw)-rGO Electrodes for Supercapacitor Applications”, Materials 2023, 16, 4536, https://doi.org/10.3390/ma16134536

3. M. Nicolaescu, C. Codrean, C. Orha, C. Bandas, “Synthesis and Characterization of Three-Dimensional Nanoporous Copper Oxide Materials via Dealloying and Thermal Oxidation of Amorphous Ribbons”, Eng. Proc. 2023, 48, 56, https://doi.org/10.3390/CSAC2023-15171

4. Nicolaescu M., Șerban V. A., Lazau C., Bandas C., Orha C., Vajda M., Binchiciu E., “Morphology Changes in the One-Step Synthesis of Cu₂O/CuO by Dealloying Amorphous Ribbons in Alkaline Solution”, Key Engineering Materials, 2023. Vol. 952, pp 35-41, DOI:10.4028/p-CJ0lbt

5. M.Nicolaescu, M.Vajda, C.Lazau C. Orha, C. Bandas, V. A. Serban, C. Codrean, “Fabrication of Flexible Supercapacitor Electrode Materials by Chemical Oxidation of Iron-Based Amorphous Ribbons”, Materials 2023, 16, 2820, https://doi.org/10.3390/ma16072820

Capitol de carte:

C. Bandas, C. Lazau, M.Nicolaescu, C. Orha, A. Pop, S. Căprărescu, “Microwave-assisted Hydrothermal Deposition of Reduced Graphene Oxide on Ti Foil”, Current Topics and Emerging Issues in Materials Sciences Vol. 1, Chapter 2 Print ISBN: 978-81-19217-34-2, eBook ISBN: 978-81-19217-35-9, https://doi.org/10.9734/bpi/cteims/v1/18639D

Cerere brevet inventie:

Bandas C., Nicolaescu M., Lazau C., Orha C., Casut C., „Procedeu de obtinere in conditii hidrotermale in camp de microunde a unui electrod hibrid de rGO/Zn-ZnO”, cerere de brevet inregistrata la OSIM A/00164/03.04.2023

Participari conferinte:

1.C. Bandas, C. Lazau, M. Nicolaescu, C. Orha, A. Pop, S. Caprarescu, „In-situ microwave-hydrothermal synthesis of TiO₂-rGO composite structures” 20^th International Conference on Nanosciences & Nanotechnologies (NN23) 4-7 July 2023, Thessaloniki, Greece – poster;

2. M. I. Popescu, M. Nicolaescu, C. Orha, C.Lazau, A. Pop, C. Bandas, „Development of hybrid electrodes based on Ti-TiO₂-rGO by spin-coating method for pollutant detection”, 12^th International Conference on Environmental Engineering and Management ICEEM 12, 13-16 September 2023, Iasi Romania - poster;

3. M.I. Morariu (Popescu), M. Nicolaescu, A. Pop, C. Orha, C. Lazau, C. Bandas ”Electrochemical detection of doxorubicin in water using a Ti/TiO₂-rGO anode”, 6^th International conference on emerging technologies in materials engineering, EmergeMAT, 9-10 November 2023, Bucharest, Romania – poster (conferinta online)

4. Morariu (Popescu) M., Lazau C., Bandas C., Orha C., Duteanu N., Binchiciu E., Nicolaescu M., “Surface Morphology of Ti-TiO₂/rGO Electrodes for doxorubicin detection in water”, The 14^th International Conference Innovative Technologies for Joining Advanced Materials TIMA2023, 9-10 November 2023, Timisoara, Romania – prezentare orala

5. M. Nicolaescu, C.Codrean, C. Orha, C. Bandas, “Synthesis and Characterization of 3D Nanoporous Copper Oxide Materials by Dealloying and Thermal Oxidation of Amorphous Ribbons”, 2^nd International Electronic Conference on Chemical Sensors and Analytical Chemistry (CSAC2023), 16-30 September 2023 – poster (conferinta online)

6. C. Bandas, M. Nicolaescu, M.I. Morariu (Popescu), C. Orha, C. Lazau „Comparative morpho-structural and electrochemical characterization of hybrid electrode Ti-TiO₂/rGO correlated with the synthesis method”, 29^th  International  Symposium  on  Analytical  and  Environmental  Problems (ISAEP 2023), Szeged, Hungary – poster (conferinta online)

7. C. Bandas, M.Nicolaescu, C. Lazau, C. Orha, C. Casut, „Synthesis process under microwave-assisted hydrothermal conditions of an rGO/Zn-ZnO hybrid electrode”, 4^thInternational Exhibition InventCor, 14-16.09.2023, Deva, Romania – comunicare targ de inventica (online)

REZULTATE 2024:

In cadrul etapei III „ Studii comparative privind performantele electrozilor hibrizi in procesele de detectie electrochimica si eficientele de degradare fotoelectrochimica a doxorubicinei din apele sintetice” s-au realizat activitati stiintifice de cercetare care au presupus testarea comparativa a electrozilor hibrizi dezvoltati in procese de detectie electrochimice, procese de electrooxidare si procese de electrooxidare asistate fotocatalitic pentru degradarea doxorubicini din solutii sintetice. Au fost obtinute urmatoarele rezultate:

ü au fost urmariti parametri precum timpul de reactie, limitele de detectie si eficienta de degradare a doxorubicinei;

ü au fost evaluate eficientele in procesele de electrooxidare si procese de electrooxidare asistate fotocatalitic pentru toate configuratiile de electrozi de tip I (Ti-TiO₂-rGO; Ti-TiO₂-rGO-Au; Ti-TiO₂-rGO-Ag) si tip II (Zn-ZnO-rGO; Zn-ZnO-rGO-Au; Zn-ZnO-rGO-Ag)

üS-a evaluat reproductibilitatea, o serie de electrozi hibrizi optimizati fiind utilizati pentru detectia electrochimica a DOX, si deviatia standard relativa va fi masurata sub conditii cronoamperometrice in absenta iradierii UV

ü Stabilitatea electrozilor hibrizi a fost evaluata prin verificarea periodica a raspunsului curentului in prezenta respectiv absenta iradierii UV.

Diseminare:

Participari conferinte internationale:

1.Cornelia Bandas, Mina-Ionela Morariu (Popescu), Mircea Nicolaescu, Corina Orha, Aniela Pop, Narcis Duteanu, Carmen Lazau, „Fabrication of titanium/titanium dioxide/reduced graphene oxide electrode by a facile spin-coating method for the electrooxidation process of doxorubicin” BRAMAT 2024, 13th International Conference on Materials Science & Engineering, 13-16 Martie 2024, Brasov, Romania

2. Sebastian Ambruș, Petru Hididiș, Cosmin Codrean, Iosif Hulka, Corina Orha, Bandaș Cornelia, Carmen Lazau, Mircea Nicolaescu, “In situ fabrication of NPC/rGO composite by dealloying and microwave-assisted hydrothermal method” BRAMAT 2024, 13th International Conference on Materials Science & Engineering, 13-16 Martie 2024, Brasov, Romania

CONCLUZII FINALE:

Rezultatele obținute au impact semnificativ privind obținerea unor materiale de electrod hibride pe baza de oxizi metalici de tipul TiO₂ si ZnO, si oxid de grafena redusa (rGO) care pot avea aplicatii in mai multe domenii, cum sunt procese de detectie si degradare a compusilor emergenti din ape, stocare de energie (cu proprietati de supercapacitori), dezvoltare de heterojonctiuni cu aplicatii in senzoristica. Cel mai semnificativ rezultat il reprezinta obtinerea materialelor de electrod de tipul Ti/TiO₂/rGO (A/00482/09.08.2022) si Zn/ZnO/rGO (A/00164/03.04.2023) prin metoda hidrotermala in camp de microunde, o noutate pe plan national si internationa, pentru aceastea fiind depuse doua cereri de brevet inregistrate la OSIM in cadrul proiectului.

Testarea materialelor in procese de electrooxidare si electrooxidare asistate fotocatalitic a poluantilor din apa (doxorubicina) a demonstrat ca electrozii hibrizi dezvoltati in cadrul proiectului de tipul I, Ti/TiO₂/rGO dopat si nedopat prezinta caracteristici superioare electrozilor de tipul II, Zn/ZnO/rGO dopat si nedopat.