HRZZ projekt - WATPUR

Priprema poroznih tanko slojnih materijala za pročišćavanje vode koristeći tehniku Depozicije atomskih slojeva (ALD)

Voditeljica projekta: izv. prof. dr. sc. Gabriela Ambrožić

Suradnici s Odjela za fiziku:
Dr. sc. Maria Kolympadi Markovic
Doc. dr. sc. Iva Šarić
Doc. dr. sc. Ivana Jelovica Badovinac
Doc. dr. sc. Robert Peter
Doc. dr. sc. Ivna Kavre Piltaver

Vanjski suradnici: 
Prof. dr. sc. Mato Knez (CIC nanoGUNE, San Sebastian, Španjolska)
Dr. sc. Celia Rogero, Materials Physics Center (CSIC-UPV/EHU, San Sebastian, Španjolska)
Dr. sc. Maxim Ilyn (Donostia International Physics Center (DIPC), San Sebastian, Španjolska)
Izv. prof. Ivana Gobin (Medicinski fakultet, Sveučilište u Rijeci)
Prof. dr. sc. Dean Marković (Odjel za biotehnologiju, Sveučilište u Rijeci)
Doc. dr. sc. Karlo Wittine (Odjel za biotehnologiju, Sveučilište u Rijeci)

Sažetak projekta:

Cilj projekta je priprema novih fotoaktivnih keramičkih tankih filmova s kontroliranom debljinom i dobro definiranim poroznim strukturama s izrazitom primjenom za pročišćavanje vode od organskih i bioloških zagađivača. U projektu se istražuju novi pristupi u sintezi ovih materijala, koristeći tehniku Depozicije atomskih slojeva (Atomic layer deposition - ALD) u kombinaciji s visoko selektivnom „klik“ kemijom, koji će unaprijediti osnovna znanja i razviti inovacije u sintezi materijala za primjenu u pročišćavanju vode zelenim tehnologijama. Sintetski i post-sintetski procesi su osmišljeni za dobivanje materijala s naprednom funkcionalnošću koja će omogućiti: smanjenje troškova tehnologija pročišćavanja voda kroz primjenu solarne energije, selektivnu adsorpciju organskih i bioloških zagađivača, fotoinduciranu desorpciju organskih zagađivala, foto-induciranu razgradnju organskih onečišćujućih tvari i učinkovitu regeneraciju te ponovno korištenje tankoslojnih materijala. Ovi novi keramički materijali se razlikuju od tradicionalnih materijala i procesa za pročišćavanje i dezinfekciju vode upravo zbog sintetskih postupaka koje ćemo primijeniti, a koji će omogućiti narastanje potpuno novog tipa višenamjenskih keramičkih filmova deponiranih na biorazgradivom tekstilu / pamuku i anorganskim makro-poroznim podlogama. Spomenute karakteristike će proširiti potencijal keramičkih materijala u različitim smjerovima primjene: od dekontaminacije mora od naftnih izlijeva do sustava za pročišćavanje pitke vode.        



Objavljen članak u časopisu Surfaces and Interfaces

Objavljen članak u časopisu Surfaces and Interfaces
(Impact factor: 4,837, JCR 2020):

Ales Omerzu, Robert Peter, Daria Jardas, Iztok Turel, Kresimir Salamon, Matejka Podlogar, Damjan Vengust, Ivana Jelovica Badovinac, Ivna Kavre Piltaver, Mladen Petravic, Large enhancement of photocatalytic activity in ZnO thin films grown by plasma-enhanced atomic layer deposition

https://www.sciencedirect.com/science/article/abs/pii/S2468023021000614

Abstract:
In this work, we present a large, tenfold enhancement in the photocatalytic activity of thin ZnO films grown by plasma-enhanced atomic layer deposition (PE-ALD) at 100 °C, compared to values obtained for thin ZnO films deposited by a conventional thermal ALD method at the same temperature. Thus, we have demonstrated that we can deposit thin ZnO films using the PE-ALD method both at low temperatures and with a high photocatalytic ability. A number of structural (SEM, EDX, HRTEM, GIXRD, XRR, XPS, SIMS) and optical (UV-Vis, PL) experimental techniques have been employed to elucidate a possible physical origin of the observed remarkable difference in the photocatalytic activity of thin ZnO films grown by the PE-ALD method compared to those grown by the thermal ALD method.

Objavljen članak u časopisu Applied Surface Science

Objavljen članak u časopisu Applied Surface Science
(Impact factor: 6,182, JCR 2019):

I. Šarić, M. Kolympadi Markovic, R. Peter, P. Linić, K. Wittine, I. Kavre Piltaver, I. Jelovica Badovinac, D. Marković, M. Knez, G. Ambrožić, In-situ multi-step pulsed vapor phase surface functionalization of zirconia nanoparticles via copper-free click chemistry

https://www.sciencedirect.com/science/article/abs/pii/S0169433220330117?via%3Dihub

Abstract:
We report on multi-step copper-free vapor phase azide-alkyne click reactions for the functionalization of metal oxide nanopowders, automated with the atomic layer deposition (ALD) technique. The synthetic approach consists of the following reaction steps: chemisorption of propiolic acid (PA) to ZrO2 from the gas phase, followed by the formation of a triazole ring through a click reaction with 1,4-bis(azidomethyl)benzene (BisA), and, in the final step, click-coupling of the pendant azide groups with a second dose of propiolic acid (PA). The chemical composition and nature of the chemical bonding in the samples obtained after each of the ALD processing steps were investigated in detail by ATR-FTIR and XPS. As confirmed by an additional ALD deposition of ZnO, the latter reaction step introduces free polar carboxylic acid functionalities to the nanomaterial surface, which enhance the stability of the chemically modified zirconia in ethanolic dispersion. This proof-of-concept study offers great potential toward the fabrication of functional organic layers on metal oxide surfaces by sequential azide-alkyne cycloadditions performed in ALD.

Znanstveno predavanje M. Kolympadi Markovic

Dr. sc. M. Kolympadi Markovic, poslijedoktorandica na HRZZ projektu, je u organizaciji Odjela za fiziku Sveučilišta u Rijeci 21. listopada 2020. putem Google Meet servisa održala online predavanje pod nazivom "Application of atomic layer deposition (ALD) in the preparation of functional hybrid nano-materials". Sažetak predavanja nalazi se ovdje:


Nagrada za najbolji znanstveni rad u 2020.godini

U srijedu, 30. rujna 2020. održan je prijem studenata prve godine preddiplomskog studija Fizika na Odjelu za fiziku. Tom prilikom su uručene godišnje nagrade za najbolji znanstveni, diplomski i završni rad. Za nagradu „Najbolji znanstveni rad u 2020. godini“ odabran je rad HRZZ projektnog tima „Introducing the concept of pulsed vapor phase copper-free surface click chemistry using the ALD technique“ objavljen u časopisu Chemical Communications.

Objavljen članak u časopisu Thin Solid Films

Objavljen članak u časopisu Thin Solid Films
(Impact factor: 2.030, JCR 2019):

I. Jelovica Badovinac, R. Peter, A. Omerzu, K. Salamon, I. Šarić, A. Samaržija, M. Perčić, I. Kavre Piltaver, G. Ambrožić, M. Petravić, Grain size effect on photocatalytic activity of TiO2 thin films grown by atomic layer deposition

https://doi.org/10.1016/j.tsf.2020.138215

Abstract:

We have studied the effect of grain size on the photocatalytic activity of TiO2 thin films grown by atomic layer deposition technique. A number of thin films of different crystallinity (anatase, rutile, amorphous) and grain sizes (55 nm to 715 nm) were grown on Si substrates under different processing conditions, by varying the reactor temperature, deposition time or buffer layers. The films are characterized by scanning electron microscopy, grazing incidence x-ray diffraction, x-ray photoelectron spectroscopy, secondary ion mass spectrometry and atomic force microscopy. The photocatalytic activity was examined by measuring the degradation rates of methylene blue in aqueous solutions under the ultraviolet light irradiation. The photocatalytic activity exhibits a maximum for grains of average size of 200 nm, indicating existence of two competing effects, which occur when the average grain size decreases: increase of active surface area (which promotes a high photocatalytic activity) and increase of grain boundaries (which degrades the photocatalytic activity).

Objavljen članak u časopisu The Journal of Physical Chemistry C

Objavljen članak u časopisu The Journal of Physical Chemistry C
(Impact factor: 4.189, JCR 2019):

R. Peter, K. Salamon, A. Omerzu, J. Grenzer, I. Jelovica Badovinac, I. Šarić, M. Petravić, Role of Hydrogen-Related Defects in Photocatalytic Activity of ZnO Films Grown by Atomic Layer Deposition

https://doi.org/10.1021/acs.jpcc.0c01519

Abstract:

The photocatalytic activity of ZnO films, grown by atomic layer deposition on sapphire, was investigated for different amounts of residual hydrogen incorporated unintentionally into the matrix during the crystal growth. A close correlation was found between the level of incorporated hydrogen and the rate of photocatalytic degradation of methylene blue on ZnO films. The rate of degradation is consistent with predominantly zero-order reaction kinetics. An enhanced photocatalytic activity, observed for films of predominantly (001)-oriented grains and low concentration of residual hydrogen, is explained by the reduced number of hydrogen-related defects responsible for recombination of charge carriers in combination with the preferential adsorption of water on polar (001) surfaces of ZnO grains.

Objavljen članak u časopisu Nanotechnology

Objavljen članak u časopisu Nanotechnology
(Impact factor: 3.551, JCR 2019):

M. Kolympadi Marković, R. Peter, I. Jelovica Badovinac, I. Šarić, M. Perčić, R. Radičić, D. Marković, M. Knez, G. Ambrožić, "Sandwich"-like hybrid ZnO thin films produced by a combination of atomic layer deposition and wet-chemistry using a mercapto silane as single organic precursor

https://iopscience.iop.org/article/10.1088/1361-6528/ab70ce/pdf

Abstract:

This study describes a straightforward preparation of hybrid organic–inorganic thin films containing a stable 'sandwich'-like structure of two atomic layer deposited (ALD) ZnO layers separated by a thin organosilane phase, which is built from a single organic component (3-mercaptopropyl)trimethoxysilane (MPTMS). Grafting of MPTMS on the first ALD ZnO layer was performed in solution and driven by the strong affinity of the terminal thiol functionality (-SH) towards ZnO. We demonstrate that under different reaction conditions, either MPTMS monolayers are prepared or a 5 nm thick cross-linked polymeric network is formed due to the self-condensation of silane, which covers the ALD ZnO surface. This film served as a soft template for the nucleation of an ALD ZnO top layer by creation of S–Zn and Si–O–Zn bonds at the upper interface, as confirmed by XPS measurements. An increase in surface roughness, as compared to the initial ZnO film, is observed after removal of the organic layer from the hybrid structure by calcination, which is accompanied by an improvement in UVA photocatalytic activity towards the degradation of methyl orange dye. Thus, MPTMS can be used as a sacrificial agent in combination with low temperature ALD processes for building rougher and photocatalytically efficient ZnO coatings..

Objavljen članak u respektabilnom časopisu Journal of Colloid and Interface Science

Objavljen članak u respektabilnom časopisu Journal of Colloid and Interface Science
(Impact factor: 6.361, JCR 2018):

G. Ambrožić*, M. Kolympadi Markovic, R. Peter, I. Kavre Piltaver, I. Jelovica Badovinac, D. Čakara, D. Marković, M. Knez, Building organosilica hybrid nanohemispheres via thiol-ene click reaction on alumina thin films deposited by atomic layer deposition (ALD)

https://www.sciencedirect.com/science/article/abs/pii/S0021979719312615#!

Abstract:

The present work shows a surface-induced preparation of sub-100 nm organosilica nanohemispheres on atomic layer deposited (ALD) Al2O3 thin films, which was achieved by cooperative condensation/hydrolysis and thiol-ene click chemical reactions. The two-step synthetic approach consists of an initial silanization of the Al2O3 film with vinyltrimethoxysilane (VTMS), followed by a photo-promoted growth of surface-bound nanoparticles in the presence of (3-mercaptopropyl)trimethoxysilane (MPTMS). Characterization by means of FE-SEM, XPS and EDS points towards the growth of the nanohemispherical structures being governed by an initial nucleation of thiolated organosilica seeds in solution as a result of self-condensation of MPTMS and oxidation of thiols to disulfides. Once bound to the vinyl terminated Al2O3 via photo-assisted thiol-ene coupling, these seeds promote area-selective growth of the nanoparticles through binding of further MPTMS from the solution. After an additional ALD deposition of ZnO, the resulting thin hybrid film exhibits enhanced hydrophobicity when compared to ZnO films deposited directly on Al2O3 under the same processing conditions.

Sudjelovanje na Solid-State Science & Research 2019 (SCIRES 2019)


Studentica Rafaela Radičić je predstavila poster vezan uz rezultate svog završnog rada izrađenog u sklopu ovog projekta na konferenciji "Solid-State and Research 2019". Znanstveni skup održan je u Zagrebu od 27. do 29. lipnja 2019. 
 
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