1. |
2. |
3. Characterization of smart and biocompatible materials based on chitosan:cellulose composites containing sporopollenin exine capsulesHanna Budasheva, Patricia Cazon Diaz, Dorota Korte, Mladen Franko, 2022, objavljeni povzetek znanstvenega prispevka na konferenci Ključne besede: chitosan:cellulose composites, biocompatible materials, beam deflection spectrometry, porosity determination, structural characterisation, thermal properties
Objavljeno v RUNG: 30.06.2022; Ogledov: 798; Prenosov: 52
 Celotno besedilo (84,71 KB) |
4. |
5. |
6. |
7. PHOTO-EXCITATION ENERGY INFLUENCE ON THE PHOTOCONDUCTIVITY OF ORGANIC SEMICONDUCTORSNadiia Pastukhova, 2018, doktorska disertacija Opis: In this work, we experimentally studied the influence of photoexcitation energy
influence on the charge transport in organic semiconductors. Organic semiconductors
were small molecules like corannulene, perylene and pentacene derivatives, polymers
such as polythiophene and benzothiophene derivatives, and graphene, along with
combinations of these materials in heterojunctions or composites.
The first part of this study is focused on the photoexcitation energy influence on
the transient photoconductivity of non-crystalline curved π-conjugated corannulene
layers. The enhanced photoconductivity, in the energy range where optical absorption
is absent, is deduced from theoretical predictions of corannulene gas-phase excited
state spectra. Theoretical analysis reveals a consistent contribution involving
transitions to Super Atomic Molecular Orbitals (SAMOs), a unique set of diffuse
orbitals typical of curved π-conjugated molecules. More, the photoconductivity of the
curved corannulene was compared to the π-conjugated planar N,N′-1H,1H-
perfluorobutyldicyanoperylene-carboxydi-imide
(PDIF-CN2),
where
the
photoexcitation energy dependence of photocurrent closely follows the optical
absorption spectrum.
We next characterized charge transport in poly(3-hexylthiophene) (P3HT) layers
deposited from solution. Our results indicate that time-of-flight (TOF) mobility
depends on the photoexcitation energy. It is 0.4× 10 −3 cm 2 /Vs at 2.3 eV (530 nm) and
doubles at 4.8 eV (260 nm). TOF mobility was compared to field-effect (FET) mobility
of P3HT field-effect transistors (OFETs). The FET mobility was similar to the 2.3 eV
excitation TOF mobility. In order to improve charge mobility, graphene nanoparticles
were blended within a P3HT solution before the deposition. We found that the mobility
significantly improves upon the addition of graphene nanoparticles of a weight ratio
as low as 0.2 %. FET mobility increases with graphene concentration up to a value of
2.3× 10 −2 cm 2 /Vs at 3.2 %. The results demonstrate that phase segregation starts to
influence charge transport at graphene concentration of 0.8 % and above. Hence, the
graphene cannot form a bridged conduction channel between electrodes, which would
cancel the semiconducting effect of the polymer composite.
An alternative approach to enhance mobility is to optimize the molecular ordering
of organic semiconductors. For that purpose, we studied an innovative nanomesh
device. Free-standing nanomesh devices were used to form nanojunctions of N,N′-
iiDioctyl-3,4,9,10-perylenedicarboximide (PTCDI-C8) nanowires and crystalline
bis(triisopropylsilylethinyl)pentacene (TIPS-PEN). We characterized the photocurrent
response time of this novel nanomesh scaffold device. The photoresponse time
depends on the photon energy. It is between 4.5 − 5.6 ns at 500 nm excitation
wavelength and between 6.7 − 7.7 ns at 700 nm excitation wavelength. In addition, we
found that thermal annealing reduces charge carrier trapping in crystalline nanowires.
This confirms that the structural defects are crucial to obtaining high photon-to-charge
conversion efficiency and subsequent transport from pn junction in heterostructured
materials.
Structural defects also influence the power conversion efficiency of organic
heterostructured photovoltaics (OPVs). Anticipating that polymers with different
backbone lengths produce different level of structural defects, we examined charge
transport
dependence
on
the
molecular
weight
of
poly[4,8-bis(5-(2-
ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b']dithiophene-2,6-diyl-alt-(4-(2-
ethylhexyl)-3-fluorothieno[3,4-b]thiophene-)-2-carboxylate-2-6-diyl]
(PTB7-Th)
from 50 kDa to 300 kDa. We found p-type hopping transport in PTB7-Th,
characterized by 0.1 – 3× 10 −2 cm 2 /Vs mobility, which increases with temperature and
electric field. The polymer molecular weight exhibits a non-trivial influence on charge
transport. FET mobility in the saturation regime increases with molecular weight. A
similar trend is observed in TOF mobility and FET mobility in the linear regime,
except for the 100kDa polymer, which manifests in the highest mobility due to reduced
charge trapping. The lowest trapping at the dielectric interface of OFET is observed at
200 kDa. In addition, the 200 kDa polymer exhibits the lowest activation energy of the
charge transport. Although the 100 kDa polymer indicates the highest mobility, OPVs
using the 200 kDa polymer exhibit the best performance in terms of power conversion
efficiency.
Ključne besede: organic
semiconductors, optical
absorption
spectroscopy, time-of-flight
photoconductivity, transient photocurrent spectroscopy, organic thin film transistors, atomic force microscopy, superatomic molecular orbitals, pn heterojunction, organic
nanowires, graphene, composites, charge mobility, charge trapping, temperature
dependence, photodetector, photovoltaic, solar cell, organic electronics
Objavljeno v RUNG: 08.10.2018; Ogledov: 4809; Prenosov: 160
Celotno besedilo (4,56 MB) |
8. Synthesis and characterization of metal/semiconductor nanocomposites for photocatalysisTina Mavrič, doktorska disertacija Opis: The doctoral dissertation focused on improving photocatalytic activity of nanopowdered ZnO by constructing I) Metal-Semiconductor and II) Semiconductor-Semiconductor heterostructures. Both heterostructure types have been reported to have a beneficial effect on photocatalytic efficiency. For the first part (I) Ag/ZnO nanocomposite was synthesized. Here we investigated an influence of polyvinylpyrrolidone (PVP) addition during the synthesis on the particle properties and their photoactivity. The second part (II) describes procedure development of ZnO based semiconductor-semiconductor composite that resulted in synthesis of highly efficient ZnO/CuWO4 composite.
Ag/ZnO nanocomposite was synthesized from precursors in ethylene glycol (EG) in a hydrothermal reactor at 180 °C for 3h. No further thermal treatment was required after the synthesis since all samples showed good crystallinity. Silver precursor loading was 2.7 wt%, because this amount has shown the best photoactivity in preliminary sample testings. Two separate batches of Ag/ZnO nanopowders were prepared, one with addition of PVP, one without (labelled Ag/ZnO and Ag/ZnO*, respectively). All powders were in nanometer range, TEM images showed a major difference between the samples with and without PVP. While Ag nanoparticles were deposited uniformly over ZnO, Ag/ZnO* exhibited a substantial agglomeration of Ag. The photocatalytic efficiency was assessed under UV-Vis light. Ag/ZnO reached complete decolourization of 10–5 M methyl orange (MO) already in 80 min after the beginning of irradiation. The calculated degradation rate constant (k) for the Ag/ZnO was almost 2-times larger than for TiO2 P25 and 4-times larger than for ZnO. Ag/ZnO* also showed higher activity than pure ZnO*, but was inferior to Ag/ZnO (1.6-times of Ag/ZnO*). A reusability test performed on Ag/ZnO showed an excellent photoactivity of reused powders; second and third cycle exhibited higher photoactivity than the first cycle. The supreme photocatalytic activity of Ag/ZnO was also confirmed by degradation of terephthalic acid.
To develop an efficient semiconductor-semiconductor heterostructure we have synthesized a combination of several materials with ZnO. We performed preliminary photocatalytic tests in order to assess the functionality of these heterostructures. The tested systems were the following: ZnO/MWCNT, ZnO/GO, ZnO/SiC, ZnO/Co3O4, ZnO/AgVO3. The synthesis of heterostructures was done via hydrothermal synthesis. The commercial or synthesized powers were dispersed together with the ZnO precursor in EG medium (180 °C/3h). The aim was to obtain higher photoactivity than that of pure ZnO. None of these systems was able to outperform pure ZnO.
ZnO/CuWO4 system has, however, significantly improved ZnO photoactivity. Several synthesis routes were investigated, including the influence of different structure directing agents (PVP, CTAB, starch). The best performing system was obtained by separate hydrothermal synthesis of ZnO and CuWO4 in water with PVP. XRD analysis confirmed that to obtain the crystalline CuWO4 thermal treatment (500 °C) is needed. The heterostructure was also synthesized in ethanolic solution. ZnO particles were in a nanometer range, CuWO4 were larger and ranged from 200 to 400 nm. CuWO4 has successfully decreased the charge recombination in ZnO, which was confirmed by transient absorption spectroscopy studies. The photocatalytic activity was assessed for both MO and TPA (10–4 M) degradation. The ZnO/CuWO4 composite has completely decolourized the dye in 60 min of UV-Vis irradiation. k for ZnO/CuWO4 was ~2.5-times larger than that of ZnO. A 3-cycle reusability test with MO showed a small decrease in efficiency in the last cycle. TPA degradation has revealed lower efficiency for ZnO/CuWO4 in air but high efficiency in O2 and N2 atmosphere, where it reached 90% and 55% degradation rate, respectively.
Ključne besede: photocatalysis, zinc oxide, heterostructures, powders, Ag/ZnO composites, ZnO/CuWO4 composites
Objavljeno v RUNG: 31.05.2017; Ogledov: 5648; Prenosov: 357
Celotno besedilo (4,11 MB) |
9. |
10. Development of Advanced TiO2/SiO2 Photocatalyst for Indoor Air CleaningAndraž Šuligoj, 2015, doktorska disertacija Opis: TiO2 - SiO2 composites were synthesized by low-temperature sol-gel impregnation method, using four different titania sources (P-25 from Degussa, PC500 from Millennium, CCA 100 AS and CCA 100 BS from Cinkarna, later denoted as AS and BS, respectively) and deposited on aluminium and glass carriers. Ordered and disordered mesoporous silicas were impregnated with ce{TiO2} in powder or suspension form in the Ti : Si molar ratio 1 : 1. Structure, size, band gap, chemical composition and specific surface area of nanoparticles were determined by X-ray diffraction (XRD), scanning (SEM) and transmission electron microscopy (TEM), UV-vis diffuse reflectance spectroscopy (DR-UV-vis), Fourier transform infrared spectroscopy (FT-IR) and ce{N2} physisorption. Additionally, quantity of surface hydroxyl groups, surface acidity and mechanical stability of the coatings were determined by temperature programmed Fourier transform infrared spectroscopy (TPD-IR) and Wolff-Wilborn method, respectively. The photocatalytic activity of TiO2 and TiO2 - SiO2 composites was evaluated in the photodegradation of toluene and formaldehyde, as model VOCs, under UVA light irradiation in lab-made photoreactor system with two different regimes; batch and plug-flow mode. These two VOCs are being considered as examples of two of the six major classes of indoor air contaminants.
Adsorption properties of the samples with toluene, have shown that the addition of mesoporous silica was beneficial. The increase of the adsorption of the bare AS TiO2 (9.5 %) was higher in the case of ordered silica, SBA-15 (2.8 times for AS/SBA15 to 26.8 %) than disordered SiO2 KIL-2 (2.4 times for AS/KIL2 to 22.7 %) although it was significant in both types of mesoporous silica supports (over 20 %). Adsorption was found to be dependent mostly on the quantity of surface Si-OH groups.
Regarding the photocatalytic activities towards toluene degradation, the results with pure TiO2 showed the fastest kinetics in case of sample AS followed by PC500 and P25. The observed behaviour was ascribed to smaller particle size, and consequently higher specific surface area. Grafting titania onto silica showed the importance of structural parameters. Most importantly, if the pore structure of bare TiO2 collapsed, this resulted in decreased activity. On the other hand, retainment of the pore structure improved the distribution of nanoparticles, crystallinity and optical properties, which resulted in improved photocatalytic activity.
In the degradation of formaldehyde, it was found that adsorption and degradation abilities of the materials were much more dependent on the structural properties of the samples, i.e., the pore structure. This was explained as a consequence of the different degradation mechanisms of both pollutants. Toluene degradation is governed by the oxidation through photogenerated holes - direct oxidation, whereas in the degradation of formaldehyde, the major oxidative species are OH radicals. In addition, the same as in toluene oxidation, the activity was dependent mainly on the number of crystal defects and the band gap values, that is the oxidation and reduction potentials of the catalysts. The degradation efficiency was increased from 88 % in pure AS TiO2 to 97 % when this titania was grafted onto colloidal silica (7C).
An important highlight of the thesis is synthesis of a novel photocatalyst, labelled AS7C, which comprises an acidic colloidal suspension AS as TiO2 source and colloidal silica, using a low-temperature sol-gel impregnation method. This sample used all the above mentioned properties that improve photocatalytic activity towards both pollutants. Mechanical stability of the samples was also tested. The tests showed that binder, in the form of colloidal SiO2 (in size of 25 nm) in combination with colloidal titania of appropriate size - 6 nm, produced the highest mechanical stability of the coatings, which also showed excellent photocatalytic activity. Stability of the coatings, using AS as titania source, was greatly improved. The Wolff-Wilborn test on AS coating showed no mechanical resistance, while with the optimal (in terms of photocatalytic performance) addition of 7C SiO2 binder stability was excellent (F, which is in the middle of 6B-6H hardness scale). This sample (AS7C) was also tested for release of aerosols, during operation of the reactor, which could be harmful for human health at longer exposure times. It was found that aerosols are formed, probably as a consequence of detachment of nanoparticles in the first period of photodegradation test. However, their formation in consecutive tests was greatly reduced. Last but not least, a pilot plug-flow reactor was constructed to test the photocatalyst's efficiency in one-pass degradation of toluene. Sample AS7C was able to degrade toluene at conditions applied (v= 400 mL/min, m(catalyst) = 1049 mg, C(0) = 1 ppmv), which means that the out-flow from reactor was clean of the pollutant and any possible intermediates, comprising only of humid air and CO2. Deactivation of the catalyst was found at higher air flow and higher initial concentration of the pollutant. However, the concentrations of pollutants in living conditions are few orders of magnitude lower, hence this is a promising result.
Ključne besede: Air remediation, TiO2 photocatalysis, Immobilization, Thin layers, TiO2/SiO2 composites
Objavljeno v RUNG: 31.08.2015; Ogledov: 7967; Prenosov: 194
Celotno besedilo (33,47 MB) |
