Seznam abstraktů 2019: WORKSHOP

Introduction of the Project NanoEnviCz

In the framework of the research infrastructure NanoEnviCz novel nanomaterials were synthesized for the application in environmental photocatalysis and catalysis, photoelectrochemistry and sensorics.
A quantitative electrophoretic deposition technique was developed for the preparation of composite rGO/TiO2 porous layers. Compared to the pristine TiO2, the novel layers exhibited a three-fold increase in the degradation reaction rate with complete mineralization of chlorophenols.
Owing to the enhanced effect of strongly acidic proximate protons in ZSM-5, the turnover rates for the conversion of propene to C4-C9 olefins were 5-8 times higher and that to BTX aromatics were up to 20 times higher over proximate Brønsted protons compared with that of single far distant sites.
We introduced a concept for zeolite catalysts with significantly increased concentration and functionality of the acid sites and ions of transition metals, as active sites for important catalytic reactions for hydrocarbon processing and emission control, respectively.
Novel facile procedure was developed to prepare thin films of TiO2 from thin titanium layers on different substrates. The blocking quality was monitored by the model redox probes and optimized through the film thickness and the heat-treatment.
The optical lithography was used to prepare marks that enabled making heterostructures of 2D materials (graphene, WS2, MoS, hBN). Furthermore, contacts for electrical measurements on such 2D samples were made in order to study transport properties."
ACKNOWLEDGEMENTS: The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM2015073.

The NanoEnviCz project is formed by the network of academic institutions from Czech Republic. All of these institutions are working on the similar topics. Generally, nanomaterials and nanotechnologies for environment protection and sustainable future. Each institution focuses on this topic from different point of view as synthesis in laboratory and pilot scale, all possible types of characterization and toxicological studies. The NanoEnviCz project offer easy way how to enter this network and to get possibilities to cooperate without any need to apply a big project.
The project success is supported by outputs as publications, thesis (PhD, Ms, Bc) or proposal of new project. Generally, the focus of IIC is on 2D materials as graphene, graphene oxide, LDH (layered double hydroxide) etc. and metal oxides as TiO2, CeO2 etc. The results supported by our institutions were mainly on student theses and also publications. The majority support was by the equipment and scientific support. The equipment as high power ultrasound was used for study of optimal conditions for preparation of graphene by exfoliation process. The equipment for preparation of samples suitable for TEM (transmission electron microscopy) was necessary for study of samples for corrosion attack of organ pipes made of SnPb alloys or structural and mechanical analysis of 3D printed metallic biomaterials.
The IIC CAS is offering within the NanoEnviCZ the technics as for example: FTIR+DRIFT, HRSEM, HRTEM, photocatalytic degradation in liquid phase, Surface Area and Pore Size Analyzer-BET etc.
ACKNOWLEDGEMENTS: The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM2015073.

The goal of our work was to develop and optimize a process for the preparation of chitosan-based nanofibers, which could be further used for biomedical applications. This process should be suitable for industrial production, which is associated with its technical feasibility, the minimization of costs and last but not least, the whole process being reasonable in terms of time consumption.
Our work led to a new method for preparation of crosslinked nanofibrous material made of chitosan. The stabilization of the nanofibers is based on a photoinitiated covalent crosslinking of the modified chitosan. It seems that this could be a great choice for the preparation of stable chitosan-based nanofibers, especially when combined with the electrospinning method NanospiderTM.
Besides optimizing the whole process, water resistance tests as well as experiments in culturing mammalian cells on the surface of the nanofibers were made. The results showed that the nanofibrous materials prepared by our newly designed process have great potential for a wide range of biomedical applications.
ACKNOWLEDGEMENTS: The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM2015073.

Air pollutants have been shown to cause a vast amount of different adverse health effects. These effects include impairment of many respiratory (e.g. asthma, chronic obstructive pulmonary disease) and cardiovascular (ischemic heart disease, infarction, stroke) diseases. However, in recent years, the evidence showing effects beyond the lungs and circulatory system are becoming more evident. Neurological diseases, namely Alzheimer´s disease (AD) has shown to be associated with living near traffic. However, reason for this has remained unresolved until today. Our new H2020 project TUBE aims on revealing the mechanisms of action of ultrafine particles involved in neurological diseases. The TUBE consortium includes experts in areas of aerosol technology, emission research, engine and fuel research, human clinical studies, epidemiology, emission inventories, inhalation toxicology, neurotoxicology and disease mechanism studies. This enables research of resolving the effects of nanoparticles from different traffic modes for both air quality and concomitant toxic effect of these air pollutants. We will investigate adverse effects of air pollutants using cell cultures, animal exposures and volunteered human exposures as well as the material from epidemiological cohort study. These are going to be compared according to inflammatory, cytotoxic and genotoxic changes and furthermore beyond the current state of the art to neurotoxic and brain health effects. With this approach, we are aiming to a comprehensive understanding of the adverse brain effects of nanoparticles from traffic.

In the green chemistry context, there are currently three promising laser-based nanoparticle synthesis alternatives explored at the TUL: Laser Synthesis of Colloids (LSC), Laser Surface Modification of Materials (LSMM) and laser-mediated photoreduction of metal salts in solution 1,2,3. Laser Synthesis of Colloids is a versatile technique that enables the synthesis of complex nanostructures from almost any kind of solid material [4]. An ultra-fast laser source with peak intensities above 1013 W/cm2 in shorter times than the conventional electronic relaxation time (10-12 s), is used to irradiate a solid target immersed in a liquid medium. The laser-matter interaction leads to the efficient detachment of small pieces from the material, providing the desired nanostructures. Carbon quantum dots synthesis will be discussed as an example [5]. Laser Surface Modification of Materials takes advantage of the above mentioned extreme laser-matter interactions to structurally modify the surface of almost any kind of solid target. The example that will be mentioned is the synthesis of Ag nanoparticle/α Ag2WO4 composites and its use as potent antifungal agents [6]. The third technique is the laser-mediated photoreduction of metal salts in solution, without laser interaction with solid target. In this technique, an ultra-fast laser source is focalized in a solution of precursor metal salts; the laser energy produces the optical breakdown of the liquid, which promotes the dissociation of solvent molecules into radicals. Finally, the radicals-promoted reduction of metal ions leads to the formation of nanoparticles. An example of Fe-Cu oxide nanocrystals laser-assisted synthesis will be presented [7].
ACKNOWLEDGEMENTS: The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM204573.
REFERENCES: [1] Odom T. W. and Pileni M.-P. Nanoscience. Accounts of Chemical Research, 2008, vol. 12, no 41, p. 1565-1565. [2] Venema L. Nanoscience: Small talk. Nature, 2006, vol. 442, no 7106, p. 994. [3] Sheldon R. A. Fundamentals of green chemistry: efficiency in reaction design. Chemical Society Reviews, 2012, vol. 41, no 4, p. 1437-1451. [4] Zhang D., Gökce B. and Barcikowski S. Laser synthesis and processing of colloids: fundamentals and applications. Chemical Reviews, 2017, vol. 117, no 5, p. 3990-4103. [5] Doñate-Buendía C., et al. Fabrication by Laser Irradiation in a Continuous Flow Jet of Carbon Quantum Dots for Fluorescence Imaging. ACS Omega, 2018, vol. 3, no 3, p. 2735-2742. [6] Assis M., Robeldo T., Foggi C. C., Kubo A. M., Mínguez-Vega G., Condoncillo E., Beltran-Mir H., Torres-Mendieta R., Andrés J., Oliva M., Vergani C., Barbugli P., Camargo E., Borra R. nad Longo E. Ag Nanoparticles/α-Ag2WO4 Composite Formed by Electron Beam and Femtosecond Irradiation as Potent Antifungal and Antitumor Agents. Scientific reports, 2019, vol. 9, no 1, p. 9927. [7] Torres-Mendieta R., Havelka O., Urbánek M., Cvek M., Wacławek S., Padil V. V. T., Jašíková D., Kotek M. and Černík M. Laser-assisted synthesis of Fe-Cu oxide nanocrystals. Applied Surface Science, 2019, vol. 469, p. 1007-1015.

The topic of this paper addresses unique properties of functionalized graphene and related carbon materials, along with examples of the collaborative research conducted with the aid of “NANOENVICZ” research infrastructure facilities.[1-5] The entrapment of mixed-valence copper onto functionalized graphene will be demonstrated as a way towards highly efficient single-atom metal catalysts used in the oxidative coupling of amines.[1] Applications of graphene-metal-based hybrids, derived from various metal organic frameworks, in Li-ion batteries and Li-ion capacitors will be also described.[2,3] The synthesis and electronic properties of nitrogen-doped graphene providing both localized spin centers and spin-containing sites with itinerant electron properties will be introduced.[4] Such a material exhibits spin-switch behavior (on-off-on) controlled by microwave irradiation and offers broad application potential in advanced electronics including new types of switches, filters and spintronic devices. Finally, the smart strategy towards room-temperature ferromagnetic graphene based on creation of zigzag sp2 carbon chains passing through an sp3 framework will be discussed as a path to non-metallic 2D ferromagnets.[5]
ACKNOWLEDGEMENTS: The authors acknowledge the assistance provided by the Research Infrastructure NanoEnviCz, supported by the Ministry of Education, Youth and Sports of the Czech Republic under Project No. LM2015073.
REFERENCES:
[1] BAKANDRITSOS, Aristides, KADAM, Ravishankar G., KUMAR, Pawan, ZOPPELLARO, Giorgio, MEDVEĎ, Miroslav, TUČEK, Jiří, MONTINI, Tiziano, TOMANEC, Ondřej, ANDRÝSKOVÁ, Pavlína, DRAHOŠ, Bohuslav, VARMA, Rajender S., OTYEPKA, Michal, GAWANDE, Manoj B., FORNASIERO, Paolo and ZBOŘIL, Radek. Mixed‐Valence Single‐Atom Catalyst Derived from Functionalized Graphene. Advanced Materials, 2019, vol. 31, no. 17, p. 1900323.
[2] JAYARAMULU, Kolleboyina, DUBAL, Deepak P., SCHNEEMANN, Andreas, RANC, Václav, PEREZ-REYES, Cecilia, STRÁSKÁ, Jana, KMENT, Štěpán, OTYEPKA, Michal, FISCHER, Roland A. and ZBOŘIL, Radek. Shape‐Assisted 2D MOF/Graphene Derived Hybrids as Exceptional Lithium‐Ion Battery Electrodes. Advanced Functional Materials, 2019, vol. 29, no. 38, p. 1902539.
[3] DUBAL, Deepak P., JAYARAMULU, Kolleboyina, SUNIL, Janaky, KMENT, Štěpán, GOMEZ-ROMERO, Pedro, NARAYANA, Chandrabhas, ZBOŘIL, Radek and FISCHER, Roland A. Metal-Organic Framework (MOF) Derived Electrodes with Robust and Fast Lithium Storage for Li‐Ion Hybrid Capacitors. Advanced Functional Materials, 2019, vol. 29, no. 19, p. 1900532.
[4] ZOPPELLARO, Giorgio, BAKANDRITSOS, Aristides, TUČEK, Jiří, BŁOŃSKI, Piotr, SUSI, Toma, LAZAR, Petr, BAĎURA, Zdeněk, STEKLÝ, Tomáš, OPLETALOVÁ, Ariana, OTYEPKA, Michal and ZBOŘIL, Radek. Microwave Energy Drives “On-Off-On” Spin‐Switch Behavior in Nitrogen‐Doped Graphene. Advanced Materials, 2019, vol. 31, no. 37, p. 1902587.
[5] TUČEK, Jiří, HOLÁ, Kateřina, ZOPPELLARO, Giorgio, BŁOŃSKI, Piotr, LANGER, Rostislav, MEDVEĎ, Miroslav, SUSI, Toma, OTYEPKA, Michal and ZBOŘIL, Radek. Zigzag sp2 Carbon Chains Passing through an sp3 Framework: A Driving Force toward Room-Temperature Ferromagnetic Graphene. ACS Nano, 2018, vol. 12, no. 12, pp. 12847-12859.