List of Abstracts 2017: WORKSHOP

In a co-operation with a Czech company, the concentration of highly dangerous NOx in the polluted urban air was shown to be significantly reduced by the photocatalytic process. Its efficiency depends on a number of parameters, which for the most part have not been addressed in prior studies. The photocatalytic coatings can maintain high efficiency in removing NOx from the contaminated air even after two years under harsh conditions.
The structural characterization and application of nanomaterials enabled development of new nanostructured heterogeneous catalysts for efficient abatement of emissions of NOx from industrial processes and automotive transport. The effectivity of the new generation of catalysts for abatement of emissions of nitrogen oxides is sufficient to meet increasingly more stringent environmental limits. The novel effective catalyst for elimination of N2O emissions from nitric acid production plants is indispensable to producing this acid without having an adverse environmental impact.
Homogenous ultrathin TiO2 layers deposited by high impulse power magnetron sputtering were shown auspicious for the application in photocatalytic and solar technologies providing blocking functionality and efficient electron transport at the same time. A method was developed for steering the selectivity of photocatalytic reduction of CO2 to methane and CO on TiO2 surface based on the control of the nature of acidic surface sites.

The NanoenviCz project is research infrastructure focused on nanomaterials and nanotechnology for environmental protection. The Institute of Inorganic Chemistry is one of the six institutes that offer expertise and access to selected instruments to the external users for cooperation in this field.
The speciality of our part is research of nanomaterials, metal oxides applied for sorption and/or degradation of radionuclides, pesticides, nerve-agent simulants etc., 2D materials used also for preparations of composites with polymers, metal oxides etc. with similar applications, other nanomaterials used as a filler in the polymer matrix used for permeable membranes.
The instruments available for cooperation are: AFM, HRSEM, HRTEM; GC/MS; FTIR + DRIFT degradation, DXR Raman microscope; X-ray powder diffraction; Surface Area and Pore Size Analyzer-BET; Photocatalytic degradation liquid phase; Particle Size Distribution Laser Scattering using ZEN 1600 equipment; Supercritical Drying Procedure, Power Tome Ultramicrotome, Precision Ion Polishing System, Precision Etching Coating System.
This project offers large platform for national and international cooperation. Many national and five international cooperation were supported by NanoEnviCz project. The outputs of these collaborations are eleven publications and one bachelor thesis in nearly 2 years.
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.

Whereas last year we introduced the equipment available to study possible toxicity of nanoparticles (NPs) within NanoEnviCz, this year we demonstrate selected two examples of the successful projects using the research infrastructure (RI). Within the first project (VŠB-Technical university of Ostrava, CR), the cytotoxicity of NPs of a different chemical composition was evaluated depending on the various surface modifications, with a potential use as consolidants in the restoration of works of art. Metabolic activity and cell membrane integrity were investigated using WST-1 and LDH assays, respectively, as markers of cell viability in a lung epithelial A549 cells upon exposure to NPs. The results may be applicable in developing both safer and more efficient nano-based products for restoration practice. The second example of the project (National Institute of Occupational Health, Oslo, Norway) deals with in vitro transformation of human lung epithelial cells with diesel exhaust particles (DEP) and tobacco smoke (TS), well known sources of the combustion generated NPs. It uses transcriptomics to identify genes and biological pathways affected by DEP and TS. Understanding the mechanisms of the action enables identification of the most dangerous particle components which should be removed from emissions of relevant sources. Currently, there are 13 ongoing projects and 5 finalized projects within Workpackage 9 focused on the adverse effects of NPs and using equipment involved in NanoEnviCz.
The authors also 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.

Laboratory- to pilot plant- scale syntheses of specifically designed nanocrystalline metal-oxide based materials at UJEP serve as a basis for their further research in numerous partners´ institutions; a few examples include:
• Development of reactive sorbents capable to destroy the most dangerous CWAs (soman, VX agent); (CWAs – chemical warfare agents), their incorporation into nanotextiles and a development of smart (self-decontaminating) clothings (cooperation with Technical University in Liberec, Military Research Institute, National Institute for Nuclear, Chemical and Biological Protection).
• Preparation and application of multifunctional magnetically separable sorbents for the removal of inorganic as well as organic pollutants from waters (cooperation with Technical University of Ostrava, MicroChem Ltd.).
The research activities focus also on investigations of magnetic properties of these materials with potential applications in spintronics and on their biological activity with numerous applications in nanobiology, bio-engineering and nanomedicine (enzyme-mimetic ability).
Significant results were achieved by the UJEP team in the field of the nanotextile applications in a cooperation with the Nanovia Ltd.:
• Antimicrobial nanofibrous membranes have been developed using one-step procedure and Nanospider technology. These membranes based on nylon 6 nanofibers modified by chlorhexidine and dodecyltrimethylammonium bromide designed for air filtration exhibited antimicrobial activity against large scale of bacteria and good chemical and mechanical stability.
• Nanofibrous composite membranes prepared by Nanospider technology designed for wounds cover have been developed in cooperation with Nanovia Ltd. Due to novel patent-pending production technology based on post-electrospinning stabilization of biopolymer chitosan by photocrosslinking process, the key properties of the resulting nanomaterial (e.g. stability in water environment) can be easily controlled and tailored for final applications.

In the present talk, the strategies towards various graphene derivatives and their hybrids will be introduced through examples of nanomaterials developed and studied in collaboration with many partners exploiting the facilities of “NANOENVICZ” Research Infrastructure. Thus, the syntheses, properties and applications of a broad family of graphene derivatives involving sulfur- and nitrogen-doped graphene, hydroxofluorographene, cyanographene or graphene acid will be described. [1 - 5] The specific attention will be devoted to controllable chemistry of fluorographene enabling to prepare well-defined 2D materials with exceptional magnetic, electronic, and catalytic properties. The non-covalent hybrids of fluorinated graphene derivatives with metal organic frameworks (MOFs) will be demonstrated as superior materials for oil/water separation technologies. [6, 7] Finally, the composite materials of graphene oxide with noble metals and metal sulfide species will be discussed considering their extraordinary properties in heterogeneous catalysis and electrocatalysis, respectively. [8, 9]
REFERENCES: [1] Blonski, P.; Tucek, J.; Sofer, Z.; Mazanek, V.; Petr, M.; Pumera, M.; Otyepka, M.; Zboril, R. J. Am. Chem. Soc. 2017, 139, 3171-3180.; [2] Tucek, J; Błoński, P.; Sofer, Z.; Šimek, P.; Petr, M.; Pumera, M.; Otyepka, M.; Zboril, R. Adv. Mater. 2016, 28, 5045–5053.; [3] Tucek, J.; Hola, K.; Bourlinos, A.B.; Blonski, P.; Bakandritsos, A.; Ugolotti, J.; Dubecky, M.; Karlicky, F.; Ranc, V.; Cepe, K.; Otyepka, M.; Zboril, R. Nat. Comm. 2017, 8, 14525.; [4] Bakandritsos, A.; Pykal, M.; Blonski, P.; Jakubec, P.; Chronopoulos, D.D. K. Polakova, V. Georgakilas, K. Čépe, O. Tomanec, V. Ranc, A. B. Bourlinos, R. Zboril, M. Otyepka, ACS Nano 2017, 11, 2982-2991.; [5] Tucek, J.; Sofer, Z.; Bousa, D.; Pumera, M.; Hola, K.; Mala, A.; Polakova, K.; Havrdova, M.; Cepe, K.; Tomanec, O.; Zboril R. Nat. Comm. 2016, 7, 12879.; [6] Jayaramulu, K.; Geyer, F.; Petr, M.; Zboril, R.; Vollmer, D.; Fischer, R. A. Adv. Mater. 2017, 29, 1605307.; [7] Jayaramulu, K.; Datta, K. K. R.; Rösler, C.; Petr, M.; Otyepka, M.; Zboril, R.; Fischer, R. A. Angew. Chem. 2016, 55, 1178-1182.; [8] Goswami, A.; Rathi, A.; Aparicio, C.; Tomanec, O.; Petr, M.; Pocklanova, R.; Gawande, M.B.; Varma, R.S.; Zboril R. ACS Appl. Mater. Interfaces 2017, 9, 2815-2824.; [9] Jayaramulu, K.; Masa, J.; Tomanec, O.; Peeters, D.; Ranc, V.; Schneemann, A.; Zboril, R.; Schuhmann, W.; Fischer R. A. Adv. Funct. Mater. 2017, 27, 1700451.
* As co-authors of this contribution, all the authors of above-mentioned publications are considered.

Nanofibers produced by electrospinning of polymer solutions are a traditional topic of Technical University of Liberec [1]. Current applications of electrospun nanofibers spread far from textile industry and find a place in water treatment technologies, filtration, adsorption and other environmental solutions. Functionalization, specifically tuning of hydrophobicity and antibacterial properties of nanofibrous surfaces, is performed by various plasma treatments and addition of nanoparticles.
As a first example of green nanomaterials, the application of natural tree gums will be shown. These polysaccharide nanofibers are prepared by electrospinning of their water solution. Alternatively, blends with other biopolymers and polyvinylalcohol or ethylene oxide additions are fabricated. According to the literature [2], tree hydrocolloids-based electrospun nanofibers represent a vital concept not only for water purification, but also for tissue engineering, food industry and biotechnology.
Another green chemistry approach will be presented, that enables solvent-free determination of environmental pollutants and organic biomarkers in various matrices. This approach utilizes adsorption processes for the sample injection into chromatographic systems. Nanofibers of thermally stable polymers were shown to be applicable as adsorbents for solid phase micro extraction (nano-SPME) coupled to gas chromatography and mass spectrometry systems. [3]. Polyamide, polyetherimide, polyacrylate-polyethylene glycol copolymer, polyethersulfon and other polymers with well managed technology of electrospinning will be discussed as suitable adsorbents for targeted analysis of environmental pollutants (nitrosamines, organochlorinated pesticides, polyaromatic hydrocarbons).
Key words: nanofibers, biopolymer, gum, nano- SPME, pollutant, biomarker
REFERENCES: [1] F. Cengiz, T. A. Dao, and O. Jirsak, “Influence of solution properties on the roller electrospinning of poly(vinyl alcohol),” Polym. Eng. Sci., vol. 50, no. 5, pp. 936–943, May 2010.; [2] V. V. T. Padil, S. Waclawek, and M. Cernik, “Green Synthesis: Nanoparticles and Nanofibres Based on Tree Gums for Environmental Applications,” Ecol. Chem. Eng. -Chem. Inzynieria Ekol. S, vol. 23, no. 4, pp. 533–557, Dec. 2016.; [3] A. Vojtech, H. Pavel, K. Michal, and S. Martin, “Polyetherimide Nanofibres as Sorbents for Organochlorinated Pesticides Determination,” J. Nanomater., p. 1390345, 2016.