Adsorptive and photocatalytic degradation potential of porous polymeric materials for removal of pesticides, pharmaceuticals, and dyes-based emerging contaminants from water.

Life on earth is dependent on clean water, which is crucial for survival. Water supplies are getting contaminated due to the growing human population and its associated industrialization, urbanization, and chemically improved agriculture. Currently, a large number of people struggle to find clean drinking water, a problem that is particularly serious in developing countries. To meet the enormous demand of clean water around the world, there is an urgent need of advanced technologies and materials that are affordable, easy to use, thermally efficient, portable, environmentally benign, and chemically durable. Physical, chemical and biological methods are used to eliminate insoluble materials and soluble pollutants from wastewater. In addition to cost, each treatment carries its limitations in terms of effectiveness, productivity, environmental effect, sludge generation, pre-treatment demands, operating difficulties, and the creation of potentially hazardous byproducts. To overcome the problems of traditional methods, porous polymers have distinguished themselves as practical and efficient materials for the treatment of wastewater because of their distinctive characteristics such as large surface area, chemical versatility, biodegradability, and biocompatibility. This study overviews improvement in manufacturing methods and the sustainable usage of porous polymers for wastewater treatment and explicitly discusses the efficiency of advanced porous polymeric materials for the removal of emerging pollutants viz. pesticides, dyes, and pharmaceuticals whereby adsorption and photocatalytic degradation are considered to be among the most promising methods for their effective removal. Porous polymers are considered excellent adsorbents for the mitigation of these pollutants as they are cost-effective and have greater porosities to facilitate penetration and adhesion of pollutants, thus enhance their adsorption functionality. Appropriately functionalized porous polymers can offer the potential to eliminate hazardous chemicals and making water useful for a variety of purposes thus, numerous types of porous polymers have been selected, discussed and compared especially in terms of their efficiencies against specific pollutants. The study also sheds light on numerous challenges faced by porous polymers in the removal of contaminants, their solutions and some associated toxicity issues.

Bio-fabricated bismuth-based materials for removal of emerging environmental contaminants from wastewater.

Although rapid industrialization has made life easier for humans, several associated issues are emerging and harming the environment. Wastewater is regarded as one of the key problems of the 21st century due to its massive production every year and requires immediate attention from all stakeholders to protect the environment. Since the introduction of nanotechnology, bismuth-based nanomaterials have been used in variety of applications. Various techniques, such as hydrothermal, solvo-thermal and biosynthesis, have been reported for synthesizing these materials, etc. Among these, biosynthesis is eco-friendly, cost-effective, and less toxic than conventional chemical methods. The prime focuses of this review are to elaborate biosynthesis of bismuth-based nanomaterials via bio-synthetic agents such as plant, bacteria and fungi and their application in wastewater treatment as anti-pathogen/photocatalyst for pollutant degradation. Besides this, future perspectives have been presented for the upcoming research in this field, along with concluding remarks.

Tailoring TiO2-lignin hybrid materials as a bio-filler for the synthesis of composites based on epoxy resin.

In this publication, the functional TiO2-lignin hybrid materials were designed and characterized. Based on elemental analysis and Fourier transform infrared spectroscopy, the efficiency of the mechanical method used to obtain systems was confirmed. Hybrid materials were also characterized by good electrokinetic stability, in particular in the inert and alkaline environments. The addition of TiO2 improves thermal stability in the entire analyzed range of temperatures. Similarly, as the content of inorganic component increases, the homogeneity of the system and the occurrence of smaller nanometric particles increase. In addition, a novel synthesis method of cross-linked polymer composites based on a commercial epoxy resin and an amine cross-linker was described as a part of the article, where additionally newly designed hybrids were also used. Subsequently, the obtained composites were subjected to simulated tests of accelerated UV-aging, and then their properties were studied, including changes in wettability (using water, ethylene glycol, and diiodomethane as measurement liquids) and surface free energy by the Owens-Wendt-Eabel-Kealble method. Changes in the chemical structure of the composites were monitored by FTIR spectroscopy due to aging. Microscopic studies of surfaces were also carried out as well as measurements in the field of changes in color parameters in the CIE-Lab system.

The In Situ Hydrothermal and Microwave Syntheses of Zinc Oxides for Functional Cement Composites.

This study presents the results of research on cement mortars amended with two zinc oxides obtained by two different methods: hydrothermal ZnO-H and microwave ZnO-M. Our work indicates that, in contrast to spherical ZnO-H, ZnO-M was characterized by a columnar particle habit with a BET surface area of 8 m2/g, which was four times higher than that obtained for hydrothermally obtained zinc oxide. In addition, ZnO-M induced much better antimicrobial resistance, which was also reported in cement mortar with this oxide. Both zinc oxides showed very good photocatalytic properties, as demonstrated by the 4-chlorophenol degradation test. The reaction efficiency was high, reaching the level of 90%. However, zinc oxides significantly delayed the cement binder setting: ZnO-H by 430 min and ZnO-M by 380 min. This in turn affected the increments in compressive strength of the produced mortars. No significant change in compressive strength was observed on the first day of setting, while significant changes in the strengths of mortars with both zinc oxides were observed later after 7 and 28 days of hardening. As of these times, the compressive strengths were about 13-15.5% and 12-13% higher than the corresponding values for the reference mortar, respectively, for ZnO-H and ZnO-M. There were no significant changes in plasticity and flexural strength of mortars amended with both zinc oxides.

Bactericidal Properties of Plasmonic Photocatalysts Composed of Noble Metal Nanoparticles on Faceted Anatase Titania.

Octahedral anatase particles (OAP) with eight equivalent {101} facets and decahedral anatase particles (DAP) with two additional {001} facets were modified with nanoparticles of noble metals (silver, copper, gold and platinum) by photodeposition, and applied for inactivation of Escherichia coli K12. XRD, DRS, XPS and STEM analyses confirmed the presence of noble metals nanoparticles (NPs) on the surface of faceted titania samples. Both OAP and DAP samples modified with silver and copper exhibited high bactericidal activities under visible light irradiation. It was also found that DAP under UV irradiation showed surprisingly high bactericidal activity, which could be attributed to efficient generation of reactive oxygen species, due to intrinsic properties of DAP, i.e., charge carriers' separation (migration of electrons and holes to {101} and {001} facets, respectively). However, an unexpected decrease in activity after DAP modification with gold and platinum NPs (mainly deposited on {101} facets) suggested that bacteria cells were directly decomposed on DAP surface. SEM images revealed that silver-modified samples caused severe damages of cell walls and membranes, due to antibacterial properties of silver (in the dark) and photocatalytic effect under visible and UV irradiation.

Noble metal-modified faceted anatase titania photocatalysts: Octahedron versus decahedron.

Octahedral anatase particles (OAP, with eight equivalent {101} facets) and decahedral anatase particles (DAP, with two additional {001} facets) were modified with nanoparticles of noble metals (Au, Ag, Cu). The titania morphology, expressed by the presence of different arrangements of exposed crystal facets, played a key role in the photocatalytic properties of metal-modified faceted titania. In the UV/vis systems, two-faceted configuration of DAP was more favorable for the reaction efficiency than single-faceted OAP because of an efficient charge separation described by the transfer of electrons to {101} facets and holes to {001} facets. Time-resolved microwave conductivity (TRMC) and reversed double-beam photoacoustic spectroscopy (RDB-PAS) confirmed that distribution of electron traps (ET) and mobility of electrons were key-factors of photocatalytic activity. In contrast, metal-modified OAP samples had higher photocatalytic activity than metal-modified DAP and metal-modified commercial titania samples under visible light irradiation. This indicates that the presence of single type of facets ({101}) is favorable for efficient electron transfer via shallow ET, whereas intrinsic properties of DAP result in fast charge carriers' recombination when gold is deposited on {101} facets (migration of "hot" electrons: Au→{101}→Au).

Enhanced Photocatalytic and Antimicrobial Performance of Cuprous Oxide/Titania: The Effect of Titania Matrix.

A simple, low-cost method was applied to prepare hybrid photocatalysts of copper (I) oxide/titania. Five different TiO2 powders were used to perform the study of the effect of titania matrix on the photocatalytic and antimicrobial properties of prepared nanocomposites. The photocatalytic efficiency of such a dual heterojunction system was tested in three reaction systems: ultraviolet-visible (UV-Vis)-induced methanol dehydrogenation and oxidation of acetic acid, and 2-propanol oxidation under visible light irradiation. In all the reaction systems considered, the crucial enhancement of photocatalytic activity in relation to corresponding bare titania was observed. The reaction mechanism for a specific reaction and the influence of titania matrix were discussed. Furthermore, antimicrobial (bactericidal and fungicidal) properties of Cu2O/TiO2 materials were analyzed. The antimicrobial activity was found under UV, visible and solar irradiation, and even for dark conditions. The origin of antimicrobial properties with emphasis on the role of titania matrix was also discussed.

Magnetic semiconductor photocatalysts for the degradation of recalcitrant chemicals from flow back water.

In the present study treatability of persistent organic compounds from the flow back water after hydrauling fracturing was investigated. The combination of TiO2 photocatalyst and magnetic oxide nanoparticles enhance the separation and recoverable property of nanosized TiO2 photocatalyst. Fe3O4/TiO2 and Fe3O4@SiO2/TiO2 nanocomposites were prepared by heteroagglomeration. The photocatalysts' characteristics by X-ray diffractometry (XRD), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS) showed that sample with the mass ratio of Fe3O4 to TiO2 equal 1:4 and molar ratio of TEOS:Fe3O4 = 8:1 and NH4OH:TEOS = 16:1 obtained by deposition TiO2 P25 (Evonik) on magnetite core had about 124 m2 g-1 specific surface area and superparamagnetic properties. The prepared composites contained TiO2 and Fe3O4 crystal phases. The photocatalytic activity was estimated by measuring the decomposition rate of three model pollutants identified in the flow back water from one of the Baltic Shale Basin. Regarding flow back water treatment after shale gas exploration, the progress of photocatalytic degradation of organic compounds was measured by chemical oxygen demand (COD) concentration. The Fe3O4@SiO2/TiO2_P25 composite nanoparticles were recovered and re-used without significant reduction of efficiency.

Transparent thin films of Cu-TiO2 with visible light photocatalytic activity.

Thin films of Cu-TiO2 with a high level of transparency were prepared by a dip-coating procedure on the glass surface. CuCl2 was used as a copper precursor added during sol-gel synthesis of TiO2. The extension of optical absorption into the visible region of as-prepared thin films was indicated by UV/Vis spectroscopy. Only the anatase phase was detected by X-ray diffraction analysis (XRD). The presence of copper in the structure of thin films was confirmed by energy dispersive X-ray spectrometry (EDS). The significant rate of phenol and 4-chlorophenol mineralization was observed during visible light irradiation. The photocatalytic activity of the prepared thin films is correlated with the optimum copper content in the structure. Copper in metallic form and cupric oxides were not detected by XRD and scanning electron microscopy analysis. It is suggested that copper may exist as dispersed ions in the TiO2 lattice.