New Insights into The Photoactivity of Shape-Tailored BiVO4 Semiconductors via Photocatalytic Degradation Reactions and Classical Reduction Processes.

In the present study, additive-free, pH-driven, hydrothermal crystallization was used to obtain shape-tailored monoclinic BiVO4 photocatalysts. The as-prepared BiVO4 products were systematically characterized, uncovering their crystallographic, morphologic and optical properties, while their applicability was verified in the visible light-driven photodegradation of oxalic acid and rhodamine B. Monoclinic clinobisvanite was obtained in most cases, with their band gap values located between 2.1 and 2.4 eV. The morphology varied from large, aggregated crystals, individual microcrystals to hierarchical microstructures. It was found that the degradation efficiency values obtained in the case of oxalic acid were directly related to the presence of (040) crystallographic plane, while the degradation of rhodamine B was partially independent by the presence of this structural feature. The importance of (040) crystallographic plane was also demonstrated via the reduction of Cu2+ to Cu, by analyzing the Raman spectra of the Cu containing samples, the mean primary crystallite size of Cu and Cu content. Furthermore, the presence of (040) crystallographic plane was directly proportional with the hydrodynamic properties of the powders as well.

Ammonium ion removal from aqueous solutions in the presence of organic compounds, using biochar from banana leaves. Competitive isotherm models.

Industrial, e.g. food industrial and domestic wastewaters contain huge amount of compounds causing eutrophication, and should be removed with high cost during wastewater treatment. However, these compounds could be utilized as fertilizers too. Biochar can remove a wide range of pollutants from water, such as ammonium, which can be found in relatively high concentration in dairy wastewaters. However, adsorption performance may be affected by the presence of other wastewater pollutants. Thus, this study aims to determine the efficiency of biochar as an adsorbent of ammonium in aqueous solutions in the presence of some selected organic compounds of typical dairy wastewaters such as bovine serum albumin (BSA), lactose, and acetic acid. Methods: The biochar was produced from banana leaves at 300 °C, modified with NaOH, and characterized by Scanning Electron Microscope - Energy Dispersive X-Ray Spectroscopy (SEM-EDX), Fourier-transform infrared spectra (FTIR) analysis, and specific surface area measurements. Batch experiments were carried out to investigate the ammonium adsorption capacity and the ion competitive adsorption mechanism. Significant Findings: Results show that the surface structure of the biochar derived from banana leaves is different from other biochars previously studied; although the specific surface area is not very considerable and despite having nitrogen within the elemental composition, the biochar studied is capable of adsorbing 2.60 mg NH4+/m2, the highest ammonium removal in 2 h occurs at pH 9 and 500 mg biochar dose. Langmuir model in the monolayer phase analysis fits better for all scenarios and the maximum NH4+ adsorption capacity was 0.97 mg/g without organic compounds. In the multilayer adsorption phase, the isotherm model that best fits the data obtained is the Harkins-Jura model without organic compounds. The presence of organic compounds in the aqueous solution significantly impacts the adsorption of ammonium by biochar since it improves the adsorption capacity (1.132 mg/g BSA, 0.975 mg/g lactose, and 1.874 mg/g acetic acid). The Aranovich-Donohue isotherm model fitted the data obtained during ion competitive adsorption experiments well.

Impact of Pyrolysis Temperature on the Physical and Chemical Properties of Non-Modified Biochar Produced from Banana Leaves: A Case Study on Ammonium Ion Adsorption.

Given the current importance of using biochar for water treatment, it is important to study the physical-chemical properties to predict the behavior of the biochar adsorbent in contact with adsorbates. In the present research, the physical and chemical characteristics of three types of biochar derived from banana leaves were investigated, which is a poorly studied raw material and is considered an agricultural waste in some Latin American, Asian, and African countries. The characterization of non-modified biochar samples pyrolyzed at 300, 400, and 500 °C was carried out through pH, scanning electron microscopy, energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, and specific surface area measurements. The adsorption properties of banana leaf-derived biochar were evaluated by ammonium ion adsorption experiments. The results demonstrated that the pyrolysis temperature has a large impact on the yield, structure, elemental composition, and surface chemistry of the biochar. Biochar prepared at 300 °C is the most efficient for NH4+ adsorption, achieving a capacity of 7.0 mg of adsorbed NH4+ on each gram of biochar used, while biochar samples prepared at 400 and 500 °C show lower values of 6.1 and 5.6 mg/g, respectively. The Harkins-Jura isotherm model fits the experimental data best for all biochar samples, demonstrating that multilayer adsorption occurs on our biochar.

TiO2-Alginate-Chitosan-Based Composites for Skin Tissue Engineering Applications.

The UV-B component of sunlight damages the DNA in skin cells, which can lead to skin cancer and premature aging. Therefore, it is necessary to use creams that also contain UV-active substances. Many sunscreens contain titanium dioxide due to its capacity to absorb UV-B wavelengths. In the present study, titan dioxide was introduced in alginate and chitosan-alginate hydrogel composites that are often involved as scaffold compositions in tissue engineering applications. Alginate and chitosan were chosen due to their important role in skin regeneration and skin protection. The composites were cross-linked with calcium ions and investigated using FT-IR, Raman, and UV-Vis spectroscopy. The stability of the obtained samples under solar irradiation for skin protection and regeneration was analyzed. Then, the hydrogel composites were assayed in vitro by immersing them in simulated body fluid and exposing them to solar simulator radiation for 10 min. The samples were found to be stable under solar light, and a thin apatite layer covered the surface of the sample with the two biopolymers and titanium dioxide. The in vitro cell viability assay suggested that the anatase phase in alginate and chitosan-alginate hydrogel composites have a positive impact.

Hungarian and Indonesian rice husk as bioadsorbents for binary biosorption of cationic dyes from aqueous solutions: A factorial design analysis.

The wastewater of the dye industry can be characterized by a complex chemical composition and consists of numerous dyes. Bioadsorbents are increasingly applied for the biosorption of dyes because they are inexpensive and environmentally friendly. Rice husk (RH) is a potential agricultural waste that can be converted into a bioadsorbents for the biosorption of cationic dyes. Herein, the removal of methylene blue (MB) and basic red 9 (BR9) dyes by Hungarian rice husk (HRH) and Indonesian rice husk (IRH) using binary biosorption was investigated. Adsorbents were characterized by zeta potential, Fourier-transform infrared spectroscopy, and scanning electron microscopy. Batch biosorption evaluated the influence of different variables, including pH, adsorbent dose, contact time, and initial concentrations. Several factors that influence the biosorption of MB and BR9 onto rice husk were assessed using main effect, Pareto charts, normal probability plots, and interaction effect in a factorial design. The optimum contact time was 60 min. Isotherm and kinetic models of MB and BR9 in binary biosorption fitted to the Brunauer-Emmett-Teller multilayer and the Elovich equation based on correlation coefficients and nonlinear chi-square. Results showed that the biosorption capacity of HRH was 10.4 mg/g for MB and 10 mg/g for BR9; values for IRH were 9.3 mg/g and 9.6 mg/g, respectively. Therefore, HRH and IRH were found to be effective adsorbents for removing MB and BR9 via binary biosorption.

Investigation of Photocatalytic PVDF Membranes Containing Inorganic Nanoparticles for Model Dairy Wastewater Treatment.

Membrane separation processes are promising methods for wastewater treatment. Membrane fouling limits their wider use; however, this may be mitigated using photocatalytic composite materials for membrane preparation. This study aimed to investigate photocatalytic polyvinylidene fluoride (PVDF)-based nanocomposite membranes for treating model dairy wastewater containing bovine serum albumin (BSA). Membranes were fabricated via physical coating (with TiO2, and/or carbon nanotubes, and/or BiVO4) and blending (with TiO2). Another objective of this study was to compare membranes of identical compositions fabricated using different techniques, and to examine how various TiO2 concentrations affect the antifouling and cleaning performances of the blended membranes. Filtration experiments were performed using a dead-end cell. Filtration resistances, BSA rejection, and photocatalytic cleanability (characterized by flux recovery ratio (FRR)) were measured. The surface characteristics (SEM, EDX), roughness (measured by atomic force microscopy, AFM), wettability (contact angle measurements), and zeta potential of the membranes were also examined. Coated PVDF membranes showed higher hydrophilicity than the pristine PVDF membrane, as evidenced by a decreased contact angle, but the higher hydrophilicity did not result in higher fluxes, unlike the case of blended membranes. The increased surface roughness resulted in increased reversible fouling, but decreased BSA retention. Furthermore, the TiO2-coated membranes had a better flux recovery ratio (FRR, 97%) than the TiO2-blended membranes (35%). However, the TiO2-coated membrane had larger total filtration resistances and a lower water flux than the commercial pristine PVDF membrane and TiO2-blended membrane, which may be due to pore blockage or an additional coating layer formed by the nanoparticles. The BSA rejection of the TiO2-coated membrane was lower than that of the commercial pristine PVDF membrane. In contrast, the TiO2-blended membranes showed lower resistance than the pristine PVDF membrane, and exhibited better antifouling performance, superior flux, and comparable BSA rejection. Increasing the TiO2 content of the TiO2-blended membranes (from 1 to 2.5%) resulted in increased antifouling and comparable BSA rejection (more than 95%). However, the effect of TiO2 concentration on flux recovery was negligible.

Outstanding Separation Performance of Oil-in-Water Emulsions with TiO2/CNT Nanocomposite-Modified PVDF Membranes.

Membrane filtration is an effective technique for separating micro- and nano-sized oil droplets from harmful oil-contaminated waters produced by numerous industrial activities. However, significant flux reduction discourages the extensive application of this technology; therefore, developing antifouling membranes is necessary. For this purpose, various titanium dioxide/carbon nanotube (TiO2/CNT) nanocomposites (containing 1, 2, and 5 wt.% multi-walled CNTs) were used for the modification of polyvinylidene fluoride (PVDF) ultrafilter (250 kDa) membrane surfaces. The effects of surface modifications were compared in relation to the flux, the filtration resistance, the flux recovery ratio, and the purification efficiency. TiO2/CNT2% composite modification reduced both irreversible and total filtration resistances the most during the filtration of 100 ppm oil emulsions. The fluxes were approximately 4-7 times higher compared to the unmodified PVDF membrane, depending on the used transmembrane pressure (510, 900, and 1340 L/m2h fluxes were measured at 0.1, 0.2, and 0.3 MPa pressures, respectively). Moreover, the flux recovery ratio (up to 68%) and the purification efficiency (95.1-99.8%) were also significantly higher because of the surface modification, and the beneficial effects were more dominant at higher transmembrane pressures. TiO2/CNT2% nanocomposites are promising to be applied to modify membranes used for oil-water separation and achieve outstanding flux, cleanability, and purification efficiency.

Effects of Different TiO2/CNT Coatings of PVDF Membranes on the Filtration of Oil-Contaminated Wastewaters.

Six different TiO2/CNT nanocomposite-coated polyvinylidene-fluoride (PVDF) microfilter membranes (including -OH or/and -COOH functionalized CNTs) were evaluated in terms of their performance in filtering oil-in-water emulsions. In the early stages of filtration, until reaching a volume reduction ratio (VRR) of ~1.5, the membranes coated with functionalized CNT-containing composites provided significantly higher fluxes than the non-functionalized ones, proving the beneficial effect of the surface modifications of the CNTs. Additionally, until the end of the filtration experiments (VRR = 5), notable flux enhancements were achieved with both TiO2 (~50%) and TiO2/CNT-coated membranes (up to ~300%), compared to the uncoated membrane. The irreversible filtration resistances of the membranes indicated that both the hydrophilicity and surface charge (zeta potential) played a crucial role in membrane fouling. However, a sharp and significant flux decrease (~90% flux reduction ratio) was observed for all membranes until reaching a VRR of 1.1-1.8, which could be attributed to the chemical composition of the oil. Gas chromatography measurements revealed a lack of hydrocarbon derivatives with polar molecular fractions (which can act as natural emulsifiers), resulting in significant coalescent ability (and less stable emulsion). Therefore, this led to a more compact cake layer formation on the surface of the membranes (compared to a previous study). It was also demonstrated that all membranes had excellent purification efficiency (97-99.8%) regarding the turbidity, but the effectiveness of the chemical oxygen demand reduction was slightly lower, ranging from 93.7% to 98%.

Anionic Polysaccharide Cryogels: Interaction and In Vitro Behavior of Alginate-Gum Arabic Composites.

In the present study, polysaccharide-based cryogels demonstrate their potential to mimic a synthetic extracellular matrix. Alginate-based cryogel composites with different gum arabic ratios were synthesized by an external ionic cross-linking protocol, and the interaction between the anionic polysaccharides was investigated. The structural features provided by FT-IR, Raman, and MAS NMR spectra analysis indicated that a chelation mechanism is the main process linking the two biopolymers. In addition, SEM investigations revealed a porous, interconnected, and well-defined structure suitable as a scaffold in tissue engineering. The in vitro tests confirmed the bioactive character of the cryogels through the development of the apatite layer on the surface of the samples after immersion in simulated body fluid, identifying the formation of a stable phase of calcium phosphate and a small amount of calcium oxalate. Cytotoxicity tests performed on fibroblast cells demonstrated the non-toxic effect of alginate-gum arabic cryogel composites. In addition, an increase in flexibility was noted for samples with a high gum arabic content, which determines an appropriate environment to promote tissue regeneration. The newly obtained biomaterials that exhibit all these properties can be successfully involved in the regeneration of soft tissues, wound management, or controlled drug release systems.

Visible-light-driven photocatalytic PVDF-TiO2/CNT/BiVO4 hybrid nanocomposite ultrafiltration membrane for dairy wastewater treatment.

Enhancing the performance of polymeric membranes by nanomaterials has become of great interest in the field of membrane technology. The present work aimed to fabricate polyvinylidene fluoride (PVDF)-hybrid nanocomposite membranes and modify them with TiO2 and/or BiVO4 nanoparticles and/or carbon nanotubes (CNTs) in various ratios. Their photocatalytic performance under visible light was also investigated. All modified PVDF membranes exhibited higher hydrophilicity (lower contact angle of water droplets) than that of the neat membrane used as a reference. The membranes were characterized by using bovine serum albumin (BSA) as model dairy wastewater. The hybrid membranes had better antifouling properties as they had lower irreversible filtration resistance than that of the neat membrane. Hybrid PVDF membranes containing TiO2/CNT/BiVO4 showed the highest flux and lowest irreversible resistance during the filtration of the BSA solution. PVDF-TiO2/BiVO4 had the highest flux recovery ratio under visible light (70% for the PVDF mixed with 0.5% TiO2 and 0.5% BiVO4). The hydrophilicity of membrane surfaces increased with the incorporation of nanoparticles, preventing BSA to bind to the surface. This resulted in a slight decrease in BSA and chemical oxygen demand rejections, which were still above 97% in all cases.

Bioactive Properties of Composites Based on Silicate Glasses and Different Silver and Gold Structures.

Using an ideal biomaterial to treat injured bones can accelerate the healing process and simultaneously exhibit antibacterial properties; thus protecting the patient from bacterial infections. Therefore, the aim of this work was to synthesize composites containing silicate-based bioactive glasses and different types of noble metal structures (i.e., AgI pyramids, AgIAu composites, Au nanocages, Au nanocages with added AgI). Bioactive glass was used as an osteoconductive bone substitute and Ag was used for its antibacterial character, while Au was included to accelerate the formation of new bone. To investigate the synergistic effects in these composites, two syntheses were carried out in two ways: AgIAu composites were added in either one step or AgI pyramids and Au nanocages were added separately. All composites showed good in vitro bioactivity. Transformation of AgI in bioactive glasses into Ag nanoparticles and other silver species resulted in good antibacterial behavior. It was observed that the Ag nanoparticles remained in the Au nanocages, which was also beneficial in terms of antibacterial properties. The presence of Au nanoparticles contributed to the composites achieving high cell viability. The most outstanding result was obtained by the consecutive addition of noble metals into the bioactive glasses, resulting in both a high antibacterial effect and good cell viability.

Rapid Synthesis Method of Ag3PO4 as Reusable Photocatalytically Active Semiconductor.

The widespread use of Ag3PO4 is not surprising when considering its higher photostability compared to other silver-based materials. The present work deals with the facile precipitation method of silver phosphate. The effects of four different phosphate sources (H3PO4, NaH2PO4, Na2HPO4, Na3PO4·12 H2O) and two different initial concentrations (0.1 M and 0.2 M) were investigated. As the basicity of different phosphate sources influences the purity of Ag3PO4, different products were obtained. Using H3PO4 did not lead to the formation of Ag3PO4, while applying NaH2PO4 resulted in Ag3PO4 and a low amount of pyrophosphate. The morphological and structural properties of the obtained samples were studied by X-ray diffractometry, diffuse reflectance spectroscopy, scanning electron microscopy, infrared spectroscopy, and X-ray photoelectron spectroscopy. The photocatalytic activity of the materials and the corresponding reaction kinetics were evaluated by the degradation of methyl orange (MO) under visible light. Their stability was investigated by reusability tests, photoluminescence measurements, and the recharacterization after degradation. The effect of as-deposited Ag nanoparticles was also highlighted on the photostability and the reusability of Ag3PO4. Although the deposited Ag nanoparticles suppressed the formation of holes and reduced the degradation of methyl orange, they did not reduce the performance of the photocatalyst.

Statistical Analysis of Synthesis Parameters to Fabricate PVDF/PVP/TiO2 Membranes via Phase-Inversion with Enhanced Filtration Performance and Photocatalytic Properties.

Non-solvent induced phase-inversion is one of the most used methods to fabricate membranes. However, there are only a few studies supported by statistical analysis on how the different fabrication conditions affect the formation and performance of membranes. In this paper, a central composite design was employed to analyze how different fabrication conditions affect the pure water flux, pore size, and photocatalytic activity of polyvinylidene fluoride (PVDF) membranes. Polyvinylpyrrolidone (PVP) was used to form pores, and titanium dioxide (TiO2) to ensure the photocatalytic activity of the membranes. The studied bath temperatures (15 to 25 °C) and evaporation times (0 to 60 s) did not significantly affect the pore size and pure water flux of the membranes. The concentration of PVDF (12.5 to 17.5%) affected the viscosity, formation capability, and pore sizes. PVDF at high concentrations resulted in membranes with small pore sizes. PVP affected the pore size and should be used to a limited extent to avoid possible hole formation. TiO2 contents were responsible for the decolorization of a methyl orange solution (10-5 M) up to 90% over the period studied (30 h). A higher content of TiO2 did not increase the decolorization rate. Acidic conditions increased the photocatalytic activity of the TiO2-membranes.

Shape tailoring of AgBr microstructures: effect of the cations of different bromide sources and applied surfactants.

Investigations regarding AgBr-based photocatalysts came to the center of attention due to their high photosensitivity. The present research focuses on the systematic investigation regarding the effect of different alkali metal cation radii and surfactants/capping agents applied during the synthesis of silver-halides. Their morpho-structural and optical properties were determined via X-ray diffractometry, diffuse reflectance spectroscopy, scanning electron microscopy, infrared spectroscopy, and contact angle measurements. The semiconductors' photocatalytic activities were investigated using methyl orange as the model contaminant under visible light irradiation. The correlation between the photocatalytic activity and the obtained optical and morpho-structural properties was analyzed using generalized linear models. Moreover, since the (photo)stability of Ag-based photoactive materials is a crucial issue, the stability of catalysts was also investigated after the degradation process. It was concluded that (i) the photoactivity of the samples could be fine-tuned using different precursors and surfactants, (ii) the as-obtained AgBr microcrystals were transformed into other Ag-containing composites during/after the degradation, and (iii) elemental bromide did not form during the degradation process. Thus, the proposed mechanisms in the literature (for the degradation of MO using AgBr) must be reconsidered.

Utilization of Carbon Nanospheres in Photocatalyst Production: From Composites to Highly Active Hollow Structures.

Titanium dioxide-carbon sphere (TiO2-CS) composites were constructed via using prefabricated carbon spheres as templates. By the removal of template from the TiO2-CS, TiO2 hollow structures (HS) were synthesized. The CS templates were prepared by the hydrothermal treatment of ordinary table sugar (sucrose). TiO2-HSs were obtained by removing CSs with calcination. Our own sensitized TiO2 was used for coating the CSs. The structure of the CSs, TiO2-CS composites, and TiO2-HSs were characterized by scanning electron microscopy (SEM), infrared spectroscopy (IR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and diffuse reflectance spectroscopy (DRS). The effect of various synthesis parameters (purification method of CSs, precursor quantity, and applied furnace) on the morphology was investigated. The photocatalytic activity was investigated by phenol model pollutant degradation under visible light irradiation (λ > 400 nm). It was established that the composite samples possess lower crystallinity and photocatalytic activity compared to TiO2 hollow structures. Based on XPS measurements, the carbon content on the surface of the TiO2-HS exerts an adverse effect on the photocatalytic performance. The synthesis parameters were optimized and the TiO2-HS specimen having the best absolute and surface normalized photocatalytic efficiency was identified. The superior properties were explained in terms of its unique morphology and surface properties. The stability of this TiO2-HS was investigated via XRD and SEM measurements after three consecutive phenol degradation tests, and it was found to be highly stable as it entirely retained its crystal phase composition, morphology and photocatalytic activity.

Decoration of Vertically Aligned Carbon Nanotubes with Semiconductor Nanoparticles Using Atomic Layer Deposition.

Vertically aligned carbon nanotubes (VACNTs or "CNT forest") were decorated with semiconductor particles (TiO2 and ZnO) by atomic layer deposition (ALD). Both the structure and morphology of the components were systematically studied using scanning (SEM) and high resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and X-ray diffraction (XRD) methods. Characterization results revealed that the decoration was successful in the whole bulk of VACNTs. The effect of a follow-up heat treatment was also investigated and its effect on the structure was proved. It was attested that atomic layer deposition is a suitable technique for the fabrication of semiconductor/vertically aligned carbon nanotubes composites. Regarding their technological importance, we hope that semiconductor/CNT forest nanocomposites find potential application in the near future.

Growth of CNT Forests on Titanium Based Layers, Detailed Study of Catalysts.

For better electrical contacts of potential devices, growth of vertically aligned carbon nanotubes (CNT forests) directly onto conductive substrates is an emerging challenge. Here, we report a systematic study on the CCVD synthesis of carbon nanotube forests on titanium based substrates. As a crucial issue, the effect of the presence of an insulating layer (alumina) on the growing forest was investigated. Other important parameters, such as the influence of water vapor or the Fe-Co catalyst ratio, were also studied during the synthesis. As-prepared CNT forests were characterized by various techniques: scanning and transmission electron microscopies, Raman spectroscopy, spectroscopic ellipsometry. CNT forests grown directly onto the conductive substrate were also tested as electrodes in hybrid halide perovskite photodetectors and found to be effective in detecting light of intensity as low as 3 nW.

Influence of synthesis parameters on CCVD growth of vertically aligned carbon nanotubes over aluminum substrate.

In the past two decades, important results have been achieved in the field of carbon nanotube (CNT) research, which revealed that carbon nanotubes have extremely good electrical and mechanical properties The range of applications widens more, if CNTs form a forest-like, vertically aligned structure (VACNT) Although, VACNT-conductive substrate structure could be very advantageous for various applications, to produce proper system without barrier films i.e. with good electrical contact is still a challenge. The aim of the current work is to develop a cheap and easy method for growing carbon nanotubes forests on conductive substrate with the CCVD (Catalytic Chemical Vapor Deposition) technique at 640 °C. The applied catalyst contained Fe and Co and was deposited via dip coating onto an aluminum substrate. In order to control the height of CNT forest several parameters were varied during the both catalyst layer fabrication (e.g. ink concentration, ink composition, dipping speed) and the CCVD synthesis (e.g. gas feeds, reaction time). As-prepared CNT forests were investigated with various methods such as scanning electron microscopy, Raman spectroscopy, and cyclic voltammetry. With such an easy process it was possible to tune both the height and the quality of carbon nanotube forests.