Search results for: tio2

Authors: Wilman Septina, Rajiv R. Prabhakar, Thomas Moehl, David Tilley

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Cupric oxide (CuO) is a promising absorber material for the fabrication of scalable, low cost solar energy conversion devices, due to the high abundance and low toxicity of copper. It is a p-type semiconductor with a band gap of around 1.5 eV, absorbing a significant portion of the solar spectrum. One of the main challenges in using CuO as solar absorber in an aqueous system is its tendency towards photocorrosion, generating Cu2O and metallic Cu. Although there have been several reports of CuO as a photocathode for hydrogen production, it is unclear how much of the observed current actually corresponds to H2 evolution, as the inevitability of photocorrosion is usually not addressed. In this research, we investigated the effect of the deposition of overlayers onto CuO thin films for the purpose of enhancing its photostability as well as performance for water splitting applications. CuO thin film was fabricated by galvanic electrodeposition of metallic copper onto gold-coated FTO substrates, followed by annealing in air at 600 °C. Photoelectrochemical measurement of the bare CuO film using 1 M phosphate buffer (pH 6.9) under simulated AM 1.5 sunlight showed a current density of ca. 1.5 mA cm-2 (at 0.4 VRHE), which photocorroded to Cu metal upon prolonged illumination. This photocorrosion could be suppressed by deposition of 50 nm-thick TiO2, deposited by atomic layer deposition. In addition, we found that insertion of an n-type CdS layer, deposited by chemical bath deposition, between the CuO and TiO2 layers was able to enhance significantly the photocurrent compared to without the CdS layer. A photocurrent of over 2 mA cm-2 (at 0 VRHE) was observed using the photocathode stack FTO/Au/CuO/CdS/TiO2/Pt. Structural, electrochemical, and photostability characterizations of the photocathode as well as results on various overlayers will be presented.

Keywords: CuO, hydrogen, photoelectrochemical, photostability, water splitting

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Authors: Emine Yılmaz, Serap Fındık

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Baker’s yeast industry uses molasses as a raw material. Molasses is end product of sugar industry. Wastewater from molasses processing presents large amount of coloured substances that give dark brown color and high organic load to the effluents. The main coloured compounds are known as melanoidins. Melanoidins are product of Maillard reaction between amino acid and carbonyl groups in molasses. Dark colour prevents sunlight penetration and reduces photosynthetic activity and dissolved oxygen level of surface waters. Various methods like biological processes (aerobic and anaerobic), ozonation, wet air oxidation, coagulation/flocculation are used to treatment of baker’s yeast effluent. Before effluent is discharged adequate treatment is imperative. In addition to this, increasingly stringent environmental regulations are forcing distilleries to improve existing treatment and also to find alternative methods of effluent management or combination of treatment methods. Sonochemical oxidation is one of the alternative methods. Sonochemical oxidation employs ultrasound resulting in cavitation phenomena. In this study, decolorization of baker’s yeast effluent was investigated by using ultrasound. Baker’s yeast effluent was supplied from a factory which is located in the north of Turkey. An ultrasonic homogenizator used for this study. Its operating frequency is 20 kHz. TiO2-ZnO catalyst has been used as sonocatalyst. The effects of molar proportion of TiO2-ZnO, calcination temperature and time, catalyst amount were investigated on the decolorization of baker’s yeast effluent. The results showed that prepared composite TiO2-ZnO with 4:1 molar proportion treated at 700°C for 90 min provides better result. Initial decolorization rate at 15 min is 3% without catalyst, 14,5% with catalyst treated at 700°C for 90 min respectively.

Keywords: baker’s yeast effluent, decolorization, sonocatalyst, ultrasound

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Authors: Prasanta Sutradhar, Mitali Saha

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With an increasing awareness of green and clean energy, zinc oxide based solar cells were found to be suitable candidates for cost-effective and environmentally friendly energy conversion devices. In this work, we have reported the green synthesis of zinc oxide nanoparticles (ZnO) by thermal method and under microwave irradiation using the aqueous extract of tomatoes as non-toxic and ecofriendly reducing material. The synthesized ZnO nanoparticles were characterised by UV-Visible spectroscopy (UV-Vis), infra-red spectroscopy (IR), particle size analyser (DLS), scanning electron microscopy (SEM), atomic force microscopy (AFM), and X- ray diffraction study (XRD). A series of ZnO nanocomposites with titanium dioxide nanoparticles (TiO2) and graphene oxide (GO) were prepared for photovoltaic application. Structural and morphological studies of these nanocomposites were carried out using UV-vis, SEM, XRD, and AFM. The current-voltage measurements of the nanocomposites demonstrated enhanced power conversion efficiency of 6.18% in case of ZnO/GO/TiO2 nanocomposite.

Keywords: ZnO, green synthesis, microwave, nanocomposites, I-V characteristics

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Authors: J. Tirano, H. Zea, C. Luhrs

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It is well known that titanium dioxide is a semiconductor with several applications in photocatalytic process. Its band gap makes it very interesting in the photoelectrodes manufacturing used in photoelectrochemical cells for hydrogen production, a clean and environmentally friendly fuel. The synthesis of 1D titanium dioxide nanostructures, such as nanotubes, makes possible to produce more efficient photoelectrodes for solar energy to hydrogen conversion. In essence, this is because it increases the charge transport rate, decreasing recombination options. However, its principal constraint is to be mainly sensitive to UV range, which represents a very low percentage of solar radiation that reaches earth's surface. One of the alternatives to modifying the TiO2’s band gap and improving its photoactivity under visible light irradiation is to dope the nanotubes with transition metals. This option requires fabricating efficient nanostructured photoelectrodes with controlled morphology and specific properties able to offer a suitable surface area for metallic doping. Hence, currently one of the central challenges in photoelectrochemical cells is the construction of nanomaterials with a proper band position for driving the reaction while absorbing energy over the VIS spectrum. This research focuses on the synthesis and characterization of Nidoped TiO2 nanotubes for improving its photocatalytic activity in solar energy conversion applications. Initially, titanium dioxide nanotubes (TNTs) with controlled morphology were synthesized by two-step potentiostatic anodization of titanium foil. The anodization was carried out at room temperature in an electrolyte composed of ammonium fluoride, deionized water and ethylene glycol. Consequent thermal annealing of as-prepared TNTs was conducted in the air between 450 °C - 550 °C. Afterwards, the nanotubes were superficially modified by nickel deposition. Morphology and crystalline phase of the samples were carried out by SEM, EDS and XRD analysis before and after nickel deposition. Determining the photoelectrochemical performance of photoelectrodes is based on typical electrochemical characterization techniques. Also, the morphological characterization associated electrochemical behavior analysis were discussed to establish the effect of nickel nanoparticles modification on the TiO2 nanotubes. The methodology proposed in this research allows using other transition metal for nanotube surface modification.

Keywords: dimensionally stable electrode, nickel nanoparticles, photo-electrode, TiO₂ nanotubes

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Authors: Mohannad Mayyas, Farshid Pahlevani, Veena Sahajwalla

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Automotive shredder residue (ASR) is an industrial waste, generated during the recycling process of End-of-life vehicles. The large increasing production volumes of ASR and its hazardous content have raised concerns worldwide, leading some countries to impose more restrictions on ASR waste disposal and encouraging researchers to find efficient solutions for ASR processing. Although a great deal of research work has been carried out, all proposed solutions, to our knowledge, remain commercially and technically unproven. While the volume of waste materials continues to increase, the production of materials from new sustainable sources has become of great importance. Advanced ceramic materials such as nitrides, carbides and borides are widely used in a variety of applications. Among these ceramics, a great deal of attention has been recently paid to Titanium nitride (TiN) owing to its unique characteristics. In our study, we propose a new sustainable approach for ASR management where TiN nanoparticles with ideal particle size ranging from 200 to 315 nm can be synthesized as a by-product. In this approach, TiN is thermally synthesized by nitriding pressed mixture of automotive shredder residue (ASR) incorporated with titanium oxide (TiO2). Results indicated that TiO2 influences and catalyses degradation reactions of ASR and helps to achieve fast and full decomposition. In addition, the process resulted in titanium nitride (TiN) ceramic with several unique structures (porous nanostructured, polycrystalline, micro-spherical and nano-sized structures) that were simply obtained by tuning the ratio of TiO2 to ASR, and a product with appreciable TiN content of around 85% was achieved after only one hour nitridation at 1550 °C.

Keywords: automotive shredder residue, nano-ceramics, waste treatment, titanium nitride, thermal conversion

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Authors: Chundong Li, V. V. Neshchimenko, M. M. Mikhailov

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The effect of the modification of ZnO powders by ZrO2, Al2O3, TiO2, SiO2, CeO2 and Y2O3 nanoparticles with a concentration of 1-30 wt % is investigated by diffuse reflectance spectra within the wavelength range 200 to 2500 nm before and after 100 keV proton and electron irradiation. It has been established that the introduction of nanoparticles ZrO2, Al2O3 enhances the optical stability of the pigments under proton irradiation, but reduces it under electron irradiation. Modifying with TiO2, SiO2, CeO2, Y2O3 nanopowders leads to decrease radiation stability in both types of irradiation. Samples modified by 5 wt. % of ZrO2 nanoparticles have the highest stability of optical properties after proton exposure. The degradation of optical properties under electron irradiation is not high for this concentration of nanoparticles. A decrease in the absorption of pigments modified with nanoparticles proton exposure is determined by a decrease in the intensity of bands located in the UV and visible regions. After electron exposure the absorption bands have in the whole spectrum range.

Keywords: irradiation, nanopowders, radiation stability, zinc oxide

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Authors: Malek Y. S. Ibrahim, Jeffrey A. Bennett, Milad Abolhasani

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Despite the potential of hydrogen (H2) storage in liquid organic carriers to achieve carbon neutrality, the energy required for H2 release and the cost of catalyst recycling has hindered its large-scale adoption. In response, a photo flow reactor packed with rhodium (Rh)/titania (TiO2) photocatalyst was reported for the continuous and selective acceptorless dehydrogenation of 1,2,3,4-tetrahydroquinoline to H2 gas and quinoline under visible light irradiation at room temperature. The tradeoff between the reactor pressure drop and its photocatalytic surface area was resolved by selective in-situ photodeposition of Rh in the photo flow reactor post-packing on the outer surface of the TiO2 microparticles available to photon flux, thereby reducing the optimal Rh loading by 10 times compared to a batch reactor, while facilitating catalyst reuse and regeneration. An example of using quinoline as a hydrogen acceptor to lower the energy of the hydrogen production step was demonstrated via the water-gas shift reaction.

Keywords: hydrogen storage, flow chemistry, photocatalysis, solar hydrogen

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Authors: Vijay K. Tomer, Ritu Malik, Satya P. Nehra, Anshu Sharma

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Highly ordered mesoporous WO₃-TiO₂ nanohybrids with large intrinsic surface area and highly ordered pore channels were synthesized using mesoporous silica, KIT-6 as hard template using a nanocasting strategy. The nanohybrid samples were characterized by a variety of physico-chemical techniques including X-ray diffraction, Nitrogen adsorption-desorption isotherms, and high resolution transmission electron microscope. The nanohybrids were tested for detection of important indoor Volatile Organic Compounds (VOCs) including acetone, ethanol, n-butanol, toluene, and xylene. The sensing result illustrates that the nanocomposite sensor was highly responsive towards xylene gas at relatively lower operating temperature. A rapid response and recovery time, highly linear response and excellent stability in the concentration ranges from 1 to 100 ppm was observed for xylene gas. It is believed that the promising results of this study can be utilized in the synthesis of ordered mesoporous nanostructures which can extend its configuration for the development of new age e-nose type sensors with enhanced gas-sensing performance.

Keywords: nanohybrids, response, sensor, VOCs, xylene

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Authors: Jaejin Han, Jinsub Choi

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Vanadium redox flow battery (VRFB) is a type of redox flow battery which uses vanadium ionic solution as electrolyte. Inside the VRFB, 2.5mm thickness of graphite is generally used as bipolar plate for anti-corrosion of current collector. In this research, thick graphite bipolar plate was substituted by 0.126mm thickness of dimensionally stable anode which was coated with IrO2 on an anodic nanotubular TiO2 substrate. It can provide dimensional advantage over the conventional graphite when the VRFB is used as multi-stack. Ir was coated by using spray coating method in order to enhance electric conductivity. In this study, various electrochemical characterizations were carried out. Cyclic voltammetry data showed activation of Ir in the positive electrode of VRFB. In addition, polarization measurements showed Ir-coated DSA had low overpotential in the positive electrode of VRFB. In cell test results, the DSA-used VRFB showed better efficiency than graphite-used VRFB in voltage and overall efficiency.

Keywords: bipolar plate, DSA (dimensionally stable anode), iridium oxide coating, TiO2 nanotubes, VRFB (vanadium redox flow battery)

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Authors: Bouafia-Chergui Souâd, Chabani Malika, Bensmaili Aicha

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Water treatment and especially, medicament pollutants are nowadays important problems. Degradation of oxytetracycline was carried out using combined process of low-frequency ultrasound (US), ultraviolet irradiation and a catalyst. The effectiveness of the coupled processes has been evaluated by studying the effects of various operating parameters including initial OTC concentration, solution pH and catalyst mass. For the photolysis process, the monochromatic ultraviolet light wavelength utilized was 365 nm. The sonolysis experiments were performed with ultrasound at a frequency of 40 kHz. The heterogeneous photocatalysis was studied in the presence of TiO2. The processes were employed individually, and simultaneously to examine the details of the processes and to investigate the contribution of each process. Low UV intensity (12W), low pH and high mass of TiO2 conditions enhanced the sono-photocatalytic degradation of OTC. The results showed that the individual contribution sonochemical and photochemical reactions are very low, however, their coupling increases the degradation rate of 8 times compared to photolysis and 2 times compared to sonolysis. There is a synergistic effect between the two modes of radiation, UV and U.S. leading to 82.04% degradation yield. An application of these combined processes on the treatment of a real pharmaceutical wastewater was examined.

Keywords: sonolysis, photocatalysis, combined process, antibiotic

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Authors: Olga Długosz, Jolanta Pulit-Prociak, Marcin Banach

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The paper presents a process to obtain glutathione-modified titanium oxide nanoparticles. The processes were carried out in a microwave radiation field. The influence of the molar ratio of glutathione to titanium oxide and the effect of the fold of NaOH vs. stoichiometric amount on the size of the formed TiO₂ nanoparticles was determined. The physicochemical properties of the obtained products were evaluated using dynamic light scattering (DLS), transmission electron microscope- energy-dispersive X-ray spectroscopy (TEM-EDS), low-temperature nitrogen adsorption method (BET), X-Ray Diffraction (XRD) and Fourier-transform infrared spectroscopy (FTIR) microscopy methods. The size of TiO₂ nanoparticles was characterized from 30 to 336 nm. The release of titanium ions from the prepared products was evaluated. These studies were carried out using different media in which the powders were incubated for a specific time. These were water, SBF and Ringer's solution. The release of titanium ions from modified products is weaker compared to unmodified titanium oxide nanoparticles. The reduced release of titanium ions may allow the use of such modified materials as substances in drug delivery systems.

Keywords: titanium dioxide, nanoparticles, drug carrier, glutathione

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Authors: Olga Długosz, Jolanta Pulit-Prociak, Marcin Banach

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The paper presents a process to obtain glutathione-modified titanium oxide nanoparticles. The processes were carried out in a microwave radiation field. The influence of the molar ratio of glutathione to titanium oxide and the effect of the fold of NaOH vs. stoichiometric amount on the size of the formed TiO₂ nanoparticles was determined. The physicochemical properties of the obtained products were evaluated using dynamic light scattering (DLS), transmission electron microscope- energy-dispersive X-ray spectroscopy (TEM-EDS), low-temperature nitrogen adsorption method (BET), X-Ray Diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR) microscopy methods. The size of TiO₂ nanoparticles was characterized from 30 to 336 nm. The release of titanium ions from the prepared products was evaluated. These studies were carried out using different media in which the powders were incubated for a specific time. These were: water, SBF, and Ringer's solution. The release of titanium ions from modified products is weaker compared to unmodified titanium oxide nanoparticles. The reduced release of titanium ions may allow the use of such modified materials as substances in drug delivery systems.

Keywords: titanium dioxide, nanoparticles, drug carrier, glutathione

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Authors: D. Olszewska, J. Niewiedzial

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In some types of Li-ion batteries carbon in the form of graphite is used. Unfortunately, carbon materials, in particular graphite, have very good electrochemical properties, but increase their volume during charge/discharge cycles, which may even lead to an explosion of the cell. The cell element may be replaced by a composite material consisting of lithium-titanium oxide Li4Ti5O12 (LTO) modified with copper and nickel ions and carbon derived from sucrose. This way you can improve the conductivity of the material. LTO is appropriate only for applications which do not require high energy density because of its high operating voltage (ca. 1.5 V vs. Li/Li+). Specific capacity of Li4Ti5O12 is high enough for utilization in Li-ion batteries (theoretical capacity 175 mAh·g-1) but it is lower than capacity of graphite anodes. Materials based on Li4Ti5O12 do not change their volume during charging/discharging cycles, however, LTO has low conductivity. Another positive aspect of the use of sucrose in the carbon composite material is to eliminate the addition of carbon black from the anode of the battery. Therefore, the proposed materials contribute significantly to environmental protection and safety of selected lithium cells. New anode materials in order to obtain Li3.8Cu0.1Ni0.1Ti5O12 have been prepared by solid state synthesis using three-way: i) stoichiometric composition of Li2CO3, TiO2, CuO, NiO (A- Li3.8Cu0.1Ni0.1Ti5O12); ii) stoichiometric composition of Li2CO3, TiO2, Cu(NO3)2, Ni(NO3)2 (B-Li3.8Cu0.1Ni0.1Ti5O12); and iii) stoichiometric composition of Li2CO3, TiO2, CuO, NiO calcined with 10% of saccharose (Li3.8Cu0.1Ni0.1Ti5O12-C). Structure of materials was studied by X-ray diffraction (XRD). The electrochemical properties were performed using appropriately prepared cell Li|Li+|Li3.8Cu0.1Ni0.1Ti5O12 for cyclic voltammetry and discharge/charge measurements. The cells were periodically charged and discharged in the voltage range from 1.3 to 2.0 V applying constant charge/discharge current in order to determine the specific capacity of each electrode. Measurements at various values of the charge/discharge current (from C/10 to 5C) were carried out. Cyclic voltammetry investigation was carried out by applying to the cells a voltage linearly changing over time at a rate of 0.1 mV·s-1 (in the range from 2.0 to 1.3 V and from 1.3 to 2.0 V). The XRD method analyzes show that composite powders were obtained containing, in addition to the main phase, 4.78% and 4% TiO2 in A-Li3.8Cu0.1Ni0.1O12 and B-Li3.8Cu0.1Ni0.1O12, respectively. However, Li3.8Cu0.1Ni0.1O12-C material is three-phase: 63.84% of the main phase, 17.49 TiO2 and 18.67 Li2TiO3. Voltammograms of electrodes containing materials A-Li3.8Cu0.1Ni0.1O12 and B-Li3.8Cu0.1Ni0.1O12 are correct and repeatable. Peak cathode occurs for both samples at a potential approx. 1.52±0.01 V relative to a lithium electrode, while the anodic peak at potential approx. 1.65±0.05 V relative to a lithium electrode. Voltammogram of Li3.8Cu0.1Ni0.1Ti5O12-C (especially for the first measurement cycle) is not correct. There are large variations in values of specific current, which are not characteristic for materials LTO. From the point of view of safety and environmentally friendly production of Li-ion cells eliminating soot and applying Li3.8Cu0.1Ni0.1Ti5O12-C as an active material of an anode in lithium-ion batteries seems to be a good alternative to currently used materials.

Keywords: anode, Li-ion batteries, Li₄O₅O₁₂, spinel

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Authors: Eka Maulana, Sholeh Hadi Pramono, Dody Fanditya, M. Julius

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In this paper, extract of papaya leaves are used as a natural dye and combined by variations of solvent concentration applied on DSSC (Dye-Sensitized Solar Cell). Indonesian geographic located on the equator line occasions the magnitude of the potential to develop organic solar cells made from extracts of chlorophyll as a substitute for inorganic materials or synthetic dye on DSSC material. Dye serves as absorbing photons which are then converted into electrical energy. A conductive coated glass layer called TCO (Transparent Conductive Oxide) is used as a substrate of electrode. TiO2 nanoparticles as binding dye molecules, redox couple iodide/ tri-iodide as the electrolyte and carbon as the counter electrode in the DSSC are used. TiO2 nanoparticles, organic dyes, electrolytes and counter electrode are arranged and combined with the layered structure of the photo-catalyst absorption layer. Dye absorption measurements using a spectrophotometer at 200-800 nm light spectrum produces a total amount of chlorophyll 80.076 mg/l. The test cell at 7 watt LED light with 5000 lux luminescence were obtained Voc and Isc of 235.5 mV and 14 μA, respectively.

Keywords: DSSC (Dye-Sensitized Solar Cell), natural dye, chlorophyll, absorption

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Authors: Heba M. Gobara, Ahmed A. M. El-Naggar, Rasha S. El-Sayed, Amal A. AlKahlawy

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In this study, metal organic framework (Cr-MIL-101) and TiO₂ nanoparticles were utilized as two semiconductors for water splitting process. The coupling of both semiconductors in order to improve the photocatalytic reactivity for the hydrogen production in presence of methanol as a hole scavenger under visible light (sunlight) has been performed. The forementioned semiconductors and the collected samples after water splitting application are characterized by several techniques viz., XRD, N₂ adsorption-desorption, TEM, ED, EDX, Raman spectroscopy and the total content of carbon. The results revealed an efficient yield of H₂ production with maximum purity 99.3% with the in-situ formation of graphene oxide nanosheets and multiwalled carbon nanotubes coated over the surface of the physically mixed Cr-MIL-101–TiO₂ system. The amount of H₂ gas produced was stored when using Cr-MIL-101 catalyst individually. The obtained data in this work provides promising candidate materials for pure hydrogen production as a clean fuel acquired from the water splitting process. In addition, the in-situ production of graphene nanosheets and carbon nanotubes is counted as promising advances for the presented process.

Keywords: hydrogen production, water splitting, photocatalysts, Graphene

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Authors: Zainab Dahrouch, Beatrix Petrovičová, Claudia Triolo, Fabiola Pantò, Angela Malara, Salvatore Patanè, Maria Allegrini, Saveria Santangelo

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Synthetic dyes dispersed in water cause environmental damage and have harmful effects on human health. Methylene blue (MB) is broadly used as a dye in the textile, pharmaceutical, printing, cosmetics, leather, and food industries. The complete removal of MB is difficult due to the presence of aromatic rings in its structure. The present study is focused on electrospun nanofibers (NFs) with engineered architecture and surface to be used as catalysts for the photodegradation of MB. Ti and/or Zn oxide NFs are produced by electrospinning precursor solutions with different Ti: Zn molar ratios (from 0:1 to 1:0). Subsequent calcination and cooling steps are operated at fast rates to generate porous NFs with capture centers to reduce the recombination rate of the photogenerated charges. The comparative evaluation of the NFs as photocatalysts for the removal of MB from an aqueous solution with a dye concentration of 15 µM under UV irradiation shows that the binary (wurtzite ZnO and anatase TiO₂) oxides exhibit higher catalytic activity compared to ternary (ZnTiO₃ and Zn₂TiO₄) oxides. The higher band gap and lower crystallinity of the ternary oxides are responsible for their lower photocatalytic activity. It has been found that the optimal load for the wurtzite ZnO is 0.66 mg mL⁻¹, obtaining a degradation rate of 7.94.10⁻² min⁻¹. The optimal load for anatase TiO₂ is lower (0.33 mg mL⁻¹) and the corresponding rate constant (1.12×10⁻¹ min⁻¹) is higher. This finding (higher activity with lower load) is of crucial importance for the scaling up of the process on an industrial scale. Indeed, the anatase NFs outperform even the commonly used P25-TiO₂ benchmark. Besides, they can be reused twice without any regeneration treatment, with 5.2% and 18.7% activity decrease after second and third use, respectively. Thanks to the scalability of the electrospinning technique, this laboratory-scale study provides a perspective towards the sustainable large-scale manufacture of photocatalysts for the treatment of industry effluents.

Keywords: anatase, capture centers, methylene blue dye, nanofibers, photodegradation, zinc oxide

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Authors: Mohanapriya Subramanian, V. Raj

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Direct methanol fuel cells (DMFCs) are considered to be one of the most promising candidates for portable and stationary applications in the view of their advantages such as high energy density, easy manipulation, high efficiency and they operate with liquid fuel which could be used without requiring any fuel-processing units. Electrolyte membrane of DMFC plays a key role as a proton conductor as well as a separator between electrodes. Increasing concern over environmental protection, biopolymers gain tremendous interest owing to their eco-friendly bio-degradable nature. Pectin is a natural anionic polysaccharide which plays an essential part in regulating mechanical behavior of plant cell wall and it is extracted from outer cells of most of the plants. The aim of this study is to develop and demonstrate pectin based polymer composite membranes as methanol impermeable polymer electrolyte membranes for DMFCs. Pectin based nanocomposites membranes are prepared by solution-casting technique wherein pectin is blended with chitosan followed by the addition of optimal amount of sulphonic acid modified Titanium dioxide nanoparticle (S-TiO2). Nanocomposite membranes are characterized by Fourier Transform-Infra Red spectroscopy, Scanning electron microscopy, and Energy dispersive spectroscopy analyses. Proton conductivity and methanol permeability are determined into order to evaluate their suitability for DMFC application. Pectin-chitosan blends endow with a flexible polymeric network which is appropriate to disperse rigid S-TiO2 nanoparticles. Resulting nanocomposite membranes possess adequate thermo-mechanical stabilities as well as high charge-density per unit volume. Pectin-chitosan natural polymeric nanocomposite comprising optimal S-TiO2 exhibits good electrochemical selectivity and therefore desirable for DMFC application.

Keywords: biopolymers, fuel cells, nanocomposite, methanol crossover

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Authors: Ines Nitoi, Petruta Oancea, Lucian Constantin, Laurentiu Dinu, Maria Crisan, Malina Raileanu, Ionut Cristea

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2,4,6-Trinitrotoluene (TNT) is the most common pollutant identified in wastewater generated from munitions plants where this explosive is synthesized or handled (munitions load, assembly and pack operations). Due to their toxic and suspected carcinogenic characteristics, nitroaromatic compounds like TNT are included on the list of prioritary pollutants and strictly regulated in EU countries. Since their presence in water bodies is risky for human health and aquatic life, development of powerful, modern treatment methods like photocatalysis are needed in order to assures environmental pollution mitigation. The photocatalytic degradation of TNT was carried out at pH=7.8, in aqueous TiO2 based catalyst suspension, under sunlight irradiation. The enhanced photo activity of catalyst in visible domain was assured by 0.5% Fe doping. TNT degradation experiments were performed using a tubular collector type solar photoreactor (26 UV permeable silica glass tubes series connected), plug in a total recycle loops. The influence of substrate concentration and catalyst dose on the pollutant degradation and mineralization by-products (NO2-, NO3-, NH4+) formation efficiencies was studied. In order to compare the experimental results obtained in various working conditions, the pollutant and mineralization by-products measured concentrations have been considered as functions of irradiation time and cumulative photonic energy Qhν incident on the reactor surface (kJ/L). In the tested experimental conditions, at tens mg/L pollutant concentration, increase of 0,5%-TiO2 dose up to 200mg/L leads to the enhancement of CB degradation efficiency. Since, doubling of TNT content has a negative effect on pollutant degradation efficiency, in similar experimental condition, prolonged irradiation time from 360 to 480 min was necessary in order to assures the compliance of treated effluent with limits imposed by EU legislation (TNT ≤ 10µg/L).

Keywords: wastewater treatment, TNT, photocatalysis, environmental engineering

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Authors: Gul Afreen, Sreedevi Upadhyayula, Mahendra K. Sunkara

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One-dimensional (1D) nanostructures like nanowires, nanotubes, and nanorods find variety of practical application owing to their unique physico-chemical properties. In this work, TiO₂ nanowires were synthesized by direct oxidation of titanium particles in a unique microwave plasma jet reactor. The prepared TiO₂ nanowires manifested the flexible features, and were characterized by using X-ray diffraction, Brunauer-Emmett-Teller (BET) surface area analyzer, UV-Visible and FTIR spectrophotometers, Scanning electron microscope, and Transmission electron microscope. Further, the photodegradation efficiency of these nanowires were tested against toxic organic dye like methylene blue (MB) and the results were compared with the commercial TiO₂. It was found that TiO₂ nanowires exhibited superior photocatalytic performance (89%) as compared to commercial TiO₂ (75%) after 60 min of reaction. This is attributed to the lower recombination rate and increased interfacial charge transfer in TiO₂ nanowire. Pseudo-first order kinetic modelling performed with the experimental results revealed that the rate constant of photodegradation in case of TiO₂ nanowire was 1.3 times higher than that of commercial TiO₂. Superoxide radical (O₂˙⁻) was found to be the major contributor in the photodegradation mechanism. Based on the trapping experiments, a plausible mechanism of the photocatalytic reaction is discussed.

Keywords: heterogeneous catalysis, photodegradation, reactive oxygen species, TiO₂ nanowires

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Authors: Z. Younsi, L. Koufi, H. Gidik, D. Lahem, W. Wim Thielemans

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This study investigated the efficiency of photocatalytic textile to remove the Volatile Organic Compounds (VOCs) present in indoor air. Functionalization of the fabric was achieved by adding a photocatalyst material active in the visible spectrum of light. This is a modified titanium dioxide photocatalyst doped with non-metal ions synthesized via sol-gel process, which should allow the degradation of the pollutants – ideally into H₂O and CO₂ – using photocatalysis based on visible light and no additionnal external energy source. The visible light photocatalytic activity of textile sample was evaluated for toluene and benzene gaseous removal, under the visible irradiation, in a test chamber with the total volume of 1m³. The suggested approach involves experimental investigations of the global behavior of the photocatalytic textile. The experimental apparatus permits simultaneous measurements of the degradation of pollutants and presence of eventually formed by-products. It also allows imposing and measuring concentration variations with respect to selected time scales in the test chamber. The observed results showed that the amount of TiO₂ incorporation improved the photocatalytic efficiency of functionalized textile significantly under visible light. The results obtained with such textile are very promising.

Keywords: benzene, C₆H₆, efficiency, photocatalytic degradation, textile fabrics, titanium dioxide, TiO₂, toluene, C₇H₈, visible light

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Authors: M. Budakoglu, M. Karaman

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Lake Acıgöl is located in area with limited influences from urban and industrial pollution sources, there is nevertheless a need to understand all potential lithological and anthropogenic sources of priority contaminants in this closed basin. This study discusses vertical and horizontal distribution pattern of major, trace elements of recent lake sediments to better understand their current geochemical analog with lithological units in the Lake Acıgöl basin. This study also provides reliable background levels for the region by the detailed surfaced lithological units data. The detail results of surface, subsurface and shallow core sediments from these relatively unperturbed ecosystems, highlight its importance as conservation area, despite the high-scale industrial salt production activity. While P2O5/TiO2 versus MgO/CaO classification diagram indicate magmatic and sedimentary origin of lake sediment, Log(SiO2/Al2O3) versus Log(Na2O/K2O) classification diagrams express lithological assemblages of shale, iron-shale, vacke and arkose. The plot between TiO2 vs. SiO2 and P2O5/TiO2 vs. MgO/CaO also supports the origin of the primary magma source. The average compositions of the 20 different lithological units used as a proxy for geochemical background in the study area. As expected from weathered rock materials, there is a large variation in the major element content for all analyzed lake samples. The A-CN-K and A-CNK-FM ternary diagrams were used to deduce weathering trends. Surface and subsurface sediments display an intense weathering history according to these ternary diagrams. The most of the sediments samples plot around UCC and TTG, suggesting a low to moderate weathering history for the provenance. The sediments plot in a region clearly suggesting relative similar contents in Al2O3, CaO, Na2O, and K2O from those of lithological samples.

Keywords: Lake Acıgöl, recent lake sediment, geochemical speciation of major and trace elements, heavy metals, Denizli, Turkey

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Authors: Gizachew Belay Adugna, Yu-Tai Tao

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Perovskite solar cells (PSCs) have been gaining impressive progress with excellent power conversion efficiency (PCE) of 25.5% in small-area devices. However, the conventional film coating approach is not applicable to large-area module fabrication. Meniscus-guided coating, including blade coating, slot-die coating, and bar coating, is solution processing and promising for large-area and cost-effective film coating to industrial-scale PSCs. Here, we develop simple and scalable solution shearing (SS) and bar coating (BC) methods to coat all layers on large-area (10x10 cm²) substrate in FTO/c-TiO₂/mp-TiO₂/ CH₃NH₃PbI₃/Spiro-OMeTAD/Ag device structure, except the Ag electrode. All solution-sheared PSC exhibited a champion power conversion efficiency of 15.89% in the conational DMF/DMSO solvent. Whereas a very high PCE of 20.30% compared to the controlled spin-coated device (SC, 17.60%) was achieved from the large area sheared perovskite film in a green ACN/MA solvent. Similarly, a remarkable PCE of 18.50% was achieved for a device fabricated from a large-area perovskite film in a simpler and more compatible Bar-coating system. This strategy demonstrates the huge potential for module fabrication and future PSC commercialization.

Keywords: Perovskite solar cells, larger area film coating, meniscus-guided film coating, solution-shearing, bar-coating, power conversion efficiency

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Authors: Ayushi Arora

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Solar photocatalysis has the potential to treat drinking water in a sustainable and cost effective manner. According to WHO, there should not be any colony forming units (CFU) per 100 mL present in drinking water, and as per the Central Pollution Control Board (CPCB) of India, the bathing water should have less than 500 CFU/100 mL and the maximum permissible limit is 2500 CFU/100 mL. In this study, 8 water sources near our collaborators, Indian Institute of Technology, Kharagpur, India, were analysed, and it was found that 6 out of 8 sources of water had significant coliform count in them. Two of them were chosen to be treated by solar photocatalysis a) well water which had a count of 4800 CFU/100 mL for total coliforms and was used by people for drinking purposes, and b) pond water which had a count of 92000 CFU/100 mL for total coliforms and 3000 CFU/mL for E.Coli and was used by people for washing and bathing purposes. In this study, a semiconductor-semiconductor, composite BTO-TiO2-RMSG & TiO2-SiO2 were tested for their ability to be activated under solar light and to reduce Total Coliforms and E.Coli bacteria in real world contaminated water, and it was found that both catalysts were both able to reduce the total coliform count in water by 99.7% and 98.2 % in 2 hrs respectively. They have also shown promising results in reusability tests. This study demonstrates the ability of solar photocatalysis to be used in real world drinking water treatment and will promote future advancements in this field.

Keywords: sustainable water treatment, waterpurification technologies, water policies, water pollution and environmental engineering

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Authors: Rayhaneh Amooaghaie, Maryam Norouzi

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In this study, the effects of nTiO₂ on seed germination and growth of six plant species (wheat, soybean, tomato, canola, cucumber, and lettuce) were evaluated in petri dish (direct exposure) and in soil in a greenhouse experiment (soil exposure). Data demonstrate that under both culture conditions, low or mild concentrations of nTiO₂ either stimulated or had no effect on seed germination, root growth and vegetative biomass while high concentrations had an inhibitory effect. However, results showed that the impacts of nTiO₂ on plant growth in soil were partially consistent with those observed in pure culture. Based on both experiment sets, among above six species, lettuce and canola were the most susceptible and the most tolerant species to nTiO₂ toxicity. However, results revealed the impacts of nTiO₂ on plant growth in soil were less than petri dish exposure probability due to dilution in soil and complexation/aggregation of nTiO₂ that would lead to lower exposure of plants. The high concentrations of nTiO₂ caused significant reductions in fresh and dry weight of aerial parts and root and chlorophyll and carotenoids contents of all species which also coincided with further accumulation of malondialdehyde (MDA). These findings suggest that decreasing growth might be the result of an nTiO₂-induced oxidative stress and disturbance of photosynthesis systems.

Keywords: chlorophyll, lipid peroxidation, nano TiO₂, seed germination

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Authors: Zhao Bo

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The TiO2-Na2SO3 and SiO2-Na2SO3 nano-fluids were prepared using ultrasonic dispertion method without any surfactant addition to study the influence of nano-fluids on the mass transfer during forced sulfite oxidation in a thermostatic stirred tank, and the kinetic viscosity of nano-fluids was measured. The influence of temperature (30 ℃ ~ 50 ℃), solid loading of fine particle (0 Kg/m³~1.0 Kg/m³), stirring speed (50 r/min ~ 400 r/min), and particle size (10 nm~100 nm) on the average oxygen absorption rate were investigated in detail. Both TiO2 nano-particles and SiO2 nano-particles could remarkably improve the gas-liquid mass transfer. Oxygen absorption enhancement factor increases with the increase of solid loading of nano-particles to a critical value and then decreases with further increase of solid loading under 30℃. Oxygen absorption rate together with absorption enhancement factor increases with stirring speed. However, oxygen absorption enhancement factor decreases with the increase of temperature due to aggregation of nano-particles. Further inherent relationship between particle size, loading, surface area, viscosity, stirring speed, temperature, adsorption, desorption, and mass transfer was discussed in depth by analyzing the interaction mechanism.

Keywords: fine particles, nano-fluid, mass transfer enhancement, solid loading

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Authors: Fadimatou Ngounouno Yamgouota, Isaac Bertrand Gbambié Mbowoub, Ismaila Ngounounob

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Barium and titanium bearing biotite from alkaline trachyte of Upper Benue valley, Northern Cameroon is studied. The iron enrichment index of mica (average I.E.=0.40) is intermediate between annite and phlogopite. The biotite phenocrysts contain up to 6.2 wt. % BaO and 9.8 wt. % TiO2. The BaO content of electron-microprobe mica is positively correlated with the Al2O3, TiO2, and FeO contents, and negatively correlated with the SiO2, K2O, and MgO contents. Ba and Ti rich micas are generally found in in SiO2 deficient rocks, whereas Ba and Ti bearing mica in this study occur in silica-saturated rocks. Most of the phenocrysts analysed have deficiencies in their octahedral and interlayer sites. Deficiencies in the octahedral sites may arise from the Ti vacancy and partly the Ti tschermakite substitution. On the other hand, deficiencies in the interlayer-site are due to the replacement of K by Ba. The substitution mechanism in the Upper Benue valley mica is characterized by Ba + 2Ti + 3Al =(K + Na + Ca) + 3(Mg + Fe + Mn) + 3Si, with an excellent correlation coefficient. Biotite compositions from the Upper Benue valley area fall between the quartz-fayalite-magnetite (QFM) and nickel-nickel-oxide (NNO) oxygen fugacity buffers. All these show that Upper Benue valley mica with high Ba and Ti contents may be formed from magmas rich in these elements.

Keywords: Benue valley, trachyte, biotite, mineral chemistry, enrichment

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Authors: A. E. Kobryn

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We present both descriptive and predictive modeling of structural properties of blends of PCBM or organic-inorganic hybrid perovskites of the type CH3NH3PbX3 (X=Cl, Br, I) with P3HT, P3BT or squaraine SQ2 dye sensitizer, including adsorption on TiO2 clusters having rutile (110) surface. In our study, we use a methodology that allows computing the microscopic structure of blends on the nanometer scale and getting insight on miscibility of its components at various thermodynamic conditions. The methodology is based on the integral equation theory of molecular liquids in the reference interaction site representation/model (RISM) and uses the universal force field. Input parameters for RISM, such as optimized molecular geometries and charge distribution of interaction sites, are derived with the use of the density functional theory methods. To compare the diffusivity of the PCBM in binary blends with P3HT and P3BT, respectively, the study is complemented with MD simulation. A very good agreement with experiment and the reports of alternative modeling or simulation is observed for PCBM in P3HT system. The performance of P3BT with perovskites, however, seems as expected. The calculated nanoscale morphologies of blends of P3HT, P3BT or SQ2 with perovskites, including adsorption on TiO2, are all new and serve as an instrument in rational design of organic/hybrid photovoltaics. They are used in collaboration with experts who actually make prototypes or devices for practical applications.

Keywords: multiscale theory and modeling, nanoscale morphology, organic-inorganic halide perovskites, three dimensional distribution

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Authors: Ifeyinwa Ijeoma Obianyo, Luqman Adedeji Taiwo, Olugbenga O. Amu, Azikiwe Peter Onwualu

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Improving the durability of building materials saves maintenance costs, construction time, and energy. In this study, titanium dioxide coated conventional and non-conventional composites were produced, and the effects of titanium dioxide coatings were investigated. Conventional composites were produced using river sand and Portland cement, whereas non-conventional composites were produced by partially replacing river sand and Portland cement with quarry dust and rice husk ash. Water absorption and thickness swelling tests were conducted on the produced coated and non-coated block samples. A reduction in water absorption was observed in the coated composite samples when compared to the non-coated composite samples, and this is an indication of the improved durability of the samples coated with titanium dioxide. However, there was an increase in the thickness swelling of coatings on the coated block samples, but this increase has a slight influence on the compressive strength of the coated samples. The outcome of this study indicates that coating composite building blocks with titanium dioxide will improve theirdurability. Also, the site exposure experiments revealed the self-cleansing properties of TiO2-coated composite block samples, while the Rhodamine B discolouration test confirmed the photocatalytic features of TiO2-coated composite block samples.

Keywords: titanium dioxide, water absorption, durability, mechanical properties, building composite

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Authors: Ildiko Fekete-Kertesz, Jade Chaker, Sylvain Berthelot, Viktoria Feigl, Monika Molnar, Lidia Favier

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There has been growing concern about emerging micropollutants in recent years, because of the possible environmental and health risk posed by these substances, which are released into the environment as a consequence of anthropogenic activities. Among them pharmaceuticals are currently not considered under water quality regulations; however, their potential effect on the environment have become more frequent in recent years. Due to the fact that these compounds can be detected in natural water matrices, it can be concluded, that the currently applied water treatment processes are not efficient enough for their effective elimination. To date, advanced oxidation processes (AOPs) are considered as highly competitive water treatment technologies for the removal of those organic micropollutants not treatable by conventional techniques due to their high chemical stability and/or low biodegradability. AOPs such as (photo)chemical oxidation and heterogeneous photocatalysis have proven their potential in degrading harmful organic compounds from aqueous matrices. However, some of these technologies generate reaction by-products, which can even be more toxic to aquatic organisms than the parent compounds. Thus, target compound removal does not necessarily result in the removal of toxicity. Therefore, to evaluate process efficiency the determination of the toxicity and ecotoxicity of the reaction intermediates is crucial to estimate the environmental risk of such techniques. In this context, the present study investigates the effectiveness of TiO2 assisted photodegradation for the removal of emerging water contaminants. Two drugs named losartan (used in high blood pressure medication) and levetiracetam (used to treat epilepsy) were considered in this work. The photocatalytic reactions were carried out with a commercial catalyst usually employed in photocatalysis. Moreover, the toxicity of the by-products generated during the process was assessed with various ecotoxicological methods applying aquatic test organisms from different trophic levels. A series of experiments were performed to evaluate the toxicity of untreated and treated solutions applying the Aliivibrio fischeri bioluminescence inhibition test, the Tetrahymena pyriformis proliferation inhibition test, the Daphnia magna lethality and immobilization tests and the Lemna minor growth inhibition test. The applied ecotoxicological methodology indicated sensitively the toxic effects of the treated and untreated water samples, hence the applied test battery is suitable for the ecotoxicological characterization of TiO2 based photocatalytic water treatment technologies and the indication of the formation of toxic by-products from the parent chemical compounds. Obtained results clearly showed that the TiO2 assisted photodegradation was more efficient in the elimination of losartan than levetiracetam. It was also observed that the treated levetiracetam solutions had more severe effect on the applied test organisms. A possible explanation would be the production of levetiracetam by-products, which are more toxic than the parent compound. The increased toxicity and the risk of formation of toxic metabolites represent one possible limitation to the implementation of photocatalytic treatment using TiO2 for the removal of losartan and levetiracetam. Our results proved that, the battery of ecotoxicity tests used in this work can be a promising investigation tool for the environmental risk assessment of photocatalytic processes.

Keywords: aquatic micropollutants, ecotoxicology, nano titanium dioxide, photocatalysis, water treatment

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Authors: Renata De Toledo Cintra, Bruno Ramos, Douglas Gouvêa

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There is a huge global concern due to the emission of greenhouse gases, consequent environmental problems, and the increase in the average temperature of the planet, caused mainly by fossil fuels, petroleum derivatives represent a big part. One of the main greenhouse gases, in terms of volume, is CO₂. Recovering a part of this product through chemical reactions that use sunlight as an energy source and even producing renewable fuel (such as ethane, methane, ethanol, among others) is a great opportunity. The process of artificial photosynthesis, through the conversion of CO₂ and H₂O into organic products and oxygen using a metallic oxide catalyst, and incidence of sunlight, is one of the promising solutions. Therefore, this research is of great relevance. To this reaction take place efficiently, an optimized reactor was developed through simulation and prior analysis so that the geometry of the internal channel is an efficient route and allows the reaction to happen, in a controlled and optimized way, in flow continuously and offering the least possible resistance. The design of this reactor prototype can be made in different materials, such as polymers, ceramics and metals, and made through different processes, such as additive manufacturing (3D printer), CNC, among others. To carry out the photocatalysis in the reactors, different types of catalysts will be used, such as ZnO deposited by spray pyrolysis in the lighting window, probably modified ZnO, TiO₂ and modified TiO₂, among others, aiming to increase the production of organic molecules, with the lowest possible energy.

Keywords: artificial photosynthesis, CO₂ reduction, photocatalysis, photoreactor design, 3D printed reactors, solar fuels

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