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Three metal-organic framework (MOF)-based photoanodes were prepared by deposition on TiO2 nanotubes using Ti as substrate (Ti/TiO2NT): i) Ti/TiO2NT-Au@ZIF-8, ii) Ti/TiO2NT-Ru3(BTC)2, iii) Ti/TiO2NT-UiO-66(Zr)NH2. These photoanodes were characterized by FEG-SEM, EDX and DRX. The analyses showed a successful modification and a high homogeneity of the different MOFs on the Ti/TiO2NT surface. The photoanodes were studied in the degradation of Contaminants of Emerging Concern (CECs) in a spiked secondary effluent from a Municipal Wastewater Treatment Plant (MWWTP). Sodium diclofenac (DCF), sulfamethazine (SMT) and carbamazepine (CBZ) were used as CECs at low concentration (200 µg/L each CEC). The samples were preconcentrated using Solid Phase Extraction (SPE) and analyzed by a HPLC-DAD system. The MOF-based photoanodes exhibited a high photoelectrochemical (PEC) activity towards the oxidation of CECs, achieving up to 50%, 70% and 80% of removal using Ti/TiO2NT-Au@ZIF-8, Ti/TiO2NT-UiO-66(Zr)NH2, Ti/TiO2NT-Ru3(BTC), respectively. The influence of the generation of hydroxyl radical was then studied. The results indicate that PEC degradation using Ti/TiO2NT-Ru3(BTC)2 and Ti/TiO2NT-UiO-66(Zr)NH2 is more affected by the concentration of the radical.

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The electrophoretic deposition of titanium dioxide (TiO2) nanoparticles (Degussa P25) onto a boron-doped diamond (BDD) substrate was carried out to produce a photoanode (TiO2/BDD) to apply in the degradation and mineralization of sodium diclofenac (DCF-Na) in an aqueous medium using photoelectrocatalysis (PEC). This study was divided into three stages: i) photoanode production through electrophoretic deposition using three suspensions (1.25%, 2.5%, 5.0% w/v) of TiO2 nanoparticles, applying 4.8 V for 15 and 20 s; ii) characterization of the TiO2/BDD photoanode using scanning electron microscopy and cyclic voltammetry response with the [Fe(CN)6]3-/4- redox system; iii) degradation of DCF-Na (25 mg L-1) through electrochemical oxidation (EO) on BDD and PEC on TiO2/BDD under dark and UVC-light conditions. The degradation of DCF-Na was evaluated using high-performance liquid chromatography and UV-Vis spectroscopy, and its mineralization measured using total organic carbon and chemical oxygen demand. The results showed that after 2 h, DCF-Na degradation and mineralization reached 98.5% and 80.1%, respectively, through PEC on the TiO2/BDD photoanode at 2.2 mA cm-2 under UVC illumination, while through EO on BDD applying 4.4 mA cm-2, degradation and mineralization reached 85.6% and 76.1%, respectively. This difference occurred because of the optimal electrophoretic formation of a TiO2 film with a 9.17 µm thickness on the BDD (2.5% w/v TiO2, time 15 s, 4.8 V), which improved the electrocatalysis and oxidative capacity of the TiO2/BDD photoanode. Additionally, PEC showed a lower specific energy consumption (1.55 kWh m-3). Thus, the use of nanostructured TiO2 films deposited on BDD is an innovative photoanode alternative for the photoelectrocatalytic degradation of DCF-Na, which substantially improves the degradation capacity of bare BDD.

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The construction of a photoanode with several layers of titanium oxysulfate as a precursor to form titanium dioxide-TiO2 on boron doped diamond-BDD (TiO2/BDD), and its application for the photoelectro-degradation of glyphosate in aqueous medium are presented. The study was divided into three stages: i) optimization of the number of layers of the TiO2 precursor to modify BDD using a novel method combining Sol-gel/Spin-Coating; ii) characterization of the TiO2/BDD electrodes, by scanning electron microscopy-SEM, dispersive energy spectroscopy-EDX, Ray diffraction-XRD, contact angle, and electrochemical response by cyclic voltammetry using [Fe(CN)6]3-/4- system; iii) degradation of glyphosate (50 mg L-1) by electrochemical oxidation on BDD and photoelectrocatalysis on TiO2/BDD in dark and UV-light conditions, at different current densities, for 5 h. The glyphosate degradation and mineralization were evaluated by High-Performance Liquid Chromatography, Total Organic Carbon, Chemical Oxygen Demand and inorganic-ions concentration (NO3-, PO43-, and NH4+). Also, the aminomethylphosphonic acid-AMPA was quantified by HPLC, as a degradation intermediate. Using five layers of the TiO2 precursor, in the construction of TiO2/BDD photoanode, and a lower contact angle, greater photoelectrocatalysis against the [Fe(CN)6]3-/4- redox system and better degradation of glyphosate compared to BDD without modification were achieved. The formation of TiO2 nanoparticles (14.79 ± 3.43 nm) in anatase phase on BDD was verified by SEM and XRD. Additionally, glyphosate degradation and mineralization were 2.3 times faster by photoelectrocatalysis on TiO2/BDD, relative to BDD, at 3 mA cm-2 and UV-light. Thus, the presence of TiO2 on BDD increases the rate and efficiency of glyphosate degradation with respect to electrochemical oxidation on BDD.

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Currently, CO2 emission is the main cause of climate change and its various related environmental impacts. Therefore, we have as a prime the development of clean sources of energy. The hydrogen economy is very attractive in this regard, however, when generated from the methane reform, there are also large-scale CO2 emissions. Thus, this research aims to develop and characterize bismuth and iron niobate-based photoanodes for hydrogen production via water photoelectrolysis. Bi2FexNbO7 films were synthesized by the sol-gel method and deposited on FTO coated glass plates by dip-coating technique. The influence of heat treatment (400, 500 and 600°C) and amount of iron on the structure (Bi2FexNbO7, x = 0, 0.8, 1, 1.2) were evaluated. Optical, structural and morphological properties were performed, as well as photoanode efficiency in photocurrent assays. The results indicate that the increase of temperature as well as the amount of iron leads to a higher absorption capacity and hence to lower band gap values. Regarding the structural properties, it was possible to observe the BFNO phase in the samples treated at 500 and 600°C. The films heat-treated at 400°C had a heterogeneous texture and a good covering. At 600°C there were some cracks in films surface. Therefore, samples with more iron and treated at 400°C showed better responses in photocurrent assays. It can be concluded that bismuth-iron niobate has a great potential to be applied in photoelectrolysis hydrogen production.

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In this work, commercially available Polymethyl-meta-acrylate (PMMA) spectroscopy cells were modified on the external walls with films of TiO2, Ti4O7 or TiO2/Ti4O7 mixtures. Film characterization was carried out using SEM and UV-vis spectroscopy. The results of photocatalytic (PC), electro-oxidation (EO), and photoelectrochemical (PEC) experiments on the decolorization of a methyl orange (MO) model dye solution showed that while anatase provides better photocatalytic properties and the partially reduced Ti4O7 larger electronic conductivity, the TiO2/Ti4O7 composite film behaves as a semiconductor substrate that combines the advantages of both materials (for PEC experiments for instance, decolorization values for the model dye solution using TiO2, Ti4O7 and a TiO2/Ti4O7 mixed film, corresponded to 35%, 46% and 53%, respectively). In order to test this film as an effective photoanode material in a 3-D type reactor for water treatment processes, a TiO2/Ti4O7 modified PMMA spectroscopy cell was inserted in an activated carbon (AC) bed so that the semiconductor material could be illuminated using an external UV source positioned inside the PMMA cell. The connected AC particles that were previously saturated with MO dye were used as cathode sites for the oxygen reduction reaction so that the photoelectrochemical reactions that take place in the anode could be complemented with coupled electro-Fenton processes in the cathode. As expected, the combination resulted in an effective decolorization of the dye solution that results from a complex combination of processes. The experimental decolorization data was successfully fitted to a pseudo-first order kinetic model so that a deeper understanding of the contribution of each process in the reactor could be obtained.

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In recent decades, there has been an increase in the research for the development and improvement of dye sensitized solar cells (DSSCs), owing to their singular advantages such as greater efficiency in energy conversion and overall performance in adverse environmental conditions. Therefore, work is carried out to enhance the energy efficiency of the components of the DSSCs: photoanode, counter-electrode, electrolyte, and dye sensitizer layer. Electrospun nanofibers in particular, have showed to be a novel alternative as components in DSSCs, mainly for energy conversion and as collector materials due in part to their tridimensional structure, high contact surface area and conductivity. Moreover, the incorporation of metallic compounds into nanofibers is advantageously employed in the electrospinning technique, owing to their conductivity and optical properties. Therefore, the present work consists of a detailed recompilation of the use of electrospun nanofibers loaded with metallic compounds and their application in DSSCs. The functionality of the components of DSSCs, parameters and experimental conditions of electrospinning, such as the intrinsic aspects in the polymer solution, are discussed and applied to the photoanode, counter-electrode and electrolyte of the DSSC. Lastly, the use of the electrospinning technique in combination with the use of metallic compounds could provide a great approach for the developing of DSSCs, with superior efficiency, high stability and durability.

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ABSTRACT The efficiency of nanostructures for photoelectrochemical water-splitting is fundamentally governed by the capability of the surface to sustain the reaction without electron trapping or recombination by photogenerated holes. This brief review will summarize the latest progress on hematite, designed with columnar morphology via chemical synthesis, for photoelectrochemical cell application. The columnar morphology efficiently minimizes the number of defects, grain boundaries, and surface traps normally present on the planar morphology. The major drawback related to hole diffusion through the solid/liquid interface was addressed by using high annealing temperature combined with dopant addition. A critical view and depth of understanding of these two parameters were discussed focusing on the molecular oxygen evolution mechanism from the sunlight-driven water oxidation reaction.

RESUMO

Molecular Co4 O4 cubane water oxidation catalysts were combined with BiVO4 electrodes for photoelectrochemical (PEC) water splitting. The results show that tuning the substituent groups on cobalt cubane allows the PEC properties of the final molecular catalyst/BiVO4 hybrid photoanodes to be tailored. Upon loading a new cubane complex featuring alkoxy carboxylato bridging ligands (1 h) on BiVO4 , an AM 1.5G photocurrent density of 5 mA cm-2 at 1.23 V vs. RHE for water oxidation was obtained, the highest photocurrent for undoped BiVO4 photoanodes. A high solar-energy conversion efficiency of 1.84 % was obtained for the integrated photoanode, a sixfold enhancement over that of unmodified BiVO4 . These results and the high surface charge separation efficiency support the role of surface-modified molecular catalysts in improving PEC performance and demonstrate the potential of molecule/semiconductor hybrids for efficient artificial photosynthesis.