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Cardiovascular diseases are considered one of the leading causes of premature mortality of patients worldwide. Therefore, rapid diagnosis of these diseases is crucial to ensure the patient's survival. During a heart attack or severe muscle damage, myoglobin is rapidly released in the body to constitute itself as a precise biomarker of acute myocardial infarction. Thus, we described the photoelectrochemical immunosensor development to detect myoglobin. It was based on fluorine-doped tin oxide modified with CdSeS/ZnSe quantum dots and barium titanate (BTO), designated as CdSeS/ZnSQDS/BTO. It was characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX), transmission electron microscopy (TEM), X-ray diffraction (XRD), electrochemical impedance spectroscopy (EIS), and amperometry. The anodic photocurrent at the potential of 0 V (vs. Ag/AgCl) and pH 7.4 was found linearly related to the myoglobin (Mb) concentration from 0.01 to 1000 ng mL-1. Furthermore, the immunosensor showed an average recovery rate of 95.7-110.7% for the determination of myoglobin.

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Perovskite have had a great impact on the solid-state physics world in the last decade not only achieving great success in photovoltaics but, more recently, also in the implementation of other optoelectronic devices. One of the main obstacles for the adoption of Pb-based perovskite technologies are the high amounts of Pb needed in the conventional preparation methods. Here we present for the first time a detailed analysis of the photophysical and photoelectrochemical properties of CsPbBr3 films directly grown on fluorine-doped tin oxide (FTO) coated glass through a novel technique based in the electrodeposition of PbO2 as CsPbBr3 precursor. This technique allows to save up to 90 % of the Pb used compared to traditional methods and can be scalable compared with the commonly used spin-coating process. The low temperature analysis of their photoluminescence spectra, performed in both steady state and time dependence, revealed a strong interaction between electrons and longitudinal optical (LO) phonons dominant at high temperatures. On the other hand, the electrochemical and photoelectrochemical analysis proves that CsPbBr3 prepared using this new method has state-of-the-art features, showing a p-type behavior under depletion regime. This is also confirmed by photoelectrochemical measurements using p-benzoquinone as target molecule. These results prove that the proposed method can be used to produce excellent CsPbBr3 films, saving much of the lead waste.

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Solar radiation is a renewable and clean energy source used in photoelectrochemical cells (PEC) to produce hydrogen gas as a powerful alternative to carbon-based fuels. Semiconductors play a vital role in this approach, absorbing the incident solar photons and converting them into electrons and holes. The hydrogen evolution reaction (HER) occurs in the interface of the p-type semiconductor that works as a photocathode in the PEC. Cu-chalcopyrites such as Cu(In, Ga)(Se,S)2 (CIGS) and CuIn(Se,S)2 (CIS) present excellent semiconductor characteristics for this purpose, but drawbacks as charge recombination, deficient chemical stability, and slow charge transfer kinetics, demanding improvements like the use of n-type buffer layer, a protective layer, and a cocatalyst material. Concerning the last one, platinum (Pt) is the most efficient and stable material, but the high price due to its scarcity imposes the search for inexpensive and abundant alternative cocatalyst. The present Minireview highlighted the use of metal alloys, transition metal chalcogenides, and inorganic carbon-based nanostructures as efficient alternative cocatalysts for HER in PEC.

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A little-studied p-type ternary oxide semiconductor, copper(I) tungstate (Cu2WO4), was assessed by a combined theoretical/experimental approach. A detailed computational study was performed to solve the long-standing debate on the space group of Cu2WO4, which was determined to be triclinic P1. Cu2WO4 was synthesized by a time-efficient, arc-melting method, and the crystalline reddish particulate product showed broad-band absorption in the UV-visible spectral region, thermal stability up to ∼260 °C, and cathodic photoelectrochemical activity. Controlled thermal oxidation of copper from the Cu(I) to Cu(II) oxidation state showed that the crystal lattice could accommodate Cu2+ cations up to ∼260 °C, beyond which the compound was converted to CuO and CuWO4. This process was monitored by powder X-ray diffraction and X-ray photoelectron spectroscopy. The electronic band structure of Cu2WO4 was contrasted with that of the Cu(II) counterpart, CuWO4 using spin-polarized density functional theory (DFT). Finally, the compound Cu2WO4 was determined to have a high-lying (negative potential) conduction band edge underlining its promise for driving energetic photoredox reactions.

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Cobalt porphyrins have emerged as promising catalysts for electrochemical and photoelectrochemical applications because of their good performance, low cost and the abundance of cobalt in the earth. Herein, a negatively charged porphyrin meso-tetra-(4-sulfonatophenyl)-porphin (TPPS) was immobilized in polypyrrole (PPy) during the electro-polymerization, and then it was metallized with cobalt to obtain meso-tetra-(4-sulfonatophenyl)-porphyrinato cobalt (II) (CoTPPS) as a dopant in PPy. The coatings were evaluated as photoelectrodes towards thiosulfate oxidation and oxygen reduction. For comparison purposes, the photoelectrochemical behavior of ClO4--doped polypyrrole films was also evaluated. Characterizations by chronoamperometry, UV-Vis spectroscopy and Raman spectroscopy showed that polypyrrole is stable under anodic and cathodic conditions, but CoTPPS and TPPS immobilized in PPy are degraded during the anodic process. Thus, decreases in photocurrent of up to 87% and 97% for CoTPPS-doped PPy and TPPS-doped PPy were observed after a 30-min chronoamperometry test. On the other hand, good stability of CoTPPS and TPPS immobilized in PPy was observed during photoelectrochemical oxygen reduction, which was reflected in almost constant photocurrents obtained by chronoamperometry. These findings are relevant to understanding the role of CoTPPS as a catalyst or pre-catalyst in photoelectrochemical applications such as water splitting. In addition, these results could pave the way for further research to include CoTPPS-doped PPy in the design of novel photocathodes.

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The freshwater scarcity and increasing energy demand are two challenging global issues. Herein, we propose a new route for desalination, self-sustained visible-light-driven electrochemical redox desalination. We propose a novel device architecture involving internal integration of a quasi-solid-state dye-sensitized solar cell and continuous redox-flow desalination units with a bifunctional platinized-graphite-paper electrode. Both the solar cell and redox-flow desalination units are integrated using the bifunctional electrode with one side facing the solar cell operating as a positive electrode and the other side facing the redox-flow desalination unit operating as a negative electrode. The solar cell contains a gel-based tri-iodide/iodide redox couple sandwiched between an N719 dye-modified photoanode and cathode. In contrast, the redox-flow desalination consists of re-circulating ferro/ferricyanide redox couple sandwiched between the anode and cathode with two salt streams located between these electrodes. The performances of bifunctional electrodes in both redox couples were thoroughly investigated by electrochemical characterization. The brackish feed can be continuously desalted to the freshwater level by utilizing visible light illumination. As a device, this architecture combines energy conversion and water desalination. This concept bypasses the need for electrical energy consumption for desalination, which provides a novel structural design using photodesalination to facilitate the development of self-sustained solar desalination technologies.

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The article describes a method for determination of tannic acid in extracts of medicinal plants. Tannic acid (TA) is an antioxidant and has anticancer and antimicrobial properties. Titanium dioxide nanoparticles (TiO2) were co-sensitized with 5-methylphenazinium methosulfate (PMS) and carboxy-functionalized cadmium telluride quantum dots (CdTe QDs), and immobilized on a fluorine-doped tin oxide electrode. The surface morphology and electrochemical properties of the modified electrode were investigated by scanning electron microscopy and amperometry, respectively. A composite consisting of TiO2, PMS and CdTe QDs in a nafion film has a response to TA under LED light higher than that observed for each separate component. Under optimized experimental conditions and at an applied voltage of +0.4 V vs Ag/AgCl, the photoelectrochemical sensor has a linear response in the 0.2 to 200 µmol L-1 TA concentration range and a detection limit of 60 nmol L-1. The sensor was successfully applied to the determination of TA in spiked extracts from three medicinal plants, with recovery values between 98.3 and 103.9 %. Graphical abstract Schematic diagram for photoelectrochemical detection of tannic acid based on a fluorine doped tin oxide electrode modified with titanium oxide, 5-methylphenazinium methosulfate and carboxy-functionalized cadmium telluride quantum dots.

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Using dual-photoelectrode photoelectrochemical (PEC) devices based on earth-abundant metal oxides for unbiased water splitting is an attractive means of producing green H2 fuel, but is challenging, owing to low photovoltages generated by PEC cells. This problem can be solved by coupling n-type BiVO4 with n-type Bi4 V2 O11 to create a virtual p/n junction due to the formation of a hole-inversion layer at the semiconductor interface. Thus, photoelectrodes with high photovoltage outputs were synthesized. The photoelectrodes exhibited features of p- and n-type semiconductors when illuminated under an applied bias, suggesting their use as photoanode and photocathode in a dual-photoelectrode PEC cell. This concept was proved by connecting a 1 mol % W-doped BiVO4 /Bi4 V2 O11 photoanode with an undoped BiVO4 /Bi4 V2 O11 photocathode, which produced a high photovoltage of 1.54 V, sufficient to drive stand-alone water splitting with 0.95 % efficiency.

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Ta3 N5 is a promising photoelectrode for solar hydrogen production; however, to date pristine Ta3 N5 electrodes without loading co-catalysts have presented limited photoelectrochemical (PEC) performance. In particular, large external biasing has been required to run water oxidation, the origin of which is investigated herein. Ta3 N5 nanotubes (NTs) prepared by nitridation were characterized by a wide range of techniques. The bandgap was confirmed by a novel PEC technique. Nondestructive synchrotron-excited XPS has shown the presence of reduced Ta species deeper in the Ta3 N5 surface. Lower photocurrent and transient spikes that were intense at lower applied biasing were observed under water oxidation; however, spikes were inhibited in the presence of a sacrificial agent and photocurrent was improved even at low biasing. It was observed for the first time that the lower PEC performance under water oxidation can be attributed to the presence of interband trapping states associated with pristine Ta3 N5 NTs/electrolyte junction. These states correspond to the structural defects in Ta3 N5 , devastate PEC performance, and present the necessity to apply higher biasing. The key to circumvent them is to use a sacrificial agent in the electrolyte or to load a suitable co-catalyst to avoid hole accumulation under water oxidation, thereby improving the phootocurrent. The findings on the interband states could also provide guidance for the investigation of PEC properties of new types of semiconducting devices.

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TiO2 and TiO2/WO3 electrodes, irradiated by a solar simulator in configurations for heterogeneous photocatalysis (HP) and electrochemically-assisted HP (EHP), were used to remediate aqueous solutions containing 10 mg L(-1) (34 µmol L(-1)) of 17-α-ethinylestradiol (EE2), active component of most oral contraceptives. The photocatalysts consisted of 4.5 µm thick porous films of TiO2 and TiO2/WO3 (molar ratio W/Ti of 12%) deposited on transparent electrodes from aqueous suspensions of TiO2 particles and WO3 precursors, followed by thermal treatment at 450 (°)C. First, an energy diagram was organized with photoelectrochemical and UV-Vis absorption spectroscopy data and revealed that EE2 could be directly oxidized by the photogenerated holes at the semiconductor surfaces, considering the relative HOMO level for EE2 and the semiconductor valence band edges. Also, for the irradiated hybrid photocatalyst, electrons in TiO2 should be transferred to WO3 conduction band, while holes move toward TiO2 valence band, improving charge separation. The remediated EE2 solutions were analyzed by fluorescence, HPLC and total organic carbon measurements. As expected from the energy diagram, both photocatalysts promoted the EE2 oxidation in HP configuration; after 4 h, the EE2 concentration decayed to 6.2 mg L(-1) (35% of EE2 removal) with irradiated TiO2 while TiO2/WO3 electrode resulted in 45% EE2 removal. A higher performance was achieved in EHP systems, when a Pt wire was introduced as a counter-electrode and the photoelectrodes were biased at +0.7 V; then, the EE2 removal corresponded to 48 and 54% for the TiO2 and TiO2/WO3, respectively. The hybrid TiO2/WO3, when compared to TiO2 electrode, exhibited enhanced sunlight harvesting and improved separation of photogenerated charge carriers, resulting in higher performance for removing this contaminant of emerging concern from aqueous solution.

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