Roxana Arce

The growing deployment of green hydrogen technologies is increasing pressure on freshwater resources, motivating the exploration of alternative water sources that do not compete with human consumption. In this work, the direct use of untreated produced water from the Shushufindi 78 oil well (Ecuador) as an electrolyte for the hydrogen evolution reaction (HER) was experimentally evaluated. A comprehensive physicochemical characterization combined with electrochemical techniques, electrochemical impedance spectroscopy (EIS), and gas chromatography (GC-TCD) was performed to correlate electrolyte composition with electrochemical performance. Despite the high salinity and complex composition of the electrolyte, hydrogen production was achieved without pretreatment. Quantitative GC-TCD analysis yielded 10.29 µmol of H₂ after 4 h of electrolysis under non-optimized laboratory conditions, corresponding to a faradaic efficiency of 43.8%. These results demonstrate the feasibility of direct hydrogen generation from untreated produced water under realistic operating conditions. Additional experiments conducted in a membrane separated H-type electrolyzer evaluated mixtures of produced water and KOH, the electrolyte commonly employed in alkaline water electrolysis. Hydrogen production increased significantly under alkaline conditions, with the PW 10% + KOH 90% electrolyte exhibiting the highest hydrogen yield and faradaic efficiency among the investigated systems. Electrochemical impedance spectroscopy revealed that KOH addition reduced solution resistance and improved ionic transport, while differences in interfacial behavior were observed depending on electrolyte composition. The combined electrochemical and chromatographic results demonstrate that untreated produced water can be directly utilized for hydrogen production and can also be partially integrated into alkaline electrolysis systems without compromising electrochemical performance. These findings highlight the potential of produced water as a non-conventional water resource for sustainable hydrogen generation and industrial wastewater valorization.

The growing deployment of green hydrogen technologies is increasing pressure on freshwater resources, motivating the exploration of alternative water sources that do not compete with human consumption. In this work, the direct use of untreated produced water from the Shushufindi 78 oil well (Ecuador) as an electrolyte for the hydrogen evolution reaction (HER) was experimentally evaluated. A comprehensive physicochemical characterization (ICP-OES, anions, BTEX), combined with electrochemical techniques (cyclic voltammetry, Tafel analysis, electrochemical impedance spectroscopy) and gas chromatography, was performed to correlate electrolyte composition with electrochemical performance. Despite the high salinity (~52 ± 5 g·kg⁻¹) and complex matrix composition, hydrogen production was achieved without pretreatment. Absolute hydrogen quantification yielded 10.29 µmol after 4 h of electrolysis, corresponding to a Faradaic efficiency of 43.8% and an electrical efficiency of 54.1% under non-optimized conditions. Comparative gas chromatography experiments using different electrolyte compositions revealed that alkaline systems, particularly mixtures of produced water with KOH, enhance hydrogen production, as evidenced by increased chromatographic peak areas. Impedance analysis showed reduced ohmic losses with KOH addition, while mineral scaling (CaCO₃ and Mg (OH)₂) increased interfacial resistance and reduced catalytic activity. These results demonstrate the feasibility of using produced water as an electrolyte for hydrogen production, highlighting the critical role of electrolyte composition within a circular economy framework.

The rhenium(I) tricarbonyl complex fac-[Re(CO)₃(5,6-epoxy-5,6-dihydro-1,10-phenanthroline)Br] (ReL) has previously demonstrated promising luminescent properties, enabling its direct application as a probe for walled cells such as Candida albicans and Salmonella enterica. In this new study, we present a significantly expanded and comprehensive characterization of ReL, incorporating a wide range of experimental and computational techniques not previously reported. These include variable-temperature ¹H and ¹³C NMR spectroscopy, CH-COSY, single-crystal X-ray diffraction, Hirshfeld surface analysis, DFT calculations, Fukui functions, non-covalent interaction (NCI) indices, and electrochemical profiling. Structural analysis confirmed a pseudo-octahedral geometry with the bromide ligand positioned cis to the epoxy group. NMR data revealed the coexistence of cis and trans isomers in solution, with the trans form being slightly more stable. DFT calculations and aromaticity descriptors indicated minimal electronic differences between isomers, supporting their unified treatment in subsequent analyses. Electrochemical studies revealed two oxidation and two reduction events, consistent with ECE and EEC mechanisms, including a Re(I) → Re(0) transition at −1.50 V vs. SCE. Theoretical redox potentials showed strong agreement with experimental data. Biological assays revealed a dose-dependent cytotoxic effect on HeLa cells, contrasting with previously reported low toxicity in microbial systems. These findings, combined with ReL’s luminescent and antimicrobial properties, underscore its multifunctional nature and highlight its potential as a bioactive and imaging agent for advanced therapeutic and microbiological applications.

Metal-free aminobenzoic acid-derived Schiff bases are attractive antimicrobial leads because their azomethine (–C=N–) functionality enables tunable electronic properties and target engagement. We investigated whether halogenation on the phenolic ring would modulate the redox behavior and enhance antibacterial potency, and hypothesized that heavier halogens would favorably tune physicochemical and electronic descriptors. We synthesized three derivatives (SB-3/Cl, SB-4/Br, and SB-5/I) and confirmed their structures using FTIR, ¹H- and ¹³C-NMR, UV-Vis, and HRMS. For SB-5, single-crystal X-ray diffraction and Hirshfeld analysis verified the intramolecular O–H⋯N hydrogen bond and key packing contacts. Cyclic voltammetry revealed an irreversible oxidation (aminobenzoic ring) and, for the halogenated series, a reversible reduction associated with the imine; peak positions and reversibility trends are consistent with halogen electronic effects and DFT-based MEP/LHS descriptors. Antimicrobial testing showed that SB-5 was selectively potent against Gram-positive aerobes, with low-to-mid micromolar MICs across the panel. Among anaerobes, activity was more substantial: Clostridioides difficile was inhibited at 0.1 µM, and SB-3/SB-5 reduced its sporulation at sub-MICs, while Blautia coccoides was highly susceptible (MIC 0.01 µM). No activity was detected against Gram-negative bacteria at the tested concentrations. In the fungal assay, Botrytis cinerea displayed only a transient fungistatic response without complete growth inhibition. In mammalian cells (HeLa), the compounds displayed clear concentration-dependent behavior. Overall, halogenation, particularly iodination, emerges as a powerful tool to couple redox tuning with selective Gram-positive activity and a favorable cellular tolerance window, nominating SB-5 as a promising scaffold for further antimicrobial optimization.

A new Schiff base, (E)-2-(((1,10-phenanthrolin-5-yl)imino)methyl)-4,6-di-tert-butylphenol (Fen-IHB), was designed to incorporate an intramolecular hydrogen bond (IHB) between the phenolic OH and the azomethine nitrogen with the goal of modulating its physicochemical and biological properties. Fen-IHB was synthesized by condensation of 5-amino-1,10-phenanthroline with 3,5-di-tert-butyl-2-hydroxybenzaldehyde and exhaustively characterized by HR-ESI-MS, FTIR, 1D/2D NMR (¹H, ¹³C, DEPT-45, HH-COSY, CH-COSY, D₂O exchange), and UV–Vis spectroscopy. Cyclic voltammetry in anhydrous CH₃CN revealed a single irreversible cathodic peak at −1.43 V (vs. Ag/Ag⁺), which is consistent with the intramolecular reductive coupling of the azomethine moiety. Density functional theory (DFT) calculations, including MEP mapping, Fukui functions, dual descriptor analysis, and Fukui potentials with dual descriptor potential, identified the exocyclic azomethine carbon as the principal nucleophilic site and the phenolic ring (hydroxyl oxygen and adjacent carbons) as the main electrophilic region. Noncovalent interaction (NCI) analysis further confirmed the strength and geometry of the intramolecular hydrogen bond (IHB). In vitro antimicrobial assays indicated that Fen-IHB was inactive against Gram-negative facultative anaerobes (Salmonella enterica serovar Typhimurium and Typhi, Escherichia coli) and strictly anaerobic Gram-positive species (Clostridioides difficile, Roseburia inulinivorans, Blautia coccoides), as any growth inhibition was indistinguishable from the DMSO control. Conversely, Fen-IHB displayed measurable activity against Gram-positive aerobes and aerotolerant anaerobes, including Bacillus subtilis, Streptococcus pyogenes, Enterococcus faecalis, Staphylococcus aureus, and Staphylococcus haemolyticus. Overall, these comprehensive characterization results confirm the distinctive chemical and electronic properties of Fen-IHB, underlining the crucial role of the intramolecular hydrogen bond and electronic descriptors in defining its reactivity profile and selective biological activity.

This study focuses on the design and optimization of a monopolar electrode configuration for the hybrid electrochemical treatment of real washing machine wastewater. A combined electrocoagulation (EC) and electro-oxidation (EO) system was optimized to maximize pollutant removal efficiency while minimizing energy consumption. The monopolar setup employed mixed metal oxide (MMO) and aluminum anodes, along with a stainless steel cathode, operating under controlled conditions with sodium chloride as the supporting electrolyte. An applied current density of 15 mA cm⁻² achieved 90% chemical oxygen demand (COD) removal, 98% surfactant degradation, complete turbidity reduction within 120 min, and pH stabilization near 8. Additionally, electrochemical disinfection achieved <2 MPN/100 mL, with no detectable phenols and the presence of organic anions such as oxalate and acetate. These results demonstrate the effectiveness of an optimized monopolar EC–EO system as a cost-efficient and sustainable strategy for wastewater treatment and potential water reuse. Further studies should focus on refining energy consumption and monitoring reaction by-products to enhance large-scale applicability.

Transition metal oxides are a great alternative to less expensive hydrogen evolution reaction (HER) catalysts. However, the lack of conductivity of these materials requires a conductor material to support them and improve the activity toward HER. On the other hand, carbon paste electrodes result in a versatile and cheap electrode with good activity and conductivity in electrocatalytic hydrogen production, especially when the carbonaceous material is agglomerated with ionic liquids. In the present work, an electrode composed of multi-walled carbon nanotubes (MWCNTs) and cobalt ferrite oxide (CoFe₂O₄) was prepared. These compounds were included on an electrode agglomerated with the ionic liquid N-octylpyridinium hexafluorophosphate (IL) to obtain the modified CoFe₂O₄/MWCNTs/IL nanocomposite electrode. To evaluate the behavior of each metal of the bimetallic oxide, this compound was compared to the behavior of MWCNTs/IL where a single monometallic iron or cobalt oxides were included (i.e., α-Fe₂O₃/MWCNTs/IL and Co₃O₄/MWCNTs/IL). The synthesis of the oxides has been characterized by X-ray diffraction (XRD), RAMAN spectroscopy, and field emission scanning electronic microscopy (FE-SEM), corroborating the nanometric character and the structure of the compounds. The CoFe₂O₄/MWCNTs/IL nanocomposite system presents excellent electrocatalytic activity toward HER with an onset potential of −270 mV vs. RHE, evidencing an increase in activity compared to monometallic oxides and exhibiting onset potentials of −530 mV and −540 mV for α-Fe₂O₃/MWCNTs/IL and Co₃O₄/MWCNTs/IL, respectively. Finally, the system studied presents excellent stability during the 5 h of electrolysis, producing 132 μmol cm⁻² h⁻¹ of hydrogen gas.

This work investigates the electrocatalytic properties of carbon paste electrodes (CPEs) modified with ionic liquids (IL) and metallic ionic liquid (ILFe) for the hydrazine oxidation reaction (HzOR). The results indicate that ILFe significantly enhances the catalytic activity of the electrode, exhibiting catalysis towards hydrazine oxidation, reducing overpotential, and increasing reaction current. It is determined that the HzOR on the MWCNT/MO/ILFe electrode involves the transfer of four electrons, with high selectivity for nitrogen formation. Additionally, ILFe is observed to improve the wettability of the electrode surface, increasing its capacitance and reaction efficiency. This study highlights the advantages of ILFe-modified CPEs in terms of simplicity, cost-effectiveness, and improved performance for electrochemical applications, demonstrating how the ionic liquid catalyzes hydrazine oxidation despite its lower conductivity.

Sulfite is a widely used additive in food and beverages, and its maximum content is limited by food regulations. For this reason, determining the sulfite concentration using fast, low-cost techniques is a current challenge. This work describes the behavior of a sensor based on an electrode formed by carbon nanotubes an ionic liquid as binder, which by electrochemical reduction, allows detecting sulfite with a detection limit of 1.6 ± 0.05 mmol L⁻¹ and presents adequate sensitivity. The advantage of detecting sulfite by reduction and not by oxidation is that the presence of antioxidants such as ascorbic acid does not affect the measurement. The electrode shown here is low-cost and easy to manufacture, robust, and stable.

In this work, the determination of gallic acid was performed using surface‐renewable carbon paste electrodes fabricated with multi‐walled carbon nanotubes (MWCNT) and a mixture of N‐octylpyridinium hexafluorophosphate (OPyPF₆) ionic liquid with mineral oil (MO) as binder. This system shows remarkable amperometric sensor characteristics and promotes a better electronic transfer. An electroanalytical study of gallic acid shows a linear range from 4.98±0.25 to 74.1±2.2 μmol L⁻¹, with R²=0.9958 and an experiment a limit of detection of 2.70±0.08 μmol L⁻¹ (S/N=3), and a sensitivity of 0.029 μA μmol⁻¹ L.