Search Results (56)

Electro-oxidation of urea (UOR) in alkaline medium is one of the most effective alternative ways of producing green hydrogen, as the oxidation potential in UOR is less and thermodynamically more favorable than conventional water oxidation. The development of cost-effective materials in catalyzing UOR is recently seeking more attention in the research hotspot. Suitably modifying the Ni-based catalysts towards active site creation and preventing surface passivation is much important in this context, following which we reported the synthesis of Ni₃S₂ (NS) supported with CuCo (CC) bimetallic (NSCC). A simple hydrothermal route for NS synthesis and the electrodeposition method for CuCo (CC) deposition is adapted in a self-supported manner. The NS and CC catalysts exhibited sheet-like morphology, as confirmed by SEM and TEM analysis. The bimetallic CC deposition prevented the surface passivation of nickel sulfide (NS) over oxygen evolution reaction (OER) and improved the charge-transfer kinetics. The NSCC catalyst catalyzed UOR in an alkaline medium, which required a lower potential of 1.335 V vs. RHE to attain the current density of 10 mAcm⁻², with a lower Tafel slope value of 131 mVdec⁻¹. In addition, a two-electrode cell setup is constructed with an operating cell voltage of 1.512 V for delivering 10 mAcm⁻² current density. This study illustrates the new strategy of designing heterostructure catalysts for electrocatalytic UOR. Full article

Electrocatalytic urea oxidation reaction (UOR) is a promising dual-purpose approach for hydrogen production and wastewater treatment, addressing critical energy and environmental challenges. However, conventional anode materials often suffer from limited active sites and high charge transfer resistance, restricting UOR efficiency. To overcome these issues, a novel NiP@PNC/NF electrocatalyst was developed via a one-step thermal annealing process under nitrogen, integrating nickel phosphide (NiP) with phosphorus and nitrogen co-doped carbon nanotubes (PNCs) on a nickel foam (NF) substrate. This design enhances catalytic activity and charge transfer, achieving current densities of 50 mA cm⁻² at 1.34 V and 100 mA cm⁻² at 1.43 V versus the reversible hydrogen electrode (RHE). The electrode’s high electrochemical surface area (235 cm²) and double-layer capacitance (94.1 mF) reflect abundant active sites, far surpassing NiP/NF (48 cm², 15.8 mF) and PNC/NF (39.5 cm², 12.9 mF). It maintains exceptional stability, with only a 16.3% performance loss after 35 h, as confirmed by HR-TEM showing an intact nanostructure. Our single-step annealing technique provides simplicity, scalability, and efficient integration of NiP nanoparticles inside a PNC matrix on nickel foam. This method enables consistent distribution and robust substrate adhesion, which are difficult to attain with multi-step or more intricate techniques. Full article

The electrochemical oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) coupled with water electrolysis for green hydrogen production is a promising strategy to address energy crises and environmental pollution. Despite the suitable adsorption energy for HMF due to their partially filled d-band electronic structures, Ni- or Co-based oxides/hydroxides still face challenges in insufficient activity and stability. In this study, a porous heterogeneous nickel cobalt oxide/hydroxide growth on nickel foam (NF), which is defined as NF@NiCo-H/O, was developed via immersion in concentrated alkali solution. Compared with the single-component NiCo oxides, the NF@NiCo-H/O catalyst exhibits a lower application potential of only 1.317 V, 1.395 V, and 1.443 V to achieve current densities of 20, 50, and 100 mA cm⁻², respectively, in an alkaline solution containing HMF. Additionally, it demonstrates rapid reaction kinetics with a Tafel slope of 27.6 mV dec⁻¹ and excellent cycling stability. Importantly, the presence of more high-valent Ni³⁺-O species on the catalyst surface contributes to its exceptional selectivity for 2,5-furandicarboxylic acid (86.7%), Faradaic efficiency (93.1%), and conversion rate (94.4%). This catalyst provides some theoretical guidance for the development of biomass electrooxidation catalysts for sustainable energy and chemical production. Full article

Electrolysis of abundant seawater resources is a promising approach for hydrogen production. However, the high-concentration chloride ion in seawater readily induces the chlorine evolution reaction (CER), resulting in catalyst degradation and decreased electrolysis efficiency. In recent years, the electrooxidation of small organic molecules (e.g., methanol), biomass-derived compounds (e.g., 5-hydroxymethylfurfural), and plastic monomers (e.g., ethylene glycol) has been seen to occur at lower potentials to substitute for the traditional oxygen evolution reaction (OER) and CER. This alternative approach not only significantly reduces energy consumption for hydrogen production but also generates value-added products at the anode. This review provides a comprehensive summary of research advancements in value-added electrooxidation reaction-assisted seawater hydrogen production technologies and emphasizes the underlying principles of various reactions and catalyst design methodologies. Finally, the current challenges in this field and potential future research directions are systematically discussed. Full article

The urgency to decarbonize fuels has contributed to a rise in biofuel production, which has culminated in a significant increase in the waste quantity of glycerol produced. Therefore, to convert glycerol waste into high-value products, electrochemical oxidation (EO) is a viable alternative for the co-generation of carboxylic acids, such as formic acid (FA) and green hydrogen (H₂), which are considered energy carriers. The aim of this study is the electroconversion of glycerol into FA by EO using a divided electrochemical cell, driven by a photovoltaic (PV) system, with a dimensionally stable anode (DSA, Ti/TiO₂-RuO₂-IrO₂) electrode as an anode and Ni-Fe stainless steel (SS) mesh as a cathode. To optimize the experimental conditions, studies were carried out evaluating the effects of applied current density (j), electrolyte concentration, electrolysis time, and electrochemical cell configuration (undivided and divided). According to the results, the optimum experimental conditions were achieved at 90 mA cm⁻², 0.1 mol L⁻¹ of Na₂SO₄ as a supporting electrolyte, and 480 min of electrolysis. In this condition, 256.21 and 211.17 mg L⁻¹ of FA were obtained for the undivided and divided cells, respectively, while the co-generation of 6.77 L of dry H₂ was achieved in the divided cell. The electroconversion process under the optimum conditions was also carried out with a real sample, where organic acids like formic and acetic acids were co-produced simultaneously with green H₂. Based on the preliminary economic analysis, the integrated-hybrid process is an economically viable and promising alternative when it is integrated with renewable energy sources such as solar energy. Full article

We introduce a novel dual redox mediator synthesized by covalently linking ferrocene dicarboxylic acid (FcDA) and thionine (TH) onto a pre-treated glassy carbon electrode. This unique structure significantly enhances the electro-oxidation of dopamine (DA) and the reduction of hydrogen peroxide (H₂O₂), offering a sensitive detection method for both analytes. The electrode exhibits exceptional sensitivity, selectivity, and stability, demonstrating potential for practical applications in biosensing. It facilitates rapid electron transfer between the analyte and the electrode surface, detecting H₂O₂ concentrations ranging from 1.5 to 60 µM with a limit of detection (LoD) of 0.49 µM and DA concentrations from 0.3 to 230 µM with an LoD of 0.07 µM. The electrode’s performance was validated through real-sample analyses, yielding satisfactory results. Full article

Electrocatalytic alcohol oxidation (EAO) is an attractive alternative to the sluggish oxygen evolution reaction in electrochemical hydrogen evolution cells. However, the development of high-performance bifunctional electrocatalysts is a major challenge. Herein, we developed a nitrogen-doped bimetallic oxide electrocatalyst (WO-N/NF) by a one-step hydrothermal method for the selective electrooxidation of benzyl alcohol to benzoic acid in alkaline electrolytes. The WO-N/NF electrode features block-shaped particles on a rough, inhomogeneous surface with cracks and lumpy nodules, increasing active sites and enhancing electrolyte diffusion. The electrode demonstrates exceptional activity, stability, and selectivity, achieving efficient benzoic acid production while reducing the electrolysis voltage. A low onset potential of 1.38 V (vs. RHE) is achieved to reach a current density of 100 mA cm⁻² in 1.0 M KOH electrolyte with only 0.2 mmol of metal precursors, which is 396 mV lower than that of water oxidation. The analysis reveals a yield, conversion, and selectivity of 98.41%, 99.66%, and 99.74%, respectively, with a Faradaic efficiency of 98.77%. This work provides insight into the rational design of a highly active and selective catalyst for electrocatalytic alcohol oxidation. Full article

Odor emissions are a crucial component of atmospheric pollution. As odor is a sensory pollutant, its management and treatment are recalcitrant. A wet scrubber (WS) is an efficient technique for odor removal, but disposal of waste liquid discharge leads to secondary pollution and CO₂ emissions during transportation. In this study, a system consisting of WS and electrooxidation (EO) was developed and installed in a swine manure fermentation facility. The absorption and EO characteristics were estimated through the practical implementation of a bench-scale WS (BSW). For EO, a dimensionally stable anode and Cl⁻ were applied. When the BSW was operated without EO, an L/G ratio of 8.88 was essential for securing the simultaneous removal rate of the four odorants (hydrogen sulfide, methyl mercaptan, ammonia, and total volatile compound). With the operation of the EO, the period to change the liquid based on equilibrium was postponed due to the continuous oxidation of the odorants absorbed in the liquid. As the applied current increased, the change period was further prolonged. However, the oxidation and absorption rates differed depending on the odor substances, due to differences in their physicochemical characteristics. Hydrogen sulfide and methyl mercaptan exhibited similar absorption and oxidation rates. Ammonia had a high absorption rate and a low oxidation rate. The acetaldehyde oxidation rate was the most sluggish among the substances. These findings demonstrate that simultaneous consideration of Henry’s constant and the reactivity of the target pollutant with HOCl renders the design of BSW appropriate for treating odor gases containing various odorants. This study contributes to efforts to address environmental problems concerning odors and also to global climate threats. Full article

The electrooxidation of organic compounds offers a promising strategy for producing value-added chemicals through environmentally sustainable processes. A key challenge in this field is the development of electrocatalysts that are both effective and durable. In this study, we grow gold nanoparticles (Au NPs) on the surface of various phases of titanium dioxide (TiO₂) as highly effective electrooxidation catalysts. Subsequently, the samples are tested for the oxidation of benzaldehyde (BZH) to benzoic acid (BZA) coupled with a hydrogen evolution reaction (HER). We observe the support containing a combination of rutile and anatase phases to provide the highest activity. The excellent electrooxidation performance of this Au-TiO₂ sample is correlated with its mixed-phase composition, large surface area, high oxygen vacancy content, and the presence of Lewis acid active sites on its surface. This catalyst demonstrates an overpotential of 0.467 V at 10 mA cm⁻² in a 1 M KOH solution containing 20 mM BZH, and 0.387 V in 100 mM BZH, well below the oxygen evolution reaction (OER) overpotential. The electrooxidation of BZH not only serves as OER alternative in applications such as electrochemical hydrogen evolution, enhancing energy efficiency, but simultaneously allows for the generation of high-value byproducts such as BZA. Full article

Hydrogen production through water splitting is a promising path to develop renewable green energy. Effective, stable, and low-cost catalysts are the key to water splitting. In the present work, a series of self-supporting nanoporous alloys are prepared by using a dealloying process followed by electrooxidation. Among them, the np-AlFeNiO-4s sample exhibits remarkable activity (10 mA cm⁻² at 32 mV for the HER and 278 mV for the OER) and good long-term stability (100 h) in alkaline conditions for both the HER and the OER. It only requires 1.56 V to reach 10 mA cm⁻² current density for total water splitting performance. The very short time of electrooxidation can significantly improve the HER performance. Electrooxidation makes the metal and metal oxide sites on the electrode surface effectively coupled, which greatly enhances the kinetic rate of the Volmer and Heyrovsky steps. Appropriate electrooxidation is a rapid and easy way to improve the activity of the electrocatalyst, which has a broad application prospect in electrochemical water splitting. Full article

This work reports the use of cellulose as a template to prepare nanosized WO₃ or NiWO₄ and its application as a co-catalyst in the electro-oxidation of ethanol and glycerol. Microcrystalline cellulose was hydrolyzed with phosphotungstic acid (H₃PW₁₂O₄₀) to prepare the nanocrystalline cellulose template. The latter was air-calcinated to remove the template and obtain nanometric WO₃. Tungsten oxide was impregnated with Ni(NO₃)₂, which was subsequently air-calcinated to obtain the nanometric NiWO₄. Elemental analysis confirmed the coexistence of nickel and tungsten, whereas thermal analysis evidenced a high thermal stability for these materials. The X-ray diffractograms displayed crystal facets of WO₃ and, when Ni(II) was added, NiWO₄. The transmission electron micrographs corroborated the formation of nanosized particles with average particle sizes in the range of 30 to 50 nm. Finally, to apply this material, Pt/WO₃-C and Pt/WO₃-NiWO₄-C were prepared and used in ethanol and glycerol electro-oxidation in an alkaline medium, observing a promotional effect of the oxide and tungstate by reducing the onset potential and increasing the current density. These materials show great potential to produce clean electricity or green hydrogen, contributing to energetic transition. Full article

We propose a new design for electrocatalysts consisting of two electrocatalysts (platinum and iron oxide) that are deposited on the surfaces of an oxidized graphene substrate. This design is based on a simple structure where the catalysts were deposited separately on both sides of oxidized graphene substrate; while the iron oxide precipitated out of the etching solution on the bottom-side, the surface of the oxidized graphene substrate was decorated with platinum using the atomic layer deposition technique. The Fe₂O₃-decorated CVD-graphene composite exhibited better hydrogen electrooxidation performance (area-normalized electrode resistance (ANR) of ~600 Ω·cm⁻²) and superior stability in comparison with bare-graphene samples (ANR of ~5800 Ω·cm⁻²). Electrochemical impedance measurements in humidified hydrogen at 240 °C for (Fe₂O₃|Graphene|Platinum) electrodes show ANR of ~0.06 Ω·cm⁻² for a platinum loading of ~60 µg_Pt·cm⁻² and Fe₂O₃ loading of ~2.4 µg_Fe·cm⁻², resulting in an outstanding mass normalized activity of almost 280 S·mg_Pt⁻¹, exceeding even state-of-the-art electrodes. This ANR value is ~30% lower than the charge transfer resistance of the same electrode composition in the absence of Fe₂O₃ nanoparticles. Detailed study of the Fe₂O₃ electrocatalytic properties reveals a significant improvement in the electrode’s activity and performance stability with the addition of iron ions to the platinum-decorated oxidized graphene cathodes, indicating that these hybrid (Fe₂O₃|Graphene|Platinum) materials may serve as highly efficient catalysts for solid acid fuel cells and beyond. Full article

Investigations of L-glutamate release in living organisms can help to identify novel L-glutamate-related pathophysiological pathways, since abnormal transmission of L-glutamate can cause many neurological diseases. For the first time, a nitrogen-modified graphene oxide (GO) sample (RGO) is prepared through a simple and facile one-pot hydrothermal reduction of GO in the presence of 20 wt.% of the dye malachite green and is used for amperometric biosensing. The biosensor demonstrates adequate stability and is easy to prepare and calibrate. The biosensor detects the current generated during the electrooxidation of hydrogen peroxide released in the L-glutamate that is converted to the alpha-ketoglutarate catalyzed by L-glutamate oxidase. The biosensor consists of a semipermeable membrane, with L-glutamate oxidase (EC 1.4.3.11) immobilized in albumin and RGO and the working Pt electrode. First, the basic version of the L-glutamate biosensor is examined in PBS to investigate its sensitivity, reliability, and stability. To demonstrate the applicability of the L-glutamate biosensor in the analysis of complex real samples, quantification of L-glutamate in bovine brain extract is performed and the accuracy of the biosensor is confirmed by alternative methods. The enhanced version of the L-glutamate biosensor is applied for L-glutamate release investigations in a newly developed strain of rats (DAT-knockout, DAT-KO). Full article

Currently, great importance has been assigned to designing cutting-edge materials for oxygen and hydrogen generation from hybrid water electrolysis as an ideal fuel alternative in energy-conversion devices. This work reports on the electrochemical organic molecule oxidation in alkaline media, intending to promote water electrolysis at early onset potential with more current densities using Sn-Cu oxidized heterostructures. The electrocatalysts were easily and rapidly synthesized by the microwave-heated synthesis process in the presence of a small quantity of ethylene glycol. The X-ray diffraction and Field Emission Scanning Electron Microscopy analyses confirm the presence of CuO and SnO₂ phases, which significantly improves the electrochemical activity of the composite toward the Oxygen Evolution Reaction (OER) in alkaline media in the presence of 1.0 mol L⁻¹ ethanol, yielding 8.0 mA cm⁻² at 1.6 V. The charge transfer resistance (R_ct) was determined using electrochemical impedance spectroscopy, and the result shows that the R_ct of SnO₂/CuO drastically decreased. The findings in this work highlight that the designed oxidized heterostructures with non-noble metals are promising candidates for energy conversion devices and sensors. Furthermore, this work confirms the advantages of using an assisted microwave heating process to develop an advanced SnO₂/CuO composite with the potential to be used in electro-oxidation processes. Full article

Molybdenum carbide co-catalyst and carbon nanofiber matrix are suggested to improve the nickel activity toward methanol electrooxidation process. The proposed electrocatalyst has been synthesized by calcination electrospun nanofiber mats composed of molybdenum chloride, nickel acetate, and poly (vinyl alcohol) under vacuum at elevated temperatures. The fabricated catalyst has been characterized using XRD, SEM, and TEM analysis. The electrochemical measurements demonstrated that the fabricated composite acquired specific activity for methanol electrooxidation when molybdenum content and calcination temperature were tuned. In terms of the current density, the highest performance is attributed to the nanofibers obtained from electrospun solution having 5% molybdenum precursor compared to nickel acetate as a current density of 107 mA/cm² was generated. The process operating parameters have been optimized and expressed mathematically using the Taguchi robust design method. Experimental design has been employed in investigating the key operating parameters of methanol electrooxidation reaction to obtain the highest oxidation current density peak. The main effective operating parameters of the methanol oxidation reaction are Mo content in the electrocatalyst, methanol concentration, and reaction temperature. Employing Taguchi’s robust design helped to capture the optimum conditions yielding the maximum current density. The calculations revealed that the optimum parameters are as follows: Mo content, 5 wt.%; methanol concentration, 2.65 M; and reaction temperature, 50 °C. A mathematical model has been statistically derived to describe the experimental data adequately with an R² value of 0. 979. The optimization process indicated that the maximum current density can be identified statistically at 5% Mo, 2.0 M methanol concentration, and 45 °C operating temperature. Full article