Search Results (171)

Microbial fuel cells (MFCs) are a sustainable approach to wastewater treatment and energy recovery. However, their practical utility is often limited by sluggish cathode kinetics. For this technology, developing cost-effective biocatalysts that do not compromise effectiveness is a primary challenge. In this study, we utilized anthocyanin molecularly functionalized Escherichia coli (Cya-WT) to promote the formation of electroactive biofilms and regulate the intrinsic catalytic activity of single cells, thereby enhancing extracellular electron transfer. MFCs incorporating Cya-WT-loaded carbon cloth (CC) biocathodes were configured to simultaneously evaluate power generation and glucose degradation activity. The results indicated that Cya-WT exhibited significantly improved oxygen reduction reaction (ORR) activity, achieving a reduction peak current of 3.61 mA cm⁻², compared to 2.02 mA cm⁻² for wild-type E. coli (WT). The assembled MFC offers a peak power density of 268 ± 13.4 μW cm⁻² and decomposes 17.1 ± 1.15 mM of glucose in 150 h, maintaining a consistent voltage output for 800 h. These results demonstrate that anthocyanin functionalization significantly enhances the electrocatalytic performance and metabolic capabilities of E. coli. This novel catalyst design method offers a new strategy for low-cost, renewable MFC cathode catalysts and shows good promise in MFC biopower generation through the assembly of carbon-based biocathodes. Full article

This study elucidates the mechanism enabling the low-voltage electrolysis of black liquor (BL) for integrated resource recovery. The process simultaneously generates protons at the anode via the oxidation of organics (OOR), which occurs at a lower potential than the oxygen evolution reaction (OER), and induces lignin precipitation. Concurrently, hydrogen and hydroxide ions are produced at the cathode through the hydrogen evolution reaction (HER). Driven by the electric field, sodium ions migrate from the anode to the cathode chamber, combining with hydroxide ions to form sodium hydroxide, thereby achieving the synchronous production of acid, alkali, hydrogen, and modified lignin in a single process. Using a platinum electrode, we conducted a mechanistic investigation through linear sweep voltammetry (LSV), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and detailed product analysis. The results show that overall efficiency is controlled by competition at the anode between OOR and OER, which directly determines proton yield. A critical trade-off exists between anodic proton generation and cathodic alkali recovery, driven by the competitive migration of protons and sodium ions across the cation-exchange membrane. The proton yield was highly dependent on the initial BL composition, with a characteristic peak observed under specific conditions. Conversely, the sodium hydroxide recovery rate was maximized when the anolyte pH remained high, minimizing competitive proton migration. This work provides fundamental insights into the interfacial mechanisms of BL electrocatalytic, establishing it as a versatile electrochemical biorefinery platform for simultaneous proton and alkali production from a renewable waste stream, beyond its role as a hydrogen source and lignin recovery. Full article

Pt-based catalysts remain the most effective materials for the oxygen reduction reaction (ORR) at the cathode of proton exchange membrane fuel cells (PEMFCs); however, platinum scarcity and high cost severely limit the large-scale deployment of the technology. Improving catalytic activity and durability through precise control of nanoparticle morphology is therefore crucial for reducing costs and enhancing sustainability, enabling PEMFC widespread adoption. In this context, carbon-supported Pt-based nanoparticles with a 30 wt.% Pt loading were synthesized by an organometallic chemistry approach using hexadecylamine (HDA) as a stabilizer, allowing fine control over nanoparticle morphology. Two distinct synthesis pathways (one-pot and two-step procedures) were used to prepare platinum catalysts supported on KetjenBlack EC-300J (KB), and their influence on the electrocatalytic activity of the obtained nanomaterials was studied. Furthermore, the effect of HDA stabilization on catalyst performance was investigated. Directly synthesized Pt/KB catalysts exhibited similar ORR mass activity, regardless of whether or not HDA was present. Pt/KB prepared by the two-step procedure showed a significantly lower performance. Additionally, despite a larger loss of electrochemical surface area during an accelerated stress test compared to a commercial Pt/C reference, Pt^HDA/KB and Pt/KB catalysts maintained stable mass activity and limited specific activity degradation, highlighting the beneficial effect of nanoparticle stabilization in the presence of HDA on prolonged electrocatalyst cycling. Full article

Urea electrolysis has emerged as a promising alternative to conventional water electrolysis for hydrogen production, owing to low electrical energy consumption as well as organic wastewater. However, the practical implementation of this approach is primarily constrained by the lack of cost-effective and efficient electrocatalysts. Thus, the development of earth-abundant, non-precious metal-based bifunctional electrocatalysts toward both the hydrogen evolution reaction (HER) and the urea oxidation reaction (UOR) is of critical importance. In this context, nanostructured, reduced nickel-cobalt tungstate supported on Ni foam is fabricated as a binder-free, freestanding electrode via a two-step hydrothermal process followed by partial thermal reduction. By systematically tuning the precursor concentrations of Ni, Co, and W, the morphology and electronic structure of the material are effectively modulated. The introduction of oxygen vacancies through partial thermal reduction plays a key role in enhancing charge transport properties. The optimized NiCo@W_0.5/NF electrode exhibits a porous, flower-like architecture and demonstrates excellent bifunctional electrocatalytic activity toward both UOR and HER, accompanied by improved mass transport behavior. When employed as both the anode and cathode for overall urea electrolysis, NiCo@W_0.5/NF requires a low cell voltage of only 1.68 V to achieve a current density of 100 mA cm⁻² and delivers impressive operational stability in an optimized electrolyte composed of 3 M KOH and 0.33 M urea. These results indicate that NiCo@W_0.5/NF is a highly promising and efficient bifunctional electrode material for urea assisted hydrogen production. Full article

The manipulation of the electrocatalyst nanoarchitecture, particularly transition metal compounds, regarding size, shape, facets, and composition, significantly enhances the electrocatalytic activity in energy transformations. This study introduces a novel methodology for the precipitation of mesoporous nanoparticles of nickel tungstate (meso-NiWO₄) using direct chemical deposition from a template of Brij^®78 surfactant liquid crystal. Physicochemical analyses revealed the formation of amorphous meso-NiWO₄ nanoparticles with dual sizes of 10 ± 3 and 120 ± 8 nm and a specific surface area of 34.2 m²/g, exceeding that of nickel tungstate deposited in the absence of surfactant (bare-NiWO₄, 4.0 m²/g). The meso-NiWO₄ nanoparticles exhibit improved electrocatalytic stability, reduced charge-transfer resistance (R_ct = 1.11 ohm), and a current mass activity of ~365 mA/cm² mg at 1.6 V vs. RHE during the electrolysis of urea in alkaline solution. Furthermore, by employing meso-NiWO₄ in a two-electrode urea electrolyzer, a remarkable 4.8-fold increase in the cathodic hydrogen concurrent production rate was achieved (373.40 µmol/h at a bias potential of 2.0 V), compared to that of the bare-NiWO₄ catalyst. The exceptional urea oxidation electroactivity and the enhanced hydrogen evolution rate arise from substantial specific surface area and mesoporous structure, facilitating effective charge transfer and mass transport through the meso-NiWO₄ catalyst. Using the surfactant liquid crystal template for electrocatalyst synthesis enables a one-pot deposition of diverse nanoarchitectures and compositions with high surface area at ambient conditions for an improved electrocatalytic and hydrogen green production process. Full article

This study investigates reduced graphene oxide (rGO)-supported bimetallic M–Pt (M = Co, Ni, Cu) alloy nanoparticles as electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media. Monometallic Pt and bimetallic M–Pt nanoparticles were synthesized and uniformly dispersed on rGO, followed by structural and compositional characterization using transmission electron microscopy and inductively coupled plasma mass spectrometry. Their electrocatalytic performance toward HER was systematically evaluated at different temperatures. All electrocatalysts exhibited enhanced activity at higher temperatures, with current densities increasing by approximately 1.68–2.65 times at 338 K compared with 298 K. Among the investigated materials, CoPt/rGO delivered the highest cathodic current densities and a Tafel slope of 75 mV dec⁻¹, indicating favorable reaction kinetics. This performance is associated with a higher electroactive surface area, as determined by cyclic voltammetry, and reduced charge-transfer resistance, as revealed by electrochemical impedance spectroscopy. Notably, the CoPt/rGO electrocatalyst demonstrated excellent short-term operational stability at a constant potential of −0.28 V vs. RHE. These results highlight the potential of rGO-supported CoPt bimetallic alloys as efficient electrocatalysts for alkaline water electrolysis. Full article

This work investigates the structural evolution and electrocatalytic activity of the amorphous metal alloy Al₈₇Y₄Gd₁Ni₄Fe₄ during short-term annealing and its effect on the kinetics of the hydrogen evolution reaction (HER) in 1 M KOH. It is shown that a 5 min heat treatment at 647 ± 2 K initiates controlled nanocrystallisation with the formation of AlFe₂Ni, GdFe₂ and Al(X) (X = Gd, Ni, Y, Fe) phases, which are uniformly dispersed in the amorphous matrix. According to XRD, DSC and HRTEM data, it was established that the formation of intermetallic nanodomains leads to a decrease in charge transfer energy barriers and the appearance of additional active centres of H* adsorption. Electrochemical studies have shown an increase in cathode current density, an increase in i₀ by 2–3 orders of magnitude, and a decrease in R_ct after annealing, confirming the improvement in HER kinetics. Potentiostatic tests showed an increase in the volumetric hydrogen evolution rate from 35.1 to 106.0 mL/(g·min) during the first immersion and up to 217.9 mL/(g·min) during reuse. SEM/EDS analysis revealed surface reconstruction and Ni enrichment after HER, which contributes to the acceleration of the H* recombination stage. The synergy of the amorphous matrix and nanophases ensures high electrocatalytic activity and stability of the system, making annealed AMA a promising low-cost catalyst for alkaline hydrogen evolution. Full article

The relatively poor cycle stability of zinc–air batteries (ZABs) hinders their widespread application, while self-supporting electrode materials have shown great potential in enhancing the cycling stability of ZABs. To construct a self-supporting electrode, bamboo was employed as a sustainable precursor, and a two-step pyrolysis strategy was implemented to integrate ZIF-67-derived catalysts onto a hierarchically porous carbon framework, yielding the composite material Co-N@CB. Benefiting from its structural and electronic advantages, Co-N@CB exhibits outstanding electrocatalytic performance. The overpotential for the oxygen evolution reaction (OER) in alkaline electrolyte is 1.5 V at 10 mA cm⁻², with a potential gap (ΔE) of 0.69 V. This material is directly used as the air cathode in ZABs, delivering over 10,000 stable cycles. This excellent cycling stability arises from the strong carbon framework provided by bamboo and the enhanced electrical conductivity achieved through the pyrolytic graphitization of ZIF-67. This study paves the way for further exploration of biomass-based self-supporting electrodes toward high-performance ZABs and emerging micro/nanoscale sensing technologies. Full article

Electrocatalytic hydrogenation (ECH) represents an environmentally friendly pathway for converting 5-hydroxymethylfurfural (HMF) into the high-value chemical 2,5-bis(hydroxymethyl)furan (BHMF). However, its selectivity and Faradaic efficiency are often constrained by competitive hydrogen evolution at the cathode and insufficient supply of active hydrogen at the surface. To address this challenge, this study developed an Ir-decorated copper oxide nanowire catalyst (denoted as CuIr) featuring a hydrogen-rich adsorption (H_ads) surface. The incorporation of Ir significantly enhances the catalyst’s water dissociation capacity, creating abundant H_ads sources that selectively accelerate HMF hydrogenation while suppressing side reactions. Under a mild applied potential of −0.45 V vs. RHE and a current density of approximately −20 mA cm⁻², the optimal CuIr₄₀ catalyst achieved near-complete conversion of HMF (99%), a BHMF yield of 99%, and a high Faradaic efficiency of 97% within 120 min of electrolysis. Mechanistic studies reveal that this catalytic leap stems from the synergistic functional interaction between Cu and Ir sites in substrate activation and hydrogen supply. This work presents a novel strategy for designing efficient electrocatalysts for biomass hydrogenation by regulating surface H_ads concentration. Full article

Electrocatalytic CO₂ reduction is a promising approach to mitigate rising atmospheric CO₂ levels while converting CO₂ into valuable products such as CH₄. Conversion into other useful substances further expands its potential applications. However, the efficiency of the CO₂ reduction reaction (CO₂RR) is strongly influenced by device geometry and CO₂ mass transfer in the electrolyte. In this work, we present and evaluate microchannel electrocatalytic devices consisting of a porous Cu cathode and a Pt anode, fabricated via metal-assisted chemical etching (MACE). The porous surfaces generated through MACE enhanced reaction activity. To study the impact of the distance between electrodes, several devices with different channel heights were fabricated and tested. The device with the highest CH₄ selectivity had a narrow inter-electrode gap of 50 μm and achieved a Faradaic efficiency of 56 ± 11% at an applied potential of −5 V versus an Ag/AgCl reference electrode. This efficiency was considerably higher than that of the device with larger inter-electrode gaps (300 and 480 μm). This reduced efficiency in the larger channel was attributed to limited CO₂ availability at the cathode surface. Bubble visualization experiments further demonstrated that the electrolyte flow rate had a strong impact on supplied CO₂ bubble morphology and mass transfer. At a flow rate of 0.75 mL/min, smaller CO₂ bubbles were formed, increasing the gas–liquid interfacial area and thereby enhancing CO₂ dissolution into the electrolyte. These results underline the critical role of electrode gap design and bubble dynamics in optimizing microchannel electrocatalytic devices for efficient CO₂RR. Full article

In this study, copper–carbon material composites, Cu/CM (where CM is reduced graphene oxide (rGO), graphitic carbon nitride (g-C₃N₄), their mixture, and N-doped reduced graphene oxide (N-rGO)), were prepared using a simple method of chemical reduction of copper cations in the presence of CM related to molecular-level mixing methods. Additionally, copper cations from its oxides present in the composites were reduced in an electrochemical cell by depositing them on the surface of a horizontally positioned cathode. The structure and morphology of the Cu/CM composites were studied using electron microscopy and X-ray diffraction analysis. The thermal stability and elemental analysis were determined for the carbon materials. The resulting Cu/CM composites were used as electrocatalysts in the electrohydrogenation of the aromatic ketone, acetophenone. Cu/rGO and Cu/N-rGO composites with a 1:1 ratio exhibited catalytic activity in this process, increasing the rate of APh hydrogenation and its degree of conversion with the selective formation of a single product, methyl phenyl carbinol (or 1-phenylethanol), compared to the electrochemical reduction of APh on a cathode without a catalyst. The Cu/N-rGO composite demonstrated the highest electrocatalytic activity. Full article

Mild steel readily corrodes in acidic environments, and most industrial corrosion inhibitors are synthetic, often toxic, and environmentally harmful. In this study, electrocatalytically active Cd–Cs mixed oxide nanocomposites were synthesized via a green route using an aqueous extract of Trachyspermum ammi (ajwain) seeds as a natural reducing, stabilizing, and capping agent. This eco-friendly method eliminates harsh chemicals while producing nanomaterials with active surfaces capable of facilitating electron transfer and scavenging free radicals. Incorporation of cesium introduces basic, electron-rich sites on the Cd–Cs oxide surface, serving as inhibition promoters that enhance charge transfer at the metal/electrolyte interface and assist in the formation of an adsorbed protective film on steel. The nanocomposites were optimized by adjusting precursor ratios, pH, temperature, and reaction time, and were characterized by UV–Vis, FTIR, XRD, SEM–EDS, HR-TEM EDS, BET, DLS, XPS, and zeta potential analyses. Strong antioxidant activity in ABTS and DPPH assays confirmed efficient catalytic quenching of reactive radicals. Corrosion inhibition potential, evaluated by using potentiodynamic polarization, electrochemical impedance spectroscopy, and gravimetric analysis in 0.5 M HCl, shows an inhibition efficiency of 90–91%. This performance is associated with an electrocatalytically active, adsorbed barrier layer that suppresses both anodic dissolution and cathodic hydrogen evolution, which depicts mixed-type inhibition. Overall, the biosynthesized Cd–Cs mixed oxide nanocomposites function as promising green synthesized nanomaterial with dual antioxidant and corrosion-inhibiting functions, underscoring their potential for advanced surface engineering and corrosion protection. Full article

Conventional two-dimensional (2D) electrocatalytic ozonation faces challenges such as low mass transfer efficiency, limited hydroxyl radical (•OH) yield, and insufficient pollutant degradation rates. To address these limitations, this study developed a novel three-dimensional electrocatalytic ozonation system using a 316 stainless-steel skeleton as the cathode. By systematically comparing the ozone decay kinetics, •OH yield, imidacloprid degradation efficiency, and ozone mass transfer characteristics among the 3D electrocatalytic ozonation system, 2D electrocatalytic ozonation system, and conventional ozonation system, combined with electrode interface reaction analysis and structural simulation, the core mechanism by which the 3D structure enhances the electrocatalytic ozonation reaction was revealed. The results showed that the 3D electrocatalytic ozonation technology primarily promotes ozone decay and •OH generation through a reaction pathway dominated by the reduction of ozone at the cathode, while simultaneously enhancing pollutant removal efficiency. The pseudo-first-order kinetic constant for ozone decay in the 3D system reached 1.0 min⁻¹, which was five times that of the 2D system (0.2 min⁻¹). The •OH yield increased to 38%, significantly higher than that of the 2D system (15%) and conventional ozonation (10%). The complete degradation of imidacloprid was achieved within 5 min, and the degradation rate (2.14 min⁻¹) was 10 times that of the 2D system. The high specific surface area (75 cm²/g, 30–90 times that of the 2D flat electrode) and 70% porosity of the 3D framework overcame the mass transfer limitation of the 2D structure, exhibiting excellent reaction activity. The ozone mass transfer amount was approximately 1.5 times that of the 2D electrode and 2 times that of conventional ozonation. This study provides theoretical support and technical basis for the engineering application of 3D electrocatalytic ozonation technology in the field of micro-pollutant control. Full article

Lithium-oxygen batteries (LOBs) are limited by sluggish oxygen redox kinetics and cathode instability. Herein, we report a cobalt particle catalyst encapsulated in nitrogen-doped carbon (Co@NC) with a three-dimensional hierarchical architecture, synthesized via a chitosan-derived hierarchical porous carbon framework. This innovative design integrates uniformly dispersed ultra-thin carbon shells (11.7 nm), pyridinic nitrogen doping, and Co particles (1.41 μm) stabilized through carbon-support electronic coupling. The hierarchical porosity facilitates rapid O₂/Li⁺ mass transport, while pyridinic N sites act as dual-function electrocatalytic centers for Li₂O₂ nucleation and charge transfer kinetics. Co@NC achieves 11,213 mAh g⁻¹ at 200 mA g⁻¹ (126.5% higher than nitrogen-doped carbon) and maintains 1.54 V overpotential (500 mAh g⁻¹). These metrics outperform benchmark catalysts, addressing kinetic and stability challenges in LOBs. The study advances electrocatalyst design by integrating structural optimization, heteroatom doping, and electronic coupling strategies for high-performance metal–air batteries. Full article

Waste lithium-ion batteries (LIBs), which usually contain dangerous organic electrolytes and transition metals, including nickel, cobalt, iron, and manganese, can hurt the environment and human health. Substantial advancements have been achieved in employing high-efficiency, economical, and environmentally sustainable techniques for the recycling of spent LIBs. Converting exhausted LIBs into efficient energy conversion catalysts straightforwardly is a good strategy for addressing metal resource constraints and clean energy concerns. This transforms waste cathodes, anodes, binders, and separators from depleted LIBs into electrocatalysts free of platinum group metals for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). The composite, including transition metal oxide, graphene oxide, and carbon mass, will be synthesized from spent LIBs, demonstrating enhanced electrocatalytic activity. Utilizing “waste-to-energy” methods for used LIBs as catalysts would provide substantial benefits in environmental preservation and the effective production of functional materials in metal–air batteries. Full article