Search Results (261)

External corrosion of buried ferrous water mains remains the dominant driver of structural failure in aging water distribution networks, yet the mechanisms linking soil physical and chemical heterogeneity to corrosion kinetics and product phase evolution have not previously been synthesized into a unified critical framework. This review evaluates three partially competing accounts of electrochemical degradation—anodic dissolution coupled to oxygen reduction within porous rust layers, redox cycling of iron oxide phases driven by seasonal soil moisture fluctuations, and microbially influenced corrosion (MIC) mediated by direct extracellular electron transfer (EMIC) and chemical metabolite pathways (M-MIC)—and assesses the weight of evidence for each. We demonstrate that corrosion products retain electrochemical activity long after formation, functioning as dynamic redox mediators that continue the reactions responsible for their own growth: the reduction of lepidocrocite under anoxic conditions regenerates Fe²⁺ ions that sustain anodic dissolution and catalyze oxygen reduction, while repeated soil moisture cycles drive the irreversible transformation of γ-FeOOH to Fe₃O₄, which fundamentally alters the conductivity and cathodic capacity of the rust layer. The widely cited universal critical-moisture threshold of 65% water-holding capacity (WHC) is evaluated and found to be a single-point approximation contradicted by texture-resolved experimental data that show the critical degree of saturation ranges from S_r ≈ 0.5 in sand to S_r ≈ 0.8 in clay. Modern machine learning analyses of field corrosion databases confirm that chloride content, pH, pipe-to-soil potential, and water content are the four highest-ranked predictors of maximum pit depth, consistent with the mechanistic framework developed here. The classical cathodic depolarization model of SRB-driven corrosion is evaluated against EMIC evidence and found insufficient: measured pure-culture SRB corrosion current densities range from 14 to 135 µA cm⁻², not the milliampere-level values reported in some earlier reviews. An explicit research agenda is proposed to address the five most consequential unresolved mechanistic questions. Full article

The Zeta-Minimizer Theorem provides a fully deductive variational foundation for the hydrogen oxidation reaction (HOR) and oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. Starting from three primitive thermodynamic axioms and the helical geometry of the phase functional, a multi-extent dynamical system is constructed that simultaneously treats the electrochemical reaction coordinates and the adsorption extents of the participating species at the solid–electrolyte interface. The combined Hessian of the phase functional yields a complete spectrum of relaxation rates whose eigenvalues and eigenvectors emerge directly from the solid blackbox constants C_k and the helical partition functions of the reactive species. Adiabatic elimination of the fast surface modes produces an effective single-extent description in which voltage (or overpotential) appears as the conjugate variable, exactly analogous to the role of pressure in the corresponding gas-phase ammonia synthesis framework. The resulting nonlinear rate law is thermodynamically consistent at all conditions, recovers the Butler–Volmer and Tafel forms as well-defined limiting cases, and incorporates the effects of temperature, dilution, and catalyst-specific interface constants without empirical activation energies or adjustable reaction orders. The framework therefore unifies equilibrium, kinetics, and modal dynamics of HOR and ORR within a single variational structure, offering a parameter-light, first-principles alternative to classical empirical electrocatalytic rate expressions while preserving transparent contact with established limiting laws. Full article

The sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at air cathodes severely restrict the practical application of rechargeable zinc–air batteries (ZABs). Herein, equimolar lanthanide-doped spinel Co₃O₄ bifunctional electrocatalysts were synthesized via a citric acid-assisted sol–gel method. Among Ce-, Pr-, La-, and Sm-doped catalysts, Sm-Co₃O₄ exhibits the optimal electrocatalytic performance with a high ORR half-wave potential of 0.72 V and superior OER activity with an overpotential of 1.65 V at 10 mA cm⁻², achieving a minimal potential gap ΔE of 0.93 V. Rotating ring-disk electrode (RRDE) measurements and Koutecky–Levich (K–L) analyses confirm the exclusive 4e⁻ ORR pathway. Characterizations reveal that Sm doping modulates the electronic structure and lattice distortion of Co₃O₄, raises the Co²⁺/Co³⁺ ratio (0.59) and creates abundant oxygen vacancies, thereby significantly lowering the overpotentials for both ORR and OER. This study provides new insights for designing high-performance spinel-based bifunctional electrocatalysts for ZABs. Full article

Bismuth hexacyanoferrate (BiHCF), a Prussian blue analogue containing redox-active Fe–CN–Bi coordination motifs, was investigated as a model electrode for cathodic processes in chloride-rich saline and hypersaline electrolytes. Rather than evaluating BiHCF solely as a hydrogen evolution catalyst, this work focuses on the coupled electrochemical and interfacial processes that govern its response in NaCl solutions and natural brines from seawater, reverse osmosis (RO) reject, and high-altitude brine environments. Structural characterization by SEM–EDS, XRD and FTIR confirmed the formation of crystalline BiHCF with rod-like micrometric morphology and preserved cyanide coordination. Linear sweep voltammetry under controlled hydrodynamic conditions revealed a progressive cathodic displacement of the mixed potential with increasing NaCl concentration, together with a marked suppression of oxygen reduction kinetics at high chloride activity. Mixed-potential analysis showed that HER kinetics remain comparatively less sensitive to salinity than ORR, whereas the anodic contribution associated with BiHCF oxidation becomes strongly affected by chloride-induced surface transformation. Post-electrochemical characterization indicates the formation of a BiOCl-rich surface layer when the BiHCF is in contact with a hypersaline electrolyte during the cathodic subprocess (close to 0 mV_SHE), which accounts for the transition from active mixed-control behaviour to a passivated interfacial regime. Density functional theory calculations suggest that elementary water activation and hydrogen-forming steps at Bi sites are intrinsically feasible, implying that the experimentally observed overpotentials originate primarily from transport, interfacial resistance and chloride-driven passivation rather than from an unfavourable molecular reaction pathway. These findings provide a mechanistic framework for understanding Bi-based Prussian blue analogue electrodes in non-purified saline electrochemical systems and highlight the dual role of chloride as both a charge-compensating electrolyte species and a passivating reactant. Full article

The oxygen reduction reaction (ORR) is the cathode cornerstone of fuel cells and metal-air batteries. Its inherent spin mismatch between triplet O₂ and singlet products causes sluggish kinetics that conventional catalyst designs cannot fully overcome. This review critically summarizes the past three years’ breakthroughs in spin-regulated ORR electrocatalysis and offers a fresh perspective beyond traditional electronic and geometric optimization. We first dissect the physical mechanism of spin-selective electron transfer required for the 4e⁻ pathway. We then systematically present four strategies for modulating the spin state of transition-metal active sites, namely strain engineering, defect engineering, heteroatom doping, and interfacial heterostructures. Subsequently, we highlight the emerging chirality-induced spin selectivity effect, where chiral organic molecules or intrinsically chiral inorganic materials act as spin filters without an external magnetic field, enabling spin-matched electron transfer and enhanced ORR performance. At the end of our review, we identify several key challenges, including the lack of in situ techniques to dynamically track spin states under operating conditions, the limited stability and universality of chiral catalysts, and the insufficient understanding of synergistic effects between spin control and traditional design parameters. We also outline future research directions, such as developing operando spin characterization, constructing robust chiral inorganic nanostructures, and employing high-throughput computational screening to integrate spin, geometric, and electronic level design. Our review provides a timely and comprehensive framework that bridges spin physics with electrocatalyst design, offering critical mechanistic insights and practical guidelines. Full article

In this study, the influence of nanostructure and morphology was used as a comparative strategy to investigate the material’s performance. For this purpose, two distinct morphologies, one of which is novel for iron tungstate (nanoplatelets) and obtained by the hydrothermal method, were tested to verify their influence on the catalytic activity, reaction kinetics, and operational stability of the oxygen evolution reaction. Although the self-organized rosette and nanoplatelet morphologies maintain a monoclinic ferberite-type structure, the 2D nanoplatelet architecture shows an almost 30% reduction in catalytic activity and a 16% increase in reaction rate in basic medium (1 M KOH), in addition to four times higher turnover frequencies (TOF). Furthermore, the new morphology (nanoplatelets) provides higher charge density, lower charge transfer resistance, and favorable band edge positions, resulting in greater oxidation capacity (10 times more). Regarding the stability factor, both morphologies show a slight degradation over 1000 cycles, but the nanoplatelet morphology maintains almost constant activity, while the self-organized rosette morphology shows a performance drop of approximately 25%. These results demonstrate that morphological engineering is an effective means of improving electrocatalytic performance. Full article

Photothermal-assisted electrocatalysis is an effective approach to enhance the efficiency of the oxygen evolution reaction (OER), but the synergistic mechanism between the photothermal effect and the regulation of catalyst electronic structure remains unclear. This work reports the construction of NiFeS/Cs_0.32WO₃ heterostructures, which integrate interfacial electron transfer and localized surface plasmon resonance (LSPR)-induced photothermal effects to enhance OER performance. The Cs_0.32WO₃ component with hexagonal tungsten bronze structure exhibits strong absorption in the near-infrared region, attributed to LSPR (1100 nm to 2500 nm) and small polaron transition (780 nm to 1100 nm), endowing the NiFeS/Cs_0.32WO₃ composite with excellent photothermal conversion capability. Under 808 nm laser irradiation, the steady-state surface temperature of the heterostructure reaches 65.1 °C. X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy analyses reveal that spontaneous electron transfer from NiFeS to Cs_0.32WO₃ occurs at the heterostructure interface, thereby optimizing the electronic structure of active sites. Electrochemical measurements demonstrate that at a current density of 50 mA cm⁻², the NiFeS/Cs_0.32WO₃ composite exhibits an overpotential of 301 mV under near-infrared irradiation, representing a reduction of 53 mV compared to NiFeS under dark conditions. At a current density of 50 mA cm⁻², the photothermal enhancement effect of the NiFeS/Cs_0.32WO₃ composite is identified as the predominant contributor to the overall performance improvement. Nevertheless, the intrinsic interfacial effect associated with the heterojunction also plays a crucial role and makes a non-negligible contribution to the enhanced electrocatalytic activity. The Tafel slope decreases from 57.8 mV dec⁻¹ to 44.5 mV dec⁻¹ under near-infrared illumination, indicating accelerated OER kinetics. This work elucidates the mechanism of synergistic enhancement between heterostructure construction and photothermal effects, providing insights for the design of advanced photothermal electrocatalysts. Full article

Seawater zinc–air batteries (SZABs) stand out as promising candidates for marine and offshore energy supply. However, their practical implementation is greatly restricted by tardy oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) kinetics at the air cathode, severe chloride ion-induced catalyst corrosion, and structural deterioration of traditional binder-containing electrodes in seawater media. Herein, we design and fabricate a binder-free integrated electrode consisting of carbon-supported iron phthalocyanine- modified star-like cobalt sulfide arrays directly grown on nickel foam. The optimal catalyst (0.3FePc-C/CoS) integrates the respective advantages of Fe single atoms and cobalt sulfide, exhibiting excellent ORR and OER activity, delivering a prominent half-wave potential of 0.89 V versus RHE, and exhibiting a low OER overpotential of 160 mV at 50 mA cm⁻² and robust stability in seawater. As a self-supported air cathode, the 0.3FePc-C/CoS-based battery attains a favorable open-circuit voltage reaching 1.48 V, prominent peak power density (126.4 mW cm⁻²), small charge–discharge potential polarization (0.52 V), excellent energy efficiency (68.8%) and extraordinary long-term cycling durability (>360 h). This work not only discloses a feasible synergistic modulation strategy for constructing high-performance bifunctional electrocatalysts but also provides a valuable reference for developing corrosion-resistant integrated air electrodes toward practical marine energy storage applications. Full article

The oxygen reduction reaction (ORR) is a key process in electrochemical energy conversion technologies such as fuel cells and metal–air batteries; however, its sluggish kinetics and reliance on precious metal catalysts limit large-scale application. This review provides a comprehensive overview of recent advances in non-precious nanoscale electrocatalysts for ORR in alkaline media. Particular emphasis is placed on reaction mechanisms, including dominant pathways, kinetics, and key intermediates, as well as the advantages of alkaline electrolytes over acidic systems. The performance of various catalyst classes is systematically discussed, including transition metal-based materials (Fe, Co, Zn, Cu, and bimetallic systems) and metal-free carbon-based electrocatalysts. Special attention is given to heteroatom-doped carbon materials, carbon nanostructures, and emerging hybrid systems such as MXene-based composites. Comparative analysis highlights the relationship between catalyst composition, structure, and electrochemical performance metrics, including half-wave potential, onset potential, Tafel slope, number of electron transfer, and operational stability. Overall, non-precious catalysts demonstrate promising activity and durability, approaching that of noble metals under alkaline conditions. The insights summarized in this review guide the rational design of efficient, cost-effective ORR electrocatalysts and support the development of sustainable energy technologies. Full article

Beauty salon wastewater is an emerging commercial greywater characterized by high chemical oxygen demand (COD), intense color, and low biodegradability due to the presence of surfactants and oxidative dye precursors. This study evaluated a solar-assisted photo-Fenton process using waste-derived iron sludge as a heterogeneous catalyst for treating real beauty salon effluent. Operational parameters, including pH, H₂O₂ concentration, iron sludge dosage, reaction time, and temperature, were optimized based on dye removal and COD reduction. Under optimal conditions (pH = 3, H₂O₂ = 400 mg L⁻¹, iron sludge = 40 mg L⁻¹), the system achieved approximately 98% dye removal and 95% COD reduction within 50 min of irradiation. Additionally, maximum performance was observed at 40 °C, while higher temperatures reduced efficiency due to non-productive H₂O₂ decomposition. Kinetic analysis was performed, and the results indicated predominant second-order behavior. Thermodynamic evaluation confirmed an endothermic process with moderate activation energy (Eₐ = 21.8 kJ mol⁻¹). Response surface methodology confirmed strong parameter interactions and high predictive accuracy. The integration of solar irradiation with iron sludge valorization provides a sustainable and decentralized solution for treating dye-loaded beauty salon wastewater. Full article

This study aimed to develop high-performance, ultra-low Pt-loading 2.1 wt% vs. 20 wt% for commercial Pt/C) oxygen reduction reaction (ORR) catalysts. Utilizing carbon nanotubes (CNTs) as templates, a PANI layer was coated onto the surface to serve as a nitrogen-doped anchoring layer for metal species. Physical and structural characterizations demonstrated that the PANI-derived nitrogen-doped carbon layer uniformly encapsulates the CNT skeleton. This architecture not only achieved highly uniform Pt nanoparticle dispersion but also induced strong metal–support electronic interactions via deep-seated Ni atoms, effectively optimizing the electronic structure of the surface Pt. Electrochemical results showed that Pt/Ni-N-CNT delivers superior ORR activity in an acidic electrolyte, with a half-wave potential of 0.846 V (vs. RHE) and limiting diffusion current density outperforming commercial Pt/C (0.81 V vs. RHE), demonstrating excellent oxygen reduction kinetics. Full article

This study investigates the morphological, compositional, and electrochemical properties of carbon materials derived from Pepsi (P) and Coca-Cola (CC) precursors, before and after chemical activation with ZnCl₂. Scanning electron microscopy revealed a lower density of surface cracks in non-activated hydrothermal carbon (NAHC) samples compared to activated carbons (ACs), indicating structural changes induced by the corrosive activation process. Particle size analysis showed an increase in average diameter after activation, particularly pronounced in CC-derived samples, which also exhibited a broader particle size distribution. Elemental mapping confirmed carbon as the dominant and homogeneously distributed element, while oxygen-containing functional groups decreased significantly after activation. Oxygen reduction reaction investigation demonstrated that all synthesized non-activated and activated samples are electrocatalytically active in alkaline solution. CC-NAHC demonstrated the lowest Tafel slope (99 mV dec⁻¹), while activated samples showed higher values, indicating slower kinetics and increased reaction limitations. Despite this, activated carbons—particularly CC-AC—displayed significantly higher diffusion-limited current densities (~−4.8 mA cm⁻² at 1600 rpm), suggesting improved mass transport and conductivity. Furthermore, electron transfer number (n) analysis indicated that P-NAHC and CC-AC follow a near four-electron ORR pathway (n ≈ 3.6–3.9). Full article

Physicochemical transformations in wine aging are strongly influenced by storage environment and scale. While kinetic modeling has been extensively applied to bulk aging systems, bottle aging is often treated as a continuation of cellar evolution despite representing a different physicochemical regime. A reaction-kinetics framework was applied to assess whether wine aging in bulk and bottle environments can be described by a unified model or instead requires divergent quantitative descriptions. A Sangiovese red wine was aged for six months under controlled conditions in inert bulk systems (stainless steel and a non-porous composite material), a porous bulk system (raw earthenware), and glass bottles. Key physicochemical parameters, including dissolved oxygen, oxidation–reduction potential, free sulfur dioxide, anthocyanins, polymerized pigments, and colorimetric indices, were monitored through non-invasive and laboratory analysis. Exploratory multivariate analysis showed that inert systems follow overlapping compositional trajectories, indicating stable chemical evolution, whereas bottle-aged wines exhibited greater variability. Kinetic analysis revealed comparable oxygen-limited behavior and buffered oxidation–reduction evolution in inert bulk systems, whilst bottle aging displayed different oxygen and sulfur dioxide dynamics, consistent with scale effects and altered oxygen partitioning. Overall, bottle aging cannot be reliably predicted by extrapolation of bulk storage kinetics and requires boundary-condition-aware descriptors accounting for scale and environmental constraints. Full article

The cathodic oxygen reduction reaction (ORR) remains a major kinetic barrier to high-efficiency proton exchange membrane fuel cells (PEMFCs), motivating the search for electrocatalysts that combine high activity, low metal usage, and long-term durability. This review examines single-atom catalysts (SACs) as an emerging platform for fuel-cell cathodes with particular emphasis on how atomic-level design, ORR mechanism, and practical deployment barriers are interrelated. The review discusses the key ORR pathways, intermediate binding principles, and scaling constraints that govern cathodic performance, and examines how metal-center selection, coordination-environment engineering, support regulation, synergistic multi-site construction, and morphology-controlled synthesis can be used to tune intrinsic activity and stabilize isolated active sites. It further highlights mechanistic insights from theoretical and operando studies, with emphasis on structure–activity relationships, dynamic active-site evolution, and approaches to mitigate scaling limitations. Major barriers to practical deployment, including carbon corrosion, demetalization, agglomeration, peroxide/reactive oxygen species attack, and the persistent gap between half-cell metrics and membrane electrode assembly performance, are also critically assessed. Rather than treating these topics separately, this review discusses them as connected factors that together determine the viability of SAC-based fuel-cell cathodes. Full article

Hydrogen-based reduction of manganese ores has attracted increasing attention as a promising route for low-carbon manganese production. In this study, the reduction behavior, microstructural evolution, and kinetics of a high-barium-rich manganese ore were investigated in both dried and calcined states under isothermal hydrogen atmospheres at 600–800 °C. The ore was characterized using XRF, XRD, optical microscopy, SEM-EDS, and porosity measurements to evaluate mineralogical and structural changes during calcination and reduction. Calcination at 900 °C transformed MnO₂ into Mn₂O₃/Mn₃O₄, removed volatile components, and generated micro-porosity that improved gas accessibility. Isothermal reduction experiments revealed a rapid initial reduction stage followed by a slower reaction regime, with increasing temperature significantly accelerating the reduction rate. Despite isothermal furnace conditions, a temporary rise in sample temperature was observed due to the exothermic nature of manganese oxide reduction by hydrogen. XRD analysis confirmed that manganese oxides were predominantly reduced to MnO, while iron oxides were converted to metallic Fe. Porosity measurements showed significant pore development during reduction at moderate temperatures due to oxygen removal and gas evolution; however, at higher temperatures, partial sintering led to pore coalescence and densification, reducing the overall porosity. Kinetic analysis showed that the Johnson–Mehl–Avrami–Kolmogorov (JMAK) model effectively describes the reduction behavior. The apparent activation energies were 21.92 kJ.mol⁻¹ for dried ore and 17.40 kJ.mol⁻¹ for calcined ore, indicating diffusion-influenced kinetics. The results demonstrate that calcination enhances hydrogen reducibility by improving gas accessibility and reducing kinetic resistance, highlighting its importance for hydrogen-based manganese pre-reduction processes. Full article