Search Results (296)

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

Electrocatalytic H₂O₂ production via the two-electron oxygen reduction reaction (ORR) is a highly sustainable alternative to industrial methods. To further optimize non-noble catalysts, we report an interfacial engineering strategy to stabilize the metastable P6₃/mmc-La₂O₃ phase on SrTiO₃. This symmetry evolution from the low-symmetry $\mathrm{P}\stackrel{\mathrm{-}}{3}\mathrm{m}1$ (trigonal) to the high-symmetry P6₃/mmc (hexagonal) space group yields a composite with >95% H₂O₂ selectivity. Mechanistic studies demonstrate that the symmetry-regulated interface optimizes *OOH conversion and suppresses O–O bond cleavage. This work offers a robust design principle for high-performance, noble-metal-free H₂O₂ electrosynthesis. Full article

The electrochemical CO₂ reduction reaction (CO₂RR) offers a sustainable route for converting greenhouse gases into high-value fuels; however, its efficiency has long been constrained by the thermodynamic stability of CO₂ molecules and the competing hydrogen evolution reaction. Using density functional theory (DFT) calculations, this work systematically investigates the catalytic performance of Ni₅ and alloy Ni₄Cu clusters anchored on divacancy graphene (DVG) for CO₂RR. The results demonstrate that the introduction of Cu atoms significantly enhances the interfacial binding energy between the cluster and the support (shifting from −6.2 eV to −7.5 eV). Charge density difference analysis combined with Bader charge analysis further reveals that interfacial charge transfer and the formation of Ni–C bonds serve as the electronic origin of this improved stability. Free energy calculations show that, compared to Ni₅/DVG, Ni₄Cu/DVG substantially reduces the energy barrier of the rate-determining step for formic acid (HCOOH) formation from 1.18 eV to 0.26 eV, thereby significantly optimizing the reaction kinetics. Crystal orbital Hamilton population (COHP) analysis demonstrates that Cu doping modulates metal–oxygen bond strength in the key *OCHO intermediate (ICOHP: Ni-O bonds at −0.697 eV/−0.976 eV vs. Cu-O bonds at −0.408 eV/−0.492 eV), optimizing the adsorption–desorption balance and steering selectivity toward HCOOH. This work elucidates the atomic-scale electronic and bonding mechanisms underlying Ni–Cu synergistic effects, providing theoretical guidance for designing efficient non-noble metal CO₂RR electrocatalysts. Full article

In this study, a three-dimensional simulation of a walking-beam reheating furnace was developed to improve the steel slab reheating process and reduce surface oxidation kinetics using computational fluid dynamics (CFD). Combustion, heat transfer, fluid dynamics, and chemical reaction models were integrated into the numerical framework of this study. In addition, dynamic mesh remeshing was coupled through user-defined functions (UDFs), enabling the simultaneous simulation of slab movement and evolution of the involved transport phenomena. Turbulence was modeled with the realizable k-ε formulation, combustion with the Eddy Dissipation model, and radiation with the P-1 model coupled with WSGGM to include CO₂ and H₂O gas radiation. Scale formation was modeled using customized functions based on Arrhenius-type kinetics and Wagner’s oxidation model, evaluating its growth as a function of time, temperature, and furnace atmosphere. The predicted thermal evolution inside the furnace was validated using industrial data, yielding an average deviation of 5%. Furthermore, the proposed operating conditions led to an average slab temperature of 1289.77 °C at the exit of the homogenization zone, which was 16 °C higher than that under the current operation but still within the target range (1250 ± 50 °C). The reduction in combustion air decreased energy losses and improved product quality, lowering the molar oxygen content in the furnace atmosphere from 4.9 × 10² mol to 6.7 × 10¹ mol. Additionally, annual savings of 4,793,472 kg of natural gas and 13,884 tons of steel were estimated owing to reduced oxidation losses. The proposed air–fuel adjustment led to estimated annual energy savings (equivalent to 4,793,472 kg of natural gas) and a reduction in material loss due to oxidation from 4.5% to 3.75% (an absolute reduction of 0.75 percentage points; relative reduction ≈ 16.7%), which has a significant industrial impact on metal conservation and descaling cost reduction. Although there are CFD studies on plate overheating and scale growth separately, this work presents three main contributions: (1) the integration, within a single numerical framework, of combustion, radiation, species transport, oxidation kinetics, and actual plate movement using a dynamic mesh; (2) validation against continuous industrial records (16 thermocouples) and quantification of operational benefits such as fuel savings and reduced material loss; and (3) a comparative analysis between actual and optimized conditions, which standardize the air–methane ratio. Full article

Metal-free electrodes are essential to promote electrochemical reactions, the core of sustainable energy resources. In search of better carbon-based electrode materials, we have explored several spatial arrangements of boron (B) within proximity in the graphene lattice, as evident in recent experimental observations. Multi-boron substitution enriches sites by tuning electronic structure and strengthens binding of key intermediates of oxygen reduction, oxygen evolution, and hydrogen evolution reactions facilitating electrocatalytic performance. Our optimal B-doped site shows near thermo-neutral H adsorption ($\Delta G_{H^{*}}$∼$\pm 0.4\mathrm{eV}$), consistent with experiments. The overpotentials are highly sensitive to the dopant motifs and the spread among configurations shows that experimentally accessible multi-B doping can serve as a practical active site engineering knob to achieve optimized multi-functional performance. In parallel, we find that specific multi-B configurations selectively capture and pre-activate NO_x (NO/NO₂) under ambient conditions while retaining weak affinity for NH₃. These sites also interact with SO₂ and related hazardous species, enabling selective air filtration and targeted NO_x control within the electrocatalytic scope of this study. Full article

Hollow nanostructures have emerged as a pivotal class of nanomaterials in electrocatalysis, offering intrinsic advantages such as high surface-to-volume ratios, reduced density, and economical utilization of precious metals. However, the prevailing research paradigm has predominantly focused on the external shell characteristics while overlooking the decisive role of the interior cavity microenvironment. This review introduces a novel conceptual framework that positions the rational engineering of the cavity microenvironment—encompassing mass transport dynamics, localized electronic structure modulation, active site exposure, and structural stability—as a unified design principle for next-generation electrocatalysts. We systematically elucidate how precise control over cavity geometry, composition, and interfacial properties can optimize electrocatalytic performance for oxygen reduction (ORR), oxygen evolution (OER), and hydrogen evolution (HER) reactions. By correlating microenvironmental parameters with catalytic metrics, we establish structure–property–performance relationships and highlight recent breakthroughs. Finally, we outline future challenges in achieving atomic-level precision in cavity design, understanding dynamic evolution under operating conditions, and scaling up synthesis for industrial applications. Full article

The water–energy–carbon (WEC) nexus provides a systems framework for minimizing trade-offs among water security, energy reliability, and carbon mitigation. Within this framework, waste-derived biochar catalysts offer a circular pathway that simultaneously valorizes residues, reduces process energy demand, and supports carbon management through stable carbon storage and catalytic co-benefits. This review consolidates recent advances in biochar-based catalysts engineered from agricultural, industrial, municipal, and sludge-derived wastes, highlighting how feedstock selection and thermochemical processing, namely pyrolysis, hydrothermal carbonization (HTC), and torrefaction, as well as activation and post-modification (heteroatom doping and metal/metal-oxide incorporation) govern structure–property–performance relationships. The synthesized catalysts have been widely applied in water and wastewater treatment, including adsorption–advanced oxidation process (AOP) hybrids, Fenton-like systems, peroxydisulfate/persulfate (PS) and peroxymonosulfate (PMS) activation, photocatalysis, and the removal of emerging contaminants. They have also demonstrated strong potential in energy conversion processes such as the hydrogen evolution reaction (HER), oxygen reduction and evolution reactions (ORR/OER), biomass reforming, and carbon dioxide (CO₂) conversion. In addition, these materials contribute to carbon management through sequestration pathways, avoided emissions, and life cycle assessment (LCA)-based sustainability evaluations. Finally, we propose a WEC-aligned design roadmap integrating techno-economic analysis (TEA), LCA, and scale-up considerations to guide next-generation biochar catalysts toward robust performance in real matrices and deployment-ready systems. 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

In this study, the feasibility of a new group of alkali-free high-entropy ABO_3-δ perovskite cathodes, in which the B-site is occupied by a mixture of 3d and 4d/5d elements, is examined. Six different materials with a general formula of La(Cu_0.2Ni_0.2X1_0.2X2_0.2Y1_0.2)O_3-δ (where X1, X2 = mixture of two Co, Ga, Fe, and Y1 = one of Nb/Ta): La(Cu_0.2Ni_0.2Co_0.2Ga_0.2Nb_0.2)O_3-δ, La(Cu_0.2Ni_0.2Co_0.2Ga_0.2Ta_0.2)O_3-δ, La(Cu_0.2Ni_0.2Fe_0.2Ga_0.2-Nb_0.2)O_3-δ, La(Cu_0.2Ni_0.2Fe_0.2Ga_0.2-Ta_0.2)O_3-δ, La(Cu_0.2Ni_0.2Co_0.2Fe_0.2Nb_0.2)O_3-δ, La(Cu_0.2Ni_0.2Co_0.2Fe_0.2Ta_0.2)O_3-δ were synthesized, with five of them possessing a single-phase, Pnma perovskite structure. While in the case of the basic properties, such as electrical conductivity or thermomechanical behavior, the studied oxides show a number of similarities, the differences between them become more apparent when low-temperature Oxygen Evolution Reaction (OER) and high-temperature Oxygen Reduction Reaction performance is evaluated. The overall best performance is achieved by La(Cu_0.2Ni_0.2Co_0.2Fe_0.2Nb_0.2)O_3-δ and La(Cu_0.2Ni_0.2Co_0.2Fe_0.2Ta_0.2)O_3-δ compositions, with the former offering slightly faster OER kinetics, and the latter exhibiting superior polarization resistance as an SOFC cathode. Overall, the materials exhibit a strong correlation between composition and properties, with potential for further development into non-equimolar compositions of superior performance. Full article

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are two processes that occur during the operation of the cathodic electrode in Zn–Air batteries, which enable the integration of alternative energy sources into electrical energy distribution systems. Transition metal oxides, such as perovskites based on LaNiO₃, are promising electrocatalysts for the ORR and OER in alkaline medium due to their versatile structure, allowing for the substitution of certain atoms with dopants, which enhances the catalytic activity for both reactions. This work reports an electrochemical study of the catalytic activity toward ORR and OER of perovskite catalysts (LaNiO3 doped with transition metals (Fe, Mn, or Pd)) in the presence of carbon-based materials as supports (multiwalled carbon nanotubes (MWCNT), graphene oxide nanosheets (GO), and graphitic carbon (C)). The results revealed interesting catalytic properties in both reactions, particularly La(Ni_0.9Pd_0.1)O₃/MWCNT, which showed an ORR activation potential of 0.87 V vs. RHE, comparable to that of the commercial Pt/C catalyst (0.99 V vs. RHE), while the overpotential for OER was lower than that of the Pt/C catalyst (1.68 V vs. RHE for La(Ni_0.9Pd_0.1)O₃/MWCNT and 1.79 V vs. RHE for the commercial Pt/C). Full article

Rechargeable zinc–air batteries (ZABs) are still impeded by the intrinsically sluggish kinetics of oxygen reduction and evolution reactions (ORR/OER) and by the instability or prohibitive price of state-of-the-art noble metal catalysts. Metal–organic frameworks (MOFs) have recently emerged as versatile sacrificial templates for next-generation air–cathode electrocatalysts. By programming pyrolytic or chemical conversion pathways, MOFs can be quantitatively transformed into hierarchically porous, heteroatom-doped carbon scaffolds that embed uniform metal, alloy, or metal-oxide nanodomains. The resulting architectures couple metallic conductivity with molecular-scale active site tunability, delivering exceptional ORR/OER activity, stability, and mass transport properties. This review critically examines the most recent advances in MOF-derived electrocatalysts for ZABs, establishing quantitative structure–composition–performance relationships across mono-, bi-, and multi-metallic systems. Emphasis is placed on deciphering how framework topology, metal–ligand coordination, and post-synthetic parameters dictate the density, electronic structure, and accessibility of surface-active moieties during catalyst evolution. We further dissect engineering strategies that enhance intrinsic activity via electronic modulation, bolster durability through encapsulation effects, and optimize hierarchical porosity for rapid O₂/water transport. This article concludes by outlining unresolved challenges and future research directions, including atomically precise active site construction, multi-scale compositional control, long-term reversibility under realistic ZABs cycles, scalable and green synthesis, providing a roadmap for translating MOF-derived catalysts from laboratory curiosities to commercially viable air–cathode materials. Full article

The selection of appropriate signal labels is a central consideration in electrochemical biosensing as it directly determines the achievable detection limits, dynamic range, and overall analytical performance. Conventional electroactive labels require low operating potentials, fast electron-transfer kinetics, and reliable attachment to electrode surfaces or recognition elements. Despite their extensive use, these labels present notable challenges for point-of-care applications, particularly in the detection of small molecules where target binding does not inherently generate a measurable electrochemical output. As a result, most sensing architectures depend on externally added redox reporters, introduced either freely into solution or covalently linked to recognition structures, which increases assay complexity and limits scalability. These limitations have motivated the transition toward energy-based electrochemical signal pathways, such as the hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), and water-splitting reactions. These reactions provide intrinsic electrochemical outputs that eliminate the need for synthetic redox mediators and can operate as built-in catalytic signal sources. Their integration into biosensing platforms simplifies assay design, enhances robustness, and broadens compatibility with diverse target molecules. This review outlines the mechanistic basis connecting HER/ORR/water-splitting reactions to signal generation in biosensors and highlights material design principles that enable their use as reagentless and label-free transduction strategies. Compared with traditional electroactive labels, energy-driven approaches offer simplicity, reduced cost, faster operation, and improved suitability for commercial translation. By establishing a unified framework for energy-based electro-recording mechanisms, this review aims to promote the development of next-generation bioanalytical methods that operate without electroactive labels and expand the applicability of electrochemical biosensing across various domains. Full article

This study presents an integrated low-temperature processing route that converts tungstic acid and ammonium paratungstate derived from scheelite ore (CaWO₄) into nanoscale tungsten trioxide (WO₃), metallic tungsten (W), and tungsten carbide (WC) via solid-state reaction, hydrogen reduction, and gas–solid reaction, respectively. This approach enables particle size control, reduced energy consumption, and enhanced functional properties, enabling evaluation of the materials’ performance in the oxygen evolution reaction (OER). X-ray diffraction (XRD) confirmed the formation of the desired phases with nanocrystalline structures and average crystallite sizes of 13.3 nm (WO₃), 31.55 nm (W), and 10.35 nm (WC). The materials exhibited homogeneous morphologies, demonstrating the effectiveness of the synthesis routes. Electrochemical measurements revealed promising OER activity; the WO₃ electrode showed the lowest overpotential of 321 mV at 10 mA cm⁻², while W and WC showed 327 mV and 340 mV, respectively, in 1.0 M KOH. Overall, the results demonstrate a strategy for scheelite valorization. Full article

This study investigates the evolution and influencing factors of non-metallic inclusions in industrial pipeline steel during the vacuum degassing (VD) process. Steel and slag samples were systematically collected at multiple intervals throughout the vacuum treatment using an automated robotic sampler, which integrated temperature measurement and sampling functions. The results indicate that the molten steel temperature and the concentrations of nitrogen, oxygen, and sulfur exhibited an overall decreasing trend, with removal kinetics characterized by a rapid initial reduction followed by a gradual stabilization. The dominant inclusion phases were identified as Mg-Al spinel and calcium aluminates. Specifically, the top slag composition was distributed within the C₃A phase field, trending toward the liquid C₁₂A₇ region, while the endogenous inclusions transitioned from CA₂ toward CA. With prolonged vacuum treatment, the relative fraction of calcium aluminates progressively increased at the expense of Mg-Al spinel due to continuous slag-metal reactions. Furthermore, quantitative analysis reveals that the population density of small equivalent circular diameter (ECD) inclusions continuously decreased, while the average inclusion size increased, indicating that the VD process promotes the collision and coalescence of inclusions. Full article

The rational design and synthesis of efficient and durable bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is of great significance and challenging for rechargeable zinc–air batteries. While much attention has been devoted to enhancing ORR performance in recent studies, the effectiveness of OER is equally crucial for charging performance of Zn–air batteries. In this work, NH₂-MIL-101(Fe) is employed as a precursor to derive Fe-NC through a straightforward pyrolysis method. Subsequently, NiFe-LDH is synthesized on the surface of Fe-NC via a wet-chemical process to obtain Fe-NC@NiFe-LDH. Capitalizing on the synergistic interplay between Fe-NC, serving as the ORR active site, and NiFe-LDH, acting as the OER active site, Fe-NC@NiFe-LDH demonstrates remarkable bifunctional electrocatalytic performance, boasting a positive half-wave potential of 0.83 V for ORR and a low potential of 1.68 V for OER at a current density of 10 mA cm⁻², alongside exceptional stability in alkaline environments. Furthermore, the Fe-NC@NiFe-LDH-based Zn–air battery exhibits outstanding discharge and charge performance, maintaining excellent cycling stability over 600 h (3600 cycles). Full article