Search Results (99)

Electrocatalytic glycerol oxidation to formic acid (FA) offers a sustainable route for biomass valorization, yet non-noble metal catalysts generally suffer from sluggish C-C bond cleavage and poor product selectivity. Here we report an amorphous nickel–cobalt oxyhydroxide bearing both metal and oxygen vacancies (D-NiCoO_xH_y-V_Cr,O), grown on nickel foam via one-step electrodeposition followed by electrochemical activation with Cr doping. The coexistence of the dual vacancies is experimentally confirmed by X-ray photoelectron spectroscopy (XPS), which reveals elevated Ni³⁺/Co³⁺ ratios and reduced lattice oxygen, and by electron paramagnetic resonance (EPR), which shows a markedly enhanced signal at g = 2.003. Building on prior Cr-leaching approaches in single-metal nickel oxides, this work extends dual-vacancy engineering to an amorphous bimetallic NiCo oxyhydroxide and correlates the defect structure with glycerol-induced interfacial responses, charge-transfer behavior, and product selectivity. The catalyst delivers 200 mA cm⁻² at 1.31 V vs. RHE and achieves 100% Faradaic efficiency for formate at 1.32 V vs. RHE. In situ electrochemical impedance spectroscopy further reveals a significantly reduced charge-transfer resistance. These results establish Cr-assisted dual-vacancy engineering in amorphous bimetallic oxyhydroxides as a promising strategy for selective biomass electrooxidation. Full article

A nitrogen-doped carbon-confined cobalt–iron bimetallic catalyst (CFNC) was fabricated through high-temperature pyrolysis of a ZIF-67-modified CoFe₂O₄ precursor and employed as a heterogeneous activator for peroxymonosulfate (PMS)-mediated Rhodamine B (RhB) degradation. The physicochemical properties of the as-prepared catalyst were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Brunauer–Emmett–Teller (BET) analysis. These analyses demonstrated that Co–Fe bimetallic species were successfully embedded within the nitrogen-doped carbon framework, forming a confined carbon-supported catalytic structure. Under optimized conditions (CFNC dosage of 20 mg L⁻¹, PMS concentration of 150 mg L⁻¹, and initial pH of 7), the CFNC/PMS system achieved 99.45% RhB removal within 10 min. Moreover, the catalyst retained 78.91% degradation efficiency after five successive cycles, indicating its satisfactory reusability and structural stability. Mechanistic investigations based on radical scavenging experiments and electron paramagnetic resonance (EPR) analysis revealed that PMS activation over CFNC involved the coexistence of radical and non-radical oxidation pathways, in which singlet oxygen (¹O₂) played a predominant role. The defect-rich nitrogen-doped carbon matrix facilitated PMS adsorption and activation, promoting the selective formation of ¹O₂, while the confined Co–Fe bimetallic sites contributed to efficient electron transfer during the catalytic process. The synergistic coupling between the Co–Fe active centers and conductive carbon framework accounted for the enhanced catalytic performance, suppressed metal leaching, and long-term stability of CFNC. This work presents a promising approach for constructing robust bimetallic carbon-based catalysts and advances the application of PMS-driven advanced oxidation processes for wastewater remediation. Full article

Pulse-reverse electrodeposition was investigated as a route to reduce Au consumption while maintaining coating continuity and corrosion performance in thin Ni/Au finishes. A pulse-plated Ni barrier layer with an average thickness of approximately 4.45 μm was first prepared on brass, followed by Au deposition from a potassium dicyanoaurate-based electrolyte containing a cobalt additive. Pulse frequency, duty cycle, forward current density, and reverse current density were evaluated with respect to Au thickness, surface morphology, corrosion potential, roughness, and electrochemical impedance. The processing window was selected hierarchically by requiring an Au thickness of 0.3–0.6 μm, a relatively noble corrosion potential, a compact surface with few visible defects, low roughness, and a consistent impedance response; charge-transfer resistance was not treated as the sole criterion. Within the present bath, substrate, electrode geometry, and power-supply configuration, 800 Hz, 22% duty cycle, 0.11 A·dm⁻² forward current density, and −0.004 A·dm⁻² reverse current density provided the most balanced overall response. Full article

This study presents an archaeometric characterization of fifteen blue-and-white Chinese porcelain sherds (17^th–19^th centuries) from the Jingdezhen, Anxi, and Dehua kiln systems, compared with fragments recovered from the Santana Convent (Lisbon), particularly eighteenth-century materials. A combination of non-invasive, minimally invasive and micro-destructive techniques, including Ground-State Diffuse Reflectance Spectroscopy (GSDR), X-ray Photoelectron Spectroscopy (XPS), micro-Raman spectroscopy, X-ray Fluorescence (XRF), X-ray diffraction (XRD), and stereomicroscopy, was employed to investigate cobalt pigments, glaze composition, firing conditions, and provenance indicators. The results reveal systematic differences between dark- and light-blue glazes, reflecting distinct pigment-processing technologies or simple concentration effects inducing different cobalt coordination environments and/or oxidation states. Raman spectroscopy confirms that cobalt occurs mainly as Co²⁺ ions dissolved in the amorphous silicate glaze matrix. No Raman-detectable crystalline cobalt silicate or cobalt aluminate phases were identified. XRF and XPS analyses show elevated Mn/Co and Fe/Co ratios combined with extremely low arsenic contents, suggesting the predominant use of domestic Chinese cobalt sources. XRD analyses identified quartz, mullite, and minor anorthite, consistent with traditional high-fired hard-paste porcelain technology. Dark-blue radiating star-shaped colored radiating features, particularlyfrequent in Dehua porcelains, were also identified in selected Santana Convent samples, suggesting their attribution to Dehua kiln production and demonstrating the value of glaze defects as complementary provenance markers. Full article

Cobalt-free Li-rich Mn-based layered oxides are promising cathode materials for next-generation lithium-ion batteries because of their high capacity and reduced reliance on cobalt resources. However, their practical application is still limited by low initial Coulombic efficiency, sluggish reaction kinetics, severe voltage decay, and progressive structural degradation during cycling. In this work, a Na-assisted sol–gel strategy was developed to construct a cobalt-free Li-rich Mn-based cathode with multiple twin boundaries, and the optimized sample with the composition of Li_1.13Na_0.06Mn_0.594Ni_0.219O₂ was denoted as SG-TB. Unlike conventional surface coating or elemental doping, this strategy focuses on regulating the bulk crystal framework through crystallographic defect engineering. Structural characterizations indicate that SG-TB contains repeatedly distributed twin-boundary-related interfaces, supporting the presence of multiple twin boundaries within the layered cathode. Benefiting from this structural feature, SG-TB delivers an initial Coulombic efficiency of 96%, an initial discharge capacity of 256 mAh/g, a discharge capacity of 167 mAh/g at 5 C, and a capacity retention of 77% after 200 cycles at 1 C. Further analyses suggest that the multiple twin boundaries help reduce electrochemical polarization, enhance Li⁺ diffusion kinetics, and improve structural retention during cycling. This work demonstrates that Na-assisted multiple twin-boundary engineering is an effective strategy for improving the reaction reversibility and structural stability of cobalt-free Li-rich Mn-based cathodes. Full article

The quest for sustainable hydrogen production via water electrolysis requires the development of efficient, non-precious-metal electrocatalysts. This work presents the sonochemical-assisted synthesis of cobalt ferrite (CoFe₂O₄) nanoparticles as a sustainable alternative to noble metal catalysts. Nanoparticles were synthesized by varying the ultrasonic tip power (40%, 50%, and 60%) to investigate the this effect on their structural and electrochemical properties. Comprehensive characterization using X-ray diffraction, Mössbauer spectroscopy, and transmission electron microscopy confirmed the formation of phase-pure nanoscale spinel structures, with crystallite size increasing from 11.28 to 21.79 nm as the sonication power increased. Electrochemical analysis revealed that the sample synthesized at 60% power (CoFe₂O₄-60) exhibited the highest electrocatalytic performance among the synthesized samples for both the hydrogen and oxygen evolution reactions (HER and OER) in alkaline media. This superior performance is attributed to its largest electrochemically active surface area (ECSA = 6.95 cm²) and lowest overpotentials (${\eta }_{10}=-360$ mV for HER and 410 mV for OER). Despite the larger crystallite size, high-power sonication induced higher density of surface defects and roughness, as evidenced by Mössbauer spectroscopy and electrochemical capacitance measurements. Furthermore, all samples exhibited excellent operational stability during 120 h of chronopotentiometric testing. Moreover, the efficiency of the electrolizer for water splitting was calculated to be 64.7%. These findings demonstrate that ultrasonic power tuning can influence the structural and electrochemical properties of CoFe₂O₄ nanoparticles, contributing to improving durability and bifunctional efficient electrocatalytic activity for alkaline water electrolysis. Full article

Wire arc additive manufacturing (WAAM) demands aluminum feedstock with tightly controlled diameter and high surface integrity. Adding hard TiC nanoparticles is a viable route to enhance the mechanical response of Al wires, yet the associated increase in contact severity can accelerate the wear of wire processing tools, particularly cemented carbide dies. This study elucidates the unidirectional sliding interaction between a TiC reinforced Al WAAM wire, and a WC/Co die material containing 5 wt% Co, using a modified scratch testing configuration under dry and lubricated conditions. Two dominant mechanisms are identified: (i) aluminum adhesion on the die surface and (ii) third body abrasion arising from WC particle pull out, promoted by preferential degradation of the cobalt binder. The presence of TiC nanoparticles reduces both the extent of Al transfer and the intensity of third body abrasion, an effect that is further amplified by lubrication. Consistently, lubrication also diminishes surface defects on the wire after sliding. The results provide a mechanistic basis to balance wire strengthening with tool life and highlight practical levers—nanoparticle reinforcement and lubrication strategies—for mitigating die damage while preserving WAAM wire surface quality. Full article

Cobalt-based catalysts are promising for propane dehydrogenation (PDH), but their practical application is hindered by limited propylene yields, rapid deactivation, and an incomplete understanding of the catalytically relevant Co species. Here, alkaline treatment was used to increase the density of silanol defects on Silicalite-1, thereby creating abundant anchoring sites for highly dispersed Co species. The resulting Co/Silicalite-1 catalyst achieved 45% propane conversion, 96% propylene selectivity, and stable operation over 60 h on stream (k_d = 0.005 h⁻¹). Combined characterization indicates that silanol defects stabilize highly dispersed, defect-anchored Co species that are responsible for the superior PDH performance. By contrast, supports with lower silanol defect densities favor aggregated CoO_x/Co₃O₄-like species, which are less selective for PDH, more susceptible to reduction to metallic Co under reducing conditions, and more prone to cracking and coke formation. These findings reveal a strong correlation between silanol defect density, Co speciation, and catalytic performance, offering mechanistic insights and design principles for the development of efficient PDH catalysts. Full article

As a potential strategic resource of critical metals, deep-sea cobalt-rich crusts represent one of the most promising metal reservoirs within oceanic seamount systems, and their metallogenic mechanism constitutes a frontier topic in deep-sea geoscience research. This review focuses on the cobalt-rich crusts from the Magellan Seamount region in the northwestern Pacific and synthesizes existing geological, mineralogical, and geochemical studies to systematically elucidate their mineralization processes and metal enrichment mechanisms from a microstructural perspective, with particular emphasis on cobalt enrichment and its controlling factors. Based on published observations and experimental evidence, the formation of cobalt-rich crusts is divided into three stages: (1) Mn/Fe colloid formation—At the chemical interface between oxygen-rich bottom water and the oxygen minimum zone (OMZ), Mn²⁺ and Fe²⁺ are oxidized to form hydrated oxide colloids such as δ-MnO₂ and Fe(OH)₃. (2) Key metal adsorption—Colloidal particles adsorb metal ions such as Co²⁺, Ni²⁺, and Cu²⁺ through surface complexation and oxidation–substitution reactions, among which Co²⁺ is further oxidized to Co³⁺ and stably incorporated into MnO₆ octahedral vacancies. (3) Colloid deposition and mineralization—Mn–Fe colloids aggregate, dehydrate, and cement on the exposed seamount bedrock surface to form layered cobalt-rich crusts. This process is dominated by the Fe/Mn redox cycle, representing a continuous evolution from colloidal reactions to solid-phase mineral formation. Biological processes play a crucial catalytic role in the microstructural evolution of the crusts. Mn-oxidizing bacteria and extracellular polymeric substances (EPS) accelerate Mn oxidation, regulate mineral-oriented growth, and enhance particle cementation, thereby significantly improving the oxidation and adsorption efficiency of metal ions. Tectonic and paleoceanographic evolution, seamount topography, and the circulation of Antarctic Bottom Water jointly control the metallogenic environment and metal sources, while crystal defects, redox gradients, and biological activity collectively drive metal enrichment. This review establishes a conceptual framework of a multi-level metallogenic model linking macroscopic oceanic circulation and geological evolution with microscopic chemical and biological processes, providing a theoretical basis for the exploration, prediction, and sustainable development of potential cobalt-rich crust deposits. Full article

Cobalt-based superalloy Co06A exhibits excellent high-temperature performance and is widely used in the repair and additive manufacturing of critical hot-end components via direct laser deposition (DLD). However, improper energy–mass input during direct laser deposition often leads to defects such as porosity, cracks, and poor surface quality, which seriously affect the performance of formed parts. In this study, a systematic experimental investigation based on an orthogonal design was carried out to examine the effects of laser power, scan speed, and powder feed rate on the dilution rate, surface roughness, and powder capture efficiency of a one-layer single Co06A track. Range analysis and multiple linear regression were employed to quantify the influence of each parameter. The results showed that the powder feed rate was the dominant factor affecting both η and Sa, while the laser power had the most significant impact on PE. Through multi-objective optimization, a balanced parameter set (u = 6.66 mm/s, f = 20.81 g/min, P = 2543 W) was recommended, which achieved a dilution rate of about 11.95%, a surface roughness of 4.64 um, and a powder capture efficiency of 79.6%. Through testing, it was found that the energy/mass input ratio was approximately 8. This work demonstrated that matching energy–mass input and adopting a constrained optimization strategy could effectively improve the forming quality and manufacturing efficiency of Co06A in the first-layer manufacturing process, providing a promising prospect in guidance for engineering applications. Full article

In this work, the results of the structural and phase state of LaNi₅-based alloys modified with Ti, Mn, and Co elements, obtained by mechanical alloying and subsequent spark plasma sintering, are presented. X-ray diffraction analysis was carried out to determine the phase composition, lattice parameters, microstrain, and average crystallite size, as well as to study the morphology and microstructure of the synthesized samples. It was established that the ball-to-powder ratio (BPR) and the milling speed affect the degree of intermetallic phase formation and the level of accumulated microstrains. The optimal mechanical alloying parameters make it possible to form the necessary precursor components for subsequent spark plasma sintering (SPS). It was determined that the SPS process effectively promotes the formation of intermetallic phases such as TiNi, LaNi₄Mn, LaNi₃Mn₂, and LaNi₄Co, ensuring high crystallinity and a reduction in defects accumulated during mechanical alloying. The morphology and microstructure of the samples with titanium, manganese, and cobalt additions showed that at the mechanical alloying stage, all systems are characterized by a dispersed and agglomerated structure, a wide particle size distribution, and a developed surface. After SPS, all series exhibited material consolidation and the formation of a dense matrix with distinct grain boundaries. Full article

Facing the increasingly scarce supply of rare-earth resources, a cobalt-doped metal–organic framework-derived carbon–metallic sulfide composite (Co-FeS₂@C) was successfully synthesized via the hydrothermal method and the following carbonization/sulfidation treatments and used for the efficient electrosorption of rare earths from aqueous solution. Comparative characterizations revealed that Co doping effectively expanded the interlayer spacing of FeS₂, introduced crystalline defects, and optimized the electronic structure, thereby synergistically enhancing active site exposure and electron transfer kinetics. In addition, the electrochemical analysis demonstrated a significant increase in the surface-controlled capacitive contribution from 57.1% to 83.3%, indicating the markedly improved electric double-layer effects and mass transport efficiency. Under the optimal conditions, the Co-FeS₂@C electrode achieved a high Yb³⁺ adsorption capacity of 129.2 mg g⁻¹ along with an exceptional cycling stability (92.63% retention after 20 cycles), substantially outperforming the undoped counterpart FeS₂ (88.4 mg g⁻¹ and 74.61%). Furthermore, the mechanistic investigations confirmed that the electrosorption process follows a monolayer physico-chemical synergistic mechanism, primarily driven by the pseudo-capacitive effect arising from the redox reaction of FeS₂ and the enhanced charge-transfer driving force resulting from the higher electronegativity of cobalt. This work provides an innovative electronic structure modulation strategy for developing the high-performance capacitive deionization electrodes for rare earth recovery via the electrosorption process. Full article

The rational design of transition metal oxides with tailored electronic structures and defect chemistries is critical for advancing high-performance supercapacitors. Herein, we report the engineering of cobalt oxide (Co₃O₄) gels through controlled sol–gel synthesis and rare earth (RE) incorporation using neodymium (Nd), gadolinium (Gd), and dual neodymium/gadolinium (Nd/Gd) doping. X-ray diffraction (XRD) confirmed the preservation of the cubic spinel structure with systematic peak shifts and broadening, evidencing lattice strain, oxygen vacancy generation, and defect enrichment. Field-emission scanning electron microscopy (FE-SEM) analyses revealed distinct morphological evolution from compact nanoparticle assemblies in pristine Co₃O₄ to highly porous, interconnected frameworks in Nd/Gd–Co₃O₄ (Nd/Gd-Co). X-ray photoelectron spectroscopy (XPS) verified the stable incorporation of RE ions, accompanied by electronic interaction with the Co–O matrix and enhanced oxygen defect states. Electrochemical measurements demonstrated that the Nd/Gd–Co electrode achieved a remarkable areal capacitance of 25 F/cm² at 8 mA/cm², superior ionic diffusion coefficients, and the lowest equivalent series resistance (0.26 Ω) among all samples. Long-term cycling confirmed 84.35% capacitance retention with 94.46% coulombic efficiency after 12,000 cycles. Furthermore, the asymmetric pouch-type supercapacitor (APSD) constructed with Nd/Gd–Co as the positive electrode and activated carbon as the negative electrode delivered a wide operational window of 1.5 V, an areal capacitance of 140 mF/cm², an energy density of 0.044 mWh/cm², and 89.44% retention after 7000 cycles. These findings establish Nd/Gd-Co gels as robust and scalable electrode materials and demonstrate that RE co-doping is an effective strategy for bridging high energy density with long-term electrochemical stability in asymmetric supercapacitors. Full article

This study employs a multi-technique approach to elucidate how graphene incorporation affects phase formation, microstructure, and thermal behavior in PVA-assisted sol–gel synthesized Ca_2.95Eu_0.05Co₄O_x nanomaterials. XRD confirms the preservation of the primary phases (hexagonal CaCO₃ and cubic CoO) alongside a distinct graphene (002) reflection; a systematic low-angle shift of the calcite (104) peak evidences partial relaxation of residual lattice strain with increasing graphene content, while Scherrer analysis indicates tunable crystallite size. Raman spectroscopy corroborates graphene incorporation through pronounced D (~1300 cm⁻¹) and G (~1580 cm⁻¹) bands and supports the XRD-identified phase coexistence via cobalt-oxide and calcite vibrations in the 200–700 cm⁻¹ region, also indicating increased defect/disorder with graphene loading. SEM shows grain refinement, denser/bridged lamellar textures, and reduced porosity at low–moderate graphene contents (1–3 wt.%), contrasted by agglomeration-driven heterogeneity at higher loadings (5–7 wt.%). EDX reveals increasing carbon with Ca/Co redistribution at accessible surfaces, and TG–DSC corroborates the removal of oxygen-containing groups and oxidative combustion of graphene at mid temperatures. Collectively, Raman–XRD-consistent evidence demonstrates that graphene provides a tunable handle over lattice strain, crystallite size, and grain-boundary architecture, establishing a processing–composition basis for optimizing functional (e.g., electrical/thermoelectric) performance. Full article

Cobalt-doped iron disulfide (FeS₂) thin films were synthesized via chemical bath deposition (CBD) followed by annealing at 450 °C, yielding phase-pure pyrite structures with multifunctional properties. A deposition temperature of 95 °C is critical for promoting Co incorporation, suppressing sulphur vacancies, and achieving structural stabilization of the film. After annealing, the dendritic morphologies transformed into compact quasi-spherical nanoparticles (~100 nm), which enhanced the crystallinity and optoelectronic performance of the films. The films exhibited strong absorption (>50%) in the visible and near-infrared regions and tunable direct bandgaps (1.14 to 0.96 eV, within the optimal range for single-junction solar cells. Electrical characterization revealed a fourth-order increase in conductivity after annealing (up to 4.78 Ω⁻¹ cm⁻¹) and confirmed stable p-type behavior associated with Co²⁺-induced acceptor states and defect passivation. These results demonstrate that CBD enabled the fabrication of Co-doped FeS₂ thin films with synergistic structural, electrical, and optical properties. The integration of earth-abundant elements and tunable electronic properties makes these films promising absorber materials for the next-generation photovoltaic devices. Full article