Search Results (6,988)

Harnessing low-grade thermal energy from industrial processes and the environment represents an attractive route toward sustainable chemical production. In this work, we report a thermoelectrocatalytic (TE-Catal) system capable of converting small temperature gradients into chemical energy for hydrogen peroxide (H₂O₂) generation. A hybrid catalyst composed of nickel-based metal–organic frameworks (Ni-MOFs) nanoparticles integrated with carbon nanotubes (CNTs), Ni-MOFs/CNTs, was synthesized through a facile one-pot strategy. Under a temperature gradient, the thermoelectric response of the Ni-MOFs induces charge carrier generation through the Seebeck effect, enabling interfacial redox reactions that produce H₂O₂. However, rapid recombination of thermally generated carriers typically limits catalytic efficiency. By coupling Ni-MOFs with conductive CNTs networks, charge separation and transport are significantly enhanced due to the strong interfacial interaction and the high electrical conductivity of CNTs. As a result, the Ni-MOFs/CNTs nanohybrids exhibit greatly improved H₂O₂ generation rate of ~111.7 µmol g⁻¹ h⁻¹ compared with pristine Ni-MOFs (31.8 µmol g⁻¹ h⁻¹). Thermoelectric electrochemical measurements confirm that the CNT incorporation effectively promotes carrier migration and suppresses recombination. This study demonstrates the potential of MOF-based thermoelectric nanostructures for transforming waste heat into valuable chemical products. Full article

Sulfur is a well-known catalyst poison, particularly for catalysts based on transition metals. Herein, we studied the adsorption of sulfur species on small nanoparticles (~1 nm in size) of the face centered cubic (fcc) transition metals (Rh, Ir, Ni, Pd, Pt, Cu, Ag, and Au) using density functional theory (DFT) modeling. At low sulfur coverage (one S atom per nanoparticle), sulfur preferentially occupies the surface hollow sites of the nanoparticles. At higher coverage, however, the subsurface diffusion of S in Ni, Pd, and Ag nanoparticles becomes energetically favorable with low activation energies. Among the considered metals, sulfur binds most strongly to Rh and Ir, and most weakly to Ag and Au. The present results shed light on the facility of S-poisoning on such metal nanoparticles, either by surface blocking or by underlying sulfurization of the metal. Full article

Ammonia decomposition represents a promising route for CO₂-free hydrogen production; however, the development of efficient and stable catalysts remains a critical challenge. In this work, a series of Al-based mixed-oxide catalysts (AlM, where M = Ni, Co, Ce) were synthesized via co-precipitation and systematically investigated to elucidate the relationship between physicochemical properties and catalytic performance in ammonia decomposition. Comprehensive characterization by X-ray diffraction (XRD), N₂ physisorption (BET), scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM–EDX), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), and pyridine-adsorbed Fourier transform infrared spectroscopy (FTIR-Py) revealed significant variations in surface area, morphology, dispersion, and acidity as a function of the incorporated metal. Among the investigated catalysts, the AlNi system exhibited superior activity, achieving the highest ammonia conversion over the studied temperature range. This enhanced performance is attributed to its high specific surface area, homogeneous mesoporous structure, and a balanced distribution of Lewis/Brønsted acid sites, which promote effective ammonia adsorption, activation and decomposition. Kinetic analysis further confirmed the favorable reaction pathway on AlNi, as evidenced by its lower apparent activation energy and higher pre-exponential factor compared to the other materials. The results demonstrate a clear correlation between surface acidity, textural properties, and catalytic performance, highlighting the pivotal role of AlM interactions in governing ammonia decomposition. These findings provide valuable insights for the rational design of efficient catalysts for hydrogen production from ammonia. Full article

Iron (Fe) and nickel (Ni) were both foundational to early metabolism, yet their biological trajectories diverged as Earth’s surface redox state changed. Here, we integrate mineral chemistry network analysis, protein metal-site coordination-sphere analysis, and curated redox comparisons to test how geochemistry and metalloprotein architecture co-evolved. Mineral network analyses show broader electronegativity variation and network diversity for Fe-bearing minerals through time relative to Ni-bearing minerals. In structural analyses of protein metal centers in a combined Fe/Ni protein structure set, it is shown that Fe- and Ni-associated environments differ in amino-acid composition, hydropathy structure, and cysteine representation. The greater chemical diversity and electronegativity variation in Fe minerals mirror the higher redox and structural versatility of Fe-binding proteins. The presence of Fe in a broader range of mineral and protein environments demonstrates the chemical adaptability of the metal, from the anoxic Archean to oxidative Earth surface conditions following the Great Oxidation Event. Iron, with its broad redox potential range in Fe-oxidoreductases, has a central role in both anaerobic and aerobic metabolisms. Nickel, by contrast, is less widespread in biology. Today, Ni is predominantly employed in deeply branching anaerobic pathways and by proteins with narrower redox potential ranges. Our results show that evolutionary processes, constrained by metal chemistry, habitually utilize Fe as a redox generalist while retaining Ni in specialized roles. The divergent paths of Ni and Fe, from rocks to proteins, demonstrate the intimate relationship between planetary geochemistry and metabolic origins on Earth and suggest that Fe/Ni geochemistry may inform habitability assessments in extraterrestrial environments when interpreted within specific planetary environmental contexts. Full article

High-nickel layered oxide cathodes, exemplified by LiNi_0.9Co_0.05Mn_0.05O₂ (NCM90), exhibit high specific capacity but suffer from severe interfacial degradation and structural instability during electrochemical cycling. Herein, we present a phosphate-based in situ modification approach that forms a durable, self-established cathode–electrolyte interphase (CEI), thereby resolving these key challenges from the root. We employ a controlled (NH₄)₂HPO₄ coating and optimized thermal treatment to fabricate a thin, dense layer of crystalline lithium phosphate on the NCM90 surface. This coherent layer serves as an artificial CEI precursor, which electrochemically evolves into a highly stable and ionically conductive interfacial shield during operation. It effectively suppresses parasitic reactions, mitigates transition metal dissolution, and alleviates mechanical strain induced by phase transitions. Comprehensive optimization of calcination temperature and coating content identifies 760 °C and 1 wt% as the optimal conditions, yielding a well-preserved layered structure and effectively suppressed Li⁺/Ni²⁺ mixing compared with the pristine NCM90. When tested at 0.1 C in the potential range of 2.75–4.3 V, the coated electrode delivers a high initial discharge specific capacity of 204.08 mAh g⁻¹. After 100 charge–discharge cycles at 1 C, it retains 89.24% of its capacity, and its rate capability is also significantly improved. Collectively, these findings verify that forming a customized CEI via precursor coating successfully suppresses interfacial degradation and improves structural integrity, thus representing a viable, scalable pathway toward advanced lithium-ion batteries with exceptionally stable cathodes. Full article

Mining and metallurgical residues represent one of the largest untapped secondary raw-material resources in Europe; however, their critical raw material (CRM) potential remains insufficiently quantified. This study applies a comprehensive mineralogical, geochemical, and geostatistical framework to evaluate nine distinct waste types from the Cartagena–La Unión Mining District (SE Spain), a historically exploited polymetallic system. A total of 79 samples were analysed using X-ray diffraction, wavelength-dispersive X-ray fluorescence, and advanced multivariate statistical techniques (correlation analysis, principal component analysis and hierarchical clustering) to identify geochemical associations controlling CRM distribution. The results reveal strong geochemical heterogeneity, with systematic enrichment in Co, Ni, Cu, Ga, Nb, and rare-earth proxies. Three dominant geochemical controls were identified: (i) a lithogenic silicate association governing Al–Si–Ti–Nb patterns, (ii) a sulphide-derived metalliferous association characterized by Cu–As–Sb, and (iii) an oxidation–adsorption association responsible for Ga–Y affinity. Several CRM concentrations approach or exceed typical global ore grades for secondary resources, particularly in flotation-derived and oxidation-rich residues. Geostatistical modelling confirms spatially coherent CRM hotspots, with base-metal enrichment linked to sulphide relics and Ga–Nb–Y controlled by Fe–Mn oxyhydroxides. Environmental assessment indicates potential metal mobility under acidic conditions, while also highlighting significant remediation benefits associated with residue reprocessing. Taken together, this study provides a robust and reproducible methodology for CRM assessment in legacy mining wastes and identifies priority residue types within the district with the highest strategic recovery potential. Full article

This study investigates the leaching behavior of the LiNi_0.65Co_0.25Mn_0.10O₂ cathode material in a phosphoric acid medium, with metallic copper recycled from spent battery components serving as a reducing agent. The aim was to develop an efficient approach for the recovery of Li, Ni, Co, and Mn while providing a mechanistic understanding. Leaching experiments were performed by varying key parameters, including copper addition, acid concentration (0.2–0.8 mol·L⁻¹), cathode mass (0.2–1.0 g), stirring rate (0–600 rpm), and temperature (35–80 °C). Thermodynamic analysis, supported by Pourbaix and species distribution diagrams, was used to interpret metal behavior. The results show that lithium is readily dissolved, whereas the extraction of Ni, Co, and Mn depends on the presence of copper, which enables their reduction and dissolution. Optimal conditions (0.4 mol·L^‒1 H₃PO₄, 0.2 g Cu, 600 rpm, 80 °C) enabled rapid extraction, exceeding 90% within 30 min, while near-complete extraction (~100%, 99%, 99%, and 97% for Li, Ni, Co, and Mn) was achieved after 60 min. Structural analysis revealed a transformation from the layered structure to spinel-like intermediates, followed by their dissolution and formation of copper phosphate phases. The proposed system represents an efficient approach for the sustainable recycling of NMC cathodes. Full article

Since the synthesis of ferrocene in 1951, metallocenes have attracted attention, making the accurate prediction of their electronic structure and ionization energy crucial for understanding their photophysical and electrochemical behavior in materials and in biological systems. Here, we combined Density Functional Theory (DFT), Complete Active Space Self-Consistent Field (CASSCF), NEVPT2 (N-Electron Valence State Perturbation Theory) and Coupled Cluster approaches (CCSD, DLPNO-CCSD(T)) to study the electronic structure, ionization energies (IEs) and absorption spectra of metallocene and metallocenium complexes in the gas phase and in THF implicit solvent. DFT IEs agree closely with NEVPT2 and DLPNO-CCSD(T) values and with experiment values (deviations 0.02–0.3 eV). For CASSCF and NEVPT2, the minimal active space of the d electrons at six orbitals is not enough for the accurate prediction of the IEs, while an extended active space incorporating all 3d metal electrons plus four ligand valence electrons into 15 orbitals improves the calculated IE values. In solution, computed oxidation energies (OEs) in THF reproduce experimental values and follow the Fe > Ni > Co ordering. Substitution of metallocene complexes with chromophore units results in similar OEs. Overall, the substitution effects remain modest: the effect of substitution on OE values results in differences up to 0.2 eV. These results clarify the effect of the metal center on IE and OE values and UV–vis absorption behavior. Full article

Electrocatalytic nitrate reduction to ammonia (NH₃) offers a sustainable alternative to the Haber–Bosch process while enabling remediation of nitrate-contaminated water. However, the mechanistic origin of performance differences among bimetallic catalysts remains poorly understood, particularly regarding the metal-dependent evolution of reaction intermediates. Here, we construct a series of phase-pure tandem Cu–M catalysts (M = Co, Ni, Fe, Sn) by physically integrating commercial nanoparticles to examine the role of the secondary metal. In this architecture, Cu governs nitrate adsorption and its initial reduction to nitrite, whereas M dictates downstream hydrogenation toward NH₃. Operando ATR–FTIR spectroscopy reveals that NH₃ FE is determined by the hydrogenation kinetics of nitrite-derived intermediates rather than nitrate activation itself. Among the examined systems, Cu–Co achieves optimal kinetic matching, enabling rapid nitrite consumption and continuous hydrogenation, delivering an ammonia Faradaic efficiency of 91.2% with minimal nitrite accumulation (~1.0%) and a yield rate of 0.86 mmol h⁻¹ cm⁻² at −0.5 V vs. RHE. In contrast, Ni and Fe exhibit sluggish hydrogenation, while Sn induces pronounced intermediate buildup. These findings identify nitrite hydrogenation as the selectivity-determining step in tandem nitrate reduction and establish the chemical nature of the secondary metal as a decisive descriptor for rational catalyst design. Full article

Severe heavy metal contamination affects the karst landscapes of Guangxi Zhuang Autonomous Region, China, which are highly polluted and complex. However, integrated assessments of heavy metal sources, distribution, ecological risks, and speciation in karst agricultural soils remain limited. Additionally, there is a gap regarding the interactions between cadmium (Cd), zinc (Zn), and selenium (Se) in natural rice fields. This study employed the pollution load index (PLI), ecological risk index (RI), and Positive Matrix Factorization (PMF) models to evaluate the sources and characteristics of heavy metal contamination in farmland soils. The results showed significant pollution in agricultural soils of Guangxi karst due to Cd, chromium (Cr), copper (Cu), and nickel (Ni). Among these, Cd poses the highest ecological risk. Heavy metal accumulation in the surface soil far exceeds that in deeper layers, and the main sources of Cd were contributed from soil parent material and agricultural activities. Speciation analysis revealed the high bioavailability of Cd, while Zn and Se existed in more stable forms. Despite elevated soil Cd levels, rice grains remained within the safety limits. Using transmission electron microscopy (TEM), Cd was primarily detected in the cell walls of rice stems and husks, which was attributed to Zn’s competitive uptake, reducing Cd absorption and Se forming complexes with Cd to enhance its fixation. Statistical correlations revealed positive associations between Cd in soil and rice. Cd also demonstrated a positive correlation with Se, but a negative correlation with Zn, suggesting a synergistic mechanism between Zn and Se that acts to mitigate the absorption of Cd. This study provides practical guidance for managing farmland soil heavy metal contamination and protecting agricultural soil resources in the karst areas. Full article

Increased soil metal concentrations may be detrimental to human health as well as the environment. This study was conducted to infer the potential environmental risks and possible sources of heavy metal pollution in serpentine soils in Alacakaya. For this purpose, the concentrations of Ni, Co, Zn, Pb, Cu, As, and Cr in 28 soil samples collected from serpentine soils in the region were determined using ICP-MS. The heavy metal pollution of soils in the region was examined by applying different indicators, and the pollution load index (PLI), contamination factor (CF) and geo-accumulation index (Igeo) were used to assess ecological risks. The average concentrations of metals were in the order of Ni (2003) > Cu (1220) > Cr (823) > Zn (206) > Co (159) > Pb (56.9) > As (38.9) mg kg⁻¹. The arsenic (As) concentration exceeded the limits permitted by the World Health Organization (WHO) in 53.6% of the soil samples, the zinc (Zn) concentration in 35.7%; the lead (Pb) concentration in 14.3%; and the Ni, Co, Cr, and Cu concentrations in 100% of the samples. The average Igeos were as follows: As 3.28 (heavily polluted); Cu, 3.23 (heavily polluted); Pb 1.04 (moderately polluted); Zn 0.71 (lightly polluted); Ni, 4.04 (heavily to extremely polluted); and Co 2.03 and Cr 2.35 (moderately to heavily polluted). According to Igeo values, it was stated that Ni, As, Cu, Cr and Co were the elements that posed the greatest ecological risk in the study area. According to the CF values, pollution is observed in all samples, and there is very serious Ni pollution. The heavy metals showing the most pollution were Cu > As > Cr > Co > Pb > Zn. Samples from the study area demonstrate strongly contaminated soil based on the PLI (mean 7.4) values. These findings provide important information for soil remediation and the removal of heavy metal contamination from soils in similar regions. Full article

Heat-assisted metal spinning comprises incremental forming routes, conventional spinning, shear spinning and flow forming, performed at elevated temperature to increase formability. This review consolidates the main advances of the last fifteen years. It outlines spinning mechanics and the rationale for heating (higher ductility, lower forming forces and microstructure control), then compares global and local heating strategies (furnace, flame, induction, laser and hot-gas convection) in terms of temperature uniformity, industrial practicality, energy efficiency and cost. Key process parameters (spindle speed, feed rate and thickness reduction) are discussed with respect to defect formation, and representative windows for defect mitigation are reported. Progress in modeling is reviewed, including coupled thermo-mechanical finite element simulations, damage/formability prediction and emerging data-driven optimization. The review also summarizes microstructural evolution under heat-assisted conditions, phase transformation, dynamic recrystallisation and grain growth, and its impact on final properties. Across more than 100 studies, evidence shows that robust thermal management can roughly double achievable deformation before failure and enables property tailoring in difficult-to-form alloys (Ni-based alloys, high-strength steels, Al, Mg and Ti). Remaining challenges include reliable in situ temperature measurement/control and improved predictive fidelity of simulations. Future opportunities include digital twins, real-time sensing and adaptive, machine-learning-assisted control. Full article

This study presents the first stream-sediment geochemical survey conducted in the western Oecusse enclave (Timor-Leste), aiming to identify geochemical anomalies associated with potential metallic mineralization in a region where mineral occurrences remain poorly documented. A total of 27 stream-sediment samples were collected from first- and second-order drainage systems and analysed for a multi-element suite using ICP-MS and INAA. Robust statistical approaches, including univariate analysis, median absolute deviation (MAD), Tukey boxplot thresholds, and compositional data analysis combined with principal component analysis (CLR–PCA), were applied to identify anomalous geochemical associations. To improve statistical robustness, PCA was performed on reduced and process-oriented variable sets. The results reveal significant geochemical variability, with maximum concentrations reaching 214 mg/kg for As, 142 mg/kg for Co, 27,220 mg/kg for Cr, 437 mg/kg for Cu, 1520 mg/kg for Ni, 67 mg/kg for Pb and 267 mg/kg for Zn. Multivariate analysis distinguishes two main geochemical signatures. The first association (Co–Cr–Ni–Mg–Fe) reflects a strong ultramafic geochemical signal consistent with contributions from mafic to ultramafic lithologies documented in the region. The second association (As–Bi–Cu–Pb–S–Sb–Se–Tl–Zn) indicates polymetallic enrichment commonly observed in sulphide-related geochemical systems. The spatial distribution of these geochemical signals highlights localized drainage basins exhibiting relative enrichment patterns. These results demonstrate the effectiveness of stream-sediment geochemistry as a first-pass exploration tool and provide new geochemical constraints for geological interpretation and future mineral exploration in Timor-Leste. The approach demonstrates the value of integrated geochemical and statistical methods for mineral exploration in data-poor regions. Full article

Mediterranean meadows of Posidonia oceanica are chronically exposed to complex mixtures of environmental contaminants, including metals and trace elements derived from coastal urbanization, maritime traffic, and industrial activities. This study aimed to assess metal-related toxicity in P. oceanica by integrating multi-element burden analysis with a panel of oxidative stress biomarkers. Concentrations of a wide suite of elements were quantified in samples of internal (juvenile), intermediate, and external (adult) leaves, reflecting the ontogenetic structure of the plant. Oxidative responses were evaluated using five biomarkers [i.e., hydrogen peroxide (H₂O₂), lipid peroxidation (TBARS), superoxide dismutase (SOD), glutathione S-transferase (GST), and catalase (CAT)] measured on each leaf compartment. Biomarker data were standardized and integrated into a merged Stress Index summarizing overall physiological toxicity. Associations between individual elements, the sum of all measured elements (ΣallElements), the Stress Index, and single biomarkers were explored using Pearson correlation analysis. Juvenile leaves exhibited the highest Stress Index values, elevated H₂O₂ and TBARS, and marked activation of SOD and GST, indicating early oxidative toxicity. Intermediate leaves showed a trend toward increased CAT activity, not reaching statistical significance, along with minimal damage, suggesting effective detoxification, whereas adult leaves accumulated higher levels of Fe, Ni, and Pb, but displayed moderate stress responses. Overall, leaf-class structure strongly modulated both exposure and toxicological response. The integration of ΣAllElements with multi-biomarker indices provides a robust framework for diagnosing metal-related toxicity in P. oceanica under realistic multi-element exposure scenarios. Full article

In this study, a brazed diamond micro-powder grinding wheel with Ni-based filler metal was fabricated, which achieved one-step grinding forming of YG-6 cemented carbide rods. The interfacial microstructure, elemental diffusion behavior, and interfacial phases of the brazed diamond micro-powder joint were systematically characterized. Furthermore, the machining performance of the brazed diamond micro-powder grinding wheel was comprehensively evaluated in combination with its service life and the surface roughness of the machined YG-6 cemented carbide rods. The results show that the Ni-based filler exhibits good wettability to diamond micro-powder particles, and the diamonds have a reasonable protrusion height in the filler layer, with no graphitization observed on the surface of the brazed diamonds. During the brazing process, the active element Cr continuously segregates toward the diamond surfaces and reacts progressively with dissolved C atoms on the diamond surfaces, eventually forming a lath-shaped Cr–C compound layer on the diamond surfaces. XRD results identify this compound as Cr₃C₂. Elemental diffusion occurs between the filler layer and the steel substrate, forming a Fe–Ni solid solution diffusion zone. Consequently, the Ni-based filler forms a reliable chemical metallurgical bond with both the diamond micro-powder particles and the steel substrate. The as-prepared brazed diamond micro-powder grinding wheel exhibits excellent service life: a single wheel can grind more than 1300 YG-6 cemented carbide rods on average before failure. The surface roughness (Ra) of the machined YG-6 cemented carbide workpieces remains below 1.6 μm throughout all processing stages, which satisfies the requirements for one-step precision grinding. Full article