Search Results (151)

The Qieliekeqi siderite deposit, located in the Tashkurgan block of western Kunlun, is a carbonate-hosted iron deposit with hydrothermal sedimentary features. This study integrates whole-rock geochemistry, stable isotopes, and zircon U–Pb–Hf data to investigate its metallogenic evolution. Coarse-grained siderite samples, formed in deeper water, exhibit average Al₂O₃/TiO₂ ratios of 29.14, δEu of 2.69, and δCe of 0.83, indicating hydrothermal fluid dominance with limited seawater mixing. Banded samples from shallower settings show an average Al₂O₃/TiO₂ of 17.07, δEu of 3.18, and δCe of 0.94, suggesting stronger seawater interaction under oxidizing conditions. Both types are enriched in Mn, Co, and Ba, with low Ti and Al contents. Stable isotope results (δ¹³C_PDB = −6.0‰ to −4.6‰; δ¹⁸O_SMOW = 16.0‰ to 16.9‰) point to seawater-dominated fluids with minor magmatic and meteoric contributions, formed under open-system conditions at avg. temperatures of 53 to 58 °C. Zircon U–Pb dating yields an age of 211.01 ± 0.82 Ma, with an average εHf(t) of −3.94, indicating derivation from the partially melted ancient crust. These results support a two-stage model involving Late Cambrian hydrothermal sedimentation and Late Triassic magmatic overprinting. Full article

This study evaluates the wear and corrosion resistance of the Cu-50Ni-5Al alloy reinforced with CeO₂ nanoparticles for potential use as anodes in molten carbonate fuel cells (MCFCs). Cu–50Ni–5Al alloys were synthesized, with and without the incorporation of 1% CeO₂ nanoparticles, by the mechanical alloying method and spark plasma sintering (SPS). The samples were evaluated using a single scratch test with a cone-spherical diamond indenter under progressive normal loading conditions. A non-contact 3D surface profiler characterized the scratched surfaces to support the analysis. Progressive loading tests indicated a reduction of up to 50% in COF with 1% NPs, with specific values drop-ping from 0.48 in the unreinforced alloy to 0.25 in the CeO₂-doped composite at 15 N of applied load. Furthermore, the introduction of CeO₂ decreased scratch depths by 25%, indicating enhanced wear resistance. The electrochemical behavior of the samples was evaluated by electrochemical impedance spectroscopy (EIS) in a molten carbonate medium under a H₂/N₂ atmosphere at 550 °C for 120 h. Subsequently, the corrosion products were characterized using X-ray diffraction (XRD), scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS), and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the CeO₂-reinforced alloy exhibits superior electro-chemical stability in molten carbonate environments (Li₂CO₃-K₂CO₃) under an H₂/N₂ atmosphere at 550 °C for 120 h. A marked reduction in polarization resistance and a pronounced re-passivation effect were observed, suggesting enhanced anodic protection. This effect is attributed to the formation of aluminum and copper oxides in both compositions, together with the appearance of NiO as the predominant phase in the materials reinforced with nanoparticles in a hydrogen-reducing atmosphere. The addition of CeO₂ nanoparticles significantly improves wear resistance and corrosion performance. Recognizing this effect is vital for creating strategies to enhance the material’s durability in challenging environments like MCFC. Full article

The use of different nanoparticles (NPs) is increasing in a wide variety of everyday products. Nevertheless, most studies concerning NP risk assessment have evaluated exposure scenarios involving a single kind of NP. A stepwise study distinguishing between the effects resulting from exposure to one kind of NP and those resulting from different co-exposure scenarios to ${\mathrm{Al}}_2{\mathrm{O}}_3$ and ${\mathrm{CeO}}_2$ NPs at concentrations below acute toxicity was conducted with different analytical techniques. As a starting point, WST-1 viability assays were performed to assess whether the chosen exposure concentrations resulted in any acute loss of viability, which would hamper further insight into the cellular response to NP exposure. Then, data on NP dissolution and uptake were obtained via single-particle inductively coupled plasma–mass spectrometry (spICP-MS) and microwave-assisted ICP-MS. Additionally, time-of-flight secondary ion mass spectrometry (ToF-SIMS) was performed to check for differences in the biological response to the exposure scenarios at the single-cell level. It was found that the proposed combined techniques provide insight into changes in biological responses as well as cellular metal contents among the exposure scenarios. In this work, a comprehensive tiered analytical strategy for evaluating the biological responses to challenging exposure scenarios is provided. The results highlight the necessity of selecting situations more closely resembling real life—including concentrations below acute toxicity and potential interactions due to multiple NPs—when estimating potential health risks. These findings thus provide a foundation and an incentive for further research into the complex processes leading to the observed effects. Full article

Carbonaceous shale has garnered significant interest as a viable alternative source of rare earth elements (REEs) besides conventional REE-bearing ores. This study characterized rare earth element + Yttrium+ Scandium (REYs) enrichment in the 11 core samples of carbonaceous shale (7) and coal (4) collected from Arnot Mine. Major elements of the studied carbonaceous shale (CS) and coal showed high amounts of SiO₂, Al₂O₃, and Fe₂O₃, indicating a high content of aluminosilicate and iron-rich minerals. The plots Na₂O + K₂O against SiO₂ suggested alkali granite, granite, and granodiorite provenance sources for the studied shale and coal. The samples showed enrichment in low and heavy rare elements crystallized from a low potassium tholeiitic and medium calc-alkaline magma based on the plots of La_N/Yb_N and K₂O vs. SiO₂. The mineralogical and maceral analysis revealed the dominant presence of kaolinite (15%–45%), and it was suggested as the cation exchange site resulting from the isomorphous substitution of Al³⁺ for Si⁴⁺. Additionally, siderite was suggested as one of the REY hosts due to the Fe³⁺ site forming a complex with the REE³⁺ ions. Furthermore, the samples were classified as lignite to sub-bituminous coal category with dominant minerals including kaolinite, quartz, and siderite. The outlook coefficient (Coutl) of REY in CS revealed a promising area for economically viable, having two enrichment types, including low (La, Ce, Pr, Nd, and Sm) and heavy (Ho, Er, Tm, Yb, and Lu). The Eu_N/Eu_N* and Ce_N/Ce_N* ratio for the current studied samples exhibited a weak negative to no anomaly, and most of the studied samples were characterized by distinctive positive Gd anomalies derived from sediment source regions weathered from alkali granite, granite, and granodiorite provenance formed from a low potassium tholeiitic and medium calc-alkaline magma. Full article

Zirconolite is a wasteform that can immobilize Pu. Herein, zirconolites comprising Ce as a Pu simulant and Al as a charge compensator of Ce/Pu were synthesized by sintering raw CaO, ZrO₂, TiO₂, CeO₂, and Al₂O₃ powder mixtures at 1400 °C in static air. The reduction behavior and phase transformation of zirconolites during their heat treatment in an Ar–H₂ gas flow were investigated. In pure and Ce–Al co-doped zirconolite compositions, 2M-zirconolite and small amounts of perovskite were obtained after sintering. In contrast, 2M-, 4M-zirconolite and relatively large amounts of perovskite were obtained in Ce-doped zirconolite composition. All zirconolite compositions first underwent reduction at ~1050 °C by forming a small domain of perovskite phase. Ce–Al co-doped zirconolite showed a smaller fraction of phase transformation in perovskite than Ce-doped zirconolite, indicating the advantage of using a charge compensator to prevent perovskite formation. Full article

Nanoparticles of GdAlO₃:Ce were synthesized with sodium dodecylbenzene sulfonate (SDBS) as the dispersant and ammonia as the precipitant by co-precipitation reaction to prepare precursors under different conditions. The phase composition of the precursors and the particle morphology were characterized by thermogravimetry-differential thermal analysis (TG-DTA), X-ray diffraction (XRD), and scanning electron microscope (SEM). The excitation and emission spectra of the resultant samples were analyzed using a photoluminescence spectroscope (PL). The results showed that the as-prepared, well-dispersed, nano-sized GdAlO₃:Ce powder displayed spherical morphology at the initial concentration of metallic salt in liquor of 0.3 mol/L; the synthesized temperature was 0 °C, and it was calcined at 1300 °C for 2 h. The relative intensity of the photoluminescence peak had the maximum value when the Ce³⁺ dopant content was 0.9 mol% (mole fraction). The concentration quench occurred when the Ce³⁺ dopant content exceeded 0.9 mol%, and the peak of the excitation spectrum appeared at a wavelength of 381 nm. Full article

Geochemical proxies are a reliable tool in deciphering the paleoenvironment and diagenetic alteration in carbonate rock units. The Lower Cretaceous Yamama Formation (LCYF) is an important carbonate unit of the Saudi Arabia region which has been studied in detail to evaluate the paleoenvironment and diagenetic alteration through geochemical studies. This study presents new data on petrography, stable isotopes, and trace and rare-earth elements to enhance our understanding on paleoenvironments, redox conditions, and paleosalinity during the deposition of these carbonate units. Field studies show that the formation is composed of thick-to-thin-bedded limestone. Petrographic studies show that the formation is mostly composed of mudstone, wackestone, packstone, and grainstone facies. The stable isotopic values of carbon (δ¹³C V-PDB = +0.58‰ to +2.23‰) and oxygen (δ¹⁸O V-PDB = −6.38‰ to −4.48‰) are directly within the range of marine signatures. CaCO₃’s dominance over SiO₂ and Al₂O₃ indicates minimal detrital contribution during the LCYF precipitation. The REE pattern suggests coeval marine signatures which include (i) a slight LREE depletion compared to HREEs (av. Nd/Yb_N = 0.70), (ii) negative Ce anomalies (av. Ce/Ce* = 0.5), and (iii) a positive La anomaly (av. La/La* = 1.70). Micritic limestone has low Hf (bdl to 0.4 µg/g), Sc (bdl to 2.5 µg/g), and Th (bdl to 0.8 µg/g) content, which suggests negligible detrital influence. The Ce content of different facies (Ce = 1u.80 to 12.85 µg/g) suggests that their deposition took place under oxic to dysoxic conditions. However, there is moderate variation during the deposition of MF-I, with higher Ce values as compared to MF-II, MF-III, and MF-IV, which suggests that the deposition of MF-I mostly took place in anoxic to dysoxic conditions. Full article

Methane and carbon dioxide, the primary contributors to global warming, are now at critical levels, threatening the extinction of numerous organisms on our planet. In this regard, dry reforming of methane reactions have gained considerable attention because of the conversion capacity of CH₄ and CO₂ into synthetic/energy-important syngas (H₂ and CO). Herein, a molecular sieve (CBV3024E; SiO₂/Al₂O₃ = 30) with ZSM-8-type pore architect, is utilized as the support for the active site of Ni and Ce promoters. Catalysts are characterized by surface area and porosity, X-ray diffraction study, Raman and infrared spectroscopy, thermogravimetry analysis, and temperature-programmed reduction/desorption techniques. A total of 2 wt.% ceria is added over 5Ni/CBV3024E to induce the optimum connectivity of aluminum in the silicate framework. NiO residing in these porous cages are mostly under “prominent interaction with support” which is reduced easily into metallic Ni as the active sites for DRM reactions. The active sites over 5Ni2Ce/CBV3024E remain stable during the DRM reaction and achieve ~58% H₂ yield after 300 min TOS at 42,000 mL/(g_cat.h) GHSV and ~70% H₂ yield after 20 h at 26,000 mL/(g_cat.h) GHSV. The high activity after a longer time stream justifies using CBV3024E molecular sieves as the support and ceria as the promoter for Ni-based catalyst towards the DRM reaction. Full article

The accumulation of greenhouse gasses (CH₄ and CO₂) results in an increase in the temperature of the atmosphere. The conversion of greenhouse gasses into chemicals and fuels with high added value benefits not only the environment but also energy development. A promising and well-studied process is the reforming of methane, where CH₄ and CO₂ are converted into syngas (CO and H₂). However, catalysts hinder the development of the process. In this paper, we investigate the conversion of CH₄ and CO₂ into syngas using a thermal conversion method. The catalysis performance was evaluated by reforming methane. Ni-based catalysts were prepared by different methods. All prepared catalysts were characterized (XRD, HRTEM et al.), and the process of reforming carbon dioxide–methane was carried out in a fixed bed reactor under atmospheric pressure and a high temperature. Ni(M) @CeO₂ is one of the most popular options due to the role of CeO₂. The deposition of coke in Ni-based catalysts was investigated. Full article

Recently, ceramic–carbonate membrane reactors have been proposed to selectively separate CO₂ at elevated temperatures and to valorize this pollutant gas by coupling a catalyzed reaction. This work explores using a membrane reactor to perform the oxidative reforming of propane by taking advantage of the CO₂- and O₂-permeating properties of a LiAlO₂/Ag–carbonate membrane. The fabricated membrane showed excellent permeation properties, such as CO₂/N₂ and O₂/N₂ selectivity, when operating in the 725–850 °C temperature range. The membrane exhibited remarkable stability during the long-term permeation test under operating conditions, exhibiting minor microstructural and permeation changes. Then, by packing a Ni/CeO₂ catalyst, the membrane reactor arrangement showed efficient syngas production, especially at temperatures above 800 °C. A hydrogen-rich syngas mixture was obtained by the contributions of the oxidative reforming and cracking reactions. Specific issues observed regarding the membrane reactor’s performance are attributed to the catalyst that was used, which experienced significant poisoning by carbon deposition during the reaction, affecting syngas production during the long-term test. Thermodynamic calculations were performed to support the experimental results. Full article

This study aims to investigate the depositional environment, sediment sources, and elemental occurrence of Upper Paleozoic coal in the Renjiazhuang Mining District, Western Ordos Basin. Furthermore, SEM-EDX, optical microscope (OM), ICP-AES, ICP-MS, and AAS were used. Compared with hard coal of the world, M3 coals were enriched in Ga, Li, Zr, Be, Ta, Hf, Nb, Pb, and Th, M5 coals were enriched in Li (CC = 10.21), Ta (CC = 6.96), Nb (CC = 6.95), Be, Sc, Ga, Hf, Th, Pb, Zr, In, and REY, while M9 coals were enriched in Li (CC = 14.79), Ta (CC = 5.41), Ga, W, Hf, Nb, Zr, Pb, and Th. In addition, minerals were mainly composed of kaolinite, dolomite, pyrite, feldspar, calcite, and quartz, locally visible minor amounts of monazite, zircon, clausthalite, chalcopyrite, iron dolomite, albite, fluorite, siderite, galena, barite, boehmite, and rutile. In addition, maceral compositions of M3 coals and M9 coals were dominated by vitrinite (up to 78.50%), while M5 coals were the main inertite (up to 76.26%), and minor amounts of liptinite. REY distribution patterns of all samples exhibited light REY enrichment and negative Eu anomalies. The geochemistry of samples (TiO₂ and Al₂O₃, Nb/Y and Zr × 0.0001/TiO₂ ratios, and REY enrichment types) indicates that the sediment sources of samples originated from felsic igneous rocks. Indicator parameters (TPI, GI, VI, GWI, V/I, Sr/Ba, Th/U, and Ce_N/Ce_N*) suggest that these coals were formed in different paleopeat swamp environments: M3 coal was formed in a lower delta plain and terrestrial (lacustrine) facies with weak oxidation and reduction, and M5 coal was formed in a terrestrial and dry forest swamp environment with weak oxidation–oxidation, while M9 coal was formed in a seawater environment of humid forest swamps and the transition from the lower delta plain to continental sedimentation with weak oxidation and reduction. Statistical methods were used to study the elemental occurrence. Moreover, Li, Ta, Hf, Nb, Zr, Pb, and Th elements were associated with aluminosilicates, and Ga occurred as silicate. Full article

Hydrothermal liquefaction technology (HTL) is a promising thermochemical method to convert biomass into novel liquid fuels. The introduction of oxides and inorganic acids/bases during the hydrothermal process significantly impacts the yield and composition of bio-oil. However, systematic research on their effects, especially at lower temperatures, remains limited. In this paper, we examine the effects of acidity and alkalinity on cotton stalk hydrothermal bio-oil by introducing homogeneous acids and bases. Given the operational challenges associated with product separation using homogeneous acids and bases, this paper further delves into the influence of heterogeneous oxide catalysts (possessing varying degrees of acidity and alkalinity, as well as distinct microstructures and pore architectures) on the production of cotton stalk hydrothermal bio-oil. The effects of nanoscale oxides (CeO₂, TiO₂, ZnO, Al₂O₃, MgO and SiO₂) and homogeneous acid–base catalysts (NaOH, K₂CO₃, Na₂CO₃, KOH, HCl, H₂SO₄, HNO₃) on the quality of cotton stalk bio-oil under moderate hydrothermal conditions (220 °C, 4 h) were investigated. Characterization techniques including infrared spectroscopy, thermogravimetric analysis, elemental analysis, and GC-MS were employed. The results revealed that CeO₂ and NaOH achieved the highest bio-oil yield due to Ce³⁺/Ce⁴⁺ redox reactions, OH-LCC disruption, and ionic swelling effects. Nano-oxides enhanced the formation of compounds like N-ethyl formamide and aliphatic aldehydes while suppressing nitrogen-containing aromatics. The total pore volume and average pore width of oxides negatively correlated with their catalytic efficiency. CeO₂ with low pore volume and width exhibited the highest energy recovery. The energy recovery of cotton stalk bio-oil was influenced by both acid and base sites on the oxide surface, with a higher weak base content favoring higher yields and a higher weak acid content inhibiting them. The findings of this research are expected to provide valuable insights into the energy utilization of agricultural solid waste, such as cotton stalks, as well as to inform the design and development of highly efficient catalysts. Full article

A series of M(x)CoCeMgAlO mixed oxides with different transition metals (M = Cu, Fe, Mn, and Ni) with an M content x = 3 at. %, and another series of Fe(x)CoCeMgAlO mixed oxides with Fe contents x ranging from 1 to 9 at. % with respect to cations, while keeping constant in both cases 40 at. % Co, 10 at. % Ce and Mg/Al atomic ratio of 3 were prepared via thermal decomposition at 750 °C in air of their corresponding layered double hydroxide (LDH) precursors obtained by coprecipitation. They were tested in a fixed bed reactor for complete methane oxidation with a gas feed of 1 vol.% methane in air to evaluate their catalytic performance. The physico-structural properties of the mixed oxide samples were investigated with several techniques, such as powder X-ray diffraction (XRD), scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX), elemental mappings, inductively coupled plasma optical emission spectroscopy (ICP-OES), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction under hydrogen (H₂-TPR) and nitrogen adsorption–desorption at −196 °C. XRD analysis revealed in all the samples the presence of Co₃O₄ crystallites together with periclase-like and CeO₂ phases, with no separate M-based oxide phase. All the cations were distributed homogeneously, as suggested by EDX measurements and elemental mappings of the samples. The metal contents, determined by EDX and ICP-OES, were in accordance with the theoretical values set for the catalysts’ preparation. The redox properties studied by H₂-TPR, along with the surface composition determined by XPS, provided information to elucidate the catalytic combustion properties of the studied mixed oxide materials. The methane combustion tests showed that all the M-promoted CoCeMgAlO mixed oxides were more active than the M-free counterpart, the highest promoting effect being observed for Fe as the doping transition metal. The Fe(x)CoCeMgAlO mixed oxide sample, with x = 3 at. % Fe displayed the highest catalytic activity for methane combustion with a temperature corresponding to 50% methane conversion, T₅₀, of 489 °C, which is ca. 40 °C lower than that of the unpromoted catalyst. This was attributed to its superior redox properties and lowest activation energy among the studied catalysts, likely due to a Fe–Co–Ce synergistic interaction. In addition, long-term tests of Fe(3)CoCeMgAlO mixed oxide were performed, showing good stability over 60 h on-stream. On the other hand, the addition of water vapors in the feed led to textural and structural changes in the Fe(3)CoCeMgAlO system, affecting its catalytic performance in methane complete oxidation. At the same time, the catalyst showed relatively good recovery of its catalytic activity as soon as the water vapors were removed from the feed. Full article

To reduce the mercury content in flue gas from coal-fired power plants and to obtain high-performance, low-cost mercury adsorbents, a novel composite material was prepared by structural design through the in situ growth method. Functionalization treatments such as the modification of functional groups and multilayer loading of polymetallic were conducted. These materials include the MOF material UiO-66 and modified biochar doped with Fe/Ce polymetallic, both of which contain unsaturated metal centrals and oxygen-containing functional groups. On the basis of obtaining the effects of adsorption temperature and composite ratio on the Hg⁰ removal characteristics, coupling and synergistic mechanisms between the various types of active centers included were investigated by using a variety of characterization and analysis tools. The active adsorption sites and oxidation sites were identified during this process, and the constitutive relationship between the physicochemical properties and the performance of Hg⁰ removal was established. The temperature-programmed desorption technique, Grand Canonical Monte Carlo simulation, and adsorption kinetic model were employed to reveal the mechanism of Hg⁰ removal. The results showed that the UiO-66-Br@MBC composite adsorbent possessed an excellent Hg⁰ removal performance at adsorption temperatures ranging from 50 to 250 °C, and targeted construction of adsorption and oxidation sites while maintaining thermal stability. The Hg⁰ removal by the composites is the result of both adsorption and oxidation. The micropores and small pore mesopores in the samples provide physical adsorption sites. The modified biochar acts as a carrier to facilitate the full exposure of the central metal zirconium ions, the formation of more active sites, and the process of electron transfer. The doping modification of the Br element can enhance the overall redox ability of the sample, and the introduced Fe and Ce polymetallic ions can work in concert to promote the oxidation process of Hg⁰. The excellent regulation of the ratio between adsorption and oxidation sites on the surface of the composite material finally led to a significant boost in the samples’ capacity to remove Hg⁰. Full article