Higher Ce Content Research Articles

Composition of ore-forming fluids in the Huangshuian carbonatite-related Mo-(REE) deposit: Insights from LA-ICP-MS analyses of fluid inclusions

The carbonatites in the southern margin of the North China Craton are distinguishable by containing abundant quartz and are closely spatially associated with Mo-(REE) deposits. Unveiling the nature of ore-forming fluids is key to understand the genesis of these Mo-(REE) deposits and to explore their potential genetic relationships with the quartz-rich carbonatites, but such issues were currently not convincingly addressed. Here, we provide detailed petrographic, microthermometric and LA-ICP-MS analyses of the fluid inclusions hosted in the primary quartz from the carbonatites in the Huangshuian Mo-(REE) deposit which is the largest Mo-(REE) one in the region, containing 0.4 million tons of Mo metal with REEs as the major by-product. Our results show that the fluid inclusions in the quartz of the carbonatites are two- and three-phase CO2-bearing types with high homogenization temperatures (average at 396 °C) and low salinities (average at 3.88 wt% NaCl equiv). The LA-ICP-MS analyses of these inclusions reveal that the primary fluids contain high concentrations of La, Ce, Pr, Nd, Sr, and Ba, similar to typical carbonatite-related fluids. In addition, they are characterized by high Y, Cu, Pb, and Zn. Such a metal association is broadly consistent with the mineral assemblages of the Huangshuian Mo-(REE) deposit, such as the widespread barite, bastnäsite, xenotime, chalcopyrite, galena, and sphalerite, strongly supporting the close genetic relation of the deposit with the quartz-rich carbonatites. Although the concentrations of Mo are extremely low in these inclusions (below the detect limit), it was constrained to be gradually enriched in evolved fluids. Considering that the recorded fluids in quartz represent earliest generation of fluids exsolved from carbonatite magmas, our new results highlight that quantifying metal budgets of fluid inclusions could be a robust way to evaluate fertility of carbonatites that are widespread in the southern margin of the North China Craton.

Highly Dispersive Cerium Atoms on Carbon Nanowires as Oxygen Reduction Reaction Electrocatalysts for Zn-Air Batteries.

Highly efficient noble-metal-free electrocatalysts for oxygen reduction reaction (ORR) are essential to reduce the costs of fuel cells and metal-air batteries. Herein, a single-atom Ce-N-C catalyst, constructed of atomically dispersed Ce anchored on N-doped porous carbon nanowires, is proposed to boost the ORR. This catalyst has a high Ce content of 8.55 wt % and a high activity with ORR half-wave potentials of 0.88 V in alkaline media and 0.75 V in acidic electrolytes, which are comparable to widely studied Fe-N-C catalysts. A Zn-air battery based on this material shows excellent performance and durability. Density functional theory calculations reveal that atomically dispersed Ce with adsorbed hydroxyl species (OH) can significantly reduce the energy barrier of the rate-determining step resulting in an improved ORR activity.

Genetic model of carbonatite hosted rare earth elements mineralization from Ambadongar Carbonatite Complex, Deccan Volcanic Province, India

Carbonatites and associated alkaline rocks are the primary sources for REE mineralization. The Ambadongar Carbonatite Complex (ADCC) from NW Deccan Volcanic Province (DVP) constitutes the largest Carbonatite Associated REE Deposits (CARD) in India. ADCC belongs to the final stages of the Late Cretaceous alkaline-carbonatite magmatism associated with main Deccan basalt volcanic activity. The ADCC is an envisioned diatreme structure in which four carbonatitic phases are recognized, mainly calcio-carbonatites and ferro-carbonatites. Each successive carbonatite phase shows higher REE enrichment. The primary REE mineralization with bastnäsite as the dominant REE phase is hosted by pervasive hydrothermally altered ferro-carbonatite plugs. The secondary mineralogy formed with barites in the main orebody during late- to post-magmatic hydrothermal fluid alteration is fluorite, quartz, ankerite, and other REE-bearing minerals like bastnäsite, parisite, synchysite, strontianite, florencite, monazite and columbite.Carbonatite samples contain 18.61% to 52.42% of CaO, and the LOI varies from 5.28% to 38.79%. Most can be classified as calcio-carbonatites. Since all the samples also contain an appreciable amount of Fe2O3 (4.13% to 20.20%) and MnO (0.07% to 5.46%), some may be classified as ferro-carbonatites. Total REE content varies from 0.6 to 4%, with a high Ce concentration and LREE/HREE ratio. The highest values for La, Ce, Pr, and Nd are 1.95%, 1.56%, 0.16%, and 0.45%, respectively.Metasomatism of SCLM from asthenospheric melts followed by the low degree partial melting of the SCLM region is responsible for fertile carbonatite generation in ADCC. The multiphase liquid immiscibility of carbonatite melts from carbonate-silicate magma followed by immiscibility of REE rich carbonatite melt and REE deficient fluoride-rich aqueous fluids explain the higher level of REE enrichment in each successive phases of carbonatites in ADCC.The mineralizing fluids were probably the result of residual magmatic volatiles that brought mainly REE and later SiO2 into the overprinted rocks. Ambadongar carbonatites' stable isotopic compositions agree with a magmatic origin (δ13C = −4.1 ± 1.9‰ [PDB] and δl8O = 10.3 ± 1.7‰ [SMOW]). The C–O stable isotopic modeling indicates re-equilibration under hydrothermal conditions between 180 °C and 70 °C. Significant amounts of REE fluorocarbonate minerals, relatively Sr- and Th-rich, were deposited during re-equilibration. The REE fluorocarbonate bastnäsite-(Ce) occurs as late individual crystals, overgrown on the synchysite and parisite polycrystals. Textural and chemical reactions between the REE fluorocarbonates provide insights into rare-earth elements' mobility during fluid-rock interaction. Early crystallization of synchysite/parisite indicates the high activity of Ca2+, OH−, (SO4)2−, Al and Si in the fluid. Later, the fluid was characterized by increased activity of F−, (SO4)2−, REE and Si, and decreased activity of Ca2+ as reflected in the association of barite, fluorite, quartz, and bastnäsite typical of strongly overprinted ferro-carbonatites.Re-equilibration and recrystallization of the primary minerals in the presence of OH−, (SO4)2−, F−, REE, Al, and Si carried in solution by the hydrothermal fluid is the leading cause behind the refixing of REE in the form of REE fluorocarbonate in REE rich ferro-carbonatites.

Photoluminescence and scintillation properties of Ce-doped SrY2O4 single crystals

Photoluminescence (PL) and scintillation properties of Ce:SrY2O4 single crystals were investigated. The PL quantum yield (QY) of the 2 % Ce-doped sample was the highest, and it decreased in the high Ce concentrations samples. The undoped SrY2O4 single crystal exhibited a broad emission band at 380 nm due to host defects, and the scintillation decay time constant was about 4.2 μs. The pulse height spectrum of 137Cs γ-rays using the undoped SrY2O4 single crystal revealed the scintillation light yield of 830 photons/MeV.

Regulation of Ce (Ⅲ) / Ce (Ⅳ) ratio of cerium oxide for antibacterial application

SummaryAntibiotics have been considered as effective weapons against bacterial infections since they were discovered. However, antibiotic resistance caused by overuse and abuse of antibiotics is an emerging public health threat nowadays. Fully defeating bacterial infections has become a tough challenge. In this work, cerium oxide was fabricated on medical titanium by thermolysis of cerium-containing metal-organic framework (Ce-BTC). Regulation of Ce (Ⅲ)/Ce (Ⅳ) ratios was realized by pyrolysis of Ce-BTC in different gas environment, and the antibacterial properties were studied. The results indicated that, in acidic conditions, ceria with a high Ce (Ⅲ)/Ce (Ⅳ) ratio owned high oxidase-like activity which could produce reactive oxygen species. Moreover, ceria with high Ce (Ⅲ) content possessed strong ATP deprivation capacity which could cut off the energy supply of bacteria. Based on this, ceria with a high Ce (Ⅲ)/Ce (Ⅳ) ratio exhibited superior antibacterial activity

Synthesis of C21H38ClN Assisted Si Pillared Clays and the Effects of CeO2 Addition on Its Supported Palladium Catalyst for Benzene Oxidation

Mesoporous silica-pillared clays (SPC) were prepared with C21H38ClN cationic surfactant as template and supported PdOx catalysts were prepared by impregnation method. The influence of addition of CeO2 on benzene combustion was evaluated. The samples were characterized by N2 adsorption–desorption, XRD, XPS, HRTEM and TPSR. Compared with the raw montmorillonite, the d001 value of SPC increased from 0.96 to 3.45 nm. Furthermore, the surface area was increased from 30 to 835 m2/g and the pore volume was increased from 0.11 to 1.30 cm3/g, respectively. The addition of CeO2 increased oxygen vacancies and improved the dispersion of PdOx on SPC, and the optimal addition of CeO2 was 10%. Therefore, of all the catalysts, 0.3%Pd/10%Ce/SPC could completely oxidize benzene at 280 °C, showing the highest catalytic activity. This catalyst showed high activity for benzene oxidation in wet conditions with or without Cl− displaying good durability, which should be related to the presence of Ce3+ on the surface of catalyst after reaction. The excellent pore structure of SPC, improved dispersion of PdOx and high concentration of Ce3+ on the catalyst surface were the key factors for the high catalytic activity of 0.3%Pd/10%Ce/SPC. Mesoporous silica-pillared clays (SPC) were synthesized and SPC supported CeO2 and PdO catalysts were prepared by impregnation method. The 0.3% Pd/10% Ce/SPC catalyst displayed the highest activity for benzene combustion.

Elastic and thermodynamic properties of cerium‐doped yttrium aluminum garnets

AbstractCerium‐doped yttrium aluminum garnets (Y3‐xCexAl5O12, Ce:YAGs) are promising yellow light‐emitting components of solid‐state white light‐emitting diodes. Although there have been numerous studies examining the effects of Ce concentrations on the luminescent properties of Y3‐xCexAl5O12, the impacts of Ce dopant on the elastic and thermodynamic properties are not well understood. In this work, we used resonant ultrasound spectroscopy (RUS) to determine the effects of Ce doping (0.025, 0.1, 1 at. %) on the elastic and thermodynamic properties of Y3‐xCexAl5O12. The elastic moduli calculated via the Voigt–Reuss–Hill (VRH) method demonstrated that low Ce dopant concentrations (≤0.1 at. %) induced negligible effects on the elasticity of the YAG host matrix, while a high Ce concentration (1 at. %) yielded significant softening. RUS spectral analysis and SEM images suggested that the elastic softening originated from microstructural differences induced at higher Ce dopant concentrations. In addition, we demonstrated an increase in elastic anisotropy at higher Ce concentrations, which further elucidated the correlations between structure and elasticity of Y3‐xCexAl5O12. Debye temperatures (θD), heat capacities (Cp), and thermal conductivities (κ) were calculated for Ce:YAGs through the relations of RUS‐derived parameters (sound velocities, elastic moduli) and previously determined thermal expansion coefficients. Ce:YAG was found to have a significant reduction in θD, Cp, and κ at Ce concentrations ≥1 at. %. Lastly, extrapolation of Cp and κ to higher temperatures allowed the modeling of thermal stress experienced by Y3‐xCexAl5O12 disks up to 1073.15 K.

Toward the Recovery of Platinum Group Metals from a Spent Automotive Catalyst with Supported Ionic Liquid Phases

We present a novel approach for the separation and recovery of Pt and Pd leached from a spent automotive catalyst relying on conventional and polymerized supported ionic liquid phases (SILPs and polySILPs, respectively). A variety of parameters with possible effects on the separation behavior, namely, acidity and concentration of the platinum group metal (PGM) containing solution, as well as different SILP and polySILP loadings, were evaluated for the separation of PGMs in the presence of high concentrations of Al, Fe, Zn, and Ce. The polySILP material demonstrated the ability to separate the PGMs from major accompanying interferences in a single separation step, while problems arising from ionic liquid leaching in the case of SILPs could be avoided. Moreover, the use of supported ionic liquid phases allowed the drastic reduction of the amount of required ionic liquid compared to conventional liquid–liquid separation, while avoiding problems arising from emulsion formation. Subsequent stripping experiments lead to further purification of the PGMs and finally desorption from the solid material into a pure solution. Eventually, the concept of chemisorbed polySILPs provides a new and convenient approach for the recycling of platinum group metals.

Agates from Paleoproterozoic Volcanic Rocks of the Onega Structure, Central Karelia

Agate mineralization in Central Karelia, Northwest Russia is related to the Paleoproterozoic volcanic rocks of the Ludicovian Superhorizon (2.05–1.95 Ga) within the Onega structure. Agates and parental volcanic rocks were studied with optical and electron microscopy, electron microprobe, X-ray diffraction, Raman spectroscopy, and ICP-MS. It is shown that fine-grained quartz, and fibrous and fine-flake chalcedony are the major minerals in the agate structure. Inclusions of coarse-crystalline calcite, and microinclusions of chlorite, iron oxides and hydroxides, hydroxylapatite, epidote, mica (phengite), apatite, pyrite, chalcopyrite, titanite, and leucoxene are present in agates. The presence of contrast rhythms within agate amygdules is marked by compositional variation in impurity mineral phases and different microtextures of silica layers represented by different-grained aggregates of quartz, fine-flake and fibrous chalcedony, and quartzine. This indicates stage-by-stage mineral crystallization at variable temperatures and pressures during agate formation, which may also reflect the heterogeneity of the initial hydrothermal fluid. High concentrations of Ti, Cr, Mn, Ni, and Cu (10–120 ppm) and the low concentrations of Li, Co, Ga, Zn, Sr, Zr, Mo, and Sn (0.5–10 ppm) are characteristic of quartz–chalcedony agates. Calcite in agates is characterized by high concentrations of Mn (1253–6675 ppm), Sс, Ti, Ni, Sr, Y, La, Ce, and Nd (5–56 ppm). The chondrite-normalized REE distribution pattern in agates shows a decay profile from La to Lu and a negative Eu anomaly in some samples. Low contents of rare metals and REE in agates compared to parental volcanic rocks indicate a gradual chemical depletion of circulating fluids during agate formation.

Two-stage magmatism and tungsten mineralization in the Nanling Range, South China: Evidence from the Jurassic Helukou deposit

Abstract The Helukou deposit, with proven reserves of 33 752 t WO3, is one of the newly exploited medium-scale tungsten (W) deposits in the Guposhan ore field, Nanling Range of South China. Skarn-type and less abundant altered granite-type tungsten orebodies were identified in this deposit. The ore mineralization in this district was a product of two-stage magmatism, as shown by LA-ICP-MS U-Pb dating of zircons and Re-Os dating of molybdenite. The former yielded U-Pb ages of 184.0 ± 3.6 Ma (MSWD = 0.15) and 163.8 ± 1.5 Ma (MSWD = 0.41) for fine-grained biotite granite and muscovite granite, respectively, as well as a U-Pb age of 181.5 ± 2.1 Ma (MSWD = 0.75) for zircon grains from altered granite-type tungsten ore. The latter yielded molybdenite Re-Os ages of 183.5 ± 2.8 Ma (without MSWD owing to a limited number of samples) and 163.4 ± 2.8 Ma (MSWD = 0.71) for altered granite-type and skarn-type tungsten deposits, respectively. Thus, two separate tungsten mineralization events occurred during the Early Jurassic and Middle Jurassic. Trace-element compositions suggest that scheelite I was controlled by the coupled substitution reactions of 2Ca2+ = Na+ + REE3+ and Ca2+ + W6+ = Nb5+ + REE3+, whereas scheelite II was controlled by the coupled reactions of 2Ca2+ = Na+ + REE3+ and 3Ca2+ = ☐Ca + 2REE3+ (where ☐ is a site vacancy). High Mo and low Ce contents suggest that both scheelite I and scheelite II were precipitated from oxidizing magmatic-hydrothermal fluids. Based on the mineral assemblage of the altered granite-type ores and geochemical characteristics of scheelite I [i.e., negative Eu anomalies (0.02–0.05; mean = 0.03 and STD = 0.01), and high 87Sr/86Sr ratios (0.70939–0.71932; mean = 0.71345 and STD = 0.00245)], we infer that fluid-rock interaction played an important role in modifying Early Jurassic ore-forming fluids. Scheelite II exhibits a geo-chemical composition [i.e., 87Sr/86Sr ratios (0.70277–0.71471; mean = 0.70940 and STD = 0.00190), Eu anomalies (0.14–0.55; mean = 0.26 and STD = 0.09), and Y/Ho ratios (16.1–33.7; mean = 27.9 and STD = 2.91)] similar to that of the Middle Jurassic Guposhan granites, suggesting inheritance of these features from granite-related magmatic-hydrothermal fluids. These results provide new insights into the two-stage magmatic and metallogenic history of the Nanling Range during the Jurassic Period.

Cerium uptake, translocation and toxicity in the salt marsh halophyte Halimione portulacoides (L.), Aellen

Halimione portulacoides plants were exposed to dissolved cerium (Ce) in a hydroponic medium for five days. Ce accumulation in plants followed the metal’s increase in the medium although with a very low translocation factor (TF < 0.01) between roots and shoots. Ce median concentrations in roots were 586, 988 and 1103 μg/g (dry wt.), while in shoots the median values reached 1.9, 3.5 and 10.0 μg/g (dry wt.), for plants exposed to 300, 600 and 1200 μg/L of Ce, respectively. No significant differences occurred in the length of roots and shoots among treatment groups, albeit plants exposed to the highest Ce concentration showed a clear loss of turgor pressure on the fifth day. An increase of hydrogen peroxide and malondialdehyde levels were observed in the plant shoots at 1200 μg/L of Ce. The highest concentration also triggered an answer by the shoots’ antioxidant enzymes with a decrease in the activity of superoxide dismutase and an increase in peroxidase. However, no significant change in catalase activity was observed, compared to the control group, which may indicate that peroxidase played a more crucial role against the oxidative stress than catalase. Combined results indicate that H. portulacoides was actively responding to a toxic effect imposed by this higher Ce concentration. Nevertheless, changes in normal environmental conditions, may increase the bioavailability of Ce, while in areas where acid mine drainage may occur, the highest Ce concentration tested in this study may be largely exceeded, placing the sustainability of halophytes and estuarine marshes at risk.

Enhancement of potassium resistance of Ce–Ti oxide catalyst for NH3-SCR reaction by modification with holmium

Alkali metal K in exhaust gas has a deactivation effect on NH3-SCR catalysts. In this work, it is discovered that the addition of Ho on CeTi catalyst can remarkably strengthen its K tolerance. The conclusions of Brunauer–Emmett–Teller (BET) , X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), NH3 temperature programmed desorption (NH3-TPD) and H2 temperature programmed reduction (H2-TPR) analyses demonstrate that the enhancement of K resistance mainly originates from its stronger surface acidity and redox capability, the higher concentration of Ce3+ species and surface chemisorbed oxygen. In situ DRIFT analysis reveals that the introduction of Ho on CeTi can remarkably improve the adsorption of NH3 and NOx species on catalyst surface, accompanied by the intensified reactivity of ad-NH3 species, which should also administer to improve the K resistance.

Synthesis of Ni-Pd decorated spindle-shape CeO2 for catalytic reduction of nitroarene

Facile single-step hydrothermal approach was developed for the synthesis of Ni and Pd decorated spindle-shape defected CeO2 catalyst for reduction of nitroarene compounds. A Ni-Pd/CeO2 catalyst showed superior activity toward nitroarene reduction than its nickel monometallic counterpart (Ni/CeO2). Addition of very small amount of Pd to Ni-CeO2 catalyst largely changed its morphology, size of active nanoparticles (NPs) as well as its catalytic activity. A synergy between active metals (Pd, Ni) and support (CeO2), strong metal-support interactions, ceria defect sites with high concentrations of Ce+3 and oxygen vacancy sites were suggested to promoting the superior activity of Ni-Pd/CeO2 compared to Ni/CeO2 catalyst.

Optimizing Ni–Ce/HZSM-5 catalysts for ex-situ conversion of pine wood pyrolytic vapours into light aromatics and phenolic compounds

The main objective of the present work is to investigate the influence of nickel to cerium ratio on hydrogen exchanged Zeolite Socony Mobil-5 (HZSM-5) towards the catalytic upgrading of pine derived oxygenated pyrolysis vapours into aromatic hydrocarbon and phenol in pyrolysis oil via ex-situ fixed bed reactor. The presence of CeO2 could change electron density of Ni, promote the reduction of Ni species, accelerate the transfer of carbon species, and suppress the production of carbon deposits (17.53%–25.11%) compared with the parent HZSM-5 catalyst (28.95%); it also improved the hydrodeoxygenation ability of all xNiyCe/HZSM-5(nickel and cerium bimetal modified HZSM-5) catalysts, resulting increases in noncondensable gas content (from 31.46% to 52.99%–65.53%). Ni to Ce ratio of 1:1 and 1:2 produced highest aromatic hydrocarbon (32.14%) and phenols (55.51%) relative peak areas. The acid center of HZSM-5 and the metal acid center of the Ni:Ce = 1:1 catalyst obviously fine-tuned the formation of coke; and promoted hydrocarbon production. Moreover, high Ni content promoted alkylation of benzene at C6–C9 and increased C10+ PAHs relative peak area; high Ce content promoted the formation of olefin and Increasing the cleavage of C–O bonds and promoted hydrogenation or dehydrogenation, reduced polycyclic aromatic hydrocarbons and coke yield, and increased phenols and alkylphenols selectivity.

Early Devonian (415–400 Ma) A-type granitoids and diabases in the Wuyishan, eastern Cathaysia: A signal of crustal extension coeval with the separation of South China from Gondwana

Abstract The evolution of the South China continental crust and its linkage to the assembly and rifting of eastern Gondwana are key issues in the understanding of the early Paleozoic evolution of eastern Asia. We report U-Pb zircon ages and geochemical and Lu-Hf isotopic data for the South Fufang and Yingshang granitoids and the Mayuan diabases from the Wuyishan of eastern South China. The zircons yielded U-Pb ages of ca. 414–404 and ca. 409–401 Ma for the granitoids and diabases, respectively. Petrographic and geochemical features indicate that the granitoids are peraluminous A-type granites, expressed by high Ga/Al ratios and high Zr, Nb, Ce, Y, and rare earth element contents. They show negative zircon εHf(t) values (–15.4 to –5.8), consistent with the derivation from a crustal source. The granitoids likely originated from partial melting of dry granulite residues in the lower crust. The diabases show depletion in Ti, and negative correlations between FeOt and Mg#, and SiO2 and TiO2/FeOt, reflecting clinopyroxene, olivine, and Fe-Ti oxide fractionation. Their negative zircon εHf(t) values (–4.5 to –0.4) indicate an ancient enriched-mantle origin. The diabases likely originated from partial melting of a sub-continental lithospheric mantle. We interpret these A-type granitoids and diabases as post-orogenic, formed during extensional collapse of thickened crust. Their generation indicates that South China experienced crustal extension during the Early Devonian. The extension occurred coevally with global rifting that led to the separation of the continental blocks of eastern Asia from eastern Gondwana, which was associated with the Early Devonian opening of the paleo–Tethys Ocean.

Utilization of metallurgical slag with presence of novel CaO-MgO-SiO2-Al2O3 as a composite sorbent for wastewater treatment contaminated by cerium

The cations of metals are the major pollutants of the lithosphere. Accumulation of cerium in natural water resources might cause serious environmental issue. Another aspect is accumulation of metallurgical slag waste. The metallurgical slag located near Chelyabinsk city in Russia was studied as a potential raw material for preparation of powder and granular calcium magnesium aluminum silicate (CaO-MgO-SiO2-Al2O3) composite sorbents capable to immobilize cerium (Ce3+) ions. Aqueous solutions with a high concentration of Ce3+ ions (1000 mg/L) were applied in sorption experiments. The migration characteristics were studied for calcium (Ca2+), magnesium (Mg2+), silicon (Si4+) and aluminum (Al3+) ions. The degree of Ce3+ ions removal for 24 h reached 93.36% for powdered and 99.98% for granular sorbents. The interaction of sorbents with sorbate was followed by the opposite transition of Ca2+ and Mg2+ ions from sorbent matrix into aqueous solution. The desorption process was investigated in distilled water. The results of study indicated a high degree of irreversible sorption of Ce3+ ions from aqueous solution observed for both powder and granular sorbents. The low price for crumbling metallurgical slag, environmental aspects of storage and high sorption capability enable recycling and use of this material as a sorbent with subsequent purification of large natural objects from Ce3+ ions.

Massive red shift of Ce3+ in Y3Al5O12 incorporating super-high content of Ce.

In light emitting diodes, Y3Al5O12:Ce (YAG:Ce) is used as a yellow phosphor in combination with blue LEDs but lacks a red component in emission. Therefore, considerable efforts have been directed toward shifting the emission of YAG:Ce to longer wavelengths. In this study, a Y3Al5O12 (YAG) crystal incorporating a high content of Ce, (Y1−xCex)3Al5O12 (0.006 ≦ x ≦ 0.21), was successfully prepared by a polymerized complex method in which low-temperature annealing (650–750 °C) was employed prior to sintering at 1080 °C. X-ray diffraction (XRD) and transmission electron microscopy (TEM) analysis indicated that the obtained sample was a single phase YAG crystal with x ≤ 0.21. Interestingly, orange-red emission was observed with x ≥ 0.07 with UV-blue light irradiation. With excitation at 450 nm, the emission peak increases from 538 nm (x = 0.006) to 606 nm (x = 0.21). This massive red shift in the high-x region was not observed without the 1st step of low-temperature annealing, which implied that low-temperature annealing was essential for incorporating a high concentration of Ce. The precursor formed by low-temperature annealing was amorphous at x = 0.04, whereas CeO2 nanocrystals were formed in the amorphous material with x ≥ 0.11, based on the XRD and TEM results. CeLIII X-ray absorption edge structure revealed that Ce existed as Ce4+ in the precursor and Ce3+ in the obtained crystal. It was speculated that CeO2 was formed at low temperature, releasing oxygen, with sintering at 1080 °C, leading to the incorporation of Y3+ in the Ce–O framework. The lattice constant increased significantly from 12.024 Å to 12.105 Å with increasing x, but the crystal field splitting did not increase and was constant from x = 0.06 to x = 0.21. Hence, the massive red shift in emission was not explained by the large crystal field splitting, but instead by the Stokes shift.

Production of syngas via CO2 methane reforming process: Effect of cerium and calcium promoters on the performance of Ni-MSC catalysts

The dry reforming of methane (DRM) over Ni-MSC catalysts promoted by different Ce/Ca ratios was compared. The different Ce/Ca ratios proportions were introduced by coprecipitation. The catalysts with different content of promoter were characterized by N2 adsorption, XRD, H2-TPR and TEM. XRD and TEM results demonstrated that Ni–4Ce1Ca-MSC catalyst modified with high Ce/Ca had the best dispersibility and the smallest Ni particle size, resulting in more surface active sites. The synergy between Ce and Ca made a great contribution to prohibiting the generation of carbon deposits and the sintering of active metal during DRM procession. In contrast, catalysts modified only with Ca or Ce exhibited poor catalytic performance, resulting in significant deposition of carbon on the surface of the Ni–5Ca-MSC catalyst. In addition, the high Ce concentration greatly increases the oxygen storage capacity, which helps to form oxygen vacancies by mutual conversion of Ce4+/Ce3+ and Ni2+/Ni0.

Cr-Doped CeO2 Nanorods for CO Oxidation: Insights into Promotional Effect of Cr on Structure and Catalytic Performance

Development of non-noble metal catalysts for oxidation of CO is an important subject for reducing the automotive emissions. Recently, shape-controlled synthesis of CeO2 has increasingly attracted the attention of researchers due to its size- and morphology-dependent unique properties. Following this line of thinking, herein, we successfully report the synthesis of Cr-doped CeO2 (Ce1−xCrxO2−δ; X = 0.05, 0.1, and 0.15) nanorods with various Cr contents by a facile hydrothermal method. Structural, surface, optical, and redox properties of the Cr-doped CeO2 nanorods were investigated by various techniques, namely, ICP-OES, TEM-HRTEM, FE-SEM/EDX/EDS, XRD, BET, Raman, UV–vis DRS, PL, XPS, H2-TPR, and O2-TPD. The catalytic performance was evaluated for CO oxidation. For comparison, the efficiency of Cr2O3 was also studied for CO oxidation under identical conditions. As revealed by various characterization results, the chromium ions were doped into the ceria lattice (formation of Ce–O–Cr solid solution), which enhanced the intrinsic properties such as oxygen vacancy concentration and surface area. It was found that the Cr-doped CeO2 nanorods show superior CO oxidation activity than the pristine counterparts (CeO2 nanorods and Cr2O3). The highest CO oxidation efficiency was achieved with the light-off temperature of T50 = 261 °C, when the Cr doping amount was 10% (Ce0.9Cr0.1O2−δ). A high specific surface area, more number of surface oxygen vacancies, a high concentration of Ce3+, and enhanced oxygen reducibility of Ce0.9Cr0.1O2−δ nanorods were found to be responsible for its superior catalytic performance. Further, the Ce0.9Cr0.1O2−δ nanorods exhibited a steady CO conversion over a period of 55 h investigated. The obtained results are expected to have a significant impact on the use of non-noble metal based Cr-doped CeO2 nanorods in environmental applications. The Cr-doped CeO2 nanorods with Ce0.9Cr0.1O2−δ composition showed enhanced CO oxidation performance at a lower temperature (~ 261 °C) than that of pristine CeO2 nanorods (338 °C) and Cr2O3 (361 °C) catalyst. This behaviour is a result of enhancement of oxygen vacancies, surface Ce3+ species, low-temperature reducibility, and high surface area.

Cationic ion-driven surface control of one-dimensional CeO2 nanocrystals to enhance catalytic performance of CO oxidation

Surface structures of one-dimensional CeO2 nanocrystals are tuned with different cationic ions in a facile and mild hydrothermal system with formate and carbonate. The synthetic key is to control the formation of anisotropic CeO2 precursors with the anion structure of formate and carbonate. The diluted concentration of Na+ ions with NH4+ ions can induce the formation of the CeO2 nanotube (NT) precursors, and yet Na+ ions can promote the production of the CeO2 nanorod (NR) precursors. CeO2 nanocrystals are applied in CO oxidation and show a very important effect of their surface structure on their catalytic performance. CeO2 NTs have rich cerium surface with the higher concentration of Ce3+ ions and can accelerate the mobility of more surface oxygen species than CeO2 NRs with difficultly reduced rich oxygen surface. However, after silver loading, CeO2 NRs can show the higher stability of CeO2 particles, more easily activated surface of CeO2 NRs with more Ce3+ ions, the promoted production of metallic Ag nanoparticles and higher mobility of more surface oxygen species on CeO2 surface. Therefore, CeO2 NTs have a higher catalytic activity of CO oxidation and conversely, after loading Ag, Ag/CeO2 NRs show the higher catalytic performance.