Rare Earth Metal Oxides Research Articles

Cold Molecular Ions via Autoionization below the Dissociation Limit.

Several diatomic transition metal oxides, rare-earth metal oxides, and fluorides have the unusual property that their bond dissociation energy is larger than their ionization energy. In these molecules, bound levels above the ionization energy can be populated via strong, resonant transitions from the ground state. The only relevant decay channel of these levels is autoionization; predissociation is energetically not possible and radiative decay is many orders of magnitude slower. Starting from translationally cold neutral molecules, translationally cold molecular ions can thus be produced with very high efficiency. By populating bound levels just above the ionization energy, internally cold molecular ions, exclusively occupying the lowest rotational level, are produced. This is experimentally shown here for the dysprosium monoxide molecule DyO, for which the lowest bond dissociation energy is determined to be 0.0831(6)eV above the ionization energy.

Construction of heterojunction based on Nd2S3 and tin dioxide for rapid detection of ethanol

The gas-sensing properties of Nd2S3 have not been previously explored. In this study, a novel composite material comprising rare-earth metal sulfide (Nd2S3) and metal oxide (SnO2) was successfully prepared using a two-step hydrothermal method for the rapid detection of ethanol. Characterization results revealed that the morphology and specific surface area of Nd2S3-SnO2 remained largely unchanged after composite formation. However, the built-in electric field established between Nd2S3 and SnO2 significantly enhanced carrier transport and separation. Additionally, the introduction of extra oxygen vacancies increased the content of chemisorbed oxygen, providing more active sites for ethanol molecules, thereby improving the gas-sensing performance. The Nd2S3-SnO2 sensor demonstrated extremely high detection accuracy (R2=0.9965) over the 20–300 ppm ethanol concentration range, with response/recovery time of 8/274 s at 100 ppm ethanol concentration and response value of 93. It also possesses excellent selectivity to ethanol, long-term stability and reversibility. This work represents a preliminary exploration of the gas-sensing properties of Nd2S3 and its underlying mechanisms through the construction of a heterojunction structure between metal sulfide and metal oxide.

Holmium doped La2O3 and its Composite with Graphitic Carbon Nitride for the Removal of Atrazine and Chlorpyrifos from Wastewater

Herein, the co-precipitation method was employed for the synthesis of rare earth metal oxide La2O3, Holmium doped La2O3, and its composite with 2D layered material i.e. graphitic carbon nitride (g-C3N4) to study their photocatalytic behavior towards organic pollutants. Pollutants employed to study are pesticides that include atrazine and chlorpyrifos. Structural, spectral, morphological, and elemental analysis were done by XRD, FTIR, SEM, and EDX respectively. Optical bandgap calculations showed the decrease in band edge positions of the bare La2O3 from 5.02eV to 3.39eV by doping of Ho in La2O3 lattice. The photocatalytic degradation efficiency of prepared samples was evaluated using a dual beam UV-Visible spectrophotometer. Experimental investigation showed that the prepared composite i.e. Ho doped La2O3@g-CN had remarkable photodegradation activity of about 60% and 86% towards the atrazine and chlorpyrifos respectively. While the pristine La2O3 showed only 41% and 65% degradation activity and Ho doped La2O3 showed 52% and 75% removal efficiency for atrazine and chlorpyrifos respectively by using 0.03g/100mL of photocatalysts under solar light exposure of about 80min. The enhanced degradation activity of composite (g-C3N4/Ho@La2O3) as compared to its other counter parts is due to its increased surface area and more active sites provided by g-C3N4 for electrons trapping to cause a delay in electron-hole pair recombination rate. The enhanced surface area also played a key role in adsorbing more pollutant molecules for degradation.

Solar light driven enhanced in photocatalytic activity of novel Gd incorporated ZnO/SnO2 heterogeneous nanocomposites

The Gd-doped ZnO/SnO2 nanocomposites with various atomic percentages (0, 0.5, 0.8, and 1.2 at%) of gadolinium (coded as GdZS0, GdZS1, GdZS2, and GdZS3) was synthesis via the sol–gel method and explored for photodegradation against dye solutions exposing solar light irradiation. The synthesized nanocomposites were characterized employing the XRD, FTIR, FE-SEM, Raman spectroscopy, BET analysis and UV–Vis spectrophotometer. The FE-SEM results indicated that the formation of nanoparticles to nanoflowers covered with Gd ions was observed with an increased doping concentration of Gd. The optical bandgap was evaluated and found in the range of 3.21–3.27 eV for GdZS nanocomposites. The GdZS nano-photocatalysts were investigated against the degradation of different organic dyes and GdZS3 shows the highest degradation efficiencies of 99.3%, 98.3% and 99.4% towards MO, MB and RhB dyes, respectively at neutral pH in aqueous media. Before and after photodegradation. Biological oxygen demand and chemical oxygen demand tests to make estimations of mineralization. The investigations are very promising for the degradation process in rare earth doped metal oxide nanocomposites. A plausible photodegradation mechanism of synthesized nanocomposites under investigation has also been proposed.

Inducing high-concentration Tb3+ with free oxygen via atomic layer deposition

Precise preparation and control of trivalent states in rare earth metal oxide films are crucial for their optical and magnetic applications. In this study, compact and continuous terbium-doped nanofilms were deposited on silica substrates using atomic layer deposition (ALD). The average nanoparticle size varied from 17.9 to 78.5 nm with increasing growth cycles. X-ray photoelectron spectroscopy showed that the Tb3+/Tb4+ ratio increased from 0.98 to 1.42. A valence reduction mechanism involving free oxygen was introduced to analyze the reasons for the enhanced Tb3+ concentration in the nanofilms. The enhanced photoluminescence of Tb3+ (5D4→7F5) ions and the increased magnetization in terbium oxide nanofilms both reveal that free oxygen ions are the effective active sites responsible for the transition from the tetravalent to the trivalent state, in excellent agreement with theoretical analysis. Size control and free oxygen induction are promising strategies for enhancing the optical and magnetic properties of multivalent rare earth oxides.

Synergistic effect of bonding heterogeneity and phonon localization in introducing excellent thermoelectric properties in layered heteroanionic NdZnSbO material

Layered rare-earth metal oxides, harnessing the dual properties of oxides and two-dimensional layered materials, exhibit remarkable thermal stability and quantum confinement effects. Therefore, this work adopts the first-principles calculation combined with the Boltzmann transport theory to predict the thermoelectric properties of NdZnSbO compound. The coexistence of weak interlayer van der Waals interactions, robust intralayer ionic bonding, and partial covalent bonding leads to remarkable bonding heterogeneity, which engenders pronounced phonon scattering and imposes constraints on thermal transport along the out-of-plane direction. The weakened chemical bonds induced by the antibonding states, together with the rattling-like behavior of the Zn atom, culminate in the profound anharmonicity in the layered NdZnSbO compound. The weakening bond and heavy element contribute to the softness of phonon modes, which significantly diminishes the phonon group velocity. The redistribution-dominated four-phonon scattering process spans a large optical gap, which effectively reduces the lattice thermal conductivity. The NdZnSbO compound exhibits direct semiconductor characteristic with a bandgap of 0.73 eV by adopting the Heyd-Scuseria-Ernzerhof (HSE06) functional in combination with spin–orbit coupling (SOC) effect. The multi-valley feature of NdZnSbO compound augur favorably for band degeneracy, thus amplifying the power factor. Consequently, an optimal figure-of-merit (ZT) of 3.40 at 900 K is achieved for the n-type NdZnSbO compound. The present study delves deeply insights into the origins for the low thermal conductivity of NdZnSbO compound and proposes an optimization scheme to enhance overall thermoelectric performance.

Cerium oxide for L-band Q-switched pulse laser generation

Cerium oxide (CeO2), a rare earth metal oxide belonging to the lanthanide group is a mature engineered nanoparticle that has been developed for various industry applications. The nanoparticle features defects in its lattice structure, which is highly advantageous for bandgap tuning, and is acclaimed for its least cytotoxicity among other metal oxides. In this work, CeO2 is employed as a saturable absorber (CeO2-SA) in the generation of an L-band Q-switched erbium-doped fiber laser. Q-switching was attained at 33.33 mW pump power threshold with a central wavelength of 1600.512 nm. Within 33.33 mW to 153.20 mW pump power range, the Q-switched laser obtained pulse repetition rates between 11.00 to 34.48 kHz, and pulse widths between 39.0 to 12.0 µs, with a high maximum pulse energy of 410 nJ. The Q-switched fiber laser remained stable over a 45-minute observation time at 153.20 mW pump power. The room temperature and direct mechanical deposition fabrication technique of the CeO2-SA in this work demonstrates the extreme simplicity and low cost of the device, which would reduce the overall cost and facilitate a wider technology adoption of pulse laser systems.

Synthesis and electrochemical performance of CeO2/NiS nanocomposite for enhanced asymmetric supercapacitor device applications

A novel CeO2/NiS nanocomposite, combining the advantageous properties of transition metal sulfides (high conductivity) and rare-earth metal oxides (excellent stability), was successfully synthesized using a simple hydrothermal method. This composite leverage synergistic effects to potentially achieve superior electrochemical performance in supercapacitor applications. To evaluate its suitability for supercapacitors, the electrochemical performance of the CeO2/NiS electrode was comprehensively investigated using a series of techniques, including cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) curves, electrochemical impedance spectroscopy (EIS), and cyclic stability analysis. The results demonstrate that the as-prepared CeO2/NiS electrode exhibits significantly improved supercapacitor performance compared to the bare CeO2 electrode. The CV curves of the CeO2/NiS electrode reveal a high specific capacitance of 825.53 F/g at a low scan rate of 5 mV/s, indicating good charge storage capability. Further insights into the charge storage mechanism were obtained using the Trasatti method. This analysis revealed that the total stored capacitance of the CeO₂/NiS electrode is 1250 F/g, with contributions from both outer surface capacitance (94 F/g) and inner diffusion capacitance (1156 F/g). Notably, the dominant contribution (92.5 %) originates from capacitive processes, highlighting the efficient charge storage at the electrode surface. The CeO2/NiS electrode also demonstrates exceptional rate capability, delivering a specific capacitance (Csp) of 710 F/g at a high current density of 1 A/g. Additionally, it exhibits impressive cycling stability, retaining approximately 96.56 % of its initial capacitance even after undergoing 3000 continuous GCD cycles at a high current density of 10 A/g. These results suggest that the CeO2/NiS composite can maintain its performance during extended charge-discharge cycles, a crucial characteristic for practical supercapacitor applications. Finally, an asymmetric supercapacitor device was fabricated using the CeO2/NiS nanocomposite. This device achieved a specific capacitance of 157 F/g, demonstrating the potential of the CeO2/NiS composite for practical energy storage applications.

OREATE as a High Yield and Purity Electrochemical Process for Transition and Rare Earth Metal Recovery

Developing a process that can consistently convert transition and rare earth metal oxides to chemically pure metals in near quantitative yield will have significant impact in many levels, from fundamental science to national security-related applications. Traditional separation methods of lanthanides and actinides from aqueous media have been based on liquid-liquid extractions that have proven to be quite efficient, though they are expensive and require complex engineering. Likewise, separation by pyro-chemistry provides a good recovery performance but requires the use of high temperatures that adds technological difficulties to the process. An alternative method that has grown interest in the last few years is the utilization of the difference in the metals’ reduction potentials from ionic state to metallic state. However, this electrochemical approach requires more negative reduction potentials than hydrogen evolution, which requires a very challenging control of their electrolytic deposition onto solid cathodes.In recent years, our team at LANL has been working on the development of OREATE (Oxide Reduction by Electrochemical Amalgamation and Thermal Extraction). OREATE is a holistic electrochemical approach that involves an initial step wherein the metal oxide is dissolved and chlorinated into an acidic medium. The dissolved metal cation is then electrochemically amalgamated via reduction using a mercury pool cathode. Finally, mercury's high vapor pressure allows an easy thermal extraction process to obtain the metal. From the conceptual perspective and preliminary results, the OREATE process appears easier and simpler than traditional separation methods and is suitable for small- and large-scale preparation of high purity metals.The results obtained using Cerium (Ce) as a surrogate metal demonstrated near quantitative yield of the electrochemical amalgamation (yield > 99%), almost complete mercury recovery during the thermal extraction (Hg recovery > 99.5%), and high purity of the Ce metal product (purity > 99%). Moreover, a variety of system parameters such as the pH of the buffered solution, concentration of cerium, reduction potential, and temperature were explored to evaluate the effect that the scaling up of the OREATE process may have on reaction rate, current efficiency, process yield, and temperature management.

(Nanocarbons Division Poster Award, 1st Place) Nd2O3 Templated Carbon Nanostructures for Energy Storage

Increased energy consumption has triggered the development of various energy storage devices. Supercapacitors have gained attention as energy storage devices due to their high-power density and long cycle life. The energy density of supercapacitor can be increased by combining electric double layer capacitance (EDLC) and pseudocapacitance (PC). A hybrid material based on rare-earth metal oxide templated carbon will be presented that combines both EDLC and PC within the same material. Specifically, neodymium hydroxide (Nd(OH)3) reacted with acetylene and steam to form carbon coated Nd2O3. Both Nd(OH)3 nanorods and nanospheres were used to prepared templated carbon followed by partial or complete washing of metal oxide. The resulting carbon exhibit the surface area of 1245 m2/g. Asymmetric coin cell was constructed with capacitance of 180.5 F/g and energy density of 76.8 Wh/kg This work paves the door to develop novel hybrid supercapacitors.

Thermoluminescence characteristics of gamma-irradiated Gd:Mg doped silica glass

This study explores the characteristics of thermoluminescence (TL) yield of silica glass doped with Gd2O3 and MgO for dosimetry via sol-gel route, with varying concentrations of rare earth metal oxides, ranging from 0.1 to 0.8 mol%. Gamma irradiation was delivered using 1.25 MeV 60Co, with entrance doses of 2–10 Gy. The characterization of Gd:Mg-doped SiO2 included assessing TL dose response, sensitivity, linearity index, glow curve, and fading. It has been found that 0.2 mol% Gd:Mg-doped SiO2 shows promising TL dosimetric properties due to its high linearity, high sensitivity, and low thermal fading. In addition, it demonstrated exceptional dosimetric response across the entire dose range studied, with a coefficient of determination R2 exceeding 91%. A computerized glow curve deconvolution method was conducted to determine the kinetic parameters by using Glowfit software. The glow curves include five peaks associated with activation energies and frequency factors with values 0.88–2.42 eV and 5.58 × 106–7.22 × 1026 s−1, respectively. The 0.2 mol% Gd:Mg-doped SiO2 demonstrates minimal fading effects, retaining a significant portion of the TL signal with ∼33% of the initial signal lost over 28 days post-irradiation. The results indicate that the Gd:Mg-doped SiO2 offers a promising performance as a low-cost passive radiation dosimeters.

Enhanced performance of electrospun PVDF membranes modified with rare-earth metal oxides for membrane distillation: A systematic study

In the presented studies, the novel type of separation materials dedicated to membrane distillation was generated and systematically analyzed. Utilizing poly(vinylidene fluoride) (PVDF) electrospun membranes as a base, hybrid organic-inorganic materials were developed to enhance performance. These materials exhibited high hydrophobicity, featuring superhydrophobicity on a micro-scale due to fractal-like structures on the inorganic domain surface. Rare-earth metal oxides (REMO) were implemented for the first time as smart modifiers, covalently attached to the functionalized membrane surface. Three REMO types were selected to investigate their impact on membrane performance in air-gap membrane distillation (AGMD) for the desalination process. Chemical attachment via long enough linkers formed a flexible active surface structure, facilitating transport and separation. Dynamic goniometric studies evaluated membrane wetting stability. Particularly noteworthy was the membrane enhanced with Ho2O3 particles, with high flux and salt rejection rates of 14.41 ± 1.35 kg m−2 h−1 and >99.5 %, respectively. The membrane stability and affinity were further examined using Hansen Solubility Parameters and Pearson's hard–soft acid–base (HSAB) theory. The potential of the hybrid membranes is seen not only in desalination. With the ability to control surface properties by using different silane linkers, oleophobicity/oleophilicity can be achieved, and practical use in wastewater treatment or oil/water separation is possible.

Modification of 110G13L steel with rare earth metal oxide powders

Modification of 110G13L steel with rare earth metal oxide powders

Potential Biomedical Applications of Terbium-Based Nanoparticles (TbNPs): A Review on Recent Advancement.

The scientific world is increasingly focusing on rare earth metal oxide nanomaterials due to their consequential biological prospects, navigated by breakthroughs in biomedical applications. Terbium belongs to rare earth elements (lanthanide series) and possesses remarkably strong luminescence at lower energy emission and signal transduction properties, ushering in wide applications for diagnostic measurements (i.e., bioimaging, biosensors, fluorescence imaging, etc.) in the biomedical sectors. In addition, the theranostic applications of terbium-based nanoparticles further permit the targeted delivery of drugs to the specific site of the disease. Furthermore, the antimicrobial properties of terbium nanoparticles induced via reactive oxygen species (ROS) cause oxidative damage to the cell membrane and nuclei of living organisms, ion release, and surface charge interaction, thus further creating or exhibiting excellent antioxidant characteristics. Moreover, the recent applications of terbium nanoparticles in tissue engineering, wound healing, anticancer activity, etc., due to angiogenesis, cell proliferation, promotion of growth factors, biocompatibility, cytotoxicity mitigation, and anti-inflammatory potentials, make this nanoparticle anticipate a future epoch of nanomaterials. Terbium nanoparticles stand as a game changer in the realm of biomedical research, proffering a wide array of possibilities, from revolutionary imaging techniques to advanced drug delivery systems. Their unique properties, including luminescence, magnetic characteristics, and biocompatibility, have redefined the boundaries of what can be achieved in biomedicine. This review primarily delves into various mechanisms involved in biomedical applications via terbium-based nanoparticles due to their physicochemical characteristics. This review article further explains the potential biomedical applications of terbium nanoparticles with in-depth significant mechanisms from the individual literature. This review additionally stands as the first instance to furnish a "single-platted" comprehensive acquaintance of terbium nanoparticles in shaping the future of healthcare as well as potential limitations and overcoming strategies that require exploration before being trialed in clinical settings.

Synthesis and Thermo-Physical Characteristics of Therminol-66 Oil Based Nanofluids with Rare-Earth Metal Oxide Nanocomposites

Synthesis and Thermo-Physical Characteristics of Therminol-66 Oil Based Nanofluids with Rare-Earth Metal Oxide Nanocomposites

Orbital ordering and ultrafast carrier dynamics anisotropies in orientation-engineered orthorhombic YMnO3 films

The rich physical properties unveiled in a plethora of transition and rare-earth metal oxides have been attributed to the intricate interplays between the orbital, charge, and spin degrees of freedom. Among them, rare-earth manganites (RMnO3) have been attracting tremendous attention owing to the ionic size-induced lattice distortion dictated by the Goldschmidt tolerance factor and the substantial Jahn–Teller distortion unique to Mn3+ ions, which evidently have resulted in a variety of emergent characteristics in electronic, magnetic, and orbital ordering. In this work, we deliberately engineered the orientation of a series of orthorhombic YMnO3 (o-YMO) films grown on SrTiO3(100) [STO(100)] and SrTiO3(110) [STO(110)] substrates by means of pulsed laser deposition. The x-ray diffraction (XRD) and reciprocal space mapping revealed that o-YMO/STO(100) is c-axis-oriented and o-YMO/STO(110) is a-axis-oriented, respectively. The XRD ϕ-scans further indicate that both films have excellent in-plane crystallinity, allowing the exploration of anisotropies along the respective crystallographic orientations. Indeed, the x-ray absorption linear dichroism spectroscopy taken along the respective crystallographic orientations evidently exhibited substantial anisotropy. Theoretical fitting with configuration interaction cluster calculations suggests that the d3z2−r2 orbitals are parallel to YMO[001]/(100), leading to stronger electron scattering along the c-axis. Independent polarization-dependent Δ R/R spectra obtained using the femtosecond pump–probe method exhibited substantial anisotropic behaviors in carrier relaxation dynamics when probing along different crystallographic orientations, presumably due to orbital ordering anisotropies.

Enhanced CO2 Photoreduction with Noble Metal‐Modified CeO2‐Synthesis, Mechanisms, and Catalytic Insights: A Minireview

AbstractComposite materials integrating precious metals (Au, Ag, Pd, Pt, Ru, Rh, Ir) with CeO2, a rare earth metal oxide, are increasingly utilized in photocatalytic CO2 reduction. CeO2, notable for its redox characteristics, oxygen storage capacity (OSC), and abundant oxygen vacancies (Ov), emerges as a key player in semiconductor catalyst research. The selection of precious metals and their application techniques are crucial in modifying CeO2′s wide bandgap and enhancing light absorption, thereby influencing the photocatalytic efficiency. Approaches for incorporating precious metals onto CeO2 include single atoms, metal clusters, and nanoparticles. This review provides an in‐depth analysis of the progress in composite photocatalysts comprising precious metals and CeO2 for CO2 reduction. It examines diverse modification strategies, such as particle size adjustment and heterojunction formation. The review concisely elucidates the principles behind converting CO2 into high‐value products (hydrocarbons, C1, C2, and C2+). Lastly, it addresses the challenges and future directions for precious metal‐CeO2 catalysts in photocatalytic CO2 reduction.

Broadband ultraviolet photodetector based on rare-earth metal oxide Nd2O3

The detection of ultraviolet (UV) radiation holds significant importance in various fields. As the demand for superior detector performance grows alongside advancements in science and technology, there is a need for detectors with larger light-to-dark rejection ratios and lower standby power consumption. This paper presents the outstanding performance of the rare earth metal oxide Nd2O3 in broadband UV detection. With a wide forbidden band width of 4.6 eV, eliminating the requirement for additional filters, Nd2O3 emerges as an ideal material for broadband UV detectors. The device exhibits remarkable characteristics, including a dark current of only 1.66 × 10−11 A at a 5 V bias voltage, a light-to-dark rejection ratio of 1.33 × 103 at 280 nm and 15 μW cm−2, a responsiveness of 0.061 A W−1, and a detection rate of 4.7 × 1012 Jones. Furthermore, the performance of the device can be significantly enhanced through the formation of a heterojunction with TiO2. The heterojunction device exhibits a shortened response time of 78.64%, a reduced recovery time of 88.97%, and an increased light-to-dark rejection ratio of 2.75 × 103 at a 5 V bias voltage. This significant improvement in performance highlights the potential of the Nd2O3/TiO2 heterojunction in broadband UV detection.

Processing of Rare Earth Metal Oxide for Use as a Master Alloy in the Metallurgical Industry

Processing of Rare Earth Metal Oxide for Use as a Master Alloy in the Metallurgical Industry

Catalyst development for O2-assisted oxidative dehydrogenation of propane to propylene.

O2-Assisted oxidative dehydrogenation of propane (O2-ODHP) could convert abundant shale gas into propylene as an important chemical raw material, meaning O2-ODHP has practical significance. Thermodynamically, high temperature is beneficial for O2-ODHP; however, high reaction temperature always causes the overoxidation of propylene, leading to a decline in its selectivity. In this regard, it is crucial to achieve low temperatures while maintaining high efficiency and selectivity during O2-ODHP. The use of catalytic technology provides more opportunities for achieving high-efficiency O2-ODHP under mild conditions. Up to now, many kinds of catalytic systems have been elaborately designed, including transition metal oxide catalysts (such as vanadium-based catalysts, molybdenum-based catalysts, etc.), transition metal-based catalysts (such as Pt nanoclusters), rare earth metal oxide catalysts (especially CeO2 related catalysts), and non-metallic catalysts (BN, other B-containing catalysts, and C-based catalysts). In this review, we have summarized the development progress of mainstream catalysts in O2-ODHP, aiming at providing a clear picture to the catalysis community and advancing this research field further.