Synthesis of the superfine high-entropy zirconate nanopowders by polymerized complex method

The high-purity and superfine high-entropy zirconate nanopowders, namely (Y0.25La0.25Sm0.25Eu0.25)2Zr2O7 nanopowders, without agglomeration, were successfully synthesized via polymerized complex method at low temperatures for the first time. The results showed that the crystallinity degree, lattice strain, and particle size of the as-synthesized powders were gradually enhanced with the increase of the synthesis temperature from 800 to 1300 °C. The as-synthesized powders involved fluorite phase in the range of 800–1200 °C while they underwent the phase evolution from fluorite to pyrochlore at 1300 °C. It is worth mentioning that the as-synthesized powders at 900 °C are of the highest quality among all the as-synthesized powders, which is due to the fact that they not only possess the particle size of 11 nm without agglomeration, but also show high purity and good compositional uniformity.

Photodegradation of Carbol Fuchsin Dye Using an Fe2−xCuxZr2−xWxO7 Photocatalyst under Visible-Light Irradiation

Fe2−xCuxZr2−xWxO7 (x: 0, 0.05, 0.015) nanoparticles were synthesized following the Pechini method and characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM), and diffuse reflectance spectroscopy (DRS) measurements to be used as photocatalysts in colored water remediation. All of the prepared materials were crystallized in a cubic fluorite phase as the major phase. The band gap was reduced upon doping with W6+ and Cu2+ from 1.96 eV to 1.47 eV for Fe1.85Cu0.15Zr1.85W0.15O7. Carbol fuchsin (CF) dye was used to determine the photocatalytic degradation efficiency of the prepared catalysts. Degradation efficiency was directly proportional to the dopant’s concentration. Complete removal of 20 mg/L CF was achieved under optimal conditions (pH 9, and catalyst loading of 1.5 g/L) using Fe1.85Cu0.15Zr1.85W0.15O7. The degradation rate followed pseudo-first-order kinetics. The reusability for photocatalysts was tested five times, decreasing its efficiency by 4% after the fifth cycle, which indicates that the prepared Fe1.85Cu0.15Zr1.85W0.15O7 photocatalyst is a promising novel photocatalyst due to its superior efficiency in dye photodegradation.

Investigation of the Heterovalent Substitution Cadmium for Lanthanum in Molybdate La2MoO6

This paper presents the investigation of the heterovalent substitution of cadmium for lanthanum in the La2-xCdxMoO6-x/2 system. The samples were synthesized by the solid state reaction method at 1000°C. The samples were characterized by X-ray powder diffraction with Rietveld refinements, scanning electron microscopy with energy-dispersive X-ray spectroscopy, and Fourier transform infrared spectroscopy methods. The study results revealed that cadmium incorporation in the lanthanum molybdate leads to the transformation of the tetragonal structure of La2MoO6 to a cubic fluorite-like one. The content of the cubic phase reaches 94% in the Lа1.4Cd0.6MoO5.7 sample. The unit cell parameter of fluorite-like-phase decreases with cadmium content rising. The preferred location of cadmium ions in the cubic structure was established by the Rietveld refinement method. The heterovalent substitution cadmium for lanthanide in tetragonal La2MoO6 molybdate leads to the cubic fluorite phase stabilization in a similar way as it occurs in the process of reduction.

CO2-Tolerant Oxygen Permeation Membranes Containing Transition Metals as Sintering Aids with High Oxygen Permeability

Chemical doping of ceramic oxides may provide a possible route for realizing high-efficient oxygen transport membranes. Herein, we present a study of the previously unreported dual-phase mixed-conducting oxygen-permeable membranes with the compositions of 60 wt.%Ce0.85Pr0.1M0.05O2-δ-40 wt.%Pr0.6Sr0.4Fe0.8Al0.2O3-δ (M = Fe, Co, Ni, Cu) (CPM-PSFA) adding sintering aids, which is expected to not only improve the electronic conductivity of fluorite phase, but also reduce the sintering temperature and improve the sintering properties of the membranes. X-ray powder diffraction (XRD) results indicate that the CPM-PSFA contain only the fluorite and perovskite two phases, implying that they are successfully prepared with a modified Pechini method. Backscattered scanning electron microscopy (BSEM) results further confirm that two phases are evenly distributed, and the membranes are very dense after sintering at 1275 °C for 5 h, which is much lower than that (1450 °C, 5 h) of the composite 60 wt.%Ce0.9Pr0.1O2-δ-40 wt.%Pr0.6Sr0.4Fe0.8Al0.2O3-δ (CP-PSFA) without sintering aids. The results of oxygen permeability test demonstrate that the oxygen permeation flux through the CPCu-PSFA and CPCo-PSFA is higher than that of undoped CP-PSFA and can maintain stable oxygen permeability for a long time under pure CO2 operation condition. Our results imply that these composite membranes with high oxygen permeability and stability provide potential candidates for the application in oxygen separation, solid oxide fuel cell (SOFC), and oxy-fuel combustion based on carbon dioxide capture.

Direct Dimethyl Carbonates Synthesis over CeO2 and Evaluation of Catalyst Morphology Role in Catalytic Performance

In recent years, direct synthesis of dimethyl carbonate (DMC) from carbon dioxide (CO2) has received considerable attention due to green and sustainable technology. Here, we report a production of DMC from major greenhouse gases and CO2 using various morphologies of cerium oxide (CeO2). Time-dependent synthesis of CeO2, with controlled morphology having various shapes including sphere, nanorods and spindle shape, along with its formation mechanism is proposed. The experimental results indicate the morphology of CeO2 was mostly dependent on the reaction time where crystal growth occurred through Ostwald ripening. The morphology, size and shape of CeO2 were observed using transmission electron microscopy (TEM) and field emission scanning electron microscopy (FESEM).The crystallographic analysis using X-ray diffraction (XRD) shows cubic fluorite phase of CeO2 with crystallite size ~72.0 nm using the Debye–Scherrer equation. The nitrogen adsorption desorption technique suggested the formation of the highly mesoporous framework of CeO2 and the excellent surface area around 104.5 m2/g obtained for CeO2 spindles by Brunauer–Emmett–Teller (BET) method. The DMC synthesis reactions were studied over CeO2 catalyst with different morphologies. The results of catalytic reactions specify that the morphology of catalyst plays an important role in their catalytic performances, where spindle shape CeO2 was the most active catalyst producing of up to13.04 mmol of DMC. Furthermore, various dehydrating agents were used to improve the DMC production at optimized reaction parameters. The overall results reveal that the higher surface area and spindle shape of CeO2 makes it a useful, reusable catalyst for one-pot DMC synthesis.

Nanoporous carbon doped ceria bismuth oxide solid solution for photocatalytic water splitting

A series of carbon-doped solid solutions of ceria bismuth oxide (CBO) was prepared by solid solution method. Highly porous solid solutions crystallized in a fluorite phase and exhibited the enhanced...

Nickel-Containing Ceria-Zirconia Doped with Ti and Nb. Effect of Support Composition and Preparation Method on Catalytic Activity in Methane Dry Reforming

Nickel-containing mixed ceria-zirconia oxides also doped by Nb and Ti have been prepared by a citrate route and by original solvothermal continuous flow synthesis in supercritical alcohols. Nickel was subsequently deposited by conventional insipient wetness impregnation. The oxides are comprised of ceria-zirconia solid solution with cubic fluorite phase. Negligible amounts of impurities of zirconia are observed for samples prepared by citrate route and doped by Ti. Supports prepared by supercritical synthesis are single-phased. XRD data, Raman, and UV-Vis DR (diffuse reflectance) spectroscopy suggest increasing lattice parameter and amount of oxygen vacancies in fluorite structure after Nb and Ti incorporation despite of the preparation method. These structural changes correlate with the catalytic activity in a methane dry reforming reaction. Catalysts synthesized under supercritical conditions are more active than the catalysts of the same composition prepared by the citrate route. The catalytic activity of samples doped with Ti and Nb is two times higher in terms of TOF (turnover frequency) and increased stability of these catalysts is attributed with the highest oxygen mobility being crucial for gasification of coke precursors.

Decolourization of crystal violet using nano-sized novel fluorite structure Ga 2 Zr 2− x W x O 7 photocatalyst under visible light irradiation

Fluorite-type Zr-based oxides with the composition Ga 2 Zr 2− x W x O 7 ( x = 0, 0.05, 0.1, 0.15 and 0.2) were prepared using the citrate technique. Appropriate characterizations of all prepared materials were carried out. X-ray diffraction clarified that the undoped and W-doped Ga 2 Zr 2 O 7 samples were crystallized in the cubic fluorite phase structure. The average particle size of the samples was in the range of 3–8 nm. The lowest band gap (1.7 eV) and the highest surface area (124.3 m 2 g −1 ) were recorded for Ga 2 Zr 0.85 W 0.15 O 7. The photocatalytic impacts of the prepared systems were studied by removal of crystal violet (CV) dye employing visible light illumination and taking into consideration the initial dye concentrations, duration of visible irradiation treatment, catalysts dose and the dopant concentration. The obtained results showed higher dye removal with the boost of the catalyst dosage. W doping shifted the absorption to the visible light range by decreasing the band gap from 4.95 eV for parent Ga 2 Zr 2 O 7 to 1.7 eV for 15 mol% tungsten-doped Ga 2 Zr 2 O 7 enhancing the photocatalytic decolourization of CV from 4.2% to 83.6% for undoped and 15 mol% W-doped Ga 2 Zr 2 O 7 , respectively, at optimum operating conditions (pH 9, 1 g l −1 catalyst dose and 300 min) while heavily doped W sample containing 20 mol% W showed lower removal than 15 mol% W-doped Ga 2 Zr 2 O 7 . Complete CV degradation using 15 mol% W-doped Ga 2 Zr 2 O 7 was attained with the assistance of 25 mmol l −1 hydrogen peroxide. The reaction is aligned to pseudo-first-order kinetics. Different scavengers were introduced to decide the significance of the reactive species in CV degradation. O 2 − ∙ and h + had the major role in the degradation of CV by Ga 2 Zr 2− x W x O 7 system compared with HO • .