Undoped CeO2 Research Articles

Tailoring sub-5 nm Fe-doped CeO2 nanocrystals within confined spaces to boost photocatalytic hydrogen evolution under visible light

This work aimed to study the efficiency of the reverse micelle (RM) preparation route in the syntheses of sub-5 nm Fe-doped CeO2 nanocrystals for boosting the visible-light-driven photocatalytic hydrogen production from methanol aqueous solutions. The effectiveness of confining precipitation reactions within micellar cages was evaluated through extensive physicochemical characterization. In particular, the nominal composition (0–5 mol% Fe) was preserved as ascertained by ICP-MS analysis, and the absence of separate iron-containing crystalline phases was supported by X-ray diffraction. The effective aliovalent doping and modulation of the optical properties were investigated using UV-Vis, Raman, and photoluminescence spectroscopies. 2.5 mol% iron was found to be an optimal content to achieve a significant decrease in the band gap, enhance the concentration of oxygen vacancy defects, and increase the charge carrier lifetime. The photocatalytic activity of Fe-doped CeO2 prepared at different Fe contents with RM preparation was studied and compared with undoped CeO2. The optimal iron load was identified to be 2.5 mol%, achieving the highest hydrogen production (7566 μmol L−1 after 240 min under visible light). Moreover, for comparison, the conventional precipitation (P) method was adopted to prepare iron containing CeO2 at the optimal content (2.5 mol% Fe). The Fe-doped CeO2 catalyst prepared by RM showed a significantly higher hydrogen production than that obtained with the sample prepared by the P method. The optimal Fe-doped CeO2, prepared by the RM method, was stable for six reuse cycles. Moreover, the role of water in the mechanism of photocatalytic hydrogen evolution under visible light was studied through the test in the presence of D2O. The obtained results evidenced that hydrogen was produced from the reduction of H+ by the electrons promoted in the conduction band, while methanol was preferentially oxidized by the photogenerated positive holes.

Comparative study of un-doped CeO2 and metal (Mn, Co, Fe)-doped CeO2 nanostructures for the removal of golden yellow dye from synthetic wastewater

ABSTRACT In this study, the activity of un-doped cerium oxide (CeO2) nanostructure with metal (Mn, Co, Fe)-doped CeO2 nanostructures was compared as effective scaffolds for the elimination of Golden Yellow (GY) Dye. For this purpose, the un-doped and doped-CeO2 nanostructures were prepared through co-precipitation treatment and characterised using the following techniques like FTIR, XRD, UV, PL, SEM and EDX analysis. The synthetic nanostructures were selected for the removal of GY through adsorption and photocatalytic degradation from wastewater. Tauc’s model was employed to determine the optical band gap, and various key parameters (contact duration, pH, nanostructure dosage and GY concentration) were optimised for the adsorption/photocatalytic degradation of GY. The adsorption and degradation processes for these nanostructures were found to be pH-dependent, with an optimum pH value of 4. UV–visible spectroscopy was employed to probe the GY adsorption followed by the GY degradation, revealing a higher removal and degradation efficiency of 39.89% and 58.46% for Mn-CeO2, 34.60% and 47.21% for Co-CeO2 and 31.67% and 39.10% for Fe-CeO2 compared to 14.05% and 30.37% for un-doped CeO2, respectively. In total, 98.35% of GY removal was achieved by Mn-CeO2 compared to 44.42% by un-doped CeO2 within 175 min via adsorption (50 min) followed by degradation (125 min). Additionally, the absorption mechanism underwent analysis, with the kinetic data aligning closely with the pseudo-first-order model. Examination of the adsorption capacity at various equilibrium concentrations of the dye solution revealed the formation of monolayers and chemisorption phenomena. Moreover, the rate constant dropped when scavengers like ethylenediaminetetraacetic acid (EDTA), isopropyl alcohol (IPA), and hydrogen peroxide (H2O2) were added because they capture holes (h+), hydroxyl radicals (·OH), and superoxide radicals (·O2 −) respectively, with EDTA showing more prominent effects.

Influence of Oxygen Vacancies Introduced via Acceptor (Gadolinium) Doping to the Pseudocapacitive Properties of Nano-Sized Cerium Oxide.

The voluntary introduction of defects can be considered an effective strategy for enhancing the electrochemical properties of metal oxide electrodes. In this study, the enhanced pseudocapacitive properties of an acceptor (Gd) doped cerium oxide nanoparticle-a sustainable metal oxide with low environmental and human toxicity-are investigated in depth using ex situ X-ray photoemission spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Interestingly, with 15at% Gd doping (15GDC), the specific capacitance of the nanoparticles measured at 1Ag-1 enhanced to 547.8Fg-1, which is fivefold higher than undoped CeO2 (98.7Fg-1 at 1Ag-1). The rate-dependent capacitance is also improved for 15GDC, which showed a 31.0% decrease in the specific capacitance upon a tenfold increase in the current density, while CeO2 showed a 49.9% decrease. The enhanced electrochemical properties are studied in depth via ex situ XPS and EIS analysis, which revealed that the oxygen vacancies at the surface of the nanoparticles played important roles in enhancing both the specific capacitance and the high-rate performance of 15GDC by acting as the active site for pseudocapacitive redox reaction and allowing fast diffusion of oxygen ions at the surface of 15GDC nanoparticles.

Surface oxygen vacancy vs oxygen storage capacity in cubic ceria based nanocatalysts for low temperature catalytic combustion of fuels

A series of praseodymium (Pr) doped cubic ceria nanoparticles (CeO2 NPs) with different ratio of cerium (Ce) and ‘Pr’ was synthesized by hydrothermal method. Manganese (‘Mn’) doped cubic CeO2 NPs with 10:90 ratio of Mn:Ce and undoped cubic CeO2 NPs have also been synthesized. The crystalline structure of the synthesized nanomaterials has been studied by powder X-Ray diffraction (XRD) and Rietveld analysis. In the Raman spectrum, the intensity of F2g signal at 450–460 cm−1 decreased while the intensity of extrinsic vacancy at 570–580 cm−1 increased by doping with ‘Pr’ or ‘Mn’ in cubic CeO2 nanocrystals. X-ray photoelectron spectroscopy (XPS) results showed that surface oxygen vacancy of cubic CeO2 NPs increased by doping with 25 % of ‘Pr’. The ‘Pr’ doped CeO2 NPs (Pr:Ce = 25:75) exhibited higher surface adsorption dynamic oxygen storage capacity (OSCDyn), while the ‘Mn’ doped cubic CeO2 NPs (Mn:Ce = 10:90) showed increased bulk lattice OSCDyn. The ‘Pr’ doped cubic CeO2 NPs (Pr:Ce = 25:75) exhibited better low temperature catalytic combustion activity, and their nanodispersion in mineral turpentine oil (MTO) added liquefied petroleum gas (LPG) exhibited better fuel efficiency with a flame temperature of 912 °C.

Highly Dispersed Mn-Doped Ceria Supported on N-Doped Carbon Nanotubes for Enhanced Oxygen Reduction Reaction.

The weak adsorption of oxygen on transition metal oxide catalysts limits the improvement of their electrocatalytic oxygen reduction reaction (ORR) performance. Herein, a dopamine-assisted method is developed to prepare Mn-doped ceria supported on nitrogen-doped carbon nanotubes (Mn-Ce-NCNTs). The morphology, dispersion of Mn-doped ceria, composition, and oxygen vacancies of the as-prepared catalysts were analyzed using various technologies. The results show that Mn-doped ceria was formed and highly dispersed on NCNTs, on which oxygen vacancies are abundant. The as-prepared Mn-Ce-NCNTs exhibit a high ORR performance, on which the average electron transfer number is 3.86 and the current density is 24.4% higher than that of commercial 20 wt % Pt/C. The peak power density of Mn-Ce-NCNTs is 68.1 mW cm-2 at the current density of 138.9 mA cm-2 for a Zn-air battery, which is close to that of 20 wt % Pt/C (69.4 mW cm-2 at 106.1 mA cm-2). Density functional theory (DFT) calculations show that the oxygen vacancy formation energies of Mn-doped CeO2(111) and pure CeO2(111) are -0.55 and 2.14 eV, respectively. Meanwhile, compared with undoped CeO2(111) (-0.02 eV), Mn-doped CeO2(111) easily adsorbs oxygen with the oxygen adsorption energy of only -0.68 eV. This work provides insights into the synergetic effect of Mn-doped ceria for facilitating oxygen adsorption and enhancing ORR performance.

Analysis of defects dominating carrier recombination in CeO2 single crystal for photocatalytic applications

In photocatalytic water splitting and CO2 reduction, recently, cerium oxide (CeO2) has been widely investigated. Defects that can directly dominate carrier recombination are essential for the photocatalytic performance of CeO2. In this study, several photoluminescence (PL) peaks are observed on the (100) face of an undoped CeO2 single crystal, indicating the presence of defects. Moreover, we characterize carrier recombination using time-resolved photoluminescence (TR-PL) and microwave photoconductivity decay (μ-PCD) measurements. The temperature dependence of decay curves is the result of carrier trapping and emission at deep levels. These decay curves are observed separately using a 565 nm band-pass filter (BPF) based on the PL spectra. The trap energy level ( ET ) and majority carrier capture cross-section ( σT ) of each defect are also analyzed using rate equations to fit the experimental results. The temperature-dependent time constants are well reproduced by a recombination model using hole traps HTinfrared and HTvisible at ET of 0.76 and 0.55 eV from the conduction or valence band, with estimated σT of the order of 10−21 and 10−22 cm2 for without and with the BPF, respectively. These findings regarding the presence of multiple defects in a single crystal indicate the necessity to focus on defect control.

Comparing the Effect of In2O3 and Eu2O3 Impurities on the Structural and Optical Properties of Cerium Oxide

This work compares the changes in optical and structural properties of cerium oxide (CeO2) when doped with different concentrations (3%,5%,7%, and 9%) of two oxides, In2O3 and Eu2O3. X-ray diffraction and spectrophotometry were employed in the visible, ultraviolet, and near-infrared regions. The findings demonstrated that CeO2 doped with In2O3 and Eu2O3 thin films were polycrystalline and had a cubic structure. The crystal size increased from 20.5 to 32.15 when Eu2O3 doping ratio increased from 0% to 7% and then decreased to 28.46 nm at 9%. While the crystal size showed an increase from 20.5 to 21.42 nm with the increase of the In2O3 doping ratio, while the lattice constant measured for cubic CeO2 changed opposite to that. The optical measurement showed that Eu2O3 and In2O3 doped CeO2 thin films have a direct band gap with allowed transition with 3.0 eV for the undoped CeO2. The band gap energy changed in a non-regular manner with the increase of the doping ratio of both oxides. The minimum band gap energy was 1.2 eV obtained for 7% Eu2O3 doped CeO2 thin film, and the minimum band gap energy was 1.4 eV obtained for 9% In2O3 doped CeO2. These results qualify them for use as absorbers in solar cell applications.

Correlation of electronic structure and magnetic properties of [formula omitted] nanostructure using synchrotron soft XAS

The present study reports crystalline structure, electronic structure and magnetic properties for nanoparticles undoped CeO2 and Ce1-xSmxO2 (x = 0.02 to 0.10, @ 0.02). The nanoparticle samples are synthesized by the co-precipitation method. XRD data shows the successful incorporation of Sm3+ ions at Ce4+ sites in the face-centered cubic (fcc) lattice. The soft X-ray absorption spectroscopy technique is utilized to get an insightful overview of electronic structural properties due to structural defects, chemical states and the development of oxygen vacancies in Ce1-xSmxO2 nanoparticles. The soft XAS spectra show a significant Ce and Sm peak in the M4,5 domain, along with the well-defined O K-edge peak. Analysis of Ce M4,5-edges indicates that Ce-ions have both 3 + and 4 + oxidation states. With the incorporation of Sm+3 ions, there is a reduction of Ce4+ states and oxidation of Ce3+ states, as well as a substantial increase in oxygen vacancy concentration. The room-temperature magnetic properties of Ce1-xSmxO2 nanoparticles reveal ferromagnetic behavior. The origin of ferromagnetism is explained by F-center exchange (FCE) coupling mechanisms mediated via development of oxygen vacancy and defects.

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

The direct synthesis of dimethyl carbonate (DMC) from methanol and CO2 presents an attractive route to turn abundant CO2 into value-added chemicals. However, insufficient DMC yields arise due to the inert nature of CO2 and the limitations of reaction equilibrium. Oxygen vacancies are known to facilitate CO2 activation and improve catalytic performance. In this work, we have demonstrated that tuning oxygen vacancies in catalysts and implementing in situ water removal can enable highly efficient DMC production from CO2. CexZryO2 nanorods with abundant oxygen vacancies were synthesized via a hydrothermal method. In liquid-phase DMC synthesis, the Ce10Zr1O2 nanorods exhibited a 1.7- and 1.4-times higher DMC yield compared to CeO2 nanoparticles and undoped CeO2 nanorods, respectively. Zr doping yielded a CeZr solid solution with increased oxygen vacancies, promoting CO2 adsorption and activation. In addition, adding 2-cyanopyridine as an organic dehydrating agent achieved an outstanding 87% methanol conversion and >99% DMC selectivity by shifting the reaction equilibrium to the desired product. Moreover, mixing CeO2 nanoparticles with hydrophobic fumed SiO2 in gas-phase DMC synthesis led to a doubling of DMC yield. This significant increase was attributed to the faster diffusion of water molecules away from the catalyst surface, facilitated by the hydrophobic SiO2. This study illustrates an effective dual strategy of enhancing oxygen vacancies and implementing in situ water removal to boost DMC production from CO2. The strategy can also be applied to other reactions impacted by water accumulation.

Synthesis, microstructural and optical characterizations of sol-gel grown gadolinium doped cerium oxide ceramics.

In this study, through the utilization of the sol-gel combustion tactic, gadolinium (Gd)-doped cerium oxide (CeO2), Ce1-xGdxO2 (x = 0.00, 0.10, 0.20 and 0.30 (GDC)) ceramics were attained. The synthesized GDC ceramics were investigated using X-ray diffraction (XRD) to scrutinize their crystal structures and phase clarities. The obtained GDC ceramics have a single-phase cubic structure and belong to the crystallographic space group fm3̄m (225). The measurement of the diffraction angle of each reflection and the subsequent smearing of the renowned Bragg's relation provided coarse d-interplanar spacings. The stacking fault (SF) values of pure and Gd-doped CeO2 ceramics were assessed. To muse the degree of preferred orientation (σ) of crystallites along a crystal plane (h k l), the texture coefficient (Ci) of each XRD peak of GDC ceramics is gauged. By determining the interplanar distance (dh k l), the Bravais theory sheds light on the material's development. By exploiting Miller indices for the prime (1 1 1) plane, the lattice constants of GDC ceramics and cell volumes were obtained. Multiple techniques were employed to ascertain the microstructural parameters of GDC ceramics. A pyrometer substantiated the density of GDC ceramics. The room temperature (RT) Fourier transform infrared (FTIR) spectra of both un-doped and Gd-doped CeO2 were obtained. The UV-vis-NIR spectrometer recorded the GDC ceramics' reflectance (R) spectra at RT. For both undoped and Gd-doped CeO2, the absorption coefficient (α) spectra showed two distinct peaks. The R-dependent refractive index (η) and the α-dependent extinction coefficient (k) were determined for all GDC samples. The optical band gap (Eg) was obtained by integrating the Tauc and Kubelka-Munk approaches for GDC ceramics. For each GDC sample, the imaginary (εi) and real (εr) dielectric constants, as well as the dissipation factor (tan δ), were determined local to the characteristic wavelength (λc). Calculations were made for the Urbach energy (EU) and Urbach absorption coefficient (α0) for GDC ceramics. The minimum and maximum values of optical (σo) and electrical (σe) conductivity for GDC ceramics were determined. The volume (VELF) and surface (SELF) energy loss functions, which depend on the constants εi and εr, were used to measure electrons' energy loss rates as they travel across the surface. Raman spectroscopy revealed various vibrational modes in GDC ceramics. Finally, the implications are discussed herein.

The influence of CeO2 abrasive size on the performance of photocatalytic assisted chemical-mechanical polishing by Y/Pr co-doping strategy

The synergistic effect of photochemical oxidation activity and tribochemical ability of CeO2 material is a necessary prerequisite for the formation of photocatalytic assisted chemical-mechanical polishing (PCMP) abrasive system. However, it is precisely due to the large band gap (∼ 3.2 eV) of CeO2 and the high recombination rate of photogenerated carriers that the improvement of the photocatalytic oxidation activity of traditional CeO2 photocatalysts is greatly limited, thus preventing the further wide application of cerium-based abrasives in PCMP. Based on this, a series of Ce1–2xYxPrxO2 abrasives were synthesized by molten salt method to improve the performance of cerium oxide based polishing paste with PCMP. The physicochemical properties of Ce1–2xYxPrxO2 samples were analyzed by a series of characterization methods. The results show that Ce1–2xYxPrxO2 abrasive has a normal octahedral shape with a particle size of 190 ∼ 260 nm. With the increase of doping amount, the particle size of abrasive decreases gradually, but the photocatalytic activity increases. Compared with undoped CeO2 abrasives, the removal rate (RR = 932.42 nm/min) of quartz glass by Ce1–2xYxPrxO2 abrasive was increased by about 87.10%. At the same time, the surface quality has been significantly improved. A smooth, flawless and low roughness surface was obtained. The improvement in surface quality can be demonstrated by reducing surface roughness (Ra). The Ra of quartz glass decreased to 0.36 nm after Y3+/Pr3+ co-doped CeO2 abrasive by PCMP (the original Ra of glass was 1.08 nm). It was considered that the size of the abrasive had a close relationship with the surface quality and the RR of the polished glass. Meanwhile, characteristic co-doping strategy was conducive to increase the Ce3+ and oxygen vacancy concentration of CeO2 particles, which optimized the separation efficiency of the photogenic carrier of the photocatalyst. This further promoted the generation of oxidizing active substances in the polishing slurry, and therefore expediting the formation and removal of the chemical reaction soft layer. The removal mechanism of Ce1–2xYxPrxO2 abrasives in PCMP process was discussed.

Role of dopant in the formation of reactive oxygen species and oxidation catalysis on CeO2(1 1 1)

We theoretically investigate the role of nine 3d–5d Groups 9–11 metals substitutionally doped into CeO2(111) in terms of i) oxygen vacancy (VO) formation; ii) H and CO adsorption; iii) H2 oxidation, C3H8 oxidative dehydrogenation, and CO oxidation. Lattice O and O2 species at the doped sites are significantly more active toward binding H and CO than in un-doped CeO2(111). All the dopants lower the VO formation energy vs. un-doped CeO2(111), which becomes negative for Ni, Pd, Pt, Cu, and Ag. The square planar structure is energetically preferred by all the doped VO. Whether doping promotes the catalysis of the oxidation reactions depends on which of the chemisorption, VO formation, and surface re-oxidation steps is the bottleneck. When the VO formation step is, doping is expected to have little promotional effect, because VO formation is an iso-reduction step whose reaction energy is independent of doping.

Oxygen vacancies mediated changes in ferromagnetic, optical, Photoluminescent and electronic structure properties of Ho-doped CeO2 nanoparticles

The undoped CeO2 and Ce1-xHoxO2 (x = 0.03, 0.05 and 0.07) nanoparticles prepared using microwave assisted co-precipitation route are investigated using X-Ray Diffraction (XRD), UV–Vis–NIR, Raman, photoluminescence, X-ray Photoelectron Spectroscopy (XPS) and SQUID-VSM magnetometer. The XRD validates the inclusion of Ho3+ at the Ce3+/Ce4+ site while maintaining the crystal structure with development of defects and oxygen vacancies with expansion of the CeO2 nanolattice. The composition of the elements with desired stoichiometry is confirmed by Energy Dispersive X-ray spectra analysis. The absorption spectroscopy analysis reports the Urbach energy along with refractive index increases with Ho3+ doping and the optical band gap is decreased indicating red shift. All the nanoparticles are subjected to PL investigations to ascertain the oxygen vacancy and defect structure of nanoparticles. Raman active modes at ∼500 - 630 cm−1 verifies the existence of oxygen vacancies (Vo)., which are seen to rise with concentration of Ho-doping in the CeO2 lattice. When Ce4+ transforms into Ce3+, oxygen vacancies are generated in the lattice to maintain the charge neutrality, as can be seen by the Ce-3d, O-1s, and Ho-4d core level XPS spectra. To demonstrate that Ho3+ doping favours ferromagnetic ordering in the CeO2 lattice, the magnetic properties using the Bound Magnetic Polaron model and F centre exchange mechanism are discussed. The development of various complexes that involve host and doped cations are mediated by Vo suggests the existence of F0, F+, and F2+ centres. The weak ferromagnetic behaviour in Ho3+-doped CeO2 nanoparticles reinforce the relationship between Vo to explain the observed magnetic properties of nanoparticles.

Reverse micelle strategy for effective substitutional Fe-doping in small-sized CeO2 nanocrystals: Assessment of adsorption and photodegradation efficiency of ibuprofen under visible light

Reverse micelle nanoreactors were successfully designed to synthesize small-sized ceria nanocrystals (3.5–4.2 nm) with a sizeable amount of substitutional iron. Undoped and doped CeO2 catalysts with an iron content (0.50–10 mol %) compliant with the nominal value were prepared and tested for the first time for the removal of ibuprofen both in the dark and under UV or visible light irradiation.The effective inclusion and distribution of iron in the ceria lattice were ascertained through in-depth physicochemical characterization. In particular, X-ray diffraction suggested the formation of an F-type crystal structure, ruling out the formation of separate iron-containing crystalline phases. On the other hand, substitutional doping of CeO2 with Fe atoms favoured the formation of Ce3+ defects and vacancy sites (VOs) with a maximum for the sample with 2.5 mol % iron (Fe2.5), as evidenced by X-ray photoelectron spectroscopy (XPS) measurements and Raman spectroscopy. UV–Vis spectroscopy showed that the optical properties were successfully modified by the presence of iron, which causes a gradual decrease in band gap as iron content increases. The experimental evidence was further verified and supported by density functional theory calculations. DFT calculations also revealed that the surface iron and oxygen vacancies are the preferential sites for ibuprofen adsorption. Nevertheless, it was found under dark conditions that adsorption capacity does not monotonically increase with iron content, revealing contrasting roles of surface characteristics. Indeed, catalytic experiments have identified a trade-off between adsorption and photodegradation, identifying Fe2.5 as the best-performing catalyst for ibuprofen removal under visible light irradiation. These results were discussed by considering the key properties of the catalysts as well as their different surface charge determined by ζ potential measurements. The best catalyst was tested through reuse experiments that proved its stability over 4 cycles. Finally, an attempt was made to identify the photodegradation by-products, allowing the detection of 1-ethenyl-4-(2-methylpropyl)benzene as the main by-product.

A DFT study of elementary reaction steps of dry reforming of methane catalyzed by Ni: Explaining the difference between Ni particles supported on CeO2 and MnO[formula omitted]-doped CeO2

With the aid of DFT calculations, we investigate the elementary reaction steps of dry reforming of methane (DRM) on Ni(111) and NiO(100) as simple models of metallic and oxidized Ni catalysts. The reaction-path calculations reveal that DRM is feasible on metallic Ni at elevated temperatures. However, a notable problem with metallic Ni catalysts is the coke formation because the activation barrier for the C* formation is not considerably higher than those of the competing reactions that lead to the DRM products. In contrast, NiO does not encounter issues with coke formation, but it is not an effective catalyst due to too high activation energies and slow surface diffusion of H*. We also explain the experimentally observed difference between the DRM catalysts consisting of Ni particles supported on undoped and MnOx-doped CeO2 supports (designated as Ni/CeO2 and Ni/MnxCeO2, respectively). Specifically, we explain the absence of the 2020 cm−1 vibrational peak on the Ni/MnxCeO2 catalyst. Calculations univocally attribute the experimentally observed 2020 cm−1 peak to CO adsorbed on a top site of metallic Ni because all other sites and involved species display considerably different frequencies. The CO stretching frequency increases as Ni oxidizes, and on NiO(100), it is similar to the vibration of CO on the CeO2(111) support, about 2100 cm−1. Current results thus provide a sound explanation of why Ni/MnxCeO2 is a superior DRM catalyst to Ni/CeO2. In particular, the presence of the 2020 cm−1 peak on the Ni/CeO2 catalyst signals that Ni particles are sufficiently metallic and thus susceptible to carbon poisoning. In contrast, the absence of the 2020 cm−1 peak on the Ni/MnxCeO2 catalyst indicates that Ni particles are oxidized, i.e., the Ni oxidation is low enough to allow the DRM reaction but high enough to reduce the catalyst’s carbon poisoning.

Construction of Oxygen Vacancies of Zr-Doped CeO2 with Enhanced Dye Adsorption Performance

Congo red (CR), a highly pigmented anionic dye, is highly toxic and resistant to degradation. The discharge of CR wastewater into the natural environment can lead to ecological destruction and harm to human health. CeO2 as an adsorbent possesses the advantages of excellent acid and alkali resistance, biocompatibility, stable physical and chemical properties, and nontoxic by-products. The impact of Zr doping on the adsorption performance of nano-CeO2 was investigated. XPS and Raman characterisation revealed that Zr doping effectively enhanced the oxygen vacancy ratio at the active sites for CR adsorption on the surface of nano-CeO2. When the doping amount of Zr was 3%, the nanoparticles with the best adsorption properties were obtained, and the adsorption amount of CR at room temperature was as high as 3642.05 mg/g, which was approximately three times the adsorption amount of undoped CeO2. This excellent adsorption property shows good prospects for the removal of anionic dyes from wastewater.

Enhanced Oxygen Storage Capacity of Porous CeO2 by Rare Earth Doping.

CeO2 is an important rare earth (RE) oxide and has served as a typical oxygen storage material in practical applications. In the present study, the oxygen storage capacity (OSC) of CeO2 was enhanced by doping with other rare earth ions (RE, RE = Yb, Y, Sm and La). A series of Undoped and RE-doped CeO2 with different doping levels were synthesized using a solvothermal method following a subsequent calcination process, in which just Ce(NO3)3∙6H2O, RE(NO3)3∙nH2O, ethylene glycol and water were used as raw materials. Surprisingly, the Undoped CeO2 was proved to be a porous material with a multilayered special morphology without any additional templates in this work. The lattice parameters of CeO2 were refined by the least-squares method with highly pure NaCl as the internal standard for peak position calibrations, and the solubility limits of RE ions into CeO2 were determined; the amounts of reducible-reoxidizable Cen+ ions were estimated by fitting the Ce 3d core-levels XPS spectra; the non-stoichiometric oxygen vacancy (VO) defects of CeO2 were analyzed qualitatively and quantitatively by O 1s XPS fitting and Raman scattering; and the OSC was quantified by the amount of H2 consumption per gram of CeO2 based on hydrogen temperature programmed reduction (H2-TPR) measurements. The maximum [OSC] of CeO2 appeared at 5 mol.% Yb-, 4 mol.% Y-, 4 mol.% Sm- and 7 mol.% La-doping with the values of 0.444, 0.387, 0.352 and 0.380 mmol H2/g by an increase of 93.04, 68.26, 53.04 and 65.22%. Moreover, the dominant factor for promoting the OSC of RE-doped CeO2 was analyzed.

Novel Mesoporous and Multilayered Yb/N-Co-Doped CeO2 with Enhanced Oxygen Storage Capacity.

A cubic fluorite-type CeO2 with mesoporous multilayered morphology was synthesized by the solvothermal method followed by calcination in air, and its oxygen storage capacity (OSC) was quantified by the amount of O2 consumption per gram of CeO2 based on hydrogen temperature programmed reduction (H2-TPR) measurements. Doping CeO2 with ytterbium (Yb) and nitrogen (N) ions proved to be an effective route to improving its OSC in this work. The OSC of undoped CeO2 was 0.115 mmol O2/g and reached as high as 0.222 mmol O2/g upon the addition of 5 mol.% Yb(NO3)3∙5H2O, further enhanced to 0.274 mmol O2/g with the introduction of 20 mol.% triethanolamine. Both the introductions of Yb cations and N anions into the CeO2 lattice were conducive to the formation of more non-stoichiometric oxygen vacancy (VO) defects and reducible-reoxidizable Cen+ ions. To determine the structure performance relationships, the partial least squares method was employed to construct two linear functions for the doping level vs. lattice parameter and [VO] vs. OSC/SBET.

Influence of Y Doping on Catalytic Activity of CeO2, MnOx, and CeMnOx Catalysts for Selective Catalytic Reduction of NO by NH3

Novel yttrium-doped CeO2, MnOx, and CeMnOx composites are investigated as catalysts for low-temperature NH3-SCR. The study involves the preparation of unmodified oxide supports using a citrate method followed by modification with Y (2 wt.%) using two approaches, including the one-pot citrate method and incipient wetness impregnation of undoped oxides. The NH3-SCR reaction is studied in a fixed-bed quartz reactor to test the ability of the prepared catalysts in NO reduction. The gas reaction mixture consists of 800 ppm NO, 800 ppm NH3, 10 vol.% O2, and He as a balance gas at a WHSV of 25,000 mL g−1 h−1. The results indicate that undoped CeMnOx mixed oxide exhibits significantly higher deNOx performance compared with undoped and Y-doped MnOx and CeO2 catalysts. Indeed, yttrium presence in CeMnOx promotes the competitive NH3-SCO reaction, reducing the amount of NH3 available for NO reduction and lowering the catalyst activity. Furthermore, the physical-chemical properties of the prepared catalysts are studied using nitrogen adsorption/desorption, XRD, Raman spectroscopy, temperature-programmed reduction with hydrogen, and temperature-programmed desorption of ammonia. This study presents a promising approach to enhancing the performance of NH3-SCR catalysts at low temperatures that can have significant implications for reducing NO emissions.

Ultra-fast photocatalytic degradation and seed germination of band gap tunable nickel doping ceria nanoparticles

Doping transition metal ions into cerium oxide (CeO2) results in interesting modifications to the material, including an increase in surface area, a high isoelectric point, biocompatibility, greater ionic conductivity, and catalytic activity. Herein, various concentrations (1–5%, 10% and 20%) of nickel (Ni) doped CeO2 nanoparticle have been made by a facile chemical process. Using a variety of cutting-edge analytical techniques, the structural, optical, and photocatalytic properties of undoped and varied concentrations (1–5%, 10%, and 20%) of Ni doped CeO2 nanoparticles have been investigated. Pure cubic fluorite structure with average crystallite sizes in the region of 12–15 nm was determined by X-ray diffraction (XRD) investigation. Transmission electron microscopy (TEM), which revealed highly homogeneous hexagonal shape of the particles with average size of 15 nm, was also used to determine microstructural information. According to the optical absorption, the band gaps of Ni doped and undoped CeO2 nanoparticles were found to be 2.96 eV and 1.95 eV, respectively. When exposed to sunlight, the narrow band gap Ni doped CeO2 nanoparticles worked as an active visible light catalyst to remove the dyes Rose Bengal (RB) and Direct Yellow (DY). The best photodegradation efficiencies for RB and DY dyes were found about 93% and 97%, respectively, using the 5% Ni-doped CeO2 catalyst. The apparent rate constant values of 0.039 for RB and 0.040 min−1 were attained for DY. As well, the treated, untreated dye solution and control solutions were utilized to assess the toxicity of commercially accessible Vigna Radiata seeds. In this study exhibits percentages of length and germination increased by 30–35% when compared to dye pollutant solution. The Ni doped CeO2 can provide a substantial alternative for current industrial waste management because of its quick photocatalytic activity and remarkable seed germination results.