Understanding the synergistic effects,optical and electronic properties of ternary Fe/C/S‐doped TiO2 anatase within the DFT + U approach

Although TiO₂ is an efficient photocatalyst, its large band gap limits its photocatalytic activity only to the ultraviolet region. An experimentally synthesized ternary Fe/C/S‐doped TiO₂ anatase showed improved visible light photocatalytic activity. However, a theoretical study of the underlying mechanism of the enhanced photocatalytic activity and the interaction of ternary Fe/C/S‐doped TiO₂ has not yet been investigated. In this study, the defect formation energy, electronic structure and optical property of TiO₂ doped with Fe, C, and S are investigated in detail using the density functional theory + U method. The calculated band gap (3.21 eV) of TiO₂ anatase agree well with the experimental band gap (3.20 eV). The defect formation energy shows that the co‐ and ternary‐doped systems are thermodynamically favorable under oxygen‐rich condition. Compared to the undoped TiO₂, the absorption edge of the mono‐, co‐, and ternary‐doped TiO₂ is significantly enhanced in the visible light region. We have shown that ternary doping with C, S, and Fe induces a clean band structure without any impurity states. Moreover, the ternary Fe/C/S‐doped TiO₂ exhibit an enhanced photocatalytic activity, a smaller band gap and negative formation energy compared to the mono‐ and co‐doped systems. Moreover, the band edges of Fe/C/S‐doped TiO₂ align well with the redox potentials of water, which shows that the ternary Fe/C/S‐doped TiO₂ is promising photocatalysts to split water into hydrogen and oxygen. These findings rationalize the available experimental results and can assist the design of TiO₂‐based photocatalyst materials.     

Growth and Electronic Properties of Ag Nanoparticles on Reduced CeO2-x(111) Films

Ag nanoparticles grown on reduced CeO_2-x thin films have been studied by X-ray photoelec-tron spectroscopy and resonant photoelectron spectroscopy of the valence band to understand the effect of oxygen vacancies in the CeO_2-x thin films on the growth and interfacial elec-tronic properties of Ag. Ag grows as three-dimensional particles on the CeO_2-x(111) surface at 300 K. Compared to the fully oxidized ceria substrate surface, Ag favors the growth of smaller particles with a larger particle density on the reduced ceria substrate surface, which can be attributed to the nucleation of Ag on oxygen vacancies. The binding energy of Ag3d increases when the Ag particle size decreases, which is mainly attributed to the final-state screening. The interfacial interaction between Ag and CeO_2-x(111) is weak. The resonant enhancement of the 4f level of Ce³⁺ species in RPES indicates a partial Ce⁴⁺→Ce³⁺ re-duction after Ag deposited on reduced ceria surface. The sintering temperature of Ag on CeO_1.85(111) surface during annealing is a little higher than that of Ag on CeO₂(111) surface, indicating that Ag nanoparticles are more stable on the reduced ceria surface.     

Analysis of Dopant Atom Distribution and Quantification of Oxygen Vacancies on Individual Gd‐Doped CeO2 Nanocrystals

This work reports the analysis of the distribution of Gd atoms and the quantification of O vacancies applied to individual CeO₂ and Gd‐doped CeO₂ nanocrystals by electron energy‐loss spectroscopy. The concentration of O vacancies measured on the undoped system (6.3±2.6 %) matches the expected value given the typical Ce³⁺ content previously reported for CeO₂ nanoparticles. The doped nanoparticles have an uneven distribution of dopant atoms and an atypical amount of O vacant sites (37.7±4.1 %). The measured decrease of the O content induced by Gd doping cannot be explained solely by the charge balance including Ce³⁺ and Gd³⁺ ions.     

Structural and Electrochemical Properties of Sol-Gel Derived Mo : CeO2, Si : Mo : CeO2 and Si : CeO2 Nanocrystalline Films for Electrochromic Devices

Mo:CeO₂, Si:CeO₂ and Mo:Si:CeO₂ films were made by the sol-gel dip-coating technique. XRD investigations of the analogously prepared powders revealed that particle grain size of CeO₂ with the addition of Mo, Si or both decreased. FT/IR spectra of the corresponding films showed that no separate Mo-oxide phase was formed while the Si containing CeO₂ films had nanocrystallites of ceria as well as amorphous silica. Electrochemical investigations (cyclic voltammetry, chronocoulometry) performed in protic (0.1M LiOH) and aprotic (1M LiClO₄/propylene carbonate(PC)) electrolytes showed that additions of Mo:, Si: and Mo: Si:-to ceria increased ion storage ability. The suitability of films as optically passive counter electrodes was demonstrated by making electrochromic cells with asymmetric and symmetric configurations using a Li⁺ doped ionic conductor (ormolyte^®) and an electrochromic tungstophosphoric acid (WPA)/TiO₂ gel film.     

Electronic and Structural Properties of Highly Aluminum Ion Doped TiO2 Nanoparticles: A Combined Experimental and Theoretical Study

This study presents the experimental and theoretical study of highly internally Al‐doped TiO₂ nanoparticles. Two synthesis methods were used and detailed characterization was performed. There were differences in the doping and the crystallinity, but the nanoparticles synthesized with the different methods share common features. Anatase to rutile transformation occurred at higher temperatures with Al doping. X‐ray photoelectron spectroscopy showed the generation of oxygen vacancies, which is an interesting feature in photocatalysis. In turn, the band‐gap energy and the valence band did not change appreciably. Periodic density functional calculations were performed to model the experimentally doped structures, the formation of the oxygen vacancies, and the band gap. Calculation of the density of states confirmed the experimental band‐gap energies. The theoretical results confirmed the presence of Ti⁴⁺ and Al³⁺. The charge density study and electron localization function analysis indicated that the inclusion of Al in the anatase structure resulted in a strengthening of the Ti?O bonds around the vacancy.     

Multifunctional silicene/CeO2 heterojunctions: Desirable electronic material and promising water-splitting photocatalyst

The first-principles calculations demonstrate that covalently bonded (cb) heterojunction and van der Waals (vdW) heterojunction can coexist in silicene/CeO₂ heterojunctions, due to the different stacking patterns. Especially, the cb heterojunction with band gap of 1.97 eV, forms a type-II heterojunction, exhibits good redox performance and has high-effective optical absorption spectra, thus it is a promising photocatalyst for overall water splitting. Besides, for the vdW heterojunction, the Dirac cone of silicene is well kept on CeO₂ semiconducting substrate, with a considerable energy gap of 0.43 eV, which can be an ideal material in building silicene-based electronic device. These results may open a new gateway in both of nanoelectronic device and energy conversion for silicene/CeO₂ nanocomposites.     

Outstanding Methane Oxidation Performance of Palladium‐Embedded Ceria Catalysts Prepared by a One‐Step Dry Ball‐Milling Method

By carefully mixing Pd metal nanoparticles with CeO₂ polycrystalline powder under dry conditions, an unpredicted arrangement of the Pd‐O‐Ce interface is obtained in which an amorphous shell containing palladium species dissolved in ceria is covering a core of CeO₂ particles. The robust contact that is generated at the nanoscale, along with mechanical forces generated during mixing, promotes the redox exchange between Pd and CeO₂ and creates highly reactive and stable sites constituted by PdO_x embedded into CeO₂ surface layers. This specific arrangement outperforms conventional Pd/CeO₂ reference catalysts in methane oxidation by lowering light‐off temperature by more than 50°C and boosting the reaction rate. The origin of the outstanding activity is traced to the structural properties of the interface, modified at the nanoscale by mechanochemical interaction.     

Preparation and characterization of Ce1−xSmxO2−δ (x = 0.1–0.3) as electrolyte material for intermediate temperature SOFC

The effect of Sm doping on CeO₂ for its use as a solid electrolyte material for intermediate temperature solid oxide fuel cells (IT-SOFCs) has been explored here. Ce_1−xSm_xO_2−δ (x = 0.1–0.3) samples are successfully synthesized by carbonate co-precipitation method. TG–DTA, XRD, Raman, UV–Vis, FT-IR, SEM and ac-impedance are used for structural and electrical characterization. From the XRD patterns, well-crystalline cubic fluorite structured solid solution is confirmed. Lattice parameters increased with increase in Sm³⁺ while the crystallite size decreased. The optical absorption spectra exhibits a red shift for Sm³⁺ doped CeO₂. Raman spectra show an intense peak at 463 cm⁻¹, a characteristic peak for doped ceria. SEM shows cluster like particles. Based on ac-impedance data, the total oxygen ionic conductivity is highest for Ce_0.8Sm_0.2O_2−δ in the temperature range of 473–623 K.     

Electronic Structure and Optical Properties of K2Ti6O13 Doped with Transition Metal Fe or Ag

Based on the experimental study of the optical properties of K₂Ti₆O₁₃ doped with Fe or Ag, their electronic structures and optical properties are studied by the first-principles method based on the density functional theory (DFT). The calculated optical properties are consistent with the experiment results. K₂Ti₆O₁₃ doped with substitutional Fe or Ag has isolated impurity bands mainly stemming from the hybridization by the Fe 3d states or Ag 4d states with Ti 3d states and O 2p states and the band gap becomes narrower, the absorption edge of K₂Ti₆O₁₃ thus has a clear red shift and the absorption of visible light can be realized after doping. For Fe-doped K₂Ti₆O₁₃, the impurity bands are in the middle of the band gap, suggesting that they can be used as a bridge for valence band electrons transition to the conduction band. For Ag-doped K₂Ti₆O₁₃, the impurity bands form a shallow acceptor above the valence band and can reduce the recombination rate of photoexcited carriers. The experimental and calculated results are significant for the development of K₂Ti₆O₁₃ materials that have absorption under visible light.     

Facile Synthesis of Platinum–Cerium(IV) Oxide Hybrids Arched on Reduced Graphene Oxide Catalyst in Reverse Micelles with High Activity and Durability for Hydrolysis of Ammonia Borane

Highly dispersed Pt‐CeO₂ hybrids arched on reduced graphene oxide (Pt‐CeO₂/rGO) were facilely synthesized by a combination of the reverse micelle technique and a redox reaction without any additional reductant or surfactant. Under a N₂ atmosphere, the redox reaction between Ce³⁺ and Pt²⁺ occurs automatically in alkaline solution, which results in the formation of Pt‐CeO₂/rGO nanocomposites (NCs). The as‐synthesized Pt‐CeO₂/rGO NCs exhibit superior catalytic performance relative to that shown by the free Pt nanoparticles, Pt/rGO, Pt‐CeO₂ hybrid, and the physical mixture of Pt‐CeO₂ and rGO; furthermore, the nanocomposites show significantly better activity than the commercial Pt/C catalyst toward the hydrolysis of ammonia borane (NH₃BH₃) at room temperature. Moreover, the Pt‐CeO₂/rGO NCs have remarkable stability, and 92 % of their initial catalytic activity is preserved even after 10 runs. The excellent activity of the Pt‐CeO₂/rGO NCs can be attributed not only to the synergistic structure but also to the electronic effects of the Pt‐CeO₂/rGO NCs among Pt, CeO₂, and rGO.     

Absorption Spectroscopy Analysis of Calcium–Phosphate Glasses Highly Doped with Monovalent Copper

CaO–P₂O₅ glasses with high concentrations of monovalent copper ions were prepared by a simple melt–quench method through CuO and SnO co‐doping. Spectroscopic characterization was carried out by optical absorption with the aim of analyzing the effects of Cu⁺ ions on the optical band‐gap energies, which were estimated on the basis of indirect–allowed transitions. The copper(I) content is estimated in the CuO/SnO‐containing glasses after the assessment of the concentration dependence of Cu²⁺ absorption in the visible region for CuO singly doped glasses. An exponential dependence of the change in optical band gaps (relative to the host) with Cu⁺ concentration is inferred up to about 10 mol %. However, the entire range is divided into two distinct linear regions that are characterized by different rates of change with respect to concentration: 1) below 5 mol %, where the linear dependence presents a relatively high magnitude of the slope; and 2) from 5–10 mol %, where a lower magnitude of the slope is manifested. With increasing concentration, the mean Cu⁺?Cu⁺ interionic distance decreases, thereby decreasing the sensitivity of monovalent copper for light absorption. The decrease in optical band‐gap energies is ultimately shown to follow a linear dependence with the interionic distance, suggesting the potential of the approach to gauge the concentration of monovalent copper straightforwardly in amorphous hosts.     

The Vital Role of Buffer Anions in the Antioxidant Activity of CeO2 Nanoparticles

Cerium oxide (CeO₂) nanoparticles display excellent antioxidant properties by scavenging free radicals. However, some studies have indicated that they can cause an adverse response by generating reactive oxygen species (ROS). Hence, it is important to clarify the factors that affect the oxidant/antioxidant activities of CeO₂ nanoparticles. In this work, we report the effects of different buffer anions on the antioxidant activity of CeO₂ nanoparticles. Considering the main anions present in the body, Tris‐HCl, sulfate, and phosphate buffer solutions have been used to evaluate the antioxidant activity of CeO₂ nanoparticles by studying their DNA protective effect. The results show that CeO₂ nanoparticles can protect DNA from damage in Tris‐HCl and sulfate systems, but not in phosphate buffer solution (PBS) systems. The mechanism of action has been explored: cerium phosphate is formed on the surface of the nanoparticles, which interferes with the redox cycling between Ce³⁺ and Ce⁴⁺. As a result, the antioxidant activity of CeO₂ nanoparticles is greatly affected by the external environment, especially the anions. These results may provide guidance for the further practical application of CeO₂ nanoparticles.     

In Situ and Theoretical Studies for the Dissociation of Water on an Active Ni/CeO2 Catalyst: Importance of Strong Metal–Support Interactions for the Cleavage of O–H Bonds

Water dissociation is crucial in many catalytic reactions on oxide‐supported transition‐metal catalysts. Supported by experimental and density‐functional theory results, the effect of the support on O? H bond cleavage activity is elucidated for nickel/ceria systems. Ambient‐pressure O 1s photoemission spectra at low Ni loadings on CeO₂(111) reveal a substantially larger amount of OH groups as compared to the bare support. Computed activation energy barriers for water dissociation show an enhanced reactivity of Ni adatoms on CeO₂(111) compared with pyramidal Ni₄ particles with one Ni atom not in contact with the support, and extended Ni(111) surfaces. At the origin of this support effect is the ability of ceria to stabilize oxidized Ni²⁺ species by accommodating electrons in localized f‐states. The fast dissociation of water on Ni/CeO₂ has a dramatic effect on the activity and stability of this system as a catalyst for the water‐gas shift and ethanol steam reforming reactions.     

Preparation and characterization of Pd modified CeO2 nanoparticles for photocatalytic degradation of dye

The aim of this work was to investigate the structural and optical properties of bare cerium dioxide (CeO₂) and Pd-doped CeO₂ (0.5, 1.0, 1.5 and 2.0 wt%) photocatalysts prepared by a combination of homogeneous precipitation and the impregnation method. X–ray diffraction analysis indicated that all samples were composed of the cubic fluorite phase of CeO₂. Scanning electron micrographs revealed that all samples provided mostly spherical morphology with high agglomeration and estimated particle sizes ranging from 10 to 20 nm in diameter. The XPS core-level spectra of Pd species after incorporating 2.0 wt% Pd–doped CeO₂ showed double peaks with binding energies of Pd3d_5/2 and Pd3d_3/2 corresponding to the Pd²⁺ oxidation state. The results from diffuse reflectance UV–visible spectroscopy showed that doping with Pd increased the absorbance onset of CeO₂ to a longer wavelength, while the band gap decreased from 3.0 eV to 2.8 eV with 2.0% Pd doping concentration. This was likely due to the creation of impurity levels of Pd²⁺ inside the conduction and valence bands of CeO₂. The photoluminescence spectra (PL) indicated that the emission peak intensity of CeO₂ decreased in the presence of Pd²⁺ dopant in CeO₂. This was associated with a decrease in the electron–hole recombination rate for electronically-excited. Photocatalytic activity for methyl orange dye degradation under visible light irradiation of 1.0 wt% Pd–doped CeO₂ was determined as the optimal doping level with photocatalytic activity 5 times higher than that of bare CeO₂ photocatalyst.     

一种通过纳米粒子的组装制备基于二氧化铈中孔材料的简易方法

用HF或者HCl作联合剂,三嵌段共聚物表面活性剂作模板剂,通过二氧化铈纳米粒子(或者过渡金属掺杂的二氧化铈纳米粒子)组装形成具有热稳定和晶化孔壁的基于二氧化铈的中孔材料。焙烧该合成的超分子模板中孔结构的材料可以形成具有高比表面的基于二氧化铈的中孔材料,这些中孔材料用不同的光谱技术表征。通过D₂-OH交换测得的二氧化铈表面的羟基在组装过程和中孔材料的稳定性方面至关重要。联结剂中的卤素离子(F和Cl离子)可以替代中孔材料的表面羟基,从而影响这些中孔材料的结构稳定性和光学活性,而用具有3 d的过渡金属在组装前掺杂二氧化铈纳米粒子可以显著地提高中孔材料的光学活性,这种提高主要归结为通过掺杂可以促使能量转移的提高。     

Synthesis of Zn doped black TiO2 nanoparticles for degradation of 2, 4, 6 tri-chloro-phenol under visible light

A modified sol-gel method was used for synthesis of zinc doped black TiO₂ nanoparticles. The modified sol-gel synthesised catalyst was utilised for degradation of 2, 4, 6 tri-chloro-phenol under visible light irradiation. The catalyst was characterized using XRD, SEM, TEM, BET and DRS analysis. The nanoparticles were crystalline in nature and in anatase phase. The size of zinc doped black TiO₂ nanoparticles was 5 nm. The synthesised nanoparticles were mesoporous in nature and the specific surface area was found to be 34.15 m²/g. The band gap energy of zinc black TiO₂ nanoparticles was found to be 2.73 eV. The point of zero charge of zinc doped black TiO₂ nanoparticles was 6.7. The maximum degradation of 2, 4, 6 tri-chloro-phenol using 2 mol% zinc doped black TiO₂ was found to be 95%.     

Synthesis and Characterization of CeO2 Nanoparticles via Solution Combustion Method for Photocatalytic and Antibacterial Activity Studies

CeO₂ nanoparticles have been proven to be competent photocatalysts for environmental applications because of their strong redox ability, nontoxicity, long-term stability, and low cost. We have synthesized CeO₂ nanoparticles via solution combustion method using ceric ammonium nitrate as an oxidizer and ethylenediaminetetraacetic acid (EDTA) as fuel at 450 °C. These nanoparticles exhibit good photocatalytic degradation and antibacterial activity. The obtained product was characterized by various techniques. X-ray diffraction data confirms a cerianite structure: a cubic phase CeO₂ having crystallite size of 35 nm. The infrared spectrum shows a strong band below 700 cm⁻¹ due to the Ce−O−Ce stretching vibrations. The UV/Vis spectrum shows maximum absorption at 302 nm. The photoluminescence spectrum shows characteristic peaks of CeO₂ nanoparticles. Scanning electron microscopy (SEM) images clearly show the presence of a porous network with a lot of voids. From transmission electron microscopy (TEM) images, it is clear that the particles are almost spherical, and the average size of the nanoparticles is found to be 42 nm. CeO₂ nanoparticles exhibit photocatalytic activity against trypan blue at pH 10 in UV light, and the reaction follows pseudo first-order kinetics. Finally, CeO₂ nanoparticles also reduce Cr^VI to Cr^III and show antibacterial activity against Pseudomonas aeruginosa.     

Role of Ceria in the Design of Composite Materials for Elemental Mercury Removal

The necessity to drastically act against mercury pollution has been emphatically addressed by the United Nations. Coal‐fired power plants contribute a great deal to the anthropogenic emissions; therefore, numerous sorbents/catalysts have been developed to remove elemental mercury (Hg⁰) from flue gases. Among them, ceria (CeO₂) has attracted significant interest, due to its reversible Ce³⁺/Ce⁴⁺ redox pair, surface‐bound defects and acid‐base properties. The removal efficiency of Hg⁰ vapor depends among others, on the flue gas composition and temperature. CeO₂ can be incorporated into known materials in such a way that the abatement process can be effective at different operating conditions. Hence, the scope of this account is to discuss the role of CeO₂ as a promoter, active phase and support in the design of composite Hg⁰ sorbents/catalysts. The elucidation of each of these roles would allow the integration of CeO₂ advantageous characteristics to such degree, that tailor‐made environmental solution to complex issues can be provided within a broader application scope. Besides, it would offer invaluable input to theoretical calculations that could enable the materials screening and engineering at a low cost and with high accuracy.     

Efficient photocatalytic degradation of rhodamine-B by Fe doped CuS diluted magnetic semiconductor nanoparticles under the simulated sunlight irradiation

The present work is planned for a simple, inexpensive and efficient approach for the synthesis of Cu_1-xFe_xS (x = 0.00, 0.01, 0.03, 0.05 and 0.07) nanoparticles via simplistic chemical co-precipitation route by using ethylene diamine tetra acetic acid (EDTA) as a capping molecules. As synthesized nanoparticles were used as competent catalysts for degradation of rhodamine-B organic dye pollutant. The properties of prepared samples were analyzed with energy dispersive analysis of X-rays (EDAX), X-ray diffraction (XRD), transmission electron microscopy (TEM), UV-visible optical absorption spectroscopy, Fourier transform infrared (FTIR) spectra, Raman spectra and vibrating sample magnetometer (VSM). EDAX spectra corroborated the existence of Fe in prepared nanoparticles within close proximity to stoichiometric ratio. XRD, FTIR and Raman patterns affirmed that configuration of single phase hexagonal crystal structure as that of (P6₃/mmc) CuS, without impurity crystals. The average particle size estimated by TEM scrutiny is in the assortment of 5–10 nm. UV-visible optical absorption measurements showed that band gap narrowing with increasing the Fe doping concentration. VSM measurements revealed that 3% Fe doped CuS nanoparticles exhibited strong ferromagnetism at room temperature and changeover of magnetic signs from ferromagnetic to the paramagnetic nature with increasing the Fe doping concentration in CuS host lattice. Among all Fe doped CuS nanoparticles, 3% Fe inclusion CuS sample shows better photocatalytic performance in decomposition of RhB compared with the pristine CuS. Thus as synthesized Cu_0·97Fe_0·03S nanocatalysts are tremendously realistic compounds for photocatalytic fictionalization in the direction of organic dye degradation under visible light.     

Fundamental Aspects of Ceria Supported Au Catalysts Probed by In Situ/Operando Spectroscopy and TAP Reactor Studies

The discovery of the activity of dispersed gold nanoparticles three decades ago paved the way for a new era in catalysis. The unusual behavior of these catalysts sparked many questions about their working mechanism. In particular, Au/CeO₂ proved to be an efficient catalyst in several reactions such as CO oxidation, water gas shift, and CO₂ reduction. Here, by employing findings from operando X-ray absorption spectroscopy at the near and extended Au and Ce L_III energy edges, we focus on the fundamental aspects of highly active Au/CeO₂ catalysts, mainly in the CO oxidation for understanding their complex structure-reactivity relationship. These results were combined with findings from in situ diffuse reflectance FTIR and Raman spectroscopy, highlighting the changes of adlayer and ceria defects. For a comprehensive understanding, the spectroscopic findings will be supplemented by results of the dynamics of O₂ activation obtained from Temporal Analysis of Products (TAP). Merging these results illuminates the complex relationship among the oxidation state, size of the Au nanoparticles, the redox properties of CeO₂ support, and the dynamics of O₂ activation.