Perovskites with Enriched Oxygen Vacancies as a Family of Electrocatalysts for Efficient Nitrate Reduction to Ammonia

Electrochemical nitrate reduction to ammonia (NRA) provides an efficient, sustainable approach to convert the nitrate pollutants into value-added products, which is regarded as a promising alternative to the industrial Haber–Bosch process. Recent studies have shown that oxygen vacancies of oxide catalysts can adjust the adsorption energies of intermediates and affect their catalytic performance. Compared with other metal oxides, perovskite oxides can allow their metal cations to exist in abnormal or mixed valence states, thereby resulting in enriched oxygen vacancies in their crystal structures. Here, the catalytic activities of perovskite oxides toward NRA catalysis with respect to the amount of oxygen vacancies are explored, where four perovskite oxides with different crystal structures (including cubic LaCrO₃, orthorhombic LaMnO₃ and LaFeO₃, hexagonal LaCoO₃) are chosen and investigated. By combining X-ray photoelectron spectroscopy, electron paramagnetic resonance spectroscopy and electrochemical measurements, it is found that the amount of oxygen vacancies in these perovskite oxides surprisingly follow the same order as their activities toward NRA catalysis (LaCrO₃ < LaMnO₃ < LaFeO₃ < LaCoO₃). Further theoretical studies reveal that the existence of oxygen vacancies in LaCoO₃ perovskite can decrease the energy barriers for reduction of *HNO₃ to *NO₂, leading to its superior NRA performance.     

重铬酸钾法测定化学耗氧量消除氯离子干扰新掩蔽剂的研究

本文提出了一种以重铬酸钾为氧化剂,以硝酸银和硝酸铋为掩蔽剂消除氯离子干扰,测定化学耗氧量的新方法,并研究了消化过程中的各种条件,如硫酸浓度、消化时间等。采用硝酸银和硝酸铋联合掩蔽剂可以取代标准重铬酸钾法测定(COD)中使用的硫酸汞,从而避免汞对环境的污染,并使用这种新方法测定了多种类型的水样。结果表明,本法操作简便、快速灵敏、准确度高,并具有广泛的适应性。     

Biomolecule-assisted Solvothermal Synthesis of Bismuth Sulfide Nanorods

A simple biomolecule-assisted synthetic route has been successfully developed to prepare bismuth sulfide(Bi 2 S 3 ) nanorods under solvothermal conditions.In the synthetic system,pentahydrate bismuth nitrate was employed to supply Bi source and L-cystine was used as sulfide source and complexing agent.The morphology,structure,and phase composition of the as-prepared Bi 2 S 3 products were characterized by X-ray diffraction(XRD),energy dispersion spectroscopy(EDS),X-ray photoelectron spectroscopy(XPS),field-...     

Effect of oxygen vacancies on ferroelectric behavior of Na1/2Bi1/2TiO3–BaTiO3 single crystals

One of the important lead-free ferroelectric solid solutions, sodium bismuth titanate–barium titanate Na_1/2Bi_1/2TiO₃–BaTiO₃ (NBT–BT) was grown by the conventional flux technique. In order to study the role of oxygen vacancies on the dielectric/ferroelectric properties, some of the crystal samples oriented along (0 0 1) and (1 0 0) planes were subjected to oxygen and nitrogen annealing processes to create different concentrations of oxygen vacancies in the samples. Dielectric and its loss measurements were carried out to analyze the role of oxygen vacancies and their corresponding dielectric behavior on NBT–BT crystals. Electron energy loss spectrum (EELS) has revealed that increasing oxygen vacancies has reduced oxidation states of Ti. X-ray rocking curve analysis has confirmed the degradation in the structural quality also on increasing the oxygen vacancies.     

Ce and oxygen vacancy mediated tuning of structural and optical properties of CeO2 nanoparticles

Ceria nanoparticles were synthesized by hydrolysis of cerium nitrate in basic medium. The cubic fluorite structure of ceria was confirmed by XRD. From TEM studies ceria nanoparticles were found to be spherical in shape with an average diameter of 5 nm. The prepared nanoparticles have a predominant orientation along (2 2 2) crystallographic plane. Oxygen vacancies and Ce³⁺ lead to the lattice expansion and strain in CeO₂. Peak asymmetry and broadening of Raman active mode peak further confirms the presence of these defects. Total concentration of oxygen vacancies that are present in the ceria nanocrystallites is calculated to be 1.234 × 10²⁰ cm⁻³. These oxygen vacancies and ceria related defects result in an effective red shifting of the band gap by changing its structural regularity. The visible luminescence peaks are also caused by these Ce³⁺ and oxygen vacancy centers.     

First-principles study of A-site substitution in ferroelectric bismuth titanate

We employ density functional theory to investigate the effect of A-site rare earth substitution on the point defect formation in bismuth titanate (BIT) in the dilute substitution limit. Despite previous claims that the formation energy of neutral oxygen vacancies in La-substituted BIT (BLT) is higher than in pure BIT, our calculations show that this is only true for four out of the six distinct oxygen sites. Of these four sites, in two the difference is <0.1 eV while in the other two the difference is ~0.25 eV. In the case of +2 charged oxygen vacancies, in only two of the six distinct oxygen sites is the formation energy of the oxygen vacancy higher in BLT than in BIT, where they differ by ~0.14 eV. These results do not support the traditional explanation for the fatigue-free characteristic of BLT, which states that La substitution might avoid the ferroelectric fatigue of BIT by simply suppressing the formation of oxygen vacancies.     

Migration kinetics of oxygen vacancies in Mn-modified BiFeO₃ thin films

Migration kinetics of oxygen vacancies in BiFe(0.95)Mn(0.05)O(3) thin film were investigated by the temperature -dependent leakage current as well as the electric field and temperature-dependent impedance spectroscopy. The BiFe(0.95)Mn(0.05)O(3) is of an abnormal leakage behavior, and an Ohmic conduction is observed regardless of varied temperatures and electric fields. The temperature-dependent impedance spectroscopy under different resistance states is used to illuminate different leakage behavior between BiFe(0.95)Mn(0.05)O(3) and pure BiFeO(3). The impedance spectroscopy under a high resistance state shows that the first ionization of oxygen vacancies is responsible for the dielectric relaxation and electrical conduction of BiFe(0.95)Mn(0.05)O(3) in the whole temperature range of 294 to 474 K; the BiFeO(3) exhibits similar dielectric relaxation and electrical conduction behavior in the low-temperature range of 294-374 K, whereas the short-range motion of oxygen vacancies was involved in the high-temperature range of 374-474 K. The impedance spectroscopy under a low resistance state demonstrates that the dielectric relaxation and conduction mechanisms almost keep unchanged for BiFe(0.95)Mn(0.05)O(3), whereas the hopping electrons of Fe(2+)-V(O)(?)-Fe(3+) and Fe(2+)-Fe(3+) are responsible for its dielectric relaxation and conduction mechanism of BiFeO(3). Different impedance spectroscopy under low and high resistance states confirms that an abnormal leakage behavior of BiFe(0.95)Mn(0.05)O(3) is related to different migration kinetics of oxygen vacancies, obviously differing from that of BiFeO(3).     

Nonthermal atmospheric pressure plasma jet-assisted formation of oxygen vacancies stabilized tetragonal zirconia particles

This study presented a controlled oxygen vacancy formation on stabilization of tetragonal zirconia particles via a nonthermal atmospheric pressure plasma jet (APPJ) with varying the supplied power. The characteristic analyses based on X-ray diffraction, field emission scanning electron microscopy, high-resolution transmission electron microscopy (HR-TEM), Raman, ultraviolet–visible spectroscopy, and ultraviolet photoemission spectroscopy confirm the existence of oxygen vacancies in tetragonal zirconia particles. Production of oxygen vacancies in the prepared zirconia powder is related to the presence of surface defects by observing HR-TEM and further decreases the bandgap as indicated by optical characterization. Thus, it can be anticipated that the research of defect engineering is a promising way to improve the optoelectronic and photocatalytic performance of oxide material via the APPJ method.     

Electronic structure and optical properties of zirconia

The effects of substitutional impurities and oxygen vacancies on the electronic structure and optical properties of cubic zirconia were studied using band-structure calculations. It is shown that oxygen vacancies produce additional states near the Fermi level, whereas impurity atoms make an insignificant contribution to the states in the valence band and at the bottom of the conduction band, and their effect has a predominantly electrostatic character. The mechanisms of the stabilization of the high-temperature ZrO₂ polymorphs are elucidated. The calculation results agree well with x-ray photoelectron spectroscopy and optical data     

Direct observation of oxygen vacancy and its effect on the microstructure, electronic and transport properties of sputtered LaNiO3 − δ films on Si substrates

Highly (100)-oriented LaNiO₃ films with different oxygen content were deposited on Si substrates by radio frequency sputtering and post-annealed in oxygen and vacuum conditions. The formation of oxygen vacancies is directly observed by a decrease of lattice oxygen ratio in O 1s core-level photoelectron spectroscopy. X-ray diffraction measurement indicates that low oxygen pressure during the deposition or annealing process has a significant influence on the lattice constant of LaNiO₃ films. Further valence-band spectra and transport measurements demonstrate that the oxygen vacancies also have a significant influence on the electronic structure and transport behaviors of final LaNiO₃ films.     

In Situ Formation of Oxygen Vacancies Achieving Near-Complete Charge Separation in Planar BiVO4 Photoanodes

Despite a suitable bandgap of bismuth vanadate (BiVO₄) for visible light absorption, most of the photogenerated holes in BiVO₄ photoanodes are vanished before reaching the surfaces for oxygen evolution reaction due to the poor charge separation efficiency in the bulk. Herein, a new sulfur oxidation strategy is developed to prepare planar BiVO₄ photoanodes with in situ formed oxygen vacancies, which increases the majority charge carrier density and photovoltage, leading to a record charge separation efficiency of 98.2% among the reported BiVO₄ photoanodes. Upon loading NiFeO_x as an oxygen evolution cocatalyst, a stable photocurrent density of 5.54 mA cm⁻² is achieved at 1.23 V versus the reversible hydrogen electrode (RHE) under AM 1.5 G illumination. Remarkably, a dual-photoanode configuration further enhances the photocurrent density up to 6.24 mA cm⁻², achieving an excellent applied bias photon-to-current efficiency of 2.76%. This work demonstrates a simple thermal treatment approach to generate oxygen vacancies for the design of efficient planar photoanodes for solar hydrogen production.     

高氧空位氧化锌晶体的制备及光催化性能

利用气相沉积法,在低氧气氛下制备高缺陷的ZnO晶体。分别将样品在800℃、900℃、1000℃下通氧退火1h,对ZnO晶体做表面修饰。PL光谱实验和光催化降解亚甲基蓝实验表明ZnO晶体的氧空位、表面态和光催化活性间存在内在联系。1000℃下退火的样品表面缺陷程度多于800℃和900℃下退火样品,光催化活性也优于后两者。     

Initial deposition and electron paramagnetic resonance defects characterization of TiO2 films prepared using successive ionic layer adsorption and reaction method

Successive ionic layer adsorption and reaction (SILAR) technique was considered promisingly to deposit ultra thin titanium dioxide (TiO₂) films under ambient condition. In this paper, the growth process, structures and paramagnetic defects of the films were characterized by complementary techniques of atomic force microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and electron paramagnetic resonance spectroscopy. The results indicate that on glass substrate the SILAR TiO₂ film nucleates in an island mode within the initial five deposition cycles but grows in a layer-by-layer mode afterwards. The growth rate was measured as 4.6 Å/cycle. In the as-deposited films, a kind of paramagnetic defects is detected at g (2.0029) and it can be attributed to oxygen vacancies. These as-received oxygen vacancies could be annealed out at 473 K. Ultraviolet irradiation on the as-deposited films can also decrease the density of the defects. The relative mechanisms on the phenomenon were discussed in this paper.     

Effect of different concentration Li-doping on the morphology,defect and photovoltaic performance of Li–ZnO nanofibers in the dye-sensitized solar cells

Low concentrations of Li in Li-doped ZnO nanofibers prepared using hydrothermal method at low temperature can introduce oxygen vacancies and intrinsic Zn ions into the structure. Photo-luminance (PL) was used to investigate oxygen vacancies in the structure of ZnO nanofibers prepared by lower annealing temperature, and the XPS technique was also employed to satisfy the PL analysis results. PL analysis showed that oxygen vacancies increase in conjunction with Li concentrations. A shift in the lower angle of XRD patterns also demonstrates the defect in ZnO structure related to Li doping. Higher-efficiency DSSCs were obtained from the lower Li concentration of 0.01 M in ZnO nanofibers. Higher concentrations of Li tended to produce large amounts of cross-like nanofibers, which increase the open circuit voltage of the DSSCs. The highest open circuit voltage (V_oc) obtained was 750 mV, which was higher than the best reported ZnO nanofibers-based DSSCs. Intensity modulation photocurrent spectroscopy (IMPS) and intensity modulation photo-voltage spectroscopy (IMVS) analysis showed that low amounts of Li-doping improved the electron injection efficiency of ZnO nanofibers in DSSCs. Lower recombination rates with higher electron transfer efficiency for 0.01 M Li-doped DSSCs exhibited higher efficiency of 0.59% than non-doped ZnO nanofibers DSSCs.     

Influence of Sb as a catalyst in the growth of ZnO nano wires and nano sheets using Nanoparticle Assisted Pulsed Laser Deposition (NAPLD)

The methodology on the synthesis of Sb-doped ZnO nanostructures by considering dopant as a catalyst is proposed and demonstrated. The nanostructures were synthesized using intrinsic ZnO as target and Sb-coated Si as substrate, where Sb simultaneously acts as dopant and the catalyst. The catalyst Sb is highly sensitive to temperature conditions resulted in two different nanostructures, the nanowires and the nanosheets. The surface, structural and optical characteristics of the nanowires and the nanosheets are comparatively investigated through SEM, EDX, XRD, Raman spectroscopy and photo luminescence (PL) spectroscopy. The nanowires showed a strong green emission in the PL spectrum and the presence of oxygen vacancies is confirmed thorough Raman peak shift at 556 cm⁻¹. In the case of nanosheets, the defect in oxygen vacancies is completely reduced, and improved UV emission is observed, which confirms the diffusion of Sb in the ZnO lattice.     

反相微乳液法制备纳米四水羟基硝酸氧铋

用Triton X-100/正己醇/环己烷/盐溶液的四元反相微乳液体系制备了纳米四水羟基硝酸氧铋((Bi6O4(OH)4)(NO3)6(H2O)4),研究了不同比例Triton X-100、正己醇、环己烷对微乳液体系的影响,绘制了反相微乳液体系的拟三元相图,确定了室温下微乳液法制取纳米四水羟基硝酸氧铋的最佳条件,制备出了棒状和片状两种产物,利用TEM、IR、XRD、TG-DSC等手段对产物的结构和性能进行了表征.     

Roles of photo-generated holes and oxygen vacancies in enhancing photocatalytic performance over CeO2 prepared by molten salt method

A series of CeO₂ photocatalysts were synthesized through the molten salt method. The photocatalytic activity was evaluated through the degradation of methyl orange (MO). Systematic characterizations including X-ray diffraction, Scanning electron microscopy, Fourier transformed infrared, X-ray photoelectron spectroscopy, Raman spectroscopy, electron spin-resonance spectroscopy, UV–vis diffuse reflectance spectroscopy, photoluminescence spectrometry, photocurrent response and electrochemical impedance spectroscopy were conducted to study the as-prepared CeO₂ samples. It was found that, under ultraviolet light irradiation, the apparent rate constants of CeO₂ prepared at 800 °C for degradation of MO was about 3.4 times higher than CeO₂ prepared at 500 °C. CeO₂ prepared at 800 °C held the higher oxygen vacancies concentration. According to the trapping experiments, it was demonstrated that photo-generated holes played a dominant role in this photocatalytic system. Furthermore, the possible photocatalytic mechanism which showed the roles of photo-generated holes and oxygen vacancies was proposed.     

Control of the structure,morphology and dielectric properties of bismuth titanate ceramics by praseodymium substitution using an intermediate fuel agent-assisted self-combustion synthesis

The volatilization of bismuth (Bi) species and bismuth oxide (Bi₂O₃) leads to the presence of the oxygen vacancies (V _O⁰⁰) and consequently restrains the properties of bismuth titanate (BIT; Bi₄Ti₃O₁₂). This report presents the incorporation of different atomic ratios of praseodymium ion (Pr³⁺: x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) into the BIT (Bi_4−x Pr _x Ti₃O₁₂) ceramics through an intermediate fuel agent-assisted self-combustion synthesis (IFSC). X-ray diffraction and Raman spectroscopy results revealed that some of bismuth ion (Bi³⁺) in the pseudo-perovskite layer containing Ti–O octahedra was substituted by Pr³⁺ ion. The substitution by ion with a smaller ionic radius caused the structure distortion and consequently resulted in the phase transformation from an orthorhombic symmetry to a tetragonal symmetry. Besides, it suppressed the volatilization of Bi and Bi₂O₃ and increased the stability of metal–oxygen octahedra in the BIT. These play a crucial role to control the crystal growth, as well as limit the V _O⁰⁰. Dense ceramic with a relative density up to 96.2% was obtained by incorporating Pr³⁺ with atomic ratio of 1.0. It exhibited high dielectric constant as 908.19 and low dissipation factor as 0.0011. The results address the possibility to control the structure, morphology and dielectric properties of BIT ceramic by incorporating Pr³⁺ ion through IFSC.     

A study on structural stability of bismuth titanate with lanthanum doping for improved ferroelectric properties

Bismuth titanate \((\hbox {Bi}_{4}\hbox {Ti}_{3}\hbox {O}_{12})\) with different lanthanum (La) concentrations (0.25, 0.50, 0.75 and 1.0 mol%) was successfully prepared via soft combustion route. It was found that the change of diffraction peaks shown by X-ray diffraction is attributed to the doping effect in \(\hbox {Bi}_{4}\hbox {Ti}_{3}\hbox {O}_{12}\). This was also supported by the presence of additional peak that corresponds to La in the range of 800–860 eV, proved by X-ray photoelectron spectroscopy. In addition, the enlarged region of Bi 4f, Bi 4d, Ti 2p, La 3d and O 1s of doping sample was clearly seen after deconvolution. Based on binding energy position, it can be unambiguously stated that the Ti ions in the tetravalent state are surrounded by the perovskite layer of \(\hbox {Bi}_{4}\hbox {Ti}_{3}\hbox {O}_{12}\), which may also imply the formation of oxygen vacancies in the vicinity of the \(\hbox {Bi}_{2}\hbox {O}_{2}\) layer. In comparison with \(\hbox {Bi}_{4}\hbox {Ti}_{3}\hbox {O}_{12}\), the green emission intensity was abruptly decreased with La doping. This indicates that La doping suppresses the formation of oxygen vacancies by stabilizing the adjacent oxide ions. Thus, the improved polarization shown by ferroelectric hysteresis loop is associated with the reduction in oxygen and bismuth vacancies due to La doping.