多晶SnO2电导值的室温振荡现象

SnO_2为n型半导体,在还原气氛中电导增加,氧化气氛中电导降低。利用这一性质,已经制成各种类型气体敏感元件。它们均工作在加热状态,以保证元件具有较高的灵敏度和快的响应恢复。我们在研究SnO_2半导体材料室温气敏性质时发现,经过适当掺杂和改性的SnO_2多晶粉末材料,其电导值即便在纯净空气中也呈现出奇异的超低频振荡性质。将这种类型的SnO_2多晶材料置于氧化或还原气氛中,其振荡波形发生明显变化。利用这种振荡现象不仅可     

ZrO2氧空位显微结构的高分辨电镜研究

基于透射电镜X射线能谱仪得到的微区成分信息及高分辨电子显微结构信息,构建具有氧空位缺陷的ZrO2晶体结构模型,用200 kV透射电子显微镜的参数进行高分辨实验像的多片层法模拟计算,观察分析了ZrO2多晶材料样品的晶格缺陷.沿[001]方向的二维晶格像及相应的傅立叶变换像显示出ZrO2样品的晶格缺陷.将计算机模拟结果与高分辨实验像进行比较,结果表明计算机模拟像的衬度及周期性与实验像之间符合良好.根据晶体结构的缺陷模型和模拟计算,阐明了氧空位缺陷引起的实验像衬度的变化.通过高分辨电子显微观察结果及计算机模拟结果,揭示了陶瓷ZrO2多晶材料样品晶格中氧空位的存在.     

基于半导体纳米SnO_2构建的气敏传感器的应用研究进展

SnO2是传统的气敏材料,由于其具有间隙锡离子和氧空位的特性,使得气体更容易吸附在材料表面,从而显示出更好的气敏性质.通过把SnO2进行贵金属附载掺杂和多种气敏性半导体氧化物的复合,探讨了一系列性能良好的气敏传感器,阐述了SnO2气敏传感的最新进展.     

Fe2O3—SnO2复合气敏材料的气敏性能研究

本文采用共沉淀方法制备超微粒子原料粉,测试了不同配比材料的气敏灵敏度,并探讨了不同粒度的Fe_2O_3原料与气敏特性之间的关系,提出Fe_2O_3-SnO_2复合气敏材料的气敏机制属体控制与表面控制兼有的混合机制·Fe_2O_3-SnO_2,复合气敏材料,选用CuO掺杂,可制出对乙炔具有高选择性和灵敏度的气敏元件。     

常温SnO_2-α-Fe_2O_3气敏元件制备

用a-Fe_2O_3研制成的加热式气敏元件功耗大(约1.5W)。常温SnO_2-a-Fe_2O_3气敏元件功耗低(约0.1W),灵敏度高,响应恢复快,稳定,具有一定选择性。 气敏元件制备方法:按62.5％,6.2％和31.3％称取SnO_2,a-Fe_2O_3和硅胶,加水研磨2小时,使其呈浆糊状,点入模具内,放入一对φ0.05mm铂丝电极,晾干,脱模,在860～890℃空气中烧结95分钟。     

受主掺杂BaPbO3晶体的缺陷化学模型

以高温平衡电导法测定高温平衡电导率随氧分压的变化为基础, 具体分析了不同氧分压范围内主要缺陷类型——包括空穴、电子、氧离子空位、铅离子空位和杂质缺陷随氧分压的变化规律, 通过一定的理论假设, 建立了以空穴、电子、氧离子空位、铅离子空位和杂质缺陷为主要缺陷类型的受主掺杂BaPbO3材料的缺陷化学模型.     

Nd2O3掺杂对SnO2气敏性质的影响

SnO_2是目前应用最广的一种气敏材料。我们曾经报道掺入La_2O_3,CeO_2,Pr_6O_(11),和Nd_2O_3后可使半导体元件的灵敏度提高,尤以对乙醇、乙醚、丙酮为显著。掺Nd_2O_3元件对乙炔的灵敏度也有提高。本文考察了SnO_2粒度和被测气氛的物化性质对掺Nd_2O_3元件灵敏度的影响。SnO_2采用水解SnCl_4法制备,纯度经光谱分析测定合格,试样用标准筛分目。在SnO_2中加1wt%Nd_2O_3(光谱纯)和适量水及甲基纤维素,混磨15分钟。将制成的悬浊液滴在一对铂     

Pr6O11对SnO2半导体气敏特性的影响

研究了添加Pr_6O_11的SnO_2半导体气敏元件的气敏特性。在丙酮、乙醇、甲烷、一氧化碳等11种气氛中测量结果表明,元件对丙酮、乙醇具有选择性,Pr_6O_(11)的最佳含量为1.0wt％左右。实验还发现,元件的限定工作温度随着Pr_6O_(11)含量的增加而下降,响应时间和恢复时间缩短,灵敏度随被测气体浓度变化的线性范围相应增大。     

钐对不同氧空位SnO2气敏性能的影响

用Ｓｍ对不同氧空位浓度的ＳｎＯ２－ｘ气敏材料进行掺杂化学改性,并进行ＸＲＤ,ＸＰＳ,ＳＥＭ分析和比表面积测定,考察改性后的气敏材料对Ｃ６Ｈ６,Ｃ６Ｈ１２,Ｃ２Ｈ５ＯＨ,ＣＯ,Ｈ２等的气敏性能。     

LaF3掺杂PbF2电导和氧敏性质

氟离子半径小,仅带一个负电荷;LaF_3中弱的共价键结合以及晶格中空位缺陷,使其表现出高的离子导电性能。有关LaF_3气敏元件的氧敏性质已有不少报道。属六方氟铈镧矿型结构的三氟化物掺杂适量的碱土金属或碱金属氟化物可提高其离子导电率。任玉芳等人研究了数种稀土复合氟化物元件的氧敏性质。掺杂PbF_2的复合稀土复化物的     

Kinetic Monte Carlo simulations of oxygen vacancy diffusion in a solid electrolyte: Computing the electrical impedance using the fluctuation–dissipation theorem

We present a new method for computing the electrical impedance of solid oxide electrolyte from kinetic Monte Carlo simulations of oxygen vacancy diffusion. The impedance values at all frequencies are obtained from a single equilibrium simulation based on the fluctuation–dissipation theorem, leading to a significant gain of efficiency over existing methods.This allows us to systematically examine the effect of dopant concentration. Increasing dopant concentration is found to decrease the infinite-frequency impedance, which is attributed to the increasing density of oxygen vacancies. The difference between the impedance values at zero- and infinite-frequency, on the other hand, shows the opposite trend, and is linked to dopant–vacancy interactions. Hence the two competing mechanisms, previously proposed to explain the existence of an optimal doping concentration, are separately quantified.Our model also predicts a significant effect of the arrangement of dopant cations on the electrolyte conductivity.     

Effect of oxygen vacancies in anodic titanium oxide films on the kinetics of the oxygen electrode reaction

The effect of oxygen vacancies in the anodic oxide film on passive titanium on the kinetics of the oxygen electrode reaction has been studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Oxide films of different donor density were prepared galvanostatically at various current densities until a potential of 20.0 V_SHE was achieved. The semiconductive properties of the oxide films were characterized using EIS and Mott-Schottky analysis, and the thickness was measured using ellipsometry. The film thickness was found to be almost constant at ∼44.7 ± 2.0 nm, but Mott-Schottky analysis of the measured high frequency interracial capacitance showed that the donor (oxygen vacancy) density in the n-type passive film decreased sharply with increasing oxide film formation rate (current density). Passive titanium surfaces covering a wide range of donor density were used as substrates for ascertaining relationships between the rates of oxygen reduction/evolution and the donor density. These studies show that the rates of both reactions are higher for passive films having higher donor densities. Possible explanations include enhancement of the conductivity of the film due to the vacancies facilitating charge transfer and the surface oxygen vacancies acting as catalytic sites for the reactions. The possible involvement of surface oxygen vacancies in the oxygen electrode reaction was explored by determining the kinetic order of the OER with respect to the donor concentration. The kinetic orders were found to be greater than zero, indicating that oxygen vacancies are involved as electrocatalytic reaction centers in both the oxygen evolution and reduction reactions. This paper was submitted in honor of the many contributions to electrochemistry that have been made by Professor Boris Grafov. The article is published in the original.     

Mixed conductivity, nonstoichiometric oxygen, and oxygen permeation properties in Co-Doped Sr3Ti2O(7-δ)

Electrical conductivity and oxygen permeation rates in Co-doped Sr(3)Ti(2)O(7-δ) with Ruddesden-Popper type structures were investigated. The effects of metal dopants (M) in the Ti site of Sr(3)Ti(2)(M)O(7-δ) on the mixed conductivity were also studied. Doping of Sr(3)Ti(2)O(7-δ) with Co was found to be effective for improving the electrical conductivity as well as the oxygen permeation rate, which could be assigned to the increased oxygen vacancy concentration by doping Co(3+) into Ti(4+) sites. The nonstoichiometric oxygen of these oxides was measured by using a thermal gravimetric method. The creation of oxygen vacancies, which is compensated with Co(3+) doping, leads to higher oxide ion conductivity. The oxygen permeation rate monotonously increased with increasing amounts of Co in the Ti site. Sr(3)Ti(0.8)Co(1.2)O(7-δ) exhibited high oxide ion conductivity and a large oxygen permeation rate. The highest oxygen permeation rate achieved a value of 2.02 cc min(-1) cm(-2) at 1273 K for Sr(3)Ti(0.8)Co(1.2)O(7-δ). Neutron diffraction analysis and redox titration suggests that the oxygen diffusion occurs through oxygen vacancies in the perovskite block, but not through excess oxygen in the rock salt block.     

Opto-electronic properties of blue phosphorene oxide with and without oxygen vacancies

Blue phosphorene is an attractive nanomaterial that exhibits some remarkable optoelectronic properties. Various studies have verified its ability to adsorb gaseous compounds and, in particular, to dissociate O₂, forming covalent bonds between phosphorus and oxygen atoms. These covalent bonds could be the reason behind the oxidation reaction that affects the blue phosphorene in normal room conditions. Theoretically, it has been demonstrated that the blue phosphorene oxide (BPO) is just as stable as the blue phosphorene. Given that metallic oxides are widely used as catalyzers and gas sensors, this opens the possibility of the BPO being presented as a gas sensor as well. For all the above, in this work the optoelectronic properties of BPO were studied, along with the generation of the oxygen vacancies. The investigation was performed within the density functional theory (DFT). In the study of the oxygen vacancy, the formation energy was calculated, and the results are similar to the formation energies of oxygen vacancies in other known oxides. It was found that the BPO with a single vacancy has a favorable energetic stability. The characterization of the vacancy is achieved using the electronic structure and the optical response. Additionally, the analysis of the adsorption of a hydrogen atom on the BPO, and the subsequent formation of hydroxide is presented.     

Kinetic lattice Monte Carlo model for oxygen vacancy diffusion in praseodymium doped ceria: Applications to materials design

Kinetic lattice Monte Carlo (KLMC) model is developed for investigating oxygen vacancy diffusion in praseodymium-doped ceria. The current approach uses a database of activation energies for oxygen vacancy migration, calculated using first-principles, for various migration pathways in praseodymium-doped ceria. Since the first-principles calculations revealed significant vacancy-vacancy repulsion, we investigate the importance of that effect by conducting simulations with and without a repulsive interaction. Initially, as dopant concentrations increase, vacancy concentration and thus conductivity increases. However, at higher concentrations, vacancies interfere and repel one another, and dopants trap vacancies, creating a “traffic jam” that decreases conductivity, which is consistent with the experimental findings. The modeled effective activation energy for vacancy migration slightly increased with increasing dopant concentration in qualitative agreement with the experiment. The current methodology comprising a blend of first-principle calculations and KLMC model provides a very powerful fundamental tool for predicting the optimal dopant concentration in ceria related materials.     

Impedance spectroscopy of reduced monoclinic zirconia

Zirconia doped with low-valent cations (e.g. Y3+ or Ca2+) exhibits an exceptionally high ionic conductivity, making them ideal candidates for various electrochemical applications including solid oxide fuel cells (SOFC) and oxygen sensors. It is nevertheless important to study the undoped, monoclinic ZrO2 as a model system to construct a comprehensive picture of the electrical behaviour. In pure zirconia a residual number of anion vacancies remains because of contaminants in the material as well as the thermodynamic disorder equilibrium, but electronic conduction may also contribute to the observed conductivity. Reduction of zirconia in hydrogen leads to the adsorption of hydrogen and to the formation of oxygen vacancies, with their concentration affected by various parameters (e.g. reduction temperature and time, surface area, and water vapour pressure). However, there is still little known about the reactivities of defect species and their effect on the ionic and electronic conduction. Thus, we applied electrochemical impedance spectroscopy to investigate the electric performance of pure monoclinic zirconia with different surface areas in both oxidizing and reducing atmospheres. A novel equivalent circuit model including parallel ionic and electronic conduction has previously been developed for titania and is used herein to decouple the conduction processes. The concentration of defects and their formation energies were measured using volumetric oxygen titration and temperature programmed oxidation/desorption.     

CO gas sensing by ultrathin tin oxide films grown by atomic layer deposition using transmission FTIR spectroscopy

Ultrathin tin oxide films were deposited on SiO2 nanoparticles using atomic layer deposition (ALD) techniques with SnCl4 and H2O2 as the reactants. These SnO(x) films were then exposed to O2 and CO gas pressure at 300 degrees C to measure and understand their ability to serve as CO gas sensors. In situ transmission Fourier transform infrared (FTIR) spectroscopy was used to monitor both the charge conduction in the SnO(x) films and the gas-phase species. The background infrared absorbance measured the electrical conductivity of the SnO(x) films based on Drude-Zener theory. O2 pressure was observed to decrease the SnO(x) film conductivity. Addition of CO pressure then increased the SnO(x) film conductivity. Static experiments also monitored the buildup of gas-phase CO2 reaction products as the CO reacted with oxygen species. These results were consistent with both ionosorption and oxygen-vacancy models for chemiresistant semiconductor gas sensors. Additional experiments demonstrated that O2 pressure was not necessary for the SnO(x) films to detect CO pressure. The background infrared absorbance increased with CO pressure in the absence of O2 pressure. These results indicate that CO can produce oxygen vacancies on the SnO(x) surface that ionize and release electrons that increase the SnO(x) film conductivity, as suggested by the oxygen-vacancy model. The time scale of the response of the SnO(x) films to O2 and CO pressure was also measured by using transient experiments. The ultrathin SnO(x) ALD films with a thickness of approximately 10 A were able to respond to O2 within approximately 100 s and to CO within approximately 10 s. These in situ transmission FTIR spectroscopy help confirm the mechanisms for chemiresistant semiconductor gas sensors.     

A concerted migration mechanism of mixed oxide ion and electron conduction in reduced ceria studied by first-principles density functional theory

Ceria based oxides are regarded as key oxide materials for energy and environmental applications, such as solid oxide fuel cells, oxygen permeation membranes, fuel cell electrodes, oxygen storage, or heterogeneous catalysis. This great versatility in applications is rendered possible by the fact that rare earth-doped ceria is a pure oxygen ion conductor while undoped ceria, CeO(2-δ), is a mixed oxygen ion-electron conductor. To get deeper insight into the mixed conduction mechanism of oxygen ions and electrons from atomistic and electronic level viewpoints we have applied first-principles density functional theory (DFT + U method). The calculation results show that oxygen vacancies strongly attract localized electrons, forming associates between them. The migration energy of an oxygen vacancy in such an associate is substantially lowered compared to the unassociated case due to the simultaneous positional rearrangement of localized electrons during the ionic jump process. Accordingly, we propose a concerted migration mechanism of oxygen vacancies and localized electrons in reduced ceria; this mechanism results in an increased diffusivity of oxygen vacancies supported by localized electrons compared with that in pure oxide ion conductors.     

Special quasirandom structures for gadolinia-doped ceria and related materials

Gadolinia doped ceria in its doped or strained form is considered to be an electrolyte for solid oxide fuel cell applications. The simulation of the defect processes in these materials is complicated by the random distribution of the constituent atoms. We propose the use of the special quasirandom structure (SQS) approach as a computationally efficient way to describe the random nature of the local cation environment and the distribution of the oxygen vacancies. We have generated two 96-atom SQS cells describing 9% and 12% gadolinia doped ceria. These SQS cells are transferable and can be used to model related materials such as yttria stabilized zirconia. To demonstrate the applicability of the method we use density functional theory to investigate the influence of the local environment around a Y dopant in Y-codoped gadolinia doped ceria. It is energetically favourable if Y is not close to Gd or an oxygen vacancy. Moreover, Y-O bonds are found to be weaker than Gd-O bonds so that the conductivity of O ions is improved.     

Sm0.5Sr0.5Co0.4M0.6O3 (M=Co,Mn, Fe)作为IT-SOFCs阴极的结构与性能

通过X射线衍射(XRD)、热重、热膨胀、电导率以及交流阻抗等测试方法, 研究了Sm0.5Sr0.5Co0.4M0.6O3(M=Co, Mn, Fe; 分别简写为SSCC, SSCM, SSCF)作为中低温固体氧化物燃料电池(IT-SOFCs)阴极的结构与性能. 研究表明, 固相法合成的Sm0.5Sr0.5Co0.4M0.6O3均为正交钙钛矿型结构, 材料的结构参数和性能都与M元素半径及M—O的键能有关. 晶胞参数随着Co、Mn、Fe的顺序增大.材料的氧空位浓度、热膨胀系数、电导率、电极催化活性随着Co、Fe、Mn的顺序降低. 同时由于SSCM较低的氧空位浓度, 使得电极反应受到氧在电极内的扩散过程控制, 具有较差的电极催化性能, 而SSCC和SSCF较高的氧空位浓度, 电极反应同时受到电极表面氧还原反应和氧离子在电极中的扩散过程混合控制. 由于SSCF具有较高的氧扩散系数, 使得700 ℃以上SSCF电极表面氧还原电阻(ASR)也低于SSCC的, 因而出现了SSCF的总电极催化活性高于SSCC的现象.