Resistive switching behavior and mechanism in flexible TiO2@Cf memristor crossbars

Fiber-based memristors are expected to be one of the most ideal candidates to the future wearable nonvolatile devices. In this work, Carbon fibers coated with rutile TiO₂ nanorods (TiO₂ NRs) were prepared via hydrothermal method, which were denoted as TiO₂@C_f. Flexible TiO₂@C_f memristor crossbar was facilely assembled on a polyimide (PI) film. This device exhibited bi-directional threshold switching behavior and a maximum ON/OFF ratio of 10⁵. In addition, the conductance of the memristors can be continuously adjusted by consecutive sweep cycles of bias voltages. The devices also exhibit excellent endurance over 1500 cycles with a negligible shift. The carriers transport and resistance switching of the TiO₂@C_f memristor crossbar were explained by the Fowler-Nordheim tunneling model. The oxygen vacancies (O_V) in TiO₂ drifted to the interface of TiO₂/C_f by an applied electric field, thereby reducing the depletion region and enhancing the current. This work provides a profound understanding of the resistive switching behavior and the related mechanism in flexible TiO₂@C_f memristor crossbars, and paves a new way for potential applications for memristors in artificial synapses and flexible devices.     

Visible-light irradiation improved resistive switching characteristics of a 2D Cs2Pb(SCN)2I2-Based memristor device

Two-dimensional (2D) perovskite materials show enormous potential in optoelectronic applications owing to their exceptional thermal stability and unique lattice structures. However, research into anion-substituted 2D perovskites is relatively rare, particularly in the photoelectric information storage field. Here, an anion-based 2D perovskite Cs₂Pb(SCN)₂I₂ film with high orientation and high thermal-stability is achieved by simple low-temperature solution processing and the memristor of Al/Cs₂Pb(SCN)₂I₂/FTO is established. The experimental evidence shows that: 1) In the absence of light irradiation, memristors present typical bipolar resistance switching behaviour with On/Off resistance ratio (>10³) and reliable retention (>10⁴ s); 2) By introducing light irradiation, it can achieve a more dependable memristor with decreased RS fluctuation and improved cycling endurance. In addition, by modifying the compliance current (I_cc), it can realize multi-level storage function of memories with good high temperature endurance. Finally, the logic gate function is also demonstrated with these cells. The operational principles of memristor devices are comprised of the charge trapping and conductive filament mechanisms. The light irradiation reduces the ion migration barrier and enhances the conductivity of perovskite films, thus limiting the excessive growth of conductive filaments. This work offers the groundwork for creating anionic two-dimensional perovskite photoelectric memristor devices.     

Carrier transport mechanism and bipolar resistive switching behavior of a nano-scale thin film TiO2 memristor

A titanium dioxide (TiO₂) based memristor device having an active layer thickness of 10?nm was fabricated using radio frequency (RF) reactive sputtering and its resistive switching characteristics and carrier transport mechanisms were investigated. Scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) were used to confirm the structural properties of the device. Measurement of the time-dependent current-voltage (I-V-t) was used to characterize resistive switching and memristive behavior. The characteristic pinched hysteresis I-V loops of the memristor were apparent. Bipolar and homogeneous resistive switching characteristics and a forming voltage of 2?V were detected in the device. The retention time exceeded 10³ s and the endurance test was reasonably acceptable. In addition, the carrier transport mechanism of the device was revealed. The linear region of the low electric field demonstrated ohmic behavior, whereas the non-linear high electric field region was dominated by a Schottky emission carrier transport mechanism. A Poole-Frenkel emission mechanism acted as a secondary conduction mechanism. It was proposed that the Poole-Frenkel and Schottky emission mechanisms were associated with oxygen vacancies in the TiO₂.     

The effect of CeO2 on Pt/CeO2/CNT catalyst for CO electrooxidation

Pt/CeO₂/CNT catalysts were prepared by adsorbing Pt nanoparticles on the supports of CNTs coated with CeO₂. The electrocatalytic performances in respect to the electrooxidation of chemisorbed CO were tested using potential step and stripping voltammetry methods under variable sweep rate and temperature conditions. At 10 mV s^–1, the CO stripping voltammogram exhibited the peak splitting phenomenon. The oxidation charge and the peak potential of the two voltammetric peaks changed regularly with the number of Pt and CeO₂ neighbours, the sweep rate, and the temperature. We considered that the low potential peak originated from the reaction of CO_ads with hydroxyl groups on CeO₂ adjacent to Pt sites, while the high potential peak came from the reaction of CO_ads with hydroxyl groups produced on pure Pt. Furthermore, the experimental results of the peak potential against the logarithm of the sweep rate and the logarithm of the current maximum time against the step potential were plotted and intersecting lines with different slopes in high and low potential regions in the plot were observed. The lines intersected at lower potentials on the Pt/CeO₂/CNT electrode than on the Pt/CNT electrode, which was attributed to the contribution of hydroxyl groups on CeO₂.     

不同Pt前体制备Pt/CeO2催化剂对其结构及性能的影响

Pt与载体间的相互作用会影响到本征Pt纳米粒子的催化活性,不同Pt前体制备Pt/CeO₂催化剂会使其表现出完全不同的催化性能。分别采用金属胶体粒子原位沉积法、浸渍法以及浸渍还原的方式制备了Pt/CeO₂催化剂,通过X 射线衍射、程序升温还原、X射线光电子能谱以及高分辨透射电镜对催化剂进行表征,在CO氧化以及甲苯燃烧反应中评价催化剂活性。结果表明,胶体粒子原位沉积法制备Pt/CeO₂催化剂,能够将优先合成好的Pt纳米粒子直接以金属态Pt⁰的形式负载到载体表面,且保证其高度均匀分散,丰富的表面Pt⁰很好地充当了CO、甲苯反应时的活化位点,催化剂表现出优异的性能;浸渍还原法中,Pt纳米粒子之间会发生团聚现象,同时部分Pt又以Pt²⁺的形式与CeO₂之间形成了Pt-O-Ce相互作用,载体表面暴露Pt⁰含量的下降是催化剂表现出较弱活性的主要原因;浸渍法中,以Pt离子对Pt进行负载,Pt完全以Pt²⁺的形式参与到Pt-O-Ce键成键中,表面Pt⁰缺失,催化剂表现出明显的失活现象。Pt/CeO₂催化剂中,起主要活性作用的是金属态Pt⁰,胶体粒子原位沉积法能够实现Pt⁰的直接负载,对于提高Pt基催化剂中Pt的利用率,降低Pt资源消耗都具有重要意义。     

Pt/CeO_2/RGO复合材料的制备以及对乙醇的电催化性能研究

利用改进的Hummers法合成氧化石墨烯并还原,再利用水热合成法制得Ce O2/RGO复合材料,将其修饰玻碳电极后镀铂后获得Pt/Ce O2/RGO修饰电极。通过SEM和EDS对其形貌进行了表征,同时利用紫外—可见吸收光谱和循环伏安法等方法研究了其在酸性条件下对乙醇的电催化性能。结果表明:酸性条件下RGO在0.05 V处将乙醇氧化成乙醛,在0.5 V处氧化成乙酸;复合材料RGO/Ce O2(1∶1)/Pt在0.04V处将乙醇氧化成乙醛,在0.45 V处氧化成乙酸;复合材料RGO/Ce O2(1∶2)/Pt在0.03 V处将乙醇氧化生成乙酸。     

Nanocrystalline CeO2 in SBA-15: Performance of Pt/CeO2/SBA-15 Catalyst for Water-gas-shift Reaction

CeO₂ particles confined within the pores of an SBA-15 mesoporous silica host were prepared by incipient wetness impregnation (IMP) and deposition precipitation (DP) methods. The materials were characterized by XRD, N₂-adsorption and temperature programmed reduction (TPR) to evaluate the structure, texture, and redox properties. The preparation procedure had significant impact on the assembling mode of CeO₂ inside the SBA-15 mesopores. A high dispersion of CeO₂ particles was achieved via DP, whereas the dispersion of CeO₂ prepared by IMP was found to be inhomogeneous and CeO₂ partially blocked the pores. The CO conversion in the water-gas-shift reaction was enhanced over 1 wt% Pt supported on CeO₂-modified SBA-15 obtained by DP.     

氨催化氧化催化剂Pt/CeO_2的制备及性能表征

二氧化铈具有紫外光吸收能力,以其为载体,通过光催化还原沉积可实现贵金属负载。本研究通过光催化还原沉积制备了氨氧化用Pt/CeO_2催化剂,利用X射线衍射(XRD)、扫描电镜(SEM)、X射线能谱(EDS)、透射电镜(TEM)、BET比表面积、电耦合高频等离子发射光谱(ICP)、X射线光电子能谱(XPS)、NH_3-程序升温脱附(NH_3-TPD)对样品的物理性质进行了表征,并在φ4 mm×2 mm石英反应管中对其氨催化氧化性能进行了评价。结果表明,该法制备的Pt/CeO_2催化剂活性组分铂含量仅为0.079 7%,在载体表面分散性好;在反应温度800℃,原料中O_2和NH_3比为15的条件下,氨转化率为100%,氮氧化合物收率可达80%。     

Improvement of Pt/ZrO2 by CeO2 for high pressure CH4/CO2 reforming

CH₄/CO₂ reforming over Pt/ZrO₂, Pt/CeO₂ and Pt/ZrO₂ with CeO₂ was investigated at 2 MPa. Pt/ZrO₂, which shows stable activity under 0.1 MPa, and Pt/CeO₂ showed gradual deactivation with time at the high pressure. The deactivation was suppressed drastically on Pt/ZrO₂ with CeO₂ prepared by different impregnation order (co-impregnation of Pt and CeO₂ on ZrO₂, and consecutive impregnation of Pt and CeO₂ on ZrO₂). The amount of coke deposition was found insignificant and similar among all the catalysts (including Pt/ZrO₂ and Pt/CeO₂). Catalytic activity after the reaction for 24 h was in agreement with Pt particle size after the reaction for same period, indicating that the difference of the catalytic stability is mainly dependent on the extent of Pt aggregation through catalyst preparation, H₂ reduction, and the CH₄/CO₂ reforming. Pt aggregation and the amount of coke deposition were least pronounced on (Pt–Ce)/ZrO₂ prepared by impregnation of CeO₂ on Pt/ZrO₂ and the catalyst showed highest stability.     

Ultrasound-assisted synthesis of high-efficiency Ag3PO4/CeO2 heterojunction photocatalyst

The Ag₃PO₄/CeO₂ heterojunction photocatalyst prepared by an ultrasound-assisted method exhibits an enhanced photocatalytic activity compared to pure Ag₃PO₄, CeO₂, and Ag₃PO₄/CeO₂ obtained without ultrasound action. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and ultraviolet–visible absorption spectroscopy (UV–vis), and the effects of ultrasound on the physicochemical properties and photocatalytic activity of Ag₃PO₄/CeO₂ are discussed. Results show that the ultrasound-assisted synthesis method significantly improves the photocatalytic ability. The mechanism about the improvement was discussed in details.     

Incorporation of La3+ into a Pt/CeO2/Al2O3 catalyst

The effects of La³⁺ incorporation into a Pt/CeO₂/Al₂O₃ catalyst were investigated by a combination of activity, temperature-programmed reduction (TPR), oxygen storage capacity (OSC), noble-metal surface area, and X-ray diffraction (XRD) measurements. Incorporation of La³⁺ ions into the Al₂O₃, before CeO₂ is added, promoted higher Pt and CeO₂ dispersions. The oxygen storage capacity was also higher in the presence of La³⁺. This is attributed to a combination of Pt and CeO₂ particle-size effects and possible blockage of the reaction between Al₂O₃ and CeO₂. The XRD data show that La³⁺ forms LaAlO₃ with Al₂O₃ and prevents -Al₂O₃ formation after various heat treatments.     

Kinetic modeling of CO oxidation on Pt/CeO2 in a gradientless reactor

Cerium oxide is a major additive in three-way catalysts used in emission control of automobile exhaust. Pt/CeO₂ was studied in order to better understand the role of ceria in promoting CO oxidation reaction. The kinetics of carbon monoxide oxidation on Pt/cerium oxide catalyst, was studied over the temperature range 100–170°C. Steady state kinetic measurements of CO oxidation were obtained in a computer controlled micro-CSTR reactor. Activation energies were reported to vary between 39·5 and 51·2 kJ mol⁻¹. At low concentrations of either reactant (CO, O₂) and total conversion, the catalyst exhibited multiple steady states, similar to the multiplicity behavior of Pt/Al₂O₃. The total conversion was reached at 120°C. In comparison, the total conversion at low reactant concentrations was reached at a temperature of 148°C for the alumina-supported catalyst. Langmuir–Hinshelwood mechanisms gave a good fit to the data. However, no single rate expression could effectively describe the CO oxidation data over the whole concentration in the product of the CSTR reactor. The facts gathered indicate that oxygen adsorbed on interfacial Pt/Ce sites and ceria lattice oxygen provides oxygen for CO oxidation. Cerium oxide has been found to lower CO oxidation activation energy, enhance reaction activity and tends to suppress the usual CO inhibition effect.     

Structural Features and Catalytic Properties of Pt/CeO2Catalysts Prepared by Modified Reduction-Deposition Techniques

The structural features and catalytic properties of Pt/CeO₂catalysts prepared by liquid phase reduction-deposition techniques with formaldehyde and ethylene glycol as reducing agents, respectively, were investigated. TPR and CO pulse titration measurements revealed that smaller particle size and uniform dispersion of platinum were achieved by modified polyol preparation process, which is beneficial to generate appropriate Pt-O-Ce chemical bonding. XPS analysis further demonstrated the presence of strong metal-support interaction in above Pt/CeO₂catalyst. It was observed that the reducing ability and the solvent effect play important roles in controlling the formation of nuclei as well as its growth rate. The sample prepared by modified polyol method exhibited higher catalytic activities and longer stability for the complete oxidation of dimethyl ether than Pt/CeO₂catalyst prepared by HCHO liquid phase reduction.     

二氧化铈/水基纳米流体核沸腾传热特性

对CeO₂纳米流体进行了池沸腾传热特性研究,考察了CeO₂/水基纳米流体的热导率,静态接触角以及沸腾后表面沉积情况对沸腾传热的影响。结果表明,CeO₂纳米流体可提高沸腾传热系数,且纳米流体最佳质量分数为0.05%,其沸腾传热系数较去离子水提高36%。热导率以及接触角随纳米流体质量分数的增加而增加,在本实验范围内,热导率最大增加1%;而纳米流体接触角从50.5°增加到92.9°;表面沉积随纳米流体的质量分数增加越来越明显,去离子水在沉积表面的接触角发生较大变化(51.4°～134.4°)。纳米流体的热导率影响可忽略不计;而接触角和沸腾表面颗粒沉积对纳米流体的强化传热作用影响较大。     

Pt/CeO2催化分子氧氧化脱除异辛烷中有机硫化物的研究

以空气作氧化剂,含硫1 000 g·g^-1的异辛烷为模型油,考察了Pt/CeO₂催化剂上反应温度、n（O₂）∶n（S）和空速对苯并噻吩氧化脱除的影响。结果表明,在300 ℃、n（O₂）∶n（S）=26.4和空速15.3 h^-1时,苯并噻吩脱除率达95%以上。300 ℃达到95%的硫脱除率时,Pt/CeO₂催化剂上不同硫化物的氧化脱除活性顺序为：正戊硫醇>叔丁基硫醚>苯并噻吩>噻吩>二苯并噻吩。反应后的油品及尾气经脉冲火焰光度监测器色谱(GC-PFPD)和色质联用仪(GC-MS)检测分析发现,SO₂是惟一含硫产物。在200 h的噻吩氧化反应测试中,转化率一直保持在95%,O₂利用率约40%,异辛烷损耗约0.2%,表明Pt/CeO₂催化剂在催化氧化脱硫中具有较好的活性和稳定性。     

银/铂双金属中空纳米颗粒的制备及光学性质研究

通过以Ag纳米颗粒为模板的置换和沉积反应，制备了Ag／Pt双金属复合纳米颗粒、用透射电子显微镜（TEM）对颗粒的形貌、尺寸和结构进行了表征，发现复合颗粒具有中空结构．紫外可见吸收光谱（UV-Vis）研究表明，Ag／Pt双金属中空复合纳米颗粒具有单峰的表面等离子共振吸收特征，随着反应溶液中氯铂酸和硝酸银摩尔比的增加，吸收峰先红移后蓝移．表面增强拉曼光谱实验结果表明，Ag／Pt双金属复合纳米颗粒对吡啶分子具有较好的增强效果．     

Redox properties of CeO2 and Pt-Rh/CeO2 studied by TAP method

Redox properties of CeO₂ and Pt-Rh/CeO₂ were studied by temporal analysis of products (TAP) method using alternative pulses of CO and O₂. A portion of pulsed CO was oxidized to CO₂ and a portion of CO was adsorbed on the surface. Pulsing ¹⁸O₂ onto the catalyst which has surface species derived from CO, evolved CO₂ contained no ¹⁸O suggesting that the surface species will be carbonate ions.     

Effects of Ga doping on Pt/CeO2‐Al2O3 catalysts for propane dehydrogenation

This paper describes catalytic consequencesThis paper describes catalytic consequences of Pt/CeO₂‐Al₂O₃ catalysts promoted with Ga species for propane dehydrogenation. A series of PtGa/CeO₂‐Al₂O₃ catalysts were prepared by a sequential impregnation method. The as‐prepared catalysts were characterized employing N₂ adsorption‐desorption, X‐ray diffrtaction, temperature programmed reduction, O₂ volumetric chemisorption, H₂‐O₂ titration, and transmission electron microscopy. We have shown that Ga³⁺ cations are incorporated into the cubic fluorite structure of CeO₂, enhancing both lattice oxygen storage capacity and surface oxygen mobility. The enhanced reducibility of CeO₂ is indicative of higher capability to eliminate the coke deposition and thus is beneficial to the improvement of catalytic stability. Density functional theory calculations confirm that the addition of Ga is prone to improve propylene desorption and greatly suppress deep dehydrogenation and the following coke formation. The catalytic performance shows a strong dependence on the content of Ga addition. The optimal loading content of Ga is 3 wt %, which results in the maximal propylene selectivity together with the best catalytic stability against coke accumulation. © 2016 American Institute of Chemical Engineers AIChE J, 62: 4365–4376, 2016     

Electrical and optical characteristics of transparent conducting Si-doped ZnO/hole-patterned Ag/Si-doped ZnO multilayer films

Hole-patterned Ag layers were first used to form Si-doped ZnO (SZO)/hole-patterned Ag/SZO multilayers and their optical and electrical properties were characterized. Unlike conventional oxide/metal/oxide multilayers, all samples exhibited two characteristic features: (i) a sinusoidal wavelength dependence of the transmittance with double maxima, and (ii) undulation in the visible transmittance, but not in the infrared transmittance. With increasing SZO thickness, the transmittance maxima were red-shifted, and the visible transmittance window widened. The carrier concentration decreased from 7.42×10²² to 2.4×10²² cm⁻³, and the sheet resistances varied from 7 to 10 Ω/sq with increasing SZO thickness. Haacke's figure of merit (FOM) was calculated for the SZO-based multilayer films. The 40 nm-thick SZO multilayers had the highest FOM of 15.9×10^–3 Ω^–1. Finite-difference time-domain (FDTD) simulations were undertaken to interpret the measured transmittance. Based on the FDTD simulations, the undulating transmittance was attributed to surface plasmon-polaritons.     

现代化工仿真技术的发展与应用

化工生产过程普遍存在间歇过程多、自动化程度低、工艺复杂、条件苛刻、危险性高等特点。传统的过程研究及开发手段风险大、周期长,需要消耗大量的人力、物力、财力。而利用现代仿真技术建立一套虚拟生产系统,人们可在没有危险的情况下从事相关科研工作;节省实际研究中所需的高额成本;动态搭建并分析反应流程,优化工艺参数,加快整个化工生产研究的进程;与搭建的流程进行人机交互,实时观察各相关设备的工作状态和反应现象;可人为设置故障点,或改变工艺参数, 为应急演练和操作培训提供一种新的思路和实践;为开展化工流程模拟、仿真培训与生产过程可视化监控提供有效的支持。本文介绍了最近国内外在现代化工仿真技术领域取得的进展并探讨了其未来的发展趋势。