紫外激光调控CoFe_2O_4表面氧空位以增强析氧反应催化活性（英文）

本文以尖晶石型材料CoFe_2O_4为模型催化剂,研究证实脉冲紫外激光辐照可以有效调控材料表面的氧空位含量,进而改变其析氧催化活性,得到了催化活性随辐照时间的火山型变化趋势.这种激光辐照方法可用于定量研究过渡金属化合物的表面阳离子价态、阴离子空位和物化性质间的关联.     

水在光诱导制备TiO2(110)表面BBO氧空位过程中的抑制作用 (cited: 1)

利用程序升温脱附谱研究了用266 nm激光在表面制备不同氧空位浓度的方法．实验表明利用266 nm激光能够很容易产生表面氧空位．同样90 s光照,在光子数密度大于6.7×10¹⁶ photons/cm²s的时候,表面氧空位浓度和和光子数密度成线性关系．在光照过程中,没有观测到氧气和钛原子的脱附,表明利用266 nm激光在TiO₂(110)-(1×1)制备氧空位是一种有效而且温和的方式．而在表面提前吸附水利用激光产生氧空位的速率比干净的表面慢了两个数量级．进一步研究表面,预先吸附了水后,在光照过程中水更容易脱附,导致桥氧原子的脱附被抑制,降低了氧空位产生的速率     

Bi2WO6光催化剂的γ射线辐射效应

本文首次研究了高能辐射(γ射线)对Bi₂WO₆纳米晶体结构和光催化性能的影响. 结果表明,尽管高能辐射不会改变Bi₂WO₆纳米晶体的形貌,但是Bi₂WO₆粉末的颜色在高吸收剂量辐照(507 kGy)后发生了明显的变化,并且辐照后Bi₂WO₆的XRD谱图也显示,随着吸收剂量的增加,(113)晶面对应的2θ从28.37°移到28.45°,说明晶格参数在γ射线辐照下还是发生了细微的变化. XPS表征结果证明,Bi₂WO₆晶体结构的变化源于高剂量辐射下氧空位缺陷的产生. Bi₂WO₆纳米晶体的禁带宽度(E_g)随吸收剂量的增加也出现减小的趋势. 用水溶液中亚甲基蓝的可见光照分解反应作为模型反应考察了辐照后的Bi₂WO₆纳米晶体的光催化活性,结果表明,辐照后的Bi₂WO₆纳米晶体的光催化活性随着吸收剂量的增加而逐渐升高. 将经过反应后的Bi₂WO₆纳米晶体再次回收,进行循环催化,发现这些辐照后的Bi₂WO₆纳米晶体在三次循环使用后光催化性能仍然能够保持,说明高能辐射产生的氧空位缺陷具有良好的稳定性.     

氧空位对Co掺杂TiO2稀磁半导体中杂质 分布和磁交换的影响

本文使用基于密度泛函理论的第一性原理方法研究了Co掺杂TiO₂稀磁半导体中氧空位对体系能量和磁性的影响. 通过对总能量的计算发现当引入氧空位后近邻杂质体系能量高于均匀掺杂体系, 同时氧空位易在Co近邻位置富集. 进而发现氧空位的存在及其占位可以影响Co离子间的磁交换, 近邻Co离子体系下氧空位的引入使Co离子间的铁磁耦合减弱; 非近邻Co离子体系下, 底面氧空位使Co离子间呈反铁磁耦合而顶点氧空位使Co离子间呈铁磁耦合. 总之, 氧空位的存在对Co掺杂TiO₂材料的能量及磁性都有较大影响.     

氧空位对共掺型锐钛矿TiO2能带结构的影响

基于电子密度泛函理论计算,系统研究了氧空位对V-C(p型)、Cr-N(n型)、V-N和Cr-C(电中性)四种共掺型锐钛矿TiO₂的几何和电子结构的影响．结果表明在最稳定构型中氧空位处在与金属杂质原子相连的位置．由于氧空位的出现,共掺TiO₂禁带中一些未占据的杂质态被填充满电子,掺杂体系的导带带边位置几乎不变,这有利于减少光生载流子复合,且不影响光解水过程中的产氢反应,在厌氧条件下很容易在V-N共掺TiO₂中引入氧空位．     

TiO2表面氧空位对NO分子吸附的作用

采用程序升温热脱附(TPD)实验方法测定了NO在TiO₂表面吸附后的脱附谱，利用 分子轨道 理论研究了TiO₂吸附NO的原子簇模型及吸附前后的原子簇能级变化.结果表明， NO在TiO₂表面吸附后可在两个峰值温度450 和980 K脱附出N₂.TiO ₂表面经预覆氧处理后，N₂ 的脱附量降低.吸附时NO中的O能够占据TiO₂表面氧空位并与N脱离，而N原子则 相互结合成 为N₂脱附.分子轨道理论计算证明在TiO₂(110)表面能够存在氧空位 并具备吸附NO的结构条件.     

CO2对Ba0.5Sr0.5Co0.8Fe0.2O3−δ表面氧交换的影响

采 用 了 一 种 新 的 脉 冲 同 位 素 交 换 技 术 , 研 究了CO₂对Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ(BSCF)的表面氧交换动力学的毒害作用．当BSCF暴露于CO₂时,由于在材料表面形成了碳酸盐,其表面交换率严重降低．在低CO₂浓度(1%)时,毒害作用从375 oC开始,并且随着温度的上升而变得更加明显．同时,表面交换动力学的下降导致BSCF在CO₂条件下氧渗透性能快速下降．     

外延生长La0.7Sr0.3MnO3薄膜厚度对缺陷影响的慢正电子分析

采用脉冲激光沉积方法在(LaAlO₃)_0:3(Sr₂AlTaO₆)_0:7衬底上外延生长了La_0.7Sr_0.3MnO₃薄膜,并采用慢正电子束方法分析了薄膜在不同厚度和不同退火气氛下参数S的变化. 分析表明,薄膜中包含两种机制引入的氧空位,分别是薄膜生长气氛中氧压偏低造成薄膜的氧缺乏和由于薄膜应变引入空位型缺陷. 当薄膜厚度较薄时,应变造成的晶格畸变化比较大,当薄膜的厚度大于11 nm时,薄膜的应变驰豫已经比较完全. 原位退火的样品中正电子主要是被氧缺乏引起的氧空位捕获. 在氧气中退火的样品,S随厚度的变化反映了应变对薄膜微结构的影响.     

氧含量对CaCu3Ti4O12巨介电常数和介电过程的影响

本文研究了在真空、空气和氧气中烧结制备的三种 CaCu₃Ti₄O₁₂陶瓷材料的介电特性. 交流阻抗测量结果表明在10—300 K温度范围, 三种样品的介电温谱中均出现三个平台, 其电阻实部和电容虚部在相应温度出现损耗峰, 真空条件烧结的样品具有较高的介电平台和较明显的电阻实部与电容虚部峰值, 表明氧含量和氧空位对CaCu₃Ti₄O₁₂的介电性质具有重要影响, 介电温谱出现的三个平台分别源于晶粒、晶界及氧空位陷阱.温谱分析表明晶粒的激活能与烧结气氛有较大关系,氧空位引起的电子短程跳跃及跳跃产生的极化子是晶粒电导和电容的主要起源.氧空位陷阱的激活能基本与烧结气氛无关,约为0.46 eV. 氧空位对载流子的陷阱作用是CaCu₃Ti₄O₁₂ 低频高介电常数的重要起源.     

表面缺陷对一氧化碳和甲基基团在金红石TiO2(110)表面吸附的影响

本文利用程序升温脱附技术研究了氧空位浓度对甲基基团和CO在R-TiO₂(110)表面吸附的影响. 结果表明,随着氧空位浓度的变化,吸附在桥氧位的甲基基团和吸附在五配位Ti⁴⁺位点上的CO分子的脱附温度呈现了不同的趋势,揭示了表面缺陷可能对R-TiO₂(110)不同位点上的物质吸附具有重要影响.     

调控氧空位实现高比表面积Co3O4纳米片上的产氧反应

Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here, we designed an efficient Co₃O₄ electrocatalyst using a pyrolysis strategy for oxygen evolution reaction (OER). Morphological characterization confirmed the ultra-thin structure of nanosheet. Further, the existence of oxygen vacancies was obviously evidenced by the X-ray photoelectron spectroscopy and electron spin resonance spectroscopy. The increased surface area of Co₃O₄ ensures more exposed sites, whereas generated oxygen vacancies on Co₃O₄ surface create more active defects. The two scenarios were beneficial for accelerating the OER across the interface between the anode and electrolyte. As expected, the optimized Co₃O₄ nanosheets can catalyze the OER efficiently with a low overpotential of 310 mV at current density of 10 mA/cm² and remarkable long-term stability in 1.0 mol/L KOH.     

铜纳米阵列高效电解水产氧催化剂的制备

本文报道了一种利用简单的两步牺牲模板法,在泡沫铜基底表面完成了三维氧化铜纳米晶阵列的生长. 氧化铜纳米晶阵列具有良好的导电性,稳定性,在碱性溶液中有着优秀的电解水产氧催化性能. 氧化铜纳米晶阵列催化水的电化学氧化只需400 mV的过电势即可达到100 mA/cm²的电流密度,与其它铜基电解水产氧催化剂以及贵金属IrO₂相比都有着明显的优势. 氧化铜纳米晶阵列在270 mA/cm²左右的工作电流下连续工作10 h依然可以保持良好的稳定性,是相同的工作电压下IrO₂工作电流的10倍(约25 mA/cm²).     

基于金属有机框架材料制备Ag-CoSO4复合纳米材料及其在碱性电催化析氧反应的应用研究

本文以Co-BTC金属有机框架材料为前驱体,采用连续离子交换法和进一步的高温水热处理来合成片状Ag-CoSO₄复合纳米材料. 由于少量Ag的引入有利于增强导电性并加速电子转移过程,该催化剂在1 mol/L KOH电解质溶液中表现出优异的OER性能(在10 mA/cm²的电流密度下过电位仅为282 mV),其性能甚至比RuO₂更好. 催化剂中Ag的存在有利于促进Co(IV)的产生进而提高Co(IV)浓度,并且能够调控对氧物种的吸附能而促进OER过程^*OOH中间物质的形成,加速了析氧反应过程的进行. 极低含量Ag的使用(低于百分之一原子含量)使得催化剂的成本极大的降低.     

Ni与Co掺杂Fe2O3（0001）表面增强析氧反应活性

Fe based oxides are considered as a promising catalyst for the oxygen evolution reaction (OER) due to their low cost and high stability. Here, based on density functional theory calculations, the electrocatalytic behaviors of pure and metal (Ni, Co) doped Fe-terminated Fe₂O₃(0001) are investigated. The potential-limiting step for OER is determined as the formation of O^* by dehydrogenating surface hydroxyl and it is suggested that the doping enhances the catalytic activity of Fe₂O₃(0001) by reducing the free energy change of rate limiting step on doped Ni or Co atom. Especially, the calculated over-potential of Co-doped Fe₂O₃ (0001) surface is about 0.63 eV on Co site, which is comparable with the theoretical over-potential of 0.56 eV for RuO₂.     

Effects of oxygen vacancies on the room-temperature ferromagnetism of Co-doped polycrystalline CeO2

Pure and Co-doped single-phase CeO₂ crystals were synthesized by a solid-state reaction method. Samples of different oxygen vacancy concentration were studied, including (1) as-sintered crystals, (2) powders ground from the same crystal, and (3) a cold-pressed pellet from the ground powder that was unannealed and annealed at 800 °C. By analyzing the magnetic behaviors, surface/volume ratio and O vacancy concentration, the effects of oxygen vacancies on the room-temperature ferromagnetism (RT-FM) of Co-doped CeO₂ were systematically investigated. The results confirm that the RT-FM observed in Co-doped CeO₂ has a direct relationship with the oxygen vacancy concentration, and support the oxygen vacancy mediated FM mechanism.     

Oxygen exchange kinetics of La0.58Sr0.4Co0.2Fe0.8O3 at 600 °C in dry and humid atmospheres

The time-dependent degradation of the oxygen exchange kinetics of the solid oxide fuel cell cathode material La_0.58Sr_0.4Co_0.2Fe_0.8O_3 − δ (LSCF) is investigated at 600 °C. Special emphasis is placed on systematic long-term dc-conductivity relaxation measurements (t > 1000 h) in dry as well as in humidified atmospheres in order to obtain representative trends for the application of LSCF in intermediate-temperature SOFCs. The determination of the chemical surface exchange coefficient k_chem of oxygen is combined with investigations of the elemental surface compositions and depth profiles of fresh and degraded samples by X-ray photoelectron spectroscopy (XPS), providing further insight into the mechanisms of degradation. The slow decrease of k_chem by a factor of 2 during exposure of the sample to a dry O₂-Ar reference atmosphere for 1000 h at 600 °C can be ascribed to an enrichment of La and Sr in correlation with an elevated oxygen concentration within about 30-35 nm depth. The interpretation of the XPS core level spectra indicates the formation of SrO and La₂O₃ secondary phases in this zone. The subsequent treatment in a humidified atmosphere for 1000 h results in a pronounced initial decrease of k_chem by an additional factor of 10, followed by a time dependent decay of about 15% kh^− 1. A Sr-rich silicate layer of about 10 nm thickness is identified by XPS as the major cause of the degradation in humidified atmosphere. The evidence of Si-poisoning over the whole sample surface could also be confirmed by post-test SEM analysis. In addition, indications of a re-structuring of the sample surface during the degradation are shown. These results indicate, that with LSCF as a cathode in ambient (humid) air in SOFC stacks containing various Si-sources, such as glass or glass-ceramic seals, and thermal insulation materials a significant decrease of the surface oxygen exchange coefficient can occur, even at temperatures as low as 600 °C. In order to prevent a severe Si-induced degradation, dry air should be used as an oxidant. However, even in dry atmosphere a minor decrease of k_chem can occur during long-term operation due to changes in the relative cation and oxygen content at the surface.     

NiWO3 Nanoparticles Grown on Graphitic Carbon Nitride (g‐C3N4) Supported Toray Carbon as an Efficient Bifunctional Electrocatalyst for Oxygen and Hydrogen Evolution Reactions

Catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are at the heart of water oxidation reactions. Despite continuous efforts, the development of OER/HER electrocatalysts with high activity at low cost remains a big challenge. Herein, a composite material consisting of TC@WO₃@g‐C₃N₄@Ni‐NiO complex matrix as a bifunctional electrocatalyst for the OER and HER is described. Though the catalyst has modest activity for HER, it exhibits high OER activity thereby making it a better nonprecious electrocatalyst for both OER and HER and is further improved by g‐C₃N₄. The catalytic activity arises from the synergetic effects between WO₃, Ni‐NiO, and g‐C₃N₄. A Ni‐NiO alloy and WO₃ nanoparticles decorated on the g‐C₃N₄ surface supported toray carbon (TC) matrix (TC@WO₃@g‐C₃N₄@Ni‐NiO) by a facile route that show an excellent and durable bifunctional catalytic activity for OER and HER in the alkaline medium are developed. This carbon nitride with binary metal/metal‐oxide matrix supported with TC exhibit an overpotential of 0.385 and 0.535 V versus RHE at a current density of 10 mA cm^?2 (Tafel slopes of 0.057 and 0.246 V dec^?1 for OER and HER, respectively), in 0.1 m NaOH . The catalyst is tested in water electrolysis for 17 h.     

Oxygen ion diffusion measurements in Bi0.775La0.225O1.5

The oxygen transport properties of the Bi_0.775La_0.225O_1.5 electrolyte material have been investigated. Isotopic exchange depth profiling (IEDP) technique with secondary ion mass spectrometry (SIMS) was used in order to measure the oxygen tracer diffusion coefficient D. The activation energy for oxygen tracer diffusion was found to be 115 ± 2 kJ/mol (1.19 ± 0.02 eV). The measured D values were converted using the Nernst-Einstein relationship to conductivity and compared with data from AC Impedance. The agreement of the two sets of data implies that the material is an oxygen ion conductor.     

Oxygen vacancy model for the E1′ center in SiO2

An (oxygen)^- vacancy model of the E₁^≈ center in alpha quartz, featuring an asymmetric relaxation of the two silicons adjacent to the oxygen vacancy, is presented and analyzed. This model is shown to be consistent with both theoretical calculations and experimental hyperfine data, in contrast with any model previously proposed for the E₁^≈ center.