CO2在Pd表面吸附的热力学

 用密度泛函方法和相对论有效原子实势,分别对PdCO₂,PdCO和PdH的基态几何构型进行优化, 得到PdCO₂分子基态为Cs构型, Pd与CO2分子在同一平面, 键长PdC为0.203 0 nm, CO为0.118 3 nm, CO′为0.121 0 nm, 键角∠OCO′为154.215°,电子状态为1A′; PdCO分子基态电子状态为1+, 键长PdC为0.183 4 nm, CO为0.114 0 nm, 键角∠PdCO为180°; PdH分子基态为2∑, 键长PdH为0.152 6 nm。根据电子-振动近似理论计算了不同温度下金属Pd 与CO₂,CO及H2分子反应的生成热力学函数, 导出了反应平衡压力随温度的变化关系。分析认为杂质CO₂气体引起Pd合金膜中毒可能是由于CO₂分子吸附在Pd膜表面,形成Pd的CO₂化合物后,再自发分解为PdO和CO,而使Pd表面出现O和CO中毒所致。     

甲醇分子在金红石TiO2(110)和锐钛矿TiO2(001)表面吸附和反应的活性位点

通过高分辨的扫描隧道显微术研究并比较了金红石型TiO₂(110)-(1×1)和锐钛矿型TiO₂(001)-(1×4)两种表面的活性位点． 在金红石型TiO₂(110)-(1×1)表面, 观察到氧空位缺陷是O₂和CO₂分子的活性吸附位点,而五配位的Ti原子是水分子和甲醇分子的光催化反应活性位点．在锐钛矿型TiO₂(001)-(1×4)表面,观察到完全氧化的表面,Ti原子更可能是六配位的,H₂O和O₂分子均不易在这些Ti原子上吸附．经还原后表面出现富Ti的缺陷位点, 这些缺陷位点对H₂O和O₂分子表现出明显的活性． 锐钛矿型TiO₂(001)-(1×4)表面的吸附和反应活性并不具有很高的活性,某种程度上其表现出的活性似乎低于金红石型TiO₂(110)-(1×1)表面．     

掺稀土元素(Y，La)的γ-Si3N4的电子结构和光学性质

采用基于密度泛函的平面赝势方法(PWP)和广义梯度近似(GGA)，计算了未掺杂和掺杂稀土(Y，La)的γ-Si₃N₄中N-Y(La)键的布居值和它们的键长、掺杂后能带结构和态密度.发现掺杂后的带隙要减小，并且可能形成新的半导体，这将为找到新的半导体提供一个方向.还进一步研究了掺杂稀土(Y，La)后的光学性质，掺杂后有更高的静态介电常数，可以作为新的介电材料和好的折射材料，这对于一定的光学元件有潜在的应用前景.     

Tb2Fe15.5Cr1.5化合物的本征磁致伸缩

通过x射线衍射及磁测量手段研究了Tb₂Fe_15.5Cr_1.5化 合物的热膨胀性质及本征磁致伸缩性质.研究结果表明Tb₂Fe_15.5Cr _1.5化合物在293—672K的温度范围内具有六角相的Th₂Ni_{17型结构.在432—522K的温度范围内具有负热膨胀 性质，其平均热膨胀系数=-157×10^-5/K.对本征磁致伸缩的研究结果表明Tb2Fe15.5Cr1.5化合物中存在着较强的各向异性的本 征磁致伸缩，293K时其本征体磁致伸缩约为84×10^-3，晶格畸变主要发生在c 轴方向上.磁测量研究结果表明Tb2Fe15.5Cr1.5化合物的居里温度约为494K，比其母 合金Tb2Fe17高约80K.}     

Synchrotron-Radiation Photoemission Study of Growth and Stability of Au Clusters on Rutile TiO2(110)-1×1

利用同步辐射高分辨光电子能谱研究了金团簇在部分还原TiO₂-(1×1)表面的生长和稳定性．价带谱实验结果观察到非常少量金团簇的沉积导致了Ti3+的3d峰完全消失,表明金团簇成核在TiO₂-(1×1)表面的氧缺陷位．Au4f芯电子光电子能谱实验结果证明了TiO₂-(1×1)表面氧缺陷位向金团簇转移电荷．还对比研究了化学剂量比和部分还原的TiO₂-(1×1)表面上金团簇的热稳定性．当金团簇尺寸相近时部分还原的TiO₂-(1×1)表面上金团簇要比化学剂量比的TiO₂-(1×1)面上金团簇稳定;在相同的表面上尺寸大的金团簇要比尺寸小的金团簇稳定．     

CH2和CH3自由基吸附在Cun (n=1-6)团簇上C-H对称振动模式的软化

利用密度泛函理论中杂化泛函理论方法计算了CH₂和CH₃自由基吸附在Cu_n(n=1～6)团簇上时C?H对称伸缩振动模式的软化性质,结果表明,CH₂在Cun团簇上的吸附要比CH₃的吸附强. 计算得到的C-H键的振动频率与实验上测量的这两个自由基吸附在Cu(111)表面的结果符合得很好,随着团簇尺寸的增加,C-H对称伸缩振动频率的软化(红移)越来越大.     

高性能MgB2长线材制备及性能表征

采用原位粉末装管工艺，分别以Mg粉(99.5%)，无定形B粉(99.9%)为原料，以纳米SiC(10—30nm)作为掺杂材料制备铁基MgB₂线.首先将已混合的原料在丙酮介质中球磨，真空干燥后，将粉末填入铁管内，然后通过孔型轧制、旋锻和拉拔等冷加工工艺得到11m长外径Ф1.75mm铁基MgB₂超导线.用扫描电镜，电子能谱，X射线衍射仪和超导量子干涉仪测试发现，样品微观结构整齐，晶粒大小均匀，内部仅含微量MgO，T_C(onset)=35.1K，ΔT_C＝5.3K.纳米SiC掺杂后，其中C造成MgB₂晶格畸变，形成有效磁通钉扎中心，C元素在MgB₂中分布均匀.标准四引线测试结果表明，11m线均分10段后，各点的J_c(4.2K,10T)均超过1.0×10⁴A/cm^{2，最高值达到1.2×104A/cm2.在10—18T范围各点临界电流值分布均匀，变化率小于10%.}     

Nd掺杂对Bi4Ti3O12铁电薄膜的微结构和铁电性能的影响

利用溶胶-凝胶法在Pt/Ti/SiO₂/Si(100)衬底上制备了Nd掺杂Bi₄Ti₃O₁₂(Bi_4-xNd_xTi₃O₁₂, x=0.00,0.30,0.45,0.75,0.85,1.00,1.50)铁电薄膜样品.研究了Nd掺杂对Bi₄Ti₃O₁₂薄膜的微结构和铁电性能的影响.研究结果表明:Nd掺杂未改变Bi₄Ti₃O₁₂薄膜的基本晶体结构.在掺杂量x<0.45时,Nd³⁺只取代类钙钛矿层中的A位Bi³⁺.当x=0.45时,样品剩余极化强度达最大值,在270kV·cm^-1的电场下为32.7μC·cm^-2.掺杂量进一步增加时,结构无序度开始明显增大,Nd³⁺开始进入(Bi₂O₂)²⁺层,削弱其绝缘层和空间电荷库的作用,导致材料剩余极化逐渐下降.当掺杂量x达到1.50时,掺杂离子最终破坏(Bi₂O₂)²⁺层的结构,材料发生铁电-顺电相变.     

CO2激光器五种混合气体压强优化

 应用遗传算法,以输出激光功率为目标函数,优化确定了普通CO₂激光器五种工作气体（CO₂, N₂, He, Xe, H₂）的最佳充气量。对1.2m长谐振腔,在15kV放电条件下,优化的充气量分别为p_CO2=1.15×133.3Pa, p_N2=7.32×133.3Pa, p_He=12.95×133.3Pa, p_Xe=0.36×133.3Pa和p_H2=0.01×133.3Pa。优化后激光功率比未优化前可提高1.27倍。     

α-Al2O3(0001)表面原子缺陷对ZnO吸附影响

采用基于密度泛函理论的分子动力学方法，对α-Al₂O₃(0001)表面 Al，O原子空位缺陷及其对ZnO吸附进行了理论计算.电子局域函数显示了表面空位处的电子密度变化，表面Al原子空缺处有非常明显的缺电子区域，悬挂键临近O的电子密度增大，有利于对Zn的吸附；O原子空缺处的Al原子处存在孤立电子，其ELF值为005—03，将有利于同电负性较大的O或O^2-结合.通过吸附动力学模拟与体系能量的计算发现，表面缺陷显著增强了表面 的化学吸附，空缺原子处都被吸附原子填补，吸附结合能远大于单晶表面的情况.在Al空缺的表面，由于ZnO的O与表面O形成双键，破坏了α-Al₂O₃(0001)表面O六 角对称结构，减小了 O的表面扩散，从而不利于规则的ZnO薄膜生长.相反，O的空缺表面，弥补了α-Al_{2O3(0001)表面O空位缺陷，不影响基片表面O六角对称结构.}     

Ti原子在Al(110)表面吸氢过程中催化作用的第一性原理研究

运用第一性原理方法对H₂分子在Ti掺杂和纯的Al(110)表面的吸附情况进行了研究,发现有Ti原子掺杂时,存在一个H₂分子的吸附路径,即位于Al(110)面顶位Ti原子上方的H₂分子会发生解离,并与Ti原子形成TiH₂分子,然后TiH₂分子向能量更低的空位移动并接近Al(110)表面.态密度与电荷布居分析显示,吸附完成后H原子与表面Al原子存在较强的共价键作用,这为Al-H类物质及Na_{3 关键词： 钛 吸附 解离能 第一性原理}     

Zr催化剂对NaAlH4和Na3AlH6可逆储氢性能的影响

采用基于密度泛函理论的平面波赝势方法,分别计算纯净的以及掺杂Zr的NaAlH₄和Na₃AlH₆的晶格结构常数、能量、电子局域函数和电子态密度.结果表明：NaAlH₄和Na₃AlH₆分别是带隙为46和31 eV的绝缘体;NaAlH₄和Na₃AlH₆中Al—H键是共价键,Na—H键是离子键;Zr原子替代Na原子 关键词： 储氢 4')" href="#">NaAlH₄ 3AlH₆')" href="#">Na₃AlH₆ Zr掺杂     

AlHn(n=1—3)的分子结构和AlH3热力学稳定性

在gaussian03基础上，分别用b3lyp和qcisd方法，在6-311++g^**基组水平上研究了AlH_n(n=1—3)分子及其一价阴阳离子的几何结构和谐振频率，计算了它们中性分子的离解能，第一垂直电离能，电子亲和能. 并与可能得到的实验值及文献上的理论计算值进行了比较. 发现qcisd方法得到的数据更接近实验值. 计算发现对AlH，AlH₂和AlH₃分子及其1价阳离子的Al—H键长，随着H原子数的增多，键长越短， 关键词： 3分子')" href="#">AlH₃分子 平衡几何结构 垂直电离能 垂直电子亲和能     

Crystalline Al1 − x Ti x phases in the hydrogen cycled NaAlH4 + 0.02TiCl3 system

The hydrogen (H) cycled planetary milled (PM) NaAlH₄?+?0.02TiCl₃ system has been studied by high resolution synchrotron X-ray diffraction and transmission electron microscopy during the first 10?H cycles. After the first H absorption, we observe the formation of four nanoscopic crystalline (c-) Ti-containing phases embedded on the NaAlH₄ surface, i.e. Al₂Ti, Al₃Ti, Al₈₂Ti₁₈ and Al₈₉Ti₁₁, with 100% of the originally added Ti atoms accounted for. Al₂Ti and Al₃Ti are observed morphologically as a mechanical couple on the NaAlH₄ surface, with a moderately strained interface. Electron diffraction shows that the Al₈₂Ti₁₈ phase retains some ordering from the L1₂ structure type, with the observation of forbidden (100) ordering reflections in the fcc Al₈₂Ti₁₈ lattice. After 2?H cycles the NaAlH₄?+?0.02TiCl₃ system displays only two crystalline Ti-containing phases, Al₃Ti and Al₈₉Ti₁₁. After 10?H cycles, the Al₈₉Ti₁₁ is completely converted to Al₈₅Ti_15. Al₈₉Ti₁₁, Al₈₅Ti₁₅ and Al₃Ti do not display any ordering reflections, and they are modeled in the A1 structure type. Quantitative phase analysis indicates that the Al₃Ti proportion continues to increase with further H cycles. The formation of Ti-poor Al_{1??? x} Ti _x (x?<?0.25) phases in later H cycles is detrimental to hydrogenation kinetics, compared to the starting Ti-richer near-surface Al₂Ti/NaAlH₄ interface present during the first absorption of hydrogen.     

In situ synchrotron high‐energy X‐ray diffraction analysis on phase transformations in Ti–Al alloys processed by equal‐channel angular pressing

Mixtures of 47‐Al and 53‐Ti powders (atomic %) have been consolidated using back pressure equal‐channel angular pressing starting with both raw and ball‐milled powders. In situ synchrotron high‐energy X‐ray diffraction studies are presented with continuous Rietveld analysis obtained upon a heating ramp from 300 K to 1075 K performed after the consolidation process. Initial phase distributions contain all intermetallic compounds of this system except Al, with distribution maxima in the outer regions of the concentrations (α‐Ti, TiAl₃). Upon annealing, the phase evolution and lattice parameter changes owing to chemical segregation, which is in favour for the more equilibrated phases such as γ‐TiAl, α₂‐Ti₃Al and TiAl₂, were followed unprecedentedly in detail. An initial δ‐TiH₂ content with a phase transition at about 625 K upon heating created an intermediate β‐Ti phase which played an important role in the reaction chain and gradually transformed into the final products.     

第一性原理计算MAlH4(M=Na,K)的结构和弹性性质

基于密度泛函理论研究并比较了两种储氢材料NaAlH₄和KAlH₄的晶格参数,弹性性质和电子结构.计算结果表明NaAlH₄和KAlH₄都是绝缘体,Al—H之间是共价键,M(M=Na,K)与AlH₄之间是离子键.NaAlH₄和KAlH₄的弹性常数都比较小而且NaAlH₄的弹性常数要大于KAlH₄的弹性常数,对此给予了解释. 关键词： 配位金属氢化物 电子结构 弹性性质     

Observations of nanoscopic,face centered cubic Ti and TiH<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>

Transmission electron microscopy has been used to study ball milled and H cycled NaAlH₄ with 10 mol% TiCl₃. Isolated from the main phases in this hydrogen storage system, nanocrystalline aggregates of fcc TiH _x (0≤x<0.67) were found. The value of x was determined based on the assumption of a linear increase of the TiH _x lattice parameter by increasing H content. The size of the TiH _x crystallites was in the range 10 to 20 nm, and the lattice parameter decreased from 4.22 Å in TiH_0.67 to 4.10 Å in pure fcc Ti. Non-equilibrium ball milling and subsequent H cycling in combination with a small crystallite size are believed to make the TiH _x phase stable. The present results are the first observations of fcc TiH _x with low hydrogen content, and the measured fcc lattice parameter of Ti matches first-principles calculations.     

Magnetostriction of Fe81Ga19 oriented crystals

The effect of the orientation on the magnetostriction in Fe 81 Ga 19 alloy has been investigated experimentally and theoretically.The Fe 81 Ga 19 [001] and [110] oriented crystals were prepared and the magnetostriction was measured under different pre-stress.The saturation magnetostriction of the [001] oriented crystal increases from 170×10-6 to 330×10-6 under the pre-stress from 0 to 50 MPa.The [110] oriented crystal has a saturation magnetostriction from 20×10-6 to 140×10-6 with the compressive pre-stress from 0 to 40 MPa.The magnetostriction of [001] and [110] oriented crystals has been simulated based on the phenomenological theory.The domain rotation path has been determined and the resultant magnetostriction calculated under different pre-stress.The experimental and simulated results both show that the [001] oriented crystal exhibits better magnetostriction than [110] oriented crystal.The enhancement of the saturation magnetostriction by the compressive pre-stress in the [110] oriented crystal is higher than that in the [001] oriented crystal.     

Nb-Ti-Al合金高温氧化机理电子理论研究

采用递归法计算了Nb合金的电子态密度、原子镶嵌能、亲和能和团簇能等电子结构参数,研究Nb合金高温氧化机理.研究表明,氧在Nb合金表面的吸附能较低,易在合金表面吸附,并逐渐扩散到Nb合金的基体中.氧在合金基体中镶嵌能为负值,氧的态密度和Nb相似,在Nb中具有很高的溶解度.Ti,Al在合金晶内的镶嵌能均高于各自在合金表面的镶嵌能,Ti,Al从合金内部向合金表面扩散,最终在Nb合金表面偏聚,形成富Ti,Al的表层.团簇能计算结果表明Nb合金表面的Ti,Al原子各自均有聚集倾向,分别形成Ti和Al原子团.氧与合金     

Density functional theory study of the interaction of H2 with pure and Ti-doped WO3 (002) surfaces

Density functional theory (DFT) calculations are conducted to explore the interaction of H₂ with pure and Ti-doped WO₃ (002) surfaces. Four top adsorption models of H₂ on pure and Ti-doped WO₃ (002) surfaces are investigated respectively, they are adsorption on bridging oxygen O_1c, absorption on plane oxygen O_2c, absorption on 5-fold W_5c (Ti), and absorption on 6-fold W_6c. The most stable and H₂ possible adsorption structure in the pure surface is H-end oriented to the surface plane oxygen O_2c site, while the favourable adsorption sites for H₂ in a Ti-doped surface is not only an O_2c site but also a W_6c site. The adsorption energy, the Fermi energy level E_F, and the electronic population are investigated and the H₂-sensing mechanism of a pure-doped WO₃ (002) surface is revealed theoretically: the theoretical results are in good accordance with our existing experimental results. By comparing the above three terms, it is found that Ti doping can obviously enhance the adsorption of H₂. It can be predicted that the method of Ti-doped into a WO₃ thin film is an effective way to improve WO₃ sensor sensitivity to H₂ gas.