具有高稳定性以及光催化产氢活性的奇数环状异金属钛氧纳米团簇

利用太阳能是解决当前能源危机和环境问题的有效途径.二氧化钛是一种稳定性高、环境友好的新型光催化剂.近年来,具有精确结构信息的晶态钛氧团簇(PTCs)作为TiO₂的分子结构模型受到广泛关注.目前大多数PTCs含有烷氧基,在空气中易发生水解.这在很大程度上限制了对其光催化性能的研究.在无机钛氧簇的外围修饰大量的共轭有机配体是一种有效提升PTCs稳定性的方法.此外,异金属的嵌入有助于修饰微观电子结构,从而也将影响光催化性能.铝是地球上最丰富的金属元素,其水解产物也大量存在于地壳表面.因此,Ti和Al的水解和光催化研究引起了我们的兴趣.目前,只有少数几例低核的Al掺杂PTCs晶态材料被报道,且其制备过程都需要多步反应.因此,合成高核的包含Al的PTCs材料是一项有趣且充满挑战的工作.本文利用有机配体的保护和异金属离子的掺杂成功地提高了PTCs晶体材料的稳定性.通过研究Ti和Al离子的水解,制备了一例核-壳型的纳米轮簇[Al₇Ti₁₄(μ2-O)₇(μ3-O)₁₄(L)₃₅]·2CH₃CN(1;L=苯甲酸).该轮簇中包含罕见的奇数环状结构,是目前核数最高的包含Al的PTC.借助单晶X射线衍射可以清晰观察到无机{Al₇Ti₁₄}核与有机保护配体之间的配位模式.此外,利用红外光谱、热重和漫反射光谱对该化合物进行了进一步表征.有机配体层和Al³⁺占据了T_i⁴⁺周围的烷氧基位点,使得该化合物呈现较高的空气、热以及酸碱稳定性.在已报道的PTCs晶态材料中,该化合物也展现出较高的光催化产氢速率(402.88μmol g^-1h^-1).借助催化过程中的光致变色现象、电子顺磁共振谱、荧光光谱以及光电流响应,我们推测了该化合物催化水分解产氢机理.该项工作不仅为制备稳定的PTCs材料提供了基础,也为新型光催化剂的设计提供了新的思路.     

双金属团簇Cu12Fe吸附CO和H2的理论研究

基于第一性原理密度泛函理论(DFT)方法研究了Cu₁₂Fe团簇的结构稳定性、热力学稳定性和反应活性.计算得出正二十面体Fe原子核心团簇Ih-core比正二十面体Fe原子壳层团簇Ih-shell的热力学稳定性更强.通过分析吸附能讨论了CO和H₂在Ih-core团簇上的吸附构型.计算结果表明,Ih-core团簇以顶角Corner位吸附CO时吸附能最大,吸附模型最稳定,H₂吸附过程中发生了解离,两个氢原子均形成表面Facet位吸附构型.最后,通过分析前线轨道得到吸附过程的轨道信息.     

Interpretation of TOF-SIMS data based on information entropy of spectra

Time-of-flight secondary ion mass spectrometry (TOF-SIMS), when used for the analysis of complex material samples, typically provides data that are complicated and challenging to understand. Therefore, additional data analysis techniques, such as multivariate analysis, are often required to facilitate the interpretation of TOF-SIMS data. In this study, a new method based on the information entropy (Shannon entropy) is proposed as an indicator of the outline characteristics of an unknown sample, such as changes in the material within the sample and mixing conditions. The Shannon entropy values are calculated using the relative intensity of every secondary ion normalized to the total ion count and reflect the diversity of secondary ions in the spectrum. Mixed samples containing two organic electroluminescence materials of different ratios, multilayers of Irganox 1010, and other organic materials were employed to evaluate the utility of Shannon entropy in the analysis of TOF-SIMS data. The findings demonstrate that the Shannon entropy of a spectrum indicates differences in materials and changes in the conditions of a material in a sample without the need for peak identification or the knowledge of specific peaks corresponding to the materials in the sample.     

Cluster PID Control of Viaduct Road Vibration

Cluster control to suppress the structural vibrations of viaduct roads caused by the movement of vehicles is studied. A viaduct road is modeled using the finite-element method. The structural modes of a road element are obtained. The cluster-control method is used, which is based on a finite-element model of a flat road. The modes of a flat viaduct road are classified into four groups. Each group is controlled by a PID controller. It is verified that the cluster actuation and the sensing based on PID control suppress the structural modes under consideration, and no spillover effects are observed __________ Published in Prikladnaya Mekhanika, Vol. 41, No. 10, pp. 139–144, October 2005.     

基于支持向量回归机的陀螺漂移预测模型

为了预测某导弹陀螺漂移趋势,以该陀螺漂移角速度时间序列为对象,建立了基于支持向量回归机的预测模型。针对该预测模型的特点,提出了支持向量预选取的模型优化方法。基于ε不敏感损失函数的支持向量回归机具有稀疏性,其结构由支持向量决定。因此从训练样本集中预选出有可能成为支持向量的样本,精简样本规模是提高该类支持向量回归机训练和预测效率的有效方法。针对该类支持向量回归机从分类和回归两个角度分析了支持向量的几何特征,提出了核函数空间免疫聚类的支持向量预选取方法并用于某导弹陀螺漂移预测模型的数据预处理。仿真结果表明优化后的预测模型运算量小、建模速度快,精度高。     

Computational Study of the One‐ and Two‐Dimensional Infrared Spectra of a Proton‐Transfer Mode in a Hydrogen‐Bonded Complex Dissolved in a Polar Nanocluster

The signatures of nanosolvation on the one‐ and two‐dimensional (1D and 2D) IR spectra of a proton‐transfer mode in a hydrogen‐bonded complex dissolved in polar solvent molecule nanoclusters of varying size are elucidated by using mixed quantum–classical molecular dynamics simulations. For this particular system, increasing the number of solvent molecules successively from N=7 to N=9 initiates the transition of the system from a cluster state to a bulk‐like state. Both the 1D and 2D IR spectra reflect this transition through pronounced changes in their peak intensities and numbers, but the time‐resolved 2D IR spectra also manifest spectral features that uniquely identify the onset of the cluster‐to‐bulk transition. In particular, it is observed that in the 1D IR spectra, the relative intensities of the peaks change such that the number of peaks decreases from three to two as the size of the cluster increases from N=7 to N=9. In the 2D IR spectra, off‐diagonal peaks are observed in the N=7 and N=8 cases at zero waiting time, but not in the N=9 case. It is known that there are no off‐diagonal peaks in the 2D IR spectrum of the bulk version of this system at zero waiting time, so the disappearance of these peaks is a unique signature of the onset of bulk‐like behavior. Through an examination of the trajectories of various properties of the complex and solvent, it is possible to relate the emergence of these off‐diagonal peaks to an interplay between the vibrations of the complex and the solvent polarization dynamics.     

气体团簇离子束两步能量修形法的平坦化效应

本文提出采用气体团簇离子束的两步能量修形法来改善4H-SiC(1000)晶片表面形貌.先用15 keV的高能Ar团簇离子进行整体修形,再用5 keV的低能团簇离子优化表面.结果表明,在相同的团簇离子剂量下,与单一15 keV的高能团簇处理相比,两步法修形后的表面具有更低的均方根粗糙度,两者分别为1.05 nm和0.78 nm.本文还以原子级平坦表面为研究对象,揭示了载能团簇引起的半球形离子损伤(弧坑)与团簇能量的关系,及两步能量修形法在弧坑修复中的优势.在原子力显微镜表征的基础上,引入了二维功率谱密度函数,以直观全面地给出材料的表面形貌特征及其随波长(频率)的分布.结果表明,经任何能量的团簇离子轰击的表面,在0.05—0.20μm波长范围内,团簇轰击都能有效地降低粗糙度,而在0.02—0.05μm范围内,则出现了粗化效应,这是由于形成了半球形离子损伤,但第二步更低能量的团簇离子处理可以削弱这种粗化效应.     

Survival of Virus Particles in Water Droplets: Hydrophobic Forces and Landauer’s Principle

Many small biological objects, such as viruses, survive in a water environment and cannot remain active in dry air without condensation of water vapor. From a physical point of view, these objects belong to the mesoscale, where small thermal fluctuations with the characteristic kinetic energy of k_BT (where k_B is the Boltzmann’s constant and T is the absolute temperature) play a significant role. The self-assembly of viruses, including protein folding and the formation of a protein capsid and lipid bilayer membrane, is controlled by hydrophobic forces (i.e., the repulsing forces between hydrophobic particles and regions of molecules) in a water environment. Hydrophobic forces are entropic, and they are driven by a system’s tendency to attain the maximum disordered state. On the other hand, in information systems, entropic forces are responsible for erasing information, if the energy barrier between two states of a switch is on the order of k_BT, which is referred to as Landauer’s principle. We treated hydrophobic interactions responsible for the self-assembly of viruses as an information-processing mechanism. We further showed a similarity of these submicron-scale processes with the self-assembly in colloidal crystals, droplet clusters, and liquid marbles.