Photochemistry in ordered physisorbed monolayers of dinitrogen tetroxide

The effects of physisorption and two-dimensional ordering on the photochemistry of N₂O₄ were investigated. Ordered monolayers were prepared by adsorption of NO₂ at 100 K on a water-ice surface. Irradiation with a continuous light source in the wavelength region 300–400 nm or with pulsed laser radiation at 355 nm resulted in exclusive desorption of NO₂. This desorption was induced by electronic absorption directly in the adsorbate via a transition corresponding to the ( )¹B_2u←( )¹A_g transition in N₂O₄, as in the gas phase. However, the subsequent dynamics in the excited state were markedly different from the gas-phase counterpart. Time-of-flight mass spectrometry of NO₂ photodesorbed at 355 nm revealed a most probable fragment translational energy of ca. 17 meV; and the angular distribution of the nascent NO₂ was peaked sharply in a direction around 10° from the normal. It is apparent that, despite the weak interaction with the substrate, significant energy transfer occurs in the ordered physisorbed monolayer to yield nascent NO₂ with very low translational energy and a constrained angle of escape which is consistent with a high degree of adsorbate order and alignment.     

Extraction of the neutron charge form factor G<Superscript>n</Superscript><Subscript>E</Subscript>(Q<Superscript>2</Superscript>) from the charge form factor of deuteron G<Superscript>d</Superscript><Subscript>C</Subscript>(Q<Superscript>2</Superscript>)

We extract the neutron charge form factor G ⁿ _E(Q ²) from the charge form factor of deuteron G ^d _C(Q ²) obtained from T ₂₀(Q ²) data at 0≤Q ²≤ 1.717 (GeV/c)². The extraction is based on the relativistic impulse approximation in the instant form of the relativistic Hamiltonian dynamics. Our results (12 new points) are compatible with existing values of the neutron charge form factor of other authors. We propose a fit for the whole set (36 points) taking into account the data for the slope of the form factor at Q ² = 0. Received: 26 July 2002 / Accepted: 18 September 2002 / Published online: 4 February 2003 RID="a" ID="a"e-mail: krutov@ssu.samara.ru RID="b" ID="b"e-mail: troitsky@theory.sinp.msu.ru Communicated by V.V. Anisovich     

固体吸附式制冷中热波循环的分析研究

1引言由Tehernev博士和S．V．Shelton教授提出的热波循环，是吸附式制冷中引起广泛兴趣的一种循环方式。其特点是高效回热，Shelton采用斜波法［‘］和方波法［‘］分析了热波循环，回热率达70％，热泵工况COP超过1．6。其它学者作了改进研究［‘并热波循环的模拟效果很好，但实验方面进展相当缓慢。采用螺旋板式换热器作吸附器，也发现热波循环的运行效果很不理想问。目前，相关的文献主要是系统模拟，而对其关键，热波的形成、特性研究较少。另外，研究侧重于系统性能（COP），对能量密度（SPD）考虑较少。本文将从传热的角度分析热…     

定容式吸附性能测量的实验研究

本文提出了一种定容式吸附(或解吸)性能测量装置,通过试验研究,证明其不仅可行,而且测量精度高于常用的容积法(液位法)吸附性能测试系统,而且吸附剂试样充装量少,适用于广泛的压力测量范围。利用本文的测量装置,还首次进行了部分活性炭与氯化钙混合吸附剂与氨的吸附性能测试,数据有助于为吸附制冷寻找新的高效吸附剂提供参考。     

余热驱动的传热强化吸附制冰机实验研究

以活性炭-甲醇为工质对,搭建单床吸附制冰机。采用某种粘结剂与活性炭混合。制作具有良好传热性能的固化活性炭块。吸附床即由此种炭块和带铜肋片的传热管组成。本文针对渔船制冰工况(冷量温度控制在零下7℃)对制冰机进行了模拟试验。系统的性能参数如下:COP为0.07,SCP为11W/kg活性炭。     

等离子体-吸附SO2转化机理研究

本文对SO2在等离子体和分子筛吸附联合作用下的转化现象进行了研究,开展了实验、模型建立、机理研究和理论计算等工作。研究表明,二者共同作用下可有效的将SO2转化,等离子体在转化反应中起着决定性的作用,其主要反应为OH SO2→HOSO2。理论计算和实验数据基本吻合。     

Electrical and chemical characteristics of nano-meter gold encapsulated in mesoporous and microporous channels and cages of FSM-16 and Y zeolites

The dc and ac conductivities as well as the dielectric constant () were measured for different zeolites encapsulated gold (AuCl₃) samples at different temperatures (300-500 K) and various frequencies (5 kHz-1 MHz). The conductivity was found to change in the order Au/FSM-27>Au/NaY>Au/FSM-47. Sorbed water contained inside zeolites assists greatly the proton mobility (zeolite protons) and the ion mobility (Na⁺ and Au⁺) and hence enhance the electric conduction in the temperature range 300-373 K. Raising the temperature over 373 K induces dehydration effect that assists the metallic gold formation and thus a dramatic loss in conductivity was revealed. The conduction mechanism was expected to be partially ionic and partially electronic. The IR study showed that the exposure of Au zeolites to CO gas produced a characteristic band of Au⁺-CO at 2180 cm⁻¹ that tends to decrease with temperatures and even vanishes at 376 K in favor of Au⁰-CO at 2128 cm⁻¹. Similarly, a phase transition at 338 K, that occurs in the range 300-376 K, was confirmed by DTA to further emphasize the temperature regions of either Au⁺ cations (338 K) or Au⁰ (376 K) formation.     

金属原子修饰石墨烯体系催化性能的理论研究

采用基于密度泛函理论的第一性原理方法研究了单个CO 和O2气体分子在金属原子修饰石墨烯表面的吸附和反应过程. 结果表明: 空位缺陷结构的石墨烯能够提高金属原子的稳定性, 金属原子掺杂的石墨烯体系能够调控气体分子的吸附特性. 通入混合的CO和O2作为反应气体, 石墨烯表面容易被吸附性更强的O2分子占据, 进而防止催化剂的CO 中毒. 此外, 对比分析两种催化机理(Langmuir-Hinshelwood和Eley-Rideal)对CO氧化反应的影响. 与其它金属原子相比, Al原子掺杂的石墨烯体系具有极低的反应势垒(< 0.4 eV), 更有助于CO氧化反应的迅速进行.     

铝和银在铱（111）宽范围吸附的稳定性、原子构型及电子特性研究

利用第一性原理密度泛函理论研究了铝和银在铱的111面的宽范围吸附特性。基于密度泛函理论计算了覆盖度在0.11ML到2.00ML的结构稳定性、原子构型及平均结合能。对于铝原子在铱111面的吸附,最稳定的结构是铝原子覆盖度为0.5ML位于密堆六方空位（hcp-hollow）,相应的结合能为-4.68eV;对于亚层铝原子的吸附,最稳定结构是铝原子覆盖度为1.00ML时位于octahedral位置,相应的结合能为-5.28eV。对于覆盖度为2.00ML的满覆盖度混合结构的表层及亚层吸附,最稳定结构是Al位于六方密堆及八方密堆位置,相应的结合能为-4.70eV。这意味着当铝原子以满覆盖度吸附在铱的111面上时,趋向于在铱的111面的亚层形成化学键,而非吸附于表层。相比于铝吸附在铱111面,银的吸附特性呈现出很大的不同,面心位置更为稳定,在覆盖度为0.25ML时其结合能为3.89eV,略微高出密堆六方位置处3.88eV的结合能。     

Real-time monitoring of SiO2/Si(1 1 1) interlayer etching by Brewster-angle reflectometry

A transitory etching regime after SiO₂ dissolution and before bulk Si(1 1 1) etching in neutral NH₄F solutions was monitored by in situ Brewster-angle reflectometry (BAR). An observed intermediate increase of the BAR reflectance signal is attributed to a fast dissolution of a stressed/strained interlayer beneath the SiO₂/Si(1 1 1) interface. Similar effects were observed on thin thermal oxides (18.2 nm), grown on float zone silicon, as well as on ultra-thin native oxides (1.2 nm) on Czochralsky silicon. Native oxide covered samples showed an increased surface roughness in the course of interlayer dissolution while the surface is progressively covered with compounds of fluorinated silicon. The etch rate, determined by atomic force microscopy (AFM) and compared to the etch rate of bulk silicon, is increased by a factor of four. In the limit of extended etching, the known low etch rates for silicon in 40% NH₄F are observed. Structural and chemical properties of the interfacial layer were analyzed by synchrotron radiation photoelectron spectroscopy (SRPES) which confirmed the presence of Si^3+/4+ valence states throughout the interlayer and by near open-circuit potential (N-OCP) dark current measurements. As a result, oxide etch rates in NH₄F in the pH-range 7–8 as well as the silicon interlayer depth can be assessed by in situ BAR.