Infrared study of the reactivity of CO with K2 and K3 molecules isolated in solid argon

Cocondensation of K atoms and CO molecules with an excess of argon onto a cold substrate (10 K) leads to the formation of strongly perturbed CO complexes from ground state partners only when a large proportion of K clusters is present. It is established that ground state, isolated K atoms do not react with carbon monoxide as do small potassium clusters. K₂CO, K₃CO and K₂(CO)₂ species are identified by CO stretching motions and are unambiguously characterized using systematic concentration and isotopic studies (¹²C, ¹³C and ¹⁸O) as well as triple doping K/CO/O₂/Ar experiments. K₂(CO)₂ is a very labile species which seems likely to have a C_2v doubly bridged structure. It rearranges into the well known acetylene diolate K … O-CC-O … K species upon exposure to infrared light (0.3–0.45 eV).     

N2H4在NiFe(111)合金表面吸附稳定性和电子结构的第一性原理研究

采用基于色散校正的密度泛函理论进行了第一性原理研究, 详细分析了肼(N₂H₄)在Ni₈Fe₈/Ni(111)合金表面稳定吸附构型的吸附稳定性和电子结构及成键性质. 通过比较发现, 肼分子以桥接方式吸附在表面的两个Fe原子上是最稳定的吸附构型, 其吸附能为-1.578 eV/N₂H₄. 同时发现, 肼分子在这一表面上吸附稳定性的趋势为: 桥位比顶位吸附更有利, 且在Fe原子上比在Ni原子上的吸附作用更强. 进一步分析了不同吸附位点上稳定吸附构型的电子结构、电荷密度转移以及电子局域化情况. 结果发现: 相同吸附位点的电子态密度图基本一致, 并且N原子的p轨道和与之相互作用的表面原子的d轨道之间存在态密度上的重叠; 吸附后电荷密度则主要从肼分子转移到表面原子之上; 在电子局域化函数切面图中也发现吸附后电子被局域到肼分子的N原子和相邻的表面原子之间. 这些电子结构的表征都充分说明肼分子与表面原子之间通过电荷转移形成了强烈的配位共价作用.     

RAS: An efficient probe to characterize Si(0 0 1)-(2 × 1) surfaces

A complete inspection of the capabilities of reflectance anisotropy spectroscopy (RAS) in studying the adsorption of molecules or atoms on the Si(0 0 1)-(2 × 1) surface is presented. First, a direct comparison between RA spectra recorded on the clean Si(0 0 1)-(2 × 1) and the corresponding topography of the surface obtained using scanning tunneling microscopy (STM) allows us to quantify the mixing of the two domains that are present on the surface. Characteristic RA spectra recorded for oxygen, hydrogen, water, ethylene, benzene are compared to try to elucidate the origin of the optical structures. Quantitative and qualitative information can be obtained with RAS on the kinetics of adsorption, by monitoring the RA signal at a given energy versus the dose of adsorbate; two examples are presented: H₂/Si(0 0 1) and C₆H₆/Si(0 0 1). Very different behaviours in the adsorption processes are observed, making of this technique a versatile tool for further investigations of kinetics.     

Studies of sol–gel TiO2 and Pt/TiO2 catalysts for NO reduction by CO in an oxygen-rich condition

The textural properties, morphological features, surface basicity and oxygen reduction behaviours of titania and Pt supported titania catalysts synthesized via a sol–gel method were studied by means of N₂ physisorption, SEM, TEM, CO₂-TPD and H₂-TPR techniques. Mesostructured TiO₂ shows a very narrow pore size distribution that uniformly centred at about 4 nm. High resolution TEM images confirmed that most of Pt particles on Pt/TiO₂-SG had a size smaller than 2 nm. Both the titania support and Pt loaded catalysts chiefly contained weak basic sites with small amount of strong basic sites. Loading Pt did not significantly alter the surface reduction characters of titania, indicating a weak interaction between Pt metals and titania support. Catalytic evaluation revealed that the selectivity of NO reduction over titania was insensitive to variation of textural property. On the bare titania, low NO conversion but high selectivity to N₂O was obtained. However, the Pt/TiO₂-SG catalysts exhibited high NO conversion and high selectivity to N₂, which is assumed to relate to NO dissociation catalysed by the metallic Pt clusters. In addition, when the reaction temperature was above 200 °C, 3–11% NO₂ was yielded over the Pt/TiO₂-SG catalysts, which was discussed on a basis of reaction competition, metal-support interaction and NO dissociation.     

N2在页岩干酪根上的吸附特征

采用密度泛函理论的wB97XD方法、RDG函数方法和counterpoise correction理论,研究氮气在干酪根C₂₈H₁₄O和氮掺杂干酪根C₂₇H₁₄ON上的吸附特征。结果表明：N₂在干酪根上的活性吸附位点为苯环上方中心位置,吸附能在8~10 kJ·mol^-1之间,N₂和干酪根之间的相互作用主要是范德华相互作用和空间排斥作用。氮掺杂改变了干酪根的构型和电子云分布,导致含氮杂环不再是稳定的活性吸附位点,增强了排斥作用,使吸附能略有减小。研究结果对理解干酪根吸附小分子的特征有重要意义,能够为页岩气的开采提供理论支持。     

2-噻吩甲酸在Fe3O4@Ag基底上的吸附及表面增强拉曼光谱

采用共沉淀法合成Fe₃O₄纳米颗粒,再以柠檬酸三钠还原AgNO₃获得了具有SERS活性的Fe₃O₄@Ag磁性纳米复合材料。基于密度泛函理论(DFT)的量子化学计算方法和表面增强拉曼光谱(SERS)技术,从理论计算和实验测定表征探讨了2-噻吩甲酸(2-TCA)在Fe₃O₄@Ag表面的吸附行为和增强效应。结果表明:理论计算得到的拉曼光谱与实际测得的常规拉曼光谱基本一致,而在DFT理论计算中所键连的Ag原子数越多,与实测值就越接近。溶液的浓度和pH对拉曼增强效果有很大的影响,当溶液的pH=3且浓度为1×10^-4 mol·L^-1时有最大拉曼增强效应。峰强随2-TCA浓度的增加呈现先增大后减小的趋势,浓度过大会导致大量2-TCA分子吸附聚集在Ag表面形成局部"拥堵",阻碍了激发光尤其是光谱信号的散射通过,从而减弱了拉曼增强效应。pH的变化使溶液中2-TCA分子形态发生改变,结构形态不同,其在Ag表面的吸附方式也不同。中性C₄H₃SCOOH分子以环上S:形式垂直吸附键合在Ag表面,形成S—Ag配位键而产生SERS光谱。-1价C₄H₃SCOO^-离子以S—Ag配位和O—Ag共价"双键合"侧卧方式共同吸附在Ag表面而产生SERS光谱。在Ag表面,以单独S—Ag配位键吸附或键合的能力比S—Ag配位和O—Ag共价共同吸附方式要弱,但其产生的SERS信号更强,故2-TCA中性分子比2-TCA^-离子更有利于SERS的产生。随着pH值的增加,溶液中的2-TCA由中性分子逐渐转化为-1价的C₄H₃SCOO^-离子,因而在pH>3以后,拉曼增强效应逐步减弱。     

Tunneling magnetoresistance of C2H2 molecules sandwiched between Co clusters

The tunneling magnetoresistance (TMR) of samples containing well-defined Co clusters (≈4.5 nm mean diameter) embedded in C₂H₂ matrices essentially is independent of Co-cluster volume fraction v_Co and reveals a value of about 26% at T=2 K. This result is in contrast to that obtained for Co clusters embedded in C₂H₄ matrices (Phys. Rev. B 67 (2003) 094433). In the latter system the TMR strongly decreased with increasing v_Co indicating different possible orientation of the C₂H₄ molecule sandwiched between the Co clusters. We, therefore, conclude that the C₂H₂ molecules are sandwiched in a rather well-defined orientation between the Co clusters. They probably form double layers of C₂H₂ molecules with the C–C bond axis parallel to the Co cluster surface.     

Defect induced surface chemistry: A comparison of the adsorption and thermal decomposition of C2H4 on Rh{111} and Rh{331}

The adsorption and thermal decomposition of C₂H₂ on Rh{111} is compared to the atomically stepped Rh{331} surface over a temperature range of 300 to 800 K. Using X-ray photoelectron spectroscopy (XPS) we find that the C 1s spectra as a function of C₂H₄ exposure exhibit a shift in binding energy (E_b) from 283.5 eV at 1 L C₂H₄ exposure on both surfaces to 283.8 eV on Rh{33 and to 284.1 eV on Rh{111} at saturation coverage (4 L). Careful analysis of the C 1s E_b value and full width at half maximum as a function of surface temperature after a 10 L exposure of C₂H₄ at 300 K reveals that a species consistent with a C₂H adsorbate composition is formed between 400 and 450 K on Rh{111}. This species is also observed on Rh{331} although at the lower temperature of 375 K. Computer peak deconvolution of the C 1s spectra between 500 and 700 K suggests that a CH_ads or C_ads surface fragment is formed and increases in concentration at the expense of the C₂H species as the surface temperature increases. Above 750 K a graphite overlayer is formed on both surfaces. This overlayer, however, exhibits a low degree of carbon π-character bonding on Rh{331}. The adsorption and decomposition mechanisms suggest that the 300 K C₂H₄ adsorbate on Rh{331} is ethylidyne and that the stepped surface is more thermally reactive than the flat Rh{111} surface.     

Decomposition mechanism of triethylindium (TEI) on a GaP(0 0 1)-(2×1) surface studied by LEED, AES, TPD and HREELS

Adsorption and decomposition of triethylindium (TEI: (C₂H₅)₃In) on a GaP(0 0 1)-(2×1) surface have been studied by low-energy electron diffraction (LEED), Auger electron spectroscopy (AES), temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS). It is found from the TPD result that ethyl radical and ethylene are evolved at about 300–400 and 450–550 K, respectively, as decomposition products of TEI on the surface. This result is quite different from that on the GaP(0 0 1)-(2×4) surface. The activation energy of desorption of ethyl radical is estimated to be about 93 kJ/mol. It is suggested that TEI is adsorbed molecularly on the surface at 100 K and that some of TEI molecules are dissociated into C₂H₅ to form P–C₂H₅ bonds at 300 K. The vibration modes related to ethyl group are decreased in intensity at about 300–400 and 450–550 K, which is consistent with the TPD result. The TEI molecules (including mono- and di-ethylindium) are not evolved from the surface. Based on the TPD and HREELS results, the decomposition mechanism of TEI on the GaP(0 0 1)-(2×1) surface is discussed and compared with that on the (2×4) surface.     

(C_5H_(11)N_2)~+和(C_7H_(12)N_2)~(2+)的NMR研究

结合1H NMR,13C NMR谱,分别对钨、钼配合物{WO2(C10H6O2)2(C5H11N2)2[H2N(CH2)3NH2]}3(1),{(C5H11N2)2[H2N(CH2)3NH2][MoO2(C10H6O2)2]}(2),{(C7H12N2)2[MoO2(C10H8O2)2]}(3)晶体结构中小分子环进行了归属.其中,配合物1和2中(C5H11N2)+的NMR研究证实了六元环由1,3-丙二胺和乙腈化合而成,配合物3中(C7H12N2)2+的NMR谱图证实了七元环由乙二胺和乙酰丙酮化合而成,并且推导出这些亲核加成-消除反应的反应机理.配合物1~3中的小分子环的合成在其它体系中尚未见报导,而在合成它们的反应中作为新产物随主体晶体析出,并由晶体结构解析和NMR得到了证实.     

Reaction kinetics of the Pt, O2(g)|c-ZrO2 system: precursor-mediated adsorption

A micro kinetic model of the Pt, O₂(g)|c-zirconia electrode/electrolyte system was developed in state space form (model M3). The oxygen adsorption/desorption process was modeled as a precursor-mediated surface reaction. The surface diffusion of atomic oxygen and the electrochemical reduction of atomic oxygen near the three-phase boundary (tpb) were considered. It was shown that the simulated charge-transfer behavior of M3 is significantly different from models with ordinary Langmuir kinetics (model M2). The electrochemical rate constant was estimated from selected experimental data as k₁₀=(6.05±0.25)·10⁶ m³/(mol·s). From experimental results it was concluded that only one adsorbed oxygen species is relevant for the dynamic behavior. In porous Pt electrodes binary gas phase diffusion of oxygen in O₂/N₂ gas mixtures becomes relevant at oxygen partial pressures below 10⁻³ atm. The general procedure for state and parameter estimation can be well adopted for the investigation of further reaction mechanisms.     

Effects of potassium on the adsorption and dissociation of CH3Cl on Pd(100)

The effects of potassium on the adsorption and dissociation of CH₃Cl on a Pd(100) surface has been investigated by ultraviolet photoelectron spectroscopy (UPS), Auger electron spectroscopy (AES), electron energy loss spectroscopy (in the electronic range EELS), temperature-programmed desorption (TPD) and work function change. In contrast to the clean surface, the adsorption of CH₃Cl caused a significant work function increase, 0.9-1.4 eV, of potassium-dosed Pd. Preadsorbed K enhanced the binding energy of CH₃C1 to the surface and induced the dissociation of adsorbed molecules. The extent of the dissociation increased almost linearly with the potassium content. The appearance of a new emission in the UPS spectrum at 9.2 eV, attributed to adsorbed CH₃ species, and the low-temperature formation of ethane suggest that a fraction of adsorbed CH₃Cl dissociates even at 115–125 K on potassium-dosed Pd(100). At the same time, a significant part of adsorbed CH₃ radical is stabilized, the reaction of which occurs only at 250–300 K. By means of TPD measurements, H₂, CH₄, C₂H₆, C₂H₄, KCl and K were detected in the desorbing gases. The results are interpreted by assuming a through-metal electronic interaction at low potassium coverage and by a direct interaction of the Cl in the adsorbed CH₃Cl with potassium at high potassium coverage. The latter proposal is supported by the electron excited Auger fine structure of the Cl signal and by the formation of KCl in the desorbing gases.     

Theoretical study of interaction between atoms of Au, Ag, Cu and clean Si(1 1 1) surface

To evaluate the interactions between the atoms of Au, Ag and Cu and clean Si(1 1 1) surface, two types of silicon clusters Si₄H₇ and Si₁₆H₂₀ together with their metal complexes were studied by using hybrid (U)B3LYP density functional theory method. Optimized geometries and energies on different adsorption sites indicate that: (1) the binding energies at different adsorption sites are large (ranging from 1.2 to 2.6 eV depend on the metal atoms and adsorption sites), suggesting a strong interaction between metal atom and silicon surface; (2) the most favorable adsorption site is the on top (T) site. Mulliken population analysis indicated that in the system of on top (T) site, a covalent bond is formed between metal atom and dangling bond of surface Si atom.     

The interaction of C2Cl4 with fe(110)

Quantitative adsorption studies, temperature programmed desorption (TPD) and Auger spectroscopy have been used to study the interaction of C₂Cl₄ with Fe(110) at 90 and 325 K. At 90 K, multilayer C₂Cl₄ adsorption occurs. The following desorption products are observed in the temperature range of 90–1050 K: C₂Cl₄ from the multilayer and the monolayer, FeCl₂, and a high mass iron chloride species with mass spectrometer cracking products FeCl⁺₂, FeCl⁺, and Fe⁺. Irreversible dissociative C₂Cl₄ adsorption occurs at 325 K and the only desorption product which is observed is the high mass iron chloride species. Auger spectroscopy shows that surface carbon from C₂Cl₄ starts to diffuse into the bulk of the crystal at ˜ 480 K while small coverages of chlorine remain on the surface of the crystal even after heating to 1050 K. Comparison of the behavior of C₂Cl₄ and CCl₄ on Fe(110) indicates that radical products (·CCl₃ and :CCl₂) observed to be produced from CCl₄ adsorption are not produced from C₂Cl₄ adsorption. This difference is probably due to the enhanced surface reactivity of the C=C bond in C₂Cl₄. A special reactivity of iron defect sites for C₂Cl₄ is observed through the production of associated FeCl₂ species which desorb via zero-order kinetics with an activation energy of 44.8 ± 8.5 kcal/mol, the sublimation enthalpy of FeCl₂.     

碳硼富勒烯衍生物C18B2M(M=Li,Ti, Fe)的储氢性能计算研究

本文使用密度泛函理论(density functional theory, DFT)中的广义梯度近似(generalized gradient approximation, GGA)研究了经碱金属原子Li、过渡金属原子Ti和Fe原子修饰的富勒烯C₁₈B₂M(M=Li, Ti, Fe)的储氢性能. 研究发现, C₁₈B₂由于B的替代掺杂, 比C₂₀对金属原子具有更高的结合能. 由平均吸附能分析可知: C₁₈B₂Li对H₂的吸附能力较弱, C₁₈B₂Fe对H₂的吸附能力过强, 而C₁₈B₂Ti对H₂的平均吸附能介于0.45-0.59 eV 之间, 介于物理吸附和化学吸附之间 (0.2-0.6 eV), 因此可以实现常温下的可逆储氢. C₁₈B₂M(M=Li, Ti, Fe)能够吸附的H₂数目最多分别为4, 6和4. 由储氢机理分析可知: C₁₈B₂Li主要通过碱金属离子激发的静电场来吸附H₂, 而C₁₈B₂Ti和C₁₈B₂Fe主要通过金属原子与H₂之间的Kubas作用来吸附H₂. 由于C₁₈B₂Ti既有较大的储氢数目, 又可以实现可逆储氢, 因此有望开发成新型纳米储氢材料.     

Oxygen atom-induced D2 and D2O desorption on D/Si(1 1 1) surfaces

We studied reaction of oxygen atoms with D-terminated Si(1 1 1) surfaces from a desorption point of view. As the D (1 ML)/Si(1 1 1) surface was exposed to O atoms D₂ and D₂O molecules were found to desorb from the surface. The desorption kinetics of D₂ and D₂O molecules exhibited a feature characterized with a quick rate jump at the very beginning of O exposure, which was followed by a gradual increase with a delayed maximum and then by an exponential decrease. The O-induced D₂ desorption spectra as a function of T_s appeared to be very similar to the H-induced D₂ desorption spectrum from the D/Si(1 1 1) surfaces. Possible mechanisms for the O-induced desorption reactions were discussed.     

Adsorption of N2 and N2O on Ni(7 5 5) surface: ab initio periodic density functional study

Adsorption of N₂ and N₂O at various sites on Ni(7 5 5) has been investigated by density functional theory (DFT) method (periodic DMol³). Several possible adsorption structures (attaching the nitrogen atom to the surface, or lying parallel) are found for both molecules. There is a clear binding energy preference of N₂ and N₂O for step sites in contrast to the case of CO. It is revealed that the decomposition of N₂O occurs exclusively near the step, but not on the terrace. Two decomposition channels can be considered; dissociative adsorption and spontaneous decomposition during TPD ramp. Three possible candidates for the precursor of the spontaneous decomposition of N₂O during TPD ramp are discussed.     

PVP在水/丙酮混合溶剂中分子运动行为的研究

通过对粘度、自旋-自旋弛豫时间以及1H NMR谱的测定,研究了PVP在不同体积配比的水/丙酮溶液中的特性粘数变化和分子运动规律,并讨论了引起这些变化的原因.结果表明:随着丙酮的不断加入,PVP的特性粘数[η]先增加后减小,而T2H先减小后增大.[η]出现最大值也是T2H出现最小值的时候,丙酮的体积百分数为40%.丙酮的加入破坏了水分子间自身氢键相互作用形成的网状结构,解离出来的水分子被PVP优先吸附到大分子链上,部分与羰基形成氢键,另一部分以自由水的形式被包裹在大分子线团内.水分子的不断进入以及与水形成新的氢键使PVP链逐渐伸展,引起特性粘数的增大,分子运动受阻.当丙酮含量增加到一定程度时,水的含量不足以使大分子链继续膨胀,故链呈卷缩状态,使大分子运动逐渐恢复自由.1H NMR谱中各质子的化学位移变化也证实了此过程中的氢键变化规律.     

Adsorption of NO on Au atoms and dimers supported on MgO(1 0 0): DFT studies

The adsorption of NO on single gold atoms and Au₂ dimers deposited on regular O²⁻ sites and neutral oxygen vacancies (F_s sites) of the MgO(1 0 0) surface have been studied by means of DFT calculations. For Au₁/MgO the adsorption of NO is stronger when the Au atom is supported on an anionic site than when it is on a F_s site, with adsorption binding energies of 1.1 and 0.5 eV, respectively. In the first case the spin density is mainly concentrated on the metal atom and protruding from the surface. In such a way, an active site against radicals such as NO is generated. On the F_s site, the presence of the vacancy delocalizes the spin into the substrate, weakening its coupling with NO. For Au₂/MgO, as this system has a closed-shell configuration, the NO molecules bonds weakly with Au₂. Regarding the N–O stretching frequencies, a very strong shift of 340–400 cm⁻¹ to lower frequencies is observed for Au₁/MgO in comparison with free NO.