A localized molecular orbital study on the bonding of> Mo3S4]2Mo> and> Mo3S4]CuI> versus (C6H6)2Cr and C6H6Cr(CO)3

The energy-localized CNDO/2 molecular orbitais have been calculated for the clusters containing molybdenum, > {Mo₃S₄₂Mo}⁸⁺ and> Mo₃S₄]CuI> ⁴⁺, versus the prototype arene-metal sandwich (C₆H₆)₂Cr and half-sandwich complexes C₆H₆Cr(CO)₃. The bonding characteristics of these compounds are described from a localization bonding viewpoint. There are two typical M-arene and M-[Mo₃S₄] bondings. One is formed by electron donation from the three-center two-electron π-bonds in the arene or [Mo₃S₄]⁴⁺ ligands into the vacant hybrid orbitais of the “stranger” metal atom. In the other M-arene or M-[Mo₃S₄] bond there is very little donation by the lone electron pair occupying the d AOs of the “stranger” metal atom to the arene or [Mo₃S₄]⁴⁺ ligands. The analogy of the ligand [Mo₃S₄]⁴⁺ in the clusters studied with the ligand benzene is also briefly discussed.     

铂钌团簇及电荷对甲醇活性的理论研究

采用密度泛函理论(DFT)对钌掺杂的铂团簇阳离子([Pt_nRu_m]⁺, m + n = 3, n ≥ 1)活化甲醇C―H和O―H键反应进行了理论研究;探讨了电荷对[Pt_nRu_m]团簇反应活性的影响。电荷分析表明:(1) [Pt₃]⁺团簇中正电荷在三个Pt原子上均匀分布;掺杂Ru原子后,正电荷主要分布在Ru原子上; (2)首先活化C―H键时[Pt_nRu_m]⁺的反应活性比[Pt_nRu_m]明显提高;首先活化O―H键时只有[Pt₃]⁺比[Pt₃]团簇的反应活性有明显提高。本研究可为金属团簇调控的C―H键和O―H键的活化提供更深入的理解。     

Reversible Adsorption of NOx on ZrO2-supported CeO2 Prepared in Water-in-oil Microemulsion

Nitric oxides (NOx) storage catalyst^[1] provides an alternative route for abatement of NO in presence of oxygen by first adsorbing NOx and then desorbing it by temperature swing or pressure swing. YBa₂Cu₃Oy^[2] and Mn-Zr mixed oxides^[3] were reported to have large NOx adsorption capacity, but the former suffered from a great amount of coexisting CO₂ gases. The author previously reported that high NOx adsorption capacity could be obtained on Ce modified TiO₂-pillared montmorillonite without deactivation by CO₂^[1]. Microemulsion method was reported to be effective to control particle sizes and microstructures of the metal oxides^[4]. In this paper, a thermal stable ZrO₂ with high surface area was prepared in water-in-oil microemulsion, and NOx adsorption capacity was tested on the above ZrO₂ sample after impregnating with manganese nitrate and cerium nitrate.     

六核钽铑二元混合簇合物的几何和电子结构

采用密度泛函理论对六核钽、铑八面体纯簇及其混合簇的几何结构和电子性质进行了研究.计算结果表明:大部分钽铑混合簇稳定构型的对称性均较低,为C1或Cs点群,只有[Ta2Rh4Cl4H8(CN)6]4-团簇的稳定构型对称性较高,为C2h或C4v点群;混合簇的最高占据分子轨道(HOMO)与最低未占据分子轨道(LUMO)能隙(ΔEH-L)均较小,介于0.52-1.00eV之间;混合簇的前线轨道主要由骨架金属原子的d电子贡献,随着Rh原子替代Ta原子个数的递增,Ta—Rh键对混合簇稳定构型所起作用逐渐增加,Ta—Ta键所起作用减小,而Rh—Rh键为非键或反键性质.     

The effects of surface ligands and counter cations on the stability of anionic thiolated M12Ag32 （M=Au,Ag） nanoclusters

The stabilities of [M12Ag32（SR）30]4- （M = Ag, Au and SR = SPhF2, SPhCF3, SPhF） clusters having the same structure but different surface ligands or counter cations were systematically studied. It was clearly revealed that a subtle structural change in the surface ligands or counter cations could significantly alter the overall stability of [M12Ag32（SR）30]4 although they all had an electronic structure of 18-electron superatom shell closure. SPhF2 was found as a better surface ligand than SPhCF3 or SPhF to stabilize [M12Ag32（SR）30]4-. And the use of more bulky [（PPhj）2N]＋ as the counter cations was revealed to be more deleterious to the overall stability of [M12Ag32（SR）30]4- clusters than PPh4＋. [Au12Ag32（SR）30]4- was much more stable than [Ag44（SR）30]4 with the same surface ligands and counter cations. An exceptional stability was observed on （PPh4）4[Au12Ag32（SPhF2）30] which was stable in DMF for more than 8 days in air at 80 ℃. More research efforts are still needed to deeply understand why a small structural change could result in a significant change in the stability of noble metal nanoclusters.     

Co(II), Ni(II) and Cu(II) metal complexes with a N8 azamacrocyclic ligand

Hydrated nitrate and perchlorate salts of the transitional metal ions Co²⁺, Ni²⁺ and Cu²⁺ have been used to investigate the coordination capability of the octaaza macrocycle L derived from 2,6-diformylpyridine and diethylenetriamine. The synthesis of the metal complexes was carried out in 1:1 and 2:1 metal:ligand molar ratios, but dinuclear complexes were obtained in all cases due to the size of the 24-membered ligand. The complexes have been characterized by elemental analysis, molar conductivity, mass spectrometry, IR spectroscopy, diffuse reflectance and magnetic measurements. The dinuclear nature of the compounds was confirmed by X-ray diffraction. The crystal structures of [Ni₂L(NO₃)₂](NO₃)₂, [Cu₂L(NO₃)₄] and [Cu₂L(ClO₄)₄], were determined.     

二苯并噻吩及其氧化物与离子液体相互作用的理论研究

采用密度泛函理论方法比较了DBT/DBTO₂和[BMIM]⁺[PF₆]^-/[BMIM]⁺[BF₄]^-的相互作用。对最稳定的[BMIM]⁺[PF₆]^-、[BMIM]⁺[PF₆]^--DBT、[BMIM]⁺[PF₆]^--DBTO₂、[BMIM]⁺[BF₄]^-、[BMIM]⁺[BF₄]^--DBT、[BMIM]⁺[BF₄]^--DBTO₂进行了NBO和AIM分析。结果表明,DBT和[BMIM]⁺[PF₆]^-/[BMIM]⁺[BF₄]^-中的咪唑环彼此相互平行,NBO和AIM分析表明它们之间发生了π-π相互作用。H1'和H9'形成的F…H氢键有利于π-π堆积作用的形成。DBTO₂倾向于趋近C2-H2和甲基基团形成O…H相互作用;DBTO₂优先吸附在[BMIM]⁺[PF₆]^-/[BMIM]⁺[BF₄]^-。在模拟油中,[BMIM]⁺[PF₆]^-和[BMIM]⁺[BF₄]^-离子液体对DBTO₂的萃取能力大于DBT,其原因是可能是DBTO₂具有较大的极性和O…H与F…H的氢键作用。     

Unexpected Chemisorption State of CO2 on the Si(100)-2×1 Surface Predicted by Theory

Li the past decade, the reactivity of carbon containing confounds with single crystal silicon surfaces has received extensive attention from both experimental and theoretical sides owing to its compact relevance to the growth of silicon carbide and diamond films. While considerable interest has been focused on the adsorptions of alkenes, alkanes and some other small organic molecules^[1], very few experiments^[2,3] can be found in the literature regarding the adsorption of CO₂,a greenhouse gas, on Si surfaces. We report herein the results of our recent theoretical study concerning CO₂ adsorption on the reconstructed Si(100)-2×l surface. The methods employed in our calculations are the hybrid density functional B3LYP method and a two-layer ONIOM (CCSD(T):B3LYP) approach^[4].     

Ni掺杂对Ni/MgO体系中电荷分配影响

采用密度泛函理论(DFT)计算方法,研究了载体Ni掺杂对Ni/MgO催化剂的电子结构及其对CH_4/CO_2重整反应的影响。结果显示,随着载体Ni:Mg比的增加,CH_4解离吸附和CH_x氧化过程的反应能垒均会随之升高,CH也更容易产生热解C,从而导致催化剂的活性和稳定性的下降。通过分析重整过程的Hirshfeld电荷分配,发现金属载体之间电子转移的方向会随着载体中Ni含量的上升由载体向Ni金属转移变为由Ni金属向载体转移。当Ni金属富电子时,反应物活化时电子的转移主要发生在表层Ni原子与吸附物种之间,参与氧化的CH_x物种为CH_2;当Ni金属缺电子时,反应物活化时Ni簇的电子结构基本保持稳定,电子主要在载体表层的Ni原子与反应物之间转移,CH是主要参与氧化的CH_x物种。     

八电子Pd4四面体团簇的电子结构稳定性分析

基于理论计算,我们报道了T_d对称性的[Pd₄(μ₃-SbH₃)₄(SbH₃)₄]团簇及一系列类似物的结构与成键。成键分析表明：每个Pd原子都是sp³杂化,其10个价电子与四个配体提供的8个价电子,满足18电子规则。并且,每个Pd原子与四个桥连的SbH₃配体可以形成四个离域的四中心两电子超级σ键或八中心两电子键。一方面,根据超原子网络模型,这个钯团簇可以描述成四个2电子的超原子网络。另一方面,凝胶模型表明,它可以合理化的作为电子组态是1S²1P⁶的8电子超原子。与此同时,d¹⁰…d¹⁰闭壳层相互作用在稳定Pd₄四面体结构中起到了关键性的作用。密度泛函理论计算表明：T_d对称性[Pd₄(μ₃-SbH₃)₄(SbH₃)₄]团簇表现出高度稳定性,具有充满的电子壳层,大的HOMO-LUMO带隙(2.84 eV)以及负的核独立化学位移(NICS)值。此外,基于[Pd₄(μ₃-SbH₃)₄(SbH₃)₄]结构与成键模式,我们设计了一系列稳定的类似物,其有可能被实验合成出来。     

Das perfluortriazinium-kation als oxidationsmittel in der metallorganischen synthese—ein neuer weg zur darstellung von [Cp2MCl2](M = Mo

The oxidation of Cp₂MCl₂ (M= Mo, W) with perfluortriazinium tetrafluoroborate, [(FCN)₃F]⁺[BF₄]⁻, in the presence of a flouride ion acceptor (BF₃ or PF₅) in SO₂ solution yielded the cationic metallocene complexes [Cp₂MCl ₂]²⁺[BF₄]⁻ or [C_p2MCl₂] ²⁺[BF₄]⁻[PF₆]⁻ (M = Mo, W), respectively. In these reactions, for the first time the perfluortriazinium cation has proved to be easy to handle and a useful oxidizer in organometallic chemistry. The oxidizer strength of three fluorotriazinium cations, [(XCN)₃F]⁺ (X = F, Cl, H), has been computed ab initio (HF/6 − 31 + G) and calibrated on literature data which were obtained by local density functional calculations. It was anchored to its F⁺ zero point by an experimental value for KrF⁺. ab]Die Oxidation von Cp²MCl₂ mit (M = MO, W) Perfluortriaziniumtetrafluoroborat, [(FCN)₃F]⁺[BF₄]⁻, in Anwesenheit eines Fluoridionenakzeptors (BF₃ oder PF₅) führte in SO₂-Lösung zur Bildung der kationischen Metallocen-Komplexe [Cp₂MCl₂₊]²⁺[BF₄]₂⁻ bzw. [Cp₂MCl₂]²⁺[BF₄]⁻ [PF₆]⁻ (M = Mo, W). In diesen Reaktionen konnte erstmals gezeigt werden, daß Perfluortriazinium-Kationen einfach zu handhabende und nützliche Oxidationsmittel im Bereich der metallorganischen Synthese darstellen. Das (Mdationsvermögen von drei Fluorotriazinium-Kationen, [(XCN)₃F]⁺(X = F, Cl, H), wurde ab initio berechnet (HF/6 − 31 + G) und mit Hilfe von Literaturdaten, die mittels local density functional-Berechnungen erhalten und am experimentellen Wert von KrF ⁺ bezüglich des F⁺ Nullpunktes verankert wurden, kalibriert.     

The coordinatively unsaturated cluster cations [Pt3{M(CO)3}(μ-Ph2PCH2PPh2)3] (M = Re, Mn)

The coordinatively unsaturated cluster [Pt₃(μ₃-CO)(μ-dppm)₃]²⁺ (1, dppm = Ph₂PCH₂PPh₂) reacts with Na⁺[M(CO)₅]⁻ to give the mixed metal clusters [Pt₃{M(CO)₃}(μ-dppm)₃]⁺ (M = Re, 2; Mn, 3). The new clusters are characterized by spectroscopic methods and, for M = Re, by an X-ray structure determination. The Pt₃Re core in 2 is tetrahedral with particularly short metal-metal distances.     

阴离子功能化大孔树脂用于二氧化硫的多位点高效捕集

提出了一种针对大孔树脂阴离子功能化的新策略并合成了一系列阴离子功能化大孔树脂[IRA-900][An],在20 ℃和101.3 kPa的吸附条件下实现了对SO₂的超高吸附容量(> 10 mmol·g^-1)。和常规唑基阴离子功能化大孔树脂相比,聚咪唑基硼酸阴离子功能化的大孔树脂[IRA-900][B(Im)₄]在低压条件下仍然展现了卓越的SO₂捕集能力。吸附实验发现,[IRA-900][B(Im)₄]在10.13 kPa和20 ℃的低压环境中能够保持10.62 mmol·g^-1的超高SO₂吸附量。通过红外谱学研究以及密度泛函理论(DFT)计算来进行吸附机理探究,发现聚唑基硼酸阴离子[B(Im)₄]具有独特的正四面体构型,从而打破了阴离子上N负位点之间的电子流动和共轭效应。在[IRA-900][B(Im)₄]捕集SO₂过程中,阴离子连续和SO₂分子发生化学相互作用时,吸附焓变无明显下降。因此,一个[B(Im)₄]阴离子能够提供四个有效的作用位点和SO₂发生化学吸附作用,从而在低压条件下,[IRA-900][B(Im)₄]仍然实现了超高的SO₂捕集能力。此外,我们对阴离子功能化大孔树脂[IRA-900][B(Im)₄]在低压条件下对SO₂吸附的循环稳定性做了探究。结果发现,在20 ℃和10.13 kPa的吸附环境中以及70 ℃的脱附条件下,[IRA-900][B(Im)₄]展现了良好的循环稳定性,具有极大的工业应用价值。最后,这种阴离子功能化的策略以及多位点捕集方法对实现烟气环境中SO₂的高效捕集开拓了新的思路。     

1-丁基-3-甲基咪唑硫酸氢盐离子液体与含氮化合物相互作用的理论研究

采用密度泛函理论方法研究了1-丁基-3-甲基咪唑硫酸氢盐离子液体[Bmim]HSO_4与氮化物喹啉和吲哚分子的相互作用,并进行了NBO和AIM分析。[Bmim]HSO_4离子对最稳定结构表明,[HSO_4]~-阴离子中的氧原子与咪唑环中正电性较大的C14-H20之间有较强的氢键作用。在分子水平上,NBO和AIM分析证实了喹啉和吲哚分子与[Bmim]HSO_4的阴离子之间有较强的相互作用,其中,喹啉分子中的氮原子与阴离子[HSO_4]~-中氢原子之间的作用以及吲哚分子中N-H的氢原子与[HSO_4]~-中氧原子之间的作用是该离子液体能够有效脱除氮化物的主要动力。     

Structure and bonding in cluster compounds of gold

Recently a number of high nuclearity gold cluster compounds of the type [Au(AuPR₃)_n]^x+ have been synthesised and structurally characterised using single crystal X-ray crystallographic measurements. The structures and properties of these compounds are contrasted with those of comparable high nuclearity metal carbonyl cluster compounds. In order to account for the structures of [Au(AuPR₃)_n]^x+ in the solid state and in solution it has proved necessary to develop a flexible bonding model which emphasises the topologies of the clusters rather than their detailed geometries. In this fashion the observed stereochemical non-rigidity of these compounds in solution is readily accounted for. In the solid state the structures of the higher nuclearity cluster cations can be derived either from the centred chair [Au(AuPR₃)₆], or the centred crown [Au(AuPR₃)₈] by adding edge or face capping AuPR₃ fragments. The bonding in heterometallic clusters containing the AuPR₃ fragment is also considered.     

The Preparation and Characterization of Several Metal Phosphate Catalysts

Metal phosphates have been widely used as catalysts in many organic reactions for their acid-base and redox properties^[1,2]. Their structure and properties are affected greatly by the preparation method^[2-5]. AlPO₄ is one of the most important metal phosphates. There are many different phases of AlPO₄) that is, amorphous, crystalline and molecular sieve. The usual methods of preparation of AlPO₄ are described elsewhere^[1,3], i.e. gelification of a mixture of an aluminum salt (chloride, nitrate etc.) with orthophosphoric acid (or NaH₂PO₄) in the presence of a base. Ammonia, ethylene oxide, and propylene oxide are used as base mostly.     

矿物质氧化物对燃煤烟气中砷/铅的吸附特性研究

选取典型的矿物质氧化物为吸附剂，在两段式固定床反应器中研究了模拟烟气气氛下吸附剂吸附As₂O₃、PbO的特性，吸附反应的原子态密度、吸附位、吸附能等通过密度泛函理论（DFT）计算获得。结果表明，CaO的砷吸附容量最大，900 ℃吸附砷容量为5.25 mg/g；其次是Fe₂O₃、MgO、Al₂O₃，吸附的砷以As³⁺和As⁵⁺的砷酸盐形式存在，高岭土和飞灰具有较大的PbO吸附容量，最大吸附容量分别为6.69和2.75 mg/g；其次是SiO₂和Al₂O₃，并且50%SiO₂/50%Al₂O₃ 混合吸附剂的铅吸附容量高于单一氧化物，吸附剂表面O原子是As₂O₃的吸附活性位点，吸附剂暴露的不饱和Si和Al原子是PbO的吸附活性位点，此外温度、烟气气氛对吸附容量和吸附产物有显著影响。     

阴离子插层镁铝水滑石结构及相互作用的理论研究

采用密度泛函理论(DFT)计算了MgAl-LDHs层板与无机阴离子(F^-、Cl^-、NO₃^-、CO₃^2-、SO₄^2-)和有机阴离子(水杨酸根离子([HO(C₆H₄)COO]^-)、苯甲酸根离子([(C₆H₅)COO]^-)、对二甲氨基苯甲酸根离子([p-(CH₃)₂N(C₆H₄)COO]^-)、十二烷基磺酸根离子[C₁₂H₂₅SO₃]^-、己烷基磺酸根离子[C₆H₁₃SO₃]^-、丙烷基磺酸根离子[C₃H₇SO₃]^-)间的相互作用,获得稳定超分子几何结构及相互作用能。层板主体与客体间存在较强的超分子作用,包括主客体间静电作用和氢键等。主、客体间相互作用能数值大小顺序为CO₃^2- > SO₄^2- > F^-> Cl^-> NO₃^-;[p-(CH₃)₂N(C₆H₄)COO]^-> [(C₆H₅)COO]^-> [HO(C₆H₄)COO]^-和[C₁₂H₂₅SO₃]^-> [C₆H₁₃SO₃]^- > [C₃H₇SO₃]^-。另外,还采用自然键轨道(NBO)计算和分析了LDHs 层板与阴离子间作用机理,从二阶微扰理论计算得到的稳定化能变化趋势与相互作用能数据基本吻合。     

The synthesis and lyotropic phase behaviour of some aquatetra(cyano)-dodecylaminoferrate(II) complexes

Some alkali and alkaline earth metal salts of the amphiphilic anion [Fe(CN)₄(H₂O)(C₁₂H₂₅NH₂)]^2- have been synthesized by reaction of [Fe(CN)₅NO]^3- with C₁₂H₂₅NH₂. Using optical microscopy, they have been shown to give a hexagonal (H₁) mesophase in water.     

Two New Inorganic-organic Hybrid Compounds Constructed from Different Polymolybdates and Transition Metal-amine Subunits

Two new polyoxometalate(POM)-based hybrid compounds, [Cu(en)][H₄Mo₄O₁₆]_0.5(1)(en=ethylene- diamine) and [Ag(3-C₅H₆N₂)₂][H₂PMo₁₂O₄₀](2)(3-C₅H₆N₂=3-aminopyridine), containing different transition metal-amine subunits were hydrothermally synthesized and characterized by elemental analyses, infrared spectroscopy and single-crystal X^-ray diffraction. For compound 1, each [H₄Mo₄O₁₆]^4-(Mo₄O₁₆) cluster was linked to four neighboring Mo₄O₁₆ clusters through four [Cu(en)]²⁺ subunits to yield a (2,4)-connected 2D layer, which was further extended to a 3D supramolecular network via hydrogen bonding interactions. For compound 2, the adjacent [H₂PMo₁₂O₄₀]^- clusters were bridged by [Ag(3-C₅H₆N₂)₂]⁺ subunits to generate a 1D chain. The electrochemical behaviors and the photocatalytic activities of compounds 1 and 2 were studied in detail.