纳米多孔离子液体复合材料的合成及其在酯化反应中的应用

以溴化1-丁基-3-甲基咪唑离子液体和磷钨杂多酸(H₃PW₁₂O₄₀)为原料制备了杂多酸功能化离子液体复合材料催化剂(bmim-PW12),并用于催化乙酸与正丁醇酯化合成乙酸正丁酯的反应,考察了bmim-PW12不同热处理温度对其结构以及催化酯化反应活性的影响．结果表明,bmim-PW12在500 oC热处理时杂多酸 阴离子仍保持Keggin结构,但有机阳离子在350 oC以上发生了部分分解．bmim-PW12在400 oC热处理具有纳米多孔结构和较大的酸强度,且在丁醇与乙酸酯化合成乙酸丁酯反应中,具有较高的催化活性和较好的重复使用性能.     

飞秒强激光场中异核团簇的爆炸动力学

 利用Bathe过势垒模型,对飞秒强激光场中异核分子团簇((CH₄)_n,(CD₄)_n,(D₂O)n）的爆炸动力学过程进行了理论研究。结果表明:异核团簇爆炸后产生的离子能量与团簇初始半径的平方呈线性关系,爆炸机理为典型的库仑爆炸。研究发现,异核分子团簇发生库仑爆炸后的氘离子能量高于飞秒强激光和单核的(D)>)_n团簇相互作用后产生的氘离子能量,显示异核团簇中高Z元素电离后产生的高价离子对低Z元素离子有很强的加速作用。     

离子液体掺杂聚苯胺/普鲁士蓝复合膜的高灵敏葡萄糖传感器

利用经典的循环伏安法制备出普鲁士蓝/离子液体-聚苯胺/多壁碳纳米管(PB/IL-PANI/MWNTs)复合膜．离子液体为润滑剂,能够显著增强聚苯胺链的电子去极化度并减少其链的结构缺陷．离子液 体的引入使该复合膜在H₂O₂检测中呈现出更优异的特性,线性范围为2.5～5.0 mmol/L,灵敏度为736.8 μA·(mmol/L)^-1·cm^-2,复合膜比纯PB 膜在中性溶液中稳定性好;传感器在12.5～1.75 mmol/L对葡萄糖也呈现很好的线性关系,检测限为1.1 μmol/L(信噪比为3),灵敏度为94.79 μA·(mmol/L)^-1·cm^-2．该传感器还用于检测未经过任何预处理的人血清中的血糖含量,结果和医院提供的值吻合较好．     

高能带电粒子库仑对数量子力学效应研究

 先进燃料D-3He聚变产生的高能带电粒子在本底等离子体中慢化时间的准确性直接影响到能量平衡和高能离子压强的计算结果。结果表明：高能带电粒子与本底等离子体的离子相互作用的库仑对数量子力学效应明显。应使用高能带电粒子库仑对数力学效应来研究聚变产生的高能端部粒子慢化过程；能量大于等于25Z²_iZ²_iA_i keV的高能粒子与本底等离子体中离子的相互作用库仑对数最好也使用量子截断。     

Ti+(CO2)2Ar和Ti+(CO2)n(n=3-7)络合物离子的红外光解离光谱 (cited: 1)

利用脉冲激光溅射-超声分子束载带方法制备了气相Ti⁺(CO₂)₂Ar和Ti⁺(CO₂)_n(n=3-7)络合物离子．采用红外光解离光谱研究了这些选定的质量离子的振动光谱． 对于每一种络合物离子, 在CO伸缩振动频率范围都观察到了振动峰,表明这些离子具有插入的OTi⁺CO(CO₂)_n-1结构． 对于n≦5的OTi⁺CO(CO₂)_n-1离子,其CO振动和CO₂的反对称伸缩振动频率都比自由的CO和CO₂的频率要高,表明CO和CO₂配体与中心金属离子之间主要是静电相互作用．实验结果还表明TiO⁺可以直接络合五个配体(1个CO和4个CO₂分子)．对于n=2络合物体系,除了插入的OTi⁺CO(CO₂)结构以外,还观察到了具有弯曲结构的OCO-Ti⁺-OCO异构体的存在     

2-溴丁烷在约265 nm光解离的离子速度成像

用离子速度成像结合共振增强多光子电离技术研究了2-溴丁烷分子在264.77和264.86 nm(约265 nm)的光解离动力学．从获得的离子速度图像确定了光解产物Br和Br*碎片的速度分布和角度分布．其速度分布可以由一个窄的高斯分布拟合得到,它对应于沿着C-Br伸缩模式的直接解离．2-溴丁烷在约265nm的光解离中¹Q₁←³Q₀的非绝热跃迁在Br离子碎片的产生中起到非常重要的作用, 确定Br(²P_3/2)的相对量子产额为0.621．通过约265和约234 nm处2-溴丁烷光解的比较发现,各向异性参数和相对量子产率随着波长增加而下降,³Q₀和¹Q₁态势能面交叉几率随着波长增加而降低     

SrMn0.5Fe0.5O3的自旋玻璃态和过渡金属离子价态的研究

采用固相反应法制备了SrMn_0.5Fe_0.5O₃陶瓷样品,并对样品的晶体结构,磁性和离子价态进行了系统的表征与分析. X射线衍射谱的Rietveld拟合表明样品属于理想的立方钙钛矿型结构,Mn离子和Fe离子随机占据B位的O八面体中心. X射线光电子能谱表明Mn离子为+3和+4的混合原子价态,Fe离子为+3价. 样品在大于230K的高温区域呈现Curie顺磁特性,在小于230 K的低温区域样品表现出自旋玻璃态行为,这种特性源于Mn离子和Fe离子之间的交换作用及自身价态和分布的不均匀性. 由于Fe³⁺离子占据O八面体的中心,对顺磁区的Mssbauer谱测量表现为四级分裂.     

不同晶相结构和形貌TiO2负载Ru催化剂的CO选择甲烷化

用水热法得到的钛酸纳米纤维前体,通过不同后处理方法合成了多种纳米结构的TiO₂．采用N₂等温吸附和BET比表面、X射线衍射、透射电镜和能量分散X射线分析表征了TiO₂及负载Ru催化剂的微结构,包括比表面、晶相结构和形貌以及Ru纳米颗粒尺寸分布等．对负载Ru催化剂在富氢条件下CO选择甲烷化反应活性测试表明：金红石相TiO₂和TiO₂-B为载体负载的Ru催化剂比锐钛矿相TiO₂负载的Ru催化剂表现出更高的反应性能．其活性区别说明了不同晶相结构和形貌TiO₂载体与Ru纳米颗粒的相互作用存在差异．     

磷酸钾缓冲溶液与模型细胞膜相互作用的和频光谱

利用和频光谱技术详细研究了磷酸钾缓冲溶液与带负电荷的生物仿生膜(d₅₄-DMPG磷脂双层膜)相互作用的实时过程．通过监控CD₂、CD₃、磷脂分子头部的磷酸根以及羰基官能团的光谱信号随加入磷酸钾缓冲溶液的实时变化,获得了磷脂双层膜分子结构的动力学变化．结果表明K⁺能够结合到细胞膜上,并且很快地引起了CD₂、CD₃、磷脂头部磷酸根以及羰基官能团信号的变化．根据各官能团的和频信号响应,磷酸钾缓冲溶液很可能是通过在双层膜中形成环形气孔来与磷脂双层膜发生作用．该结果可以很好地解释磷酸钾缓冲溶液环境下的离子协助蛋白质的跨膜过程．     

碱土氟化物中离子间相互作用势经验参数的确定

描述离子间非Coulomb短程互作用势的函数形式确定后，即可据此讨论离子晶体的一系列物理性质，势函数中出现的参数通过与实验数据的拟合而确定．基于电子壳模型对CaF₂，SrF₂，BaF₂离子晶体的讨论中，强调电子壳电量应一律取负值的基本前提，以经验参数化方法拟合势参数时注意引用近期实验数据．将F离子电量调整为0.97e之后，重新获得的模型参数集与上述碱土氟化物晶格形成能、弹性常数、长光学横波频率、Raman频率，以及极化率实验数据，有较满意的对应关系．     

Prediction of binding bond energy between phosphorous-based ionic liquids and CO2. Assessment of the CO2–anion interactions

The absorption of carbon dioxide (CO₂) in phosphorous-based ionic liquids was studied theoretically by the molecular modeling ab initio density functional theory (dispersion-corrected B3LYP) and second-order M?ller-Plesset perturbation methods. Several types of phosphate- and phosphite-based anions were employed and the calculation results were compared with recent published papers. The interaction energy between CO₂ and anion, following the result of Bhargava and Balasubramanian, was calculated in order to have a better understanding on the effect of different functional groups on the interaction between CO₂ and anion. The computational results indicated that the molar volume of the anion molecules played an important role on the absorption mechanism of CO₂ due to the CO₂-philicity of carbonyl and alkyl groups.     

Prediction carbon dioxide solubility in ionic liquids based on deep learning

Ionic liquids have a great potential in capture and separation of carbon dioxide (CO₂), and the solubility of CO₂ in ionic liquids is one of key data for engineering applications. In this paper, the critical properties of ionic liquids are combined with deep learning models (CP-DNN, CP-CNN, CP-RNN) to establish theoretical prediction models of CO₂ solubility in ionic liquids. The predictive performance of these framworks is able to meet or exceed the predicted effects of the method based on thermodynamic models (PR,SRK) and machine learning method (XGBoost). For CP-RNN, the coefficient of determination (R²) between experimental and predicted values is 0.988, CP-CNN is 0.999, and CP-DNN is 0.984. This research can avoid complex computational characterisation, it is to provide a theoretical method to further enrich and improve the data information analysis of the solubility of CO₂ in ionic liquids.     

The electrochemical reduction of CO2 on a copper electrode in 1‐n‐butyl‐3‐methyl imidazolium tetrafluoroborate (BMI.BF4) monitored by surface‐enhanced Raman scattering (SERS)

The electrochemical conversion of CO₂ into value‐added products using room temperature ionic liquids as solvent/electrolyte has been proposed as an alternative to minimize the environmental effects of CO₂ emissions. A key issue in the design of electrochemical systems for the reduction of CO₂ is the in situ identification of intermediate surface species as well as reaction products. Copper electrodes, besides being used as cathodes in the electrochemical reduction of CO₂, present surface‐enhanced Raman scattering (SERS) when properly activated. In this sense, the electrochemical reduction of CO₂ over a copper electrode in the room temperature ionic liquids 1‐n‐butyl‐3‐methyl imidazolium tetrafluoroborate (BMI.BF₄) was investigated by cyclic voltammetry and by in situ SERS. The cyclic voltammetries have shown that the presence of CO₂ on the BMI.BF₄ anticipates the reduction of BMI⁺ to the corresponding carbene. Fourier‐transform‐SERS spectra excited at 1064 nm and SERS spectra excited at 632.8 nm have shown vibrational signals from adsorbed CO. These SERS results indicated that CO adsorbs on the copper surface at two different surface sites. The observation of a 2275 cm⁻¹ vibration in the SERS spectra also confirmed the presence of chemically adsorbed CO₂. Other products of CO₂ reduction in BMI.BF₄, besides CO, were identified, including BMI carbene and the BMI‐CO₂ adduct. The SERS results also suggest that the presence of a thin film of Cu₂O on the copper surface anticipates the reduction of CO₂ to CO, an important component of syngas. Copyright © 2016 John Wiley & Sons, Ltd.     

1,3‐Bis(2′‐hydroxyethyl)imidazolium ionic liquids: correlating structure and properties with anion hydrogen bonding ability

A series of 1,3‐bis(2′‐hydroxyethyl)imidazolium ionic liquids is reported where ¹H NMR chemical shift values and thermal stabilities (T_d), as determined by thermogravimetric analysis, are correlated with the hydrogen bonding capability of various anions ([Cl^?], [Br^?], [CF₃CO₂^?], [NO₂^?], [MsO^?], [NO₃^?], [TfO^?], [BF₄^?], [NTf₂^?], and [PF₆^?]). Use of anions with the strongest hydrogen bonding capability, such as chloride [Cl^?], bromide [Br^?], and trifluoroacetate [CF₃CO₂^?], led to the furthest observed downfield chemical shift values in DMSO‐d₆ and the poorest thermal stabilities ([CF₃CO₂^?] < 200 °C). Thermal stabilities in excess of 350 °C and upfield chemical shift values were observed for ionic liquids, which employed the weakly coordinating triflate [OTf^?], tetrafluoroborate [BF₄^?], or bis(trifluoromethylsulfonyl)imide [NTf₂^?] anion. Optimized structures of selected ionic liquids, as determined by density functional theory calculations at the B3LYP/6‐31G + (d,p) level, indicated that the anion preferred to be located above the imidazolium ring and in close proximity to the hydroxyl groups. Calculated dissociation energies (ΔE) and a comparison of key bonding distances (C2―H, (C2)H···X, O―H, and (O)H···X) also confirmed this structural preference. Copyright © 2013 John Wiley & Sons, Ltd.     

Ultrasonic cavitation in CO2-expanded N,N-dimethylformamide (DMF)

Due to the tunability in mass transfer, solvation and solubility, gas-expanded liquids show advantages over traditional organic solvents in many characteristics. Ultrasonication is a commonly used method to promote heat and mass transfer. The introduction of ultrasonic technology into the gas-expanded liquid system can promote the polymerization of polymer monomers, enhance extraction efficiency, and control the growth size of nanocrystals, etc. Although acoustic cavitation has been extensively explored in aqueous solutions, there are still few studies on cavitation in organic liquids, especially in gas-expanded liquid systems. In this article, the development of cavitation bubble cloud structure in CO₂-expanded N, N-dimethylformamide (DMF) was observed by a high-speed camera, and the cavitation intensity was recorded using a spherical hydrophone. It was found that the magnitude of the transient cavitation energy was not only related to input power, but also closely related to CO₂ content. The combination of ultrasound (causing a rapid alternation of gas solubility) and gas-expanded liquid system (causing a decrease in viscosity and surface tension of liquids) is expected to provide a perfect platform for high-speed mass transfer.     

ESR studies on the pressure and temperature dependence of electron self-exchange kinetics between tetrathiafulvalene (TTF) and its radical cation in ionic liquids and organic solvents

The question whether chemical reactions and diffusion processes in ionic liquids are comparable with those taking place in classical organic liquids is a current issue in the literature. Pressure- and temperature-dependent investigations on simple electron self-exchange reactions between the two partners of a redox couple are good tools to get a better understanding of how the solvent influences such reactions. The electron self-exchange reaction between tetrathiafulvalene (TTF) and its radical cation has been investigated in two ionic liquids and two organic solvents using electron spin resonance (ESR) line broadening experiments at variable temperature and pressure. Rate constants are reported for the ionic liquids 1-ethyl-3methylimidazolium bis(trifluoromethylsulfonyl)imide ([emim⁺][Tf₂N^?]) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim⁺][Tf₂N^?]) within a temperature range of 298 K ≤ T ≤ 368 K and a pressure range of 0.1 MPa ≤ p ≤ 100 MPa. The self-exchange reaction of the redox couple [TTF/TTF^?+] has been found to be diffusion-controlled in the used ionic liquids over the entire temperature range. The observed rate constants in ionic liquids at higher pressures are larger than those predicted by common diffusion, and suggest that the electron transfer takes place within a solvent cage. Also, the self-exchange reaction of the [TTF/TTF^?+] redox couple in classical solvents (dimethylphthalate (DMP) and acetonitrile) was investigated and compared to the results with those obtained in ionic liquids. The high viscosity of the ionic liquids makes it difficult to extract the electron transfer rate constants reliably, making interpretation within the framework of the Marcus Theory impossible.     

Ionic liquids based on the bis(trifluoromethylsulfonyl)imide anion for high‐pressure Raman spectroscopy measurements

Assembling a diamond anvil cell for high‐pressure measurements involves placing in a gasket hole the sample of interest, a pressure transmitting fluid, and a material for pressure calibration. In this communication, we propose the use of ionic liquids containing the bis(trifluoromethylsulfonyl)imide anion ([Tf₂N]^‐), [(CF₃SO₂)₂ N]^‐, as a simultaneous pressure transmitting and calibrant material for high‐pressure Raman spectroscopy measurements of solid samples that are not soluble in ionic liquids. The position of the characteristic Raman band of the [Tf₂N]^‐ anion at 740 cm⁻¹ exhibits linear frequency shift for pressures up to 2.5 GPa. High‐pressure Raman spectra of different ionic liquids containing the same anion indicate that the actual magnitude of the pressure‐induced frequency shift of the [Tf₂N]^‐ normal mode depends on the counterion, the typical shift being 4.2 cm⁻¹/GPa. Ionic liquids based on the [Tf₂N]^‐ anion are also good pressure transmitting mediums because hydrostatic condition is kept at high pressure, and no crystallization is observed up to 4.0 GPa. Copyright © 2012 John Wiley & Sons, Ltd.     

Mixed ion effects in Na/Ag-NaZr2(PO4)3

The ionic conductivity against the ionic ratio showed a shallow minimum in Na/Ag-NaZr₂(PO₄)₃ with a three-dimensional diffusion path. The ionic conductivity of the mixed ion system Na/Ag was calculated by means of the path probability method (PPM) using a two-dimensional honeycomb lattice model, resulting from the weak interaction between two different ions.²³Na MAS NMR spectra showed the second-order quadrupole interaction with the electric field gradient. It is concluded that the mixture of two ions in NaZr₂(PO₄)₃ with a three-dimensional diffusion path led to the conductivity minimum due to the ordered distribution of Ag and Na ions. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Study of valence states of the CO2 molecule by (e, 2e) momentum spectroscopy

The (e, 2e) technique has been used to measure the binding energy spectrum and the momentum distribution of the electrons in the CO₂ molecule outer orbitals. The innermost valence states 2σ_u and 3σ_g have been localized 2 eV away from each other and evidence of configuration interaction involving 3σ_g has been found. The electron momentum distributions for the various orbitals show poor agreement with the square of the Hartree-Fock wave function Fourier transform.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.