面向贵金属纳米晶的晶相调控策略（英文）

贵金属纳米晶在催化等领域拥有广泛的应用前景.通过调控尺寸、形貌、表面结构和晶型等基本结构参数,能够进一步提升其性能、推动其更有效的催化应用.随着纳米晶合成技术的不断发展,基于尺寸、形貌和表面结构调控对贵金属纳米晶的性能影响研究已较为系统和深入,当前的研究更加关注对其晶相和晶体结构的改变和调控.因而近期有大量成功的晶相调控研究报道,其中具有更高能晶相结构的纳米晶基于独特的原子排布和电子效应,在催化等领域中表现出更为优异的性质.然而,贵金属纳米晶的原子通常采取最稳定的密堆积排列形式,合成热力学不稳定的高能晶相是一个重大的挑战.本综述详细介绍了贵金属及其合金纳米晶晶相调控的最新研究进展,讨论了贵金属纳米晶不同晶相的结构特征、表征手段,微观驱动力、调控原理、合成策略和催化应用.最后,对贵金属纳米晶晶相调控领域的未来发展提出了展望.具体而言,基于贵金属纳米晶的原子密堆积模式,我们将纳米晶的原子堆积模式分为最紧密堆积的"Barlow堆积型"和非最密堆积的"非Barlow堆积型",并分类详细介绍了其各自的结构特征.其次,我们比较了X射线粉末衍射法、电子衍射法和高分辨透射电镜法在确定晶相结构中的优势和劣势.此外,我们总结了决定贵金属纳米晶原子堆积模式的部分微观驱动力,包括d电子占据、动态稳定性、自旋有序和应变这四种微观驱动力,并从热力学的角度探讨了表面和体相能量对相变的驱动作用,进而进一步介绍了各种晶相转变的机理,包括Bain相变机理、Pitsch相变机理、Kurdjumov-Sachs相变机理、Shockley不全位错滑移机理和重构型有序化机理.基于以上这些决定晶相的微观驱动力,我们总结了各类晶相调控的方法,包括合金诱导相变法、温度诱导晶相调控法、压力诱导晶相调控法、应变诱导晶相调控法、模板诱导晶相调控法和表面吸附诱导晶相调控法.最后,以各类催化反应为例,分别对比了面心立方最密堆积、六方最密堆积、面心四方(体心四方)、体心立方等几种典型晶相的催化性质差异.     

超细磁性钴粉的制备及磁性能

在室温条件下,水溶液中以聚乙烯吡咯烷酮K30(PVP)作为分散剂,水合联氨为还原剂,制备超细磁性钴粉。用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、能谱仪(EDS)和振动样品磁强计(VSM)对其进行表征。结果显示:超细磁性钴粉为蠕虫状微球,粒径约为0.8μm,晶型为面心立方(FCC)和六方密堆积(HCP)结构,饱和磁化强度为25.6 emu·g~(-1),矫顽力为499.2 Oe(1 Oe=79.577 5 A·m~(-1),测试温度为298.15 K)。     

超细磁性钴粉的制备及磁性能

在室温条件下,水溶液中以聚乙烯吡咯烷酮K30(PVP)作为分散剂,水合联氨为还原剂,制备超细磁性钴粉。用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、能谱仪(EDS)和振动样品磁强计(VSM)对其进行表征。结果显示:超细磁性钴粉为蠕虫状微球,粒径约为0.8μm,晶型为面心立方(FCC)和六方密堆积(HCP)结构,饱和磁化强度为25.6 emu·g^-1,矫顽力为499.2 Oe(1 Oe=79.5775 A·m^-1,测试温度为298.15 K)。     

择优取向生长的Gd2O3高K栅介质薄膜

使用射频磁控溅射法在n型Si(001)基片上生长了Gd2O3薄膜。X射线衍射扫描研究和高分辨透射电子显微镜观察表明,薄膜由立方相和单斜相混合构成,且表现出立方(111)晶面和单斜(401)晶面的择优取向生长。XPS分析表明薄膜的元素组成接近化学计量比。电性能测试发现,薄膜拥有合适的介电常数,较小的漏电流密度和较大的击穿场强,厚度为15 nm的薄膜介电常数为23,漏电流密度为3.6×10-5A.cm-2(偏压为 1 V时),击穿场强为3.5 MV.cm-1。     

一种获得高活性和高稳定性甲烷无氧芳构化Mo/HZSM-5催化剂的前处理方法

 利用氢气在较低温度(623 K)下对6%Mo/HZSM-5催化剂进行预处理,考察了经低温还原预处理的催化剂在甲烷无氧芳构化反应中的催化性能. 结果表明,经过预处理的催化剂比未经预处理的催化剂表现出更好的甲烷转化活性和稳定性. 1H MAS NMR和EPR表征结果表明,在623 K氢气气氛中对Mo/HZSM-5催化剂进行预处理不会造成Mo物种在分子筛外表面的进一步分散,也不会导致外表面的Mo物种向孔道内迁移. 但是,低温还原预处理可以有效地促进Mo物种由易还原的六方密堆积结构向难还原的面心立方结构转化,后者在反应中具有更好的活性和稳定性.     

单一稀土镧在不同基底上的电沉积及其性能的研究

研究在低温熔融盐体系中于不同基底上电沉积单一稀土金属镧（La）。经X-射线能谱仪测定,在镍片基底上沉积的La的质量分数为100％,铜片基底上沉积的La质量分数为72．84％;在镍铁合金灯丝上沉积得到La-Ni合金薄膜,其中La的质量分数为50．02％,Ni的质量分数为2．48％。经扫描电子显微镜观察,所得的沉积膜为均匀、光滑、致密的黑色沉积薄膜。经X-射线衍射仪分析,镧在不同基底上沉积所得的沉积膜为不同晶型,以镍片为基底得到的单质镧为α-六方晶型;以铜片为基底得到的单质镧为面心立方晶;均与基底晶型相匹配。在镍铁合金灯丝上电沉积所得的La-Ni合金薄膜致密均匀,在无水乙醇中久浸而不脱落,并呈现强磁性。     

TiO2负载单金属镍（铂）催化剂在甲烷解离反应中抗积碳能力的理论研究

研究碳原子在TiO2(101)负载镍或铂原子上的吸附行为对于阐明积碳问题提供了一个热力学线索.广义梯度近似密度泛函理论的PBE计算结果表明,镍在TiO2表面最稳定构型的吸附能为347.16 kJ/mol,铂对应的最稳定构型的吸附能为315.9 kJ/mol,而且2种金属的最稳定构型均处于TiO2表面2个O2c原子之间的桥位.吸附金属原子后,TiO2的态密度图中各电子峰向低能量方向移动,体系趋于稳定.从态密度图可知,碳的p轨道与金属原子的d轨道发生叠加,说明碳原子与金属原子成键,从而使吸附后Ni或Pt与O原子之间的相互作用减弱.碳原子吸附在Ni/TiO2(101)和Pt/TiO2(101)表面的最佳吸附结构的吸附能分别为474.19和570.08 kJ/mol,说明TiO2负载铂催化剂在甲烷重整反应中抗积碳能力较强.     

晶相调控对金属纳米粒子催化性能的影响（英文）

尺寸在1–10 nm的金属纳米催化剂广泛地应用于石油化工,精细化学品合成,能源与环境保护等领域.大量研究表明,金属纳米粒子的催化性能与其微观结构,即尺寸、形貌和晶相等密切相关.近年来,对金属纳米粒子的尺寸和形貌效应已经有了较为系统深入的研究,但对晶相效应的研究则较少涉及.这主要是由于介稳晶相的金属纳米粒子在合成过程中或反应条件下极易转化为热力学稳定的晶相结构.根据金属原子密堆积形式,金属纳米粒子的晶相结构主要有立方面心(fcc)、立方体心(bcc)和六方密堆积(hcp)三种晶相;而金属合金由于d带电子存在着多种杂化方式,因而其晶相结构呈现出多样性且与单一金属有很大的不同.金属和合金纳米粒子晶相结构的调控,不仅会改变金属原子的配位环境,调控了其电子分布状态,还可影响反应物和产物的吸附、活化和脱附,进而调变催化性能.首先,我们简要总结了液相合成和固相转变调控金属纳米粒子晶相的原理和方法.纳米粒子的液相合成一般包括前驱体还原成核和晶核生长两个阶段,通过对液相合成条件的优化,尤其是表面活性剂的选择,可有效调控合成过程中的热力学和动力学因素,从而实现金属晶相的可控合成.固相转变则主要是对具有一定晶相结构的纳米粒子于一定气氛和温度条件下进行加热处理,利用金属粒子与活性气体之间(H2,CO等)的化学作用来实现晶相转变.利用上述方法,可以合成出fcc-Co、fcc-Ru、L10-Au Cu等热力学介稳的金属或合金纳米粒子.在此基础之上,我们分别以Co纳米粒子(fcc和hcp晶相)催化FT合成,Fe模型催化剂(fcc和bcc晶相)活化N2和CO,Ru纳米粒子(fcc和hcp晶相)催化CO氧化和氨硼烷水解制氢,Pd纳米粒子(Pd Hx物种)催化加氢等为例分析了晶相对金属纳米粒子催化性能的影响;在合金催化剂方面,以Pt3Co(无序的fcc和有序的L12),Au Pd Co(P3–m、Fm3–m和R3–m混合晶相)和Fe Pt纳米粒子(fcc和fct相)催化O2电化学还原、Pt Rh Sn(碲铂矿晶相和fcc晶相)和Zr Pt3纳米粒子(hcp和fcc晶相)催化乙醇电氧化、Ag3In合金(无序的Fm3–m相和有序的Pm3–m晶相)催化对硝基苯酚加氢、Pd Ru纳米粒子(fcc和hcp混合晶相)催化CO氧化等为例分析了合金催化剂的晶相对催化性能的影响.上述研究进展表明,金属纳米粒子的晶相也是影响制备剂高效金属催化剂的主要因素.最后,我们结合纳米催化的发展现状,提出了金属纳米粒子的晶相调控在纳米催化和纳米材料领域可能的发展态势.第一,通过对金属纳米粒子溶液相合成机理的深入研究,有助于发展出尺寸、形貌和晶相同时可控的新合成方法.第二,金属纳米粒子在晶相转化过程中往往伴随着烧结及组分的偏析等难题.利用氧化物包覆的核壳型或蛋壳型纳米结构以及碳纳米管的空间限域效应,或许有助于解决上述难题.第三,具有亚稳晶相结构的金属纳米粒子在反应条件下极易转变为热力学稳定的结构,因此,利用原位、动态、实时的表征技术对催化剂在真实工作状态下的微观结构进行细致的分析是阐明晶相效应的前提.     

密堆积六方结构Ni纳米颗粒的制备与表征

采用溶胶-凝胶方法制备前驱体, 将前驱体进行热处理制得密堆积六方结构(hcp)的Ni纳米粉末. 利用TG-DTA, XRD和TEM等测试手段对材料的合成条件、结构、形貌以及结构演变过程进行了分析. 结果表明, 于300 ℃进行热处理所合成的样品为球形的具有密堆六方结构的Ni纳米颗粒, 晶胞参数a=0.2652 nm, c=0.4334 nm, 平均晶粒尺寸约为12 nm. 随着热处理温度的升高, 样品结构发生由密堆六方结构向面心立方结构的转变.     

Fe2C晶体及低指数晶面的结构与稳定性研究

采用自旋极化的密度泛函理论(DFT)对正交与六方的Fe₂C晶体体相与表面性质进行了研究,计算了晶胞的聚合能、磁矩以及低指数晶面的表面能。研究结果表明,两种晶型Fe₂C 的磁性质相似,但正交堆积的Fe₂C比六方堆积的Fe₂C更稳定。正交晶系Fe₂C低指数晶面的稳定性以 (011) > (110) > (100) > (101) > (001) 顺序降低。对一系列碳化程度不同的碳化铁最稳定表面(Fe₂C(011)、Fe₃C(001)和Fe₄C(100))表面能的比较显示,碳化铁表面的相对稳定性与碳化度非线性相关。另外,与面心立方(BCC)铁最稳定表面(110)相比,Fe₂C、Fe₃C及Fe₄C晶体最稳定表面具有较低的表面能,表明铁表面碳化在热力学上是有利的。     

Generation and detection of levuglandins and isolevuglandins in vitro and in vivo

Levuglandins (LGs) and isolevuglandins (isoLGs), formed by rearrangement of endoperoxide intermediates generated through the cyclooxygenase and free radical induced oxidation of polyunsaturated fatty acids (PUFAs), are extraordinarily reactive, forming covalent adducts incorporating protein lysyl ε-amino groups. Because they accumulate, these adducts provide a dosimeter of oxidative injury. This review provides an updated and comprehensive overview of the generation of LG/isoLG in vitro and in vivo and the detection methods for the adducts of LG/isoLG and biological molecules in vivo.     

Enthalpies of solution of purine and adenine in water and in dimethylsulfoxide

Journal of Solution Chemistry - Enthalpies of solution of purine and adenine in water and in demethylsulfoxide were measured calorimetrically in the temperature range 25–40°C. ΔH s...     

Coassembly of Nanorods and Nanospheres in Suspensions and in Stratified Films

The entropically driven coassembly of nanorods (cellulose nanocrystals, CNCs) and nanospheres (dye‐labeled spherical latex nanoparticles, NPs) was studied in aqueous suspensions and in solid films. In mixed CNC‐latex suspensions, phase separation into an isotropic latex‐NP‐rich and a chiral nematic CNC‐rich phase took place; the latter contained a significant amount of latex NPs. Drying the mixed suspension resulted in CNC‐latex films with planar disordered layers of latex NPs, which alternated with chiral nematic CNC‐rich regions. In addition, fluorescent latex NPs were embedded in the chiral nematic domains. The stratified morphology of the films, together with a random distribution of latex NPs in the anisotropic phase, led to the films having close‐to‐uniform fluorescence, birefringence, and circular dichroism properties.     

Determination of diazepam and nordazepam in milk and plasma in the presence of oxazepam and temazepam

For studies on the excretion of drugs into milk a sensitive high-performance liquid chromatographic assay was developed to quantitate diazepam and nordazepam in the milk and plasma of humans and rabbits in the presence of their major metabolites, oxazepam and temazepam. Flurazepam was used as an internal standard. The assay involves extractions with diethyl ether and an additional acid clean-up step. Chromatographic separation was achieved by a LiChrospher 60 RP-select B (5 microns) column and KH2PO4- acetonitrile (69:31, v/v) adjusted to pH 2.80 as a mobile phase. The same extraction and chromatographic conditions were suited to both types of samples, milk and plasma. The limits of determination using ultraviolet detection at 241 nm was for diazepam 20 ng/ml and for nordazepam 15 ng/ml. The absolute recoveries of diazepam, nordazepam and flurazepam in human milk were 84, 86 and 92% and in human plasma 97, 89 and 94%, respectively. The within- and between-day accuracy and precision for diazepam and nordazepam in milk and plasma at all concentrations tested (20-1500 ng/ml) were better than 8%. The high fat content which occurs in rabbit milk presented no limitation for the extraction of lipophilic diazepam: the method was successfully used to monitor milk and plasma concentrations of diazepam and nordazepam in lactating New Zealand White rabbits during 26-h infusions of diazepam (1.4 mg/h).     

Comparison and correlation of in vitro, in vivo and in silico evaluations of alpha, beta and gamma cyclodextrin complexes of curcumin

In the present study investigated the effect of curcumin (CUR) alpha (α), beta (β) and gamma (γ) cyclodextrin (CD) complexes on its solubility and bioavailability. CUR the active principle of turmeric is a natural antioxidant agent with potent anti-inflammatory activity along with chemotherapeutic and chemopreventive properties. Poor solubility and poor oral bioavailability are the main reasons which preclude CUR use in therapy. Extent of complexation was β-CD complex (82 %) > γ-CD (71 %) > α-CD (65 %). Pulverization method resulted in significant enhancement of CUR (0.002 mg/ml) solubility with CUR α-CD complex (0.364 mg/ml) > CUR β-CD complex (0.186 mg/ml) > CUR γ-CD complex (0.068 mg/ml). Gibbs-free energy and in silico molecular docking studies favour formation of α-CD complex > β-CD complex > γ-CD complex. With reference to CUR, relative bioavailability of CUR α-CD, CUR β-CD and CUR γ-CD complexes were 460, 365 and 99 % respectively. CUR–CD complexes exhibited increased bioavailability with an increase in t_½, tmax, Cmax, AUC, Ka, and MRT; and a decrease in Ke, clearance and Vd values. AUC increase was CUR α-CD complex > CUR β-CD complex > CUR γ-CD complex. Significant difference (p < 0.05) was observed between CUR α-CD complex and CUR γ-CD complex by one-way ANOVA and Dunnett’s post hoc test for multiple comparison analysis. Correlation observed between in vitro, in vivo and in silico methods indicates potential of in silico and in vitro methods in CD selection.     

Homo- and hetero-complexes of exchangeable apolipoproteins in solution and in lipid-bound form

The self-association state of human plasma apolipoprotein E (apoE) in solution and in complexes with dimyristoylphosphatidylcholine (DMPC) varying in stoichiometry was studied in sub-micromolar concentration range by gel filtration, fluorescence anisotropy, fluorescence quenching and energy transfer measurements with apolipoprotein labeled with lysine-specific fluorescent dyes. Together, these results confirm the equilibrium scheme for various apoE structures in solution: oligomer (in aged preparations) <==> 'closed' tetramer <==> 'open' tetramer ('molten globule' state) <==> native or partially denatured monomer <==> fully denatured monomer. Within DMPC:apoE discoidal complex (125:1) the apolipoprotein association state seems to be intermediate between that in solution and in larger vesicular complex (1000:1); for both complexes, the degree of exposure of fluorescein chromophores into water phase decreased. Hetero-associates of apoA-I and apoC-III-1 in solution and in the complexes with DMPC appear to behave similarly to apoE. When extrapolated to native HDL particles, 'molten globule' state seems to be a structure responsible for the interaction of exchangeable apolipoproteins with phospholipid. For a first time, the location of various apolipoprotein molecules on disc periphery was confirmed. The lysine residue(s) seems to locate closely to reacting residue(s) within apolipoprotein molecules in associates, however, with different package constraints for discoidal versus vesicular complexes with phospholipid.     

Electrochemical Fluorination of Benzamide and Acetanilide in Anhydrous HF and in Acetonitrile

Electrochemical fluorination of benzamide in anhydrous hydrogen fluoride does not involve the amide group but occurs exclusively at the aromatic ring, yielding isomeric fluoro- and difluorobenzamides and 3,3,6,6-tetrafluoro-1,4-cyclohexadienecarboxamide. Electrochemical fluorination of benzamide in acetonitrile as solvent gives the same products, as well as benzonitrile and its fluorinated derivatives and products of hydrolysis and fluorination of acetonitrile. Electrochemical fluorination of acetanilide in anhydrous HF leads to complete tarring of the reaction mixture, while its fluorination in acetonitrile results in selective formation of m-fluoroacetanilide.