CuZnAl水滑石衍生催化剂上甲醇水蒸气重整制氢Ⅰ. 催化剂焙烧温度的影响

 以类层柱CuZnAl水滑石为前体,经不同温度焙烧制备了一系列甲醇水蒸气重整制氢催化剂. 在250 ℃、 水/甲醇比1.3和重时空速2.5 h-1下的反应结果表明, 600 ℃焙烧的催化剂具有优异的活性和稳定性,而≤500 ℃和≥700 ℃焙烧后的催化剂活性较差. 热重、 X射线衍射、 傅里叶变换红外光谱和程序升温还原分析结果表明, 600 ℃焙烧时水滑石分解较为完全,析出纳米CuO粒子的同时伴生CuAl2O4尖晶石相,进而在反应过程中对金属Cu纳米粒子和ZnO起到良好的隔离和稳定作用. 焙烧温度≥700 ℃时CuO纳米粒子发生二次团聚,同时CuAl2O4尖晶石相大量生成,造成催化活性位减少,活性较低; 而焙烧温度≤500 ℃时水滑石分解不完全,生成 (Cu,Zn)AlxOy(CO3)z复合物且无尖晶石相伴生,造成反应中金属Cu纳米粒子和ZnO聚集,导致催化剂活性较低.     

含硫液体烃燃料水蒸气重整制氢I．Pt／Ce0．8Gd0．2O1．9催化剂的制备、表征和抗硫性能

以柠檬酸溶胶-凝胶法合成的具有萤石结构的Ce0.8Gd0.2O1.9（CGO）复合氧化物为载体，用初湿浸润法制备了负载型Pt催化剂．纯异辛烷的重整反应结果显示，600和800℃焙烧的催化剂达到了热力学平衡转化，1000℃焙烧会导致Pt的聚集和氧化物的严重烧结，因而催化剂活性较差．抗硫测试表明，800℃焙烧的催化剂抗硫性能最好，在300μg／g硫存在下，100h内异辛烷均接近完全转化；在500μg／g硫存在下催化剂仍表现出良好抗硫性能．程序升温还原和X射线分析结果显示．800℃焙烧时Pt与CGO载体间的相互作用最强，同时催化剂具有良好的热稳定性，这是催化剂具有抗硫性能并且抗硫作用持久的根本原因．反应条件下噻吩硫完全转化成H2S，硫的转化可能是通过氧化-还原机理进行的．     

Influence of demulsifiers of different structures on interfacial dilational properties of an oil-water interface containing surface-active fractions from crude oil

The influences of two commercial demulsifiers that have a straight chain and branch chain, respectively, on the dilational viscoelasticity of an oil-water interfacial film containing surface-active fractions from crude oil were investigated. The branch-chain demulsifier AE-121 could efficiently substitute surface-active fractions of different average molecular weights from the oil-water interface, while straight-chain SP-169 could only efficiently substitute those of large average molecular weight. It was apt to form a mix-adsorption layer with surface-active fractions of small average molecular weight. The results showed that the molecular size (or represented by average molecular weights) of the surface-active fractions was an important factor influencing the reciprocity of demulsifiers and surface-active fractions at the oil-water interface. This effect could be well explained by the difference between sizes of surface-active fraction molecules and vacancies between demulsifier molecules at the interface. The results of SDBS also proved this explanation.     

Amides and Heparin‐Like Polymer Co‐Functionalized Graphene Oxide Based Core @ Polyethersulfone Based Shell Beads for Bilirubin Adsorption

Excessive bilirubin in the body of patient with liver dysfunction or metabolic obstruction may cause jaundice with irreversible brain damage, and new type of adsorbent for bilirubin is under frequent investigation. Herein, graphene oxide based core @ polyethersulfone‐based shell beads are fabricated by phase inversion method, amides and heparin‐like polymer are introduced to functionalize the core‐shell beads. The beads are successfully prepared with obvious core‐shell structure, adequate thermostability and porous shell. Clotting times and protein adsorption are investigated to inspect the hemocompatibility property of the beads. The adsorption of bilirubin is systematically investigated by evaluating the effects of contacting time, initial concentration and temperature on the adsorption, which exhibits improved bilirubin adsorption amount for the beads with amides contained cores or/and shells. It is worth believing that the amides and heparin‐like polymer co‐functionalized core‐shell beads may be utilized in the field of hemoperfusion for bilirubin adsorption.     

Variable electron-phonon coupling in isolated metallic carbon nanotubes observed by Raman scattering

We report the existence of broad and weakly asymmetric features in the high-energy (G) Raman modes of freely suspended metallic carbon nanotubes of defined chiral index. A significant variation in peak width (from 12 cm(-1) to 110 cm(-1)) is observed as a function of the nanotube's chiral structure. When the nanotubes are electrostatically gated, the peak widths decrease. The broadness of the Raman features is understood as the consequence of coupling of the phonon to electron-hole pairs, the strength of which varies with the nanotube chiral index and the position of the Fermi energy.     

Analytical analysis of anisotropic thermophoresis of a charged spheroidal colloid in aqueous media for extremely thin EDL cases

Thermophoresis of charged spheroids has been widely applied in biology and medical science. In this work, we report an analysis of the anisotropic thermophoresis of diluted spheroidal colloids in aqueous media for extremely thin EDL cases. Under the boundary layer approximation, we formulate the thermophoretic velocity, the thermophoretic force, and the thermodiffusion coefficient of a randomly dispersed spheroid. The parametric studies show that under the aforementioned conditions, the thermophoresis is anisotropic and its thermodiffusion coefficient should be considered as a vector, D _T. The thermodiffusion coefficient values and directions of D _T are strongly related to the aspect ratio and the angle θ between the externally applied temperature gradient and the particle's axis of revolution: The increasing aspect ratio enlarges the thermodiffusion coefficient value D_T of prolate (oblate) spheroids to a constant value when θ < 60° (θ > 45°), and it reduces D_T of prolate (oblate) spheroids to a constant value when θ > 60° (θ < 45°). The thermodiffusion coefficient direction of both prolate and oblate spheroids deviates slightly from −∇T_∞ for a small aspect ratio, and such deviation becomes serious for a large aspect ratio.     

磷酸盐聚酯型水性聚氨酯/纳米SiO2的合成与性能

以2-磷酸基-1,2,4-三羧酸丁烷(PBTCA)、新戊二醇(NPG)为原料,制得数均相对分子质量为1500并含有磷酸基团的聚酯多元醇。将其与异佛尔酮二异氰酸酯(IPDI)反应,经1,4-丁二醇(BDO)扩链后得到水性聚氨酯,再以KH550为偶联剂,加入纳米SiO2,合成了纳米改性的磷酸型水性聚氨酯(PWPU)。通过红外光谱(FI-IR)、热重分析(TGA)对PWPU的结构和热稳定性进行了研究,使用透射电子显微镜(TEM)对乳液的形貌进行了观察。通过TEM发现,大量粒径在110 nm左右的化合物合成,并与红外光谱联合分析得出,SiO2通过化学键与PWPU相连接。热重分析、残炭量分析和拉伸测试表明,经过纳米SiO2改性的PWPU其阻燃性、热稳定性以及力学性能均有明显的提升,具有很好的应用前景。     

纤维素直接催化转化制乙二醇及其他化学品:从基础研究发现到潜在工业应用(英)

纤维素直接催化转化制乙二醇是一条极具吸引力的生物质转化途径,有助于减轻化石能源资源的消耗。综述了从该反应途径的发现到获得高效、高稳定性催化剂的快速发展过程。基于对钨基催化剂的大量研究结果,本文讨论了反应机制,明确了反应路径、催化剂状态、钨物种及加氢催化活性中心各自在串联反应中的作用。围绕该反应过程的工业化应用需要,讨论了有关原生木质纤维素生物质催化转化以及高效反应过程的发展策略。在此基础上,将纤维素催化转化制乙二醇过程与生物质发酵制丙酮-丁醇-乙醇的生物炼制路线进行整合,构建出一个理想的反应过程潜在应用范例。最后,对纤维素催化转化制乙二醇反应过程进行了总结和前景展望.     

Field emission of comb-like chromium disilicide nanowires prepared by an in situ chloride-generated route

Large-area comb-like chromium disilicide (CrSi₂) nanowire film has been successfully synthesized on silicon wafer through an in situ chloride-generated route. The sample possesses branch-like nanowires grown out perpendicularly and evenly from both sides of a stem-like microrod, forming 2-fold comb-like hierarchical nanoarchitectures. The formation mechanism of the sample could be understood by a secondary nucleation process occurring on the surface of the firstly formed CrSi₂ microrod, followed by epitaxial growth of branch-like nanowires under conditions of proper temperature and sufficient vapor supply in the reaction system. The field-emission behavior of the sample shows a low turn-on field of 5.3–6.5 V/μm at anode-sample distances of 200–400 μm, and agrees well with the conventional Fowler–Nordheim theory. No obvious degradation was observed in a life stability experiment period for over 100 min. The relationship between the field enhancement factor and anode-sample distance follows a universal equation, developed within a two-region field-emission model. The convenient and low-cost preparation of the comb-like CrSi₂ nanowires and their remarkable field-emission performance suggest that they can serve as good candidates for field-emission applications.     

Directly suspended droplet microextraction in a rotating vial

In this paper, a novel suspended droplet microextraction method was developed for the detection of trace of organic compounds in water samples. The process was executed in a rotating extraction vial without the use of a stir bar. A single drop of octan-1-ol placed on top of the water sample was used as the solvent. The droplet remained on top of the water sample as a thin layer with an expanding surface area during the extraction stage, while during the sampling stage, the droplet was collected and sampled by inserting a needle. The volume of the microdroplet used was 3 μL or less, to ensure high organic compound sensitivity. The microextraction experimental setup was simple, utilizing centrifugal forces and possesses the advantages of low cross-contaminant/interference and applicability to water samples apt to emulsification. Nitrobenzene was selected as a model organic compound, and samples were analyzed using gas chromatography (GC) or UV-vis spectrometry. Analysis of the microextraction method results showed a relative standard deviation (RSD) less than 3.82%.