硼氢化钾还原肉桂醛合成肉桂醇的工艺研究

针对硼氢化钾还原肉桂醛制备肉桂醇的工艺,研究了反应物的物质的量之比、还原体系、反应时间、反应温度等因素对反应收率的影响.结果表明,在KBH4-THF-CH3CH2OH还原体系中,通过控制n(肉桂醛)∶n(硼氢化钾)=3∶1,在室温下反应1.5h,收率可达92.2%.     

相转移催化无溶剂合成N-(ω-溴烷基)邻苯二甲酰亚胺

本文以N-(3-溴丙基)邻苯二甲酰亚胺合成为模板反应,研究了相转移催化无溶剂合成N-(ω-溴烷基)邻苯二甲酰亚胺的影响因素,实验证实相转移催化剂及其用量、催化剂K2CO3的用量等对反应的影响明显,得到N-(3-溴丙基)邻苯二甲酰亚胺的优化合成条件为:反应物配比为PA∶C3Br2∶K2CO3∶TBAB=1∶2∶4∶0.2,反应温度80℃,反应时间1h,N-(3-溴丙基)邻苯二甲酰亚胺产率为92%。在相同反应条件下,N-(ω-溴烷基)邻苯二甲酰亚胺的产率随α,ω-二溴烷烃的烷基链长度增加而降低。     

离子液体辅助合成AuPd纳米海绵及催化性能

在功能化离子液体氯化1-羟乙基-3-甲基咪唑([HEmim]Cl)辅助下, 在室温水溶液中一步快速合成了具有多孔海绵状结构的AuPd纳米材料. 通过场发射扫描电子显微镜(FESEM)、 透射电子显微镜(TEM)、 X射线能谱(EDX)和X射线衍射分析(XRD)等对该材料进行了表征. 结果表明, AuPd纳米海绵为合金结构, 由表面粗糙的纳米颗粒聚集熔接而成. 采用不同摩尔比(3∶1, 1∶1或1∶3)的前驱物HAuCl₄和Na₂PdCl₄均可制备出海绵状AuPd合金结构. 离子液体对AuPd纳米海绵状结构的形成起关键作用. 在对硝基苯酚还原反应中, 不同组成的AuPd纳米海绵均表现出比商用Pd/C催化剂更优异的性能. 其中, Au₁Pd₃纳米海绵具有最高的催化活性, 反应在98 s内即可完成, 反应速率常数为0.0143 s ^-1, 是商用Pd/C的2.3倍. 该方法也可用于制备其它双金属(如PdCu, PtCu等)和多金属纳米海绵.     

不同矿源橄榄石对催化苯水蒸气重整的影响

在固定床反应器中,以苯为生物质气化焦油模型化合物,测试了于900℃煅烧的4种不同矿源镁橄榄石(Mg,Fe)2SiO4及其负载镍催化剂的水蒸气重整活性,并对煅烧橄榄石进行了N2吸附、X射线衍射、程序升温还原和扫描电镜等测试.结果表明,不同矿源橄榄石的组成和表面性质不同,从而导致相应催化剂的性能差别较大.在具有较高可还原氧化铁含量和比表面积的橄榄石上,苯气相碳转化率最高.Ni的引入大大提高了苯转化率和产气中CO选择性,而降低了CH4和C2H4选择性.4种橄榄石负载镍催化剂的活性存在明显的差异,可能是因为活性组分在橄榄石载体表面的分散度不同.对反应后的积炭催化剂进行了热重分析.     

KCl-LiCl-MgCl2熔盐体系中共电沉积制备Mg-Li合金及理论分析

在670 ℃的KCl-LiCl-MgCl₂熔盐体系中通过共电沉积方法制备了Mg-Li合金,并进行了理论分析。循环伏安表明：670 ℃时,锂在镁上(镁预先沉积到钼丝上)的欠电位沉积形成了液态的Mg-Li合金;当MgCl₂质量分数为10%时,出现了Mg-Li合金成核。极化曲线表明：在含有5% MgCl₂的熔盐中,MgCl₂的极限电流密度为0.35 A·cm^-2,超过此值时,Mg和Li就能产生共电沉积。对沉积物进行X射线衍射和电感耦合等离子体发射光谱(ICP)分析表明：通过恒电流电解得到了3种不同相的Mg-Li合金。在电流密度为6.21 A·cm^-2电解2 h条件下,只有当MgCl₂质量分数小于10%时,才能得到Mg-Li合金。并通过Nernst和浓差极化方程讨论了MgCl₂浓度对于Mg-Li合金形成的影响。Mg-Li合金中锂的含量能够通过熔盐中的MgCl₂浓度配比和电解参数来控制。实验证明这种直接从原料入手,通过共电沉积制备Mg-Li合金的新方法是可行的。     

Ti-MCM-41催化剂的表面性质及介质极性对

用不同的铝源改性Ti MCM 41催化剂 ,得到了具有长程有序结构、n(Si) /n(Ti) =2 5的不同Si/Al比的改性Ti MCM 41.通过研究芳烃羟化反应随催化剂表面性质的变化规律发现 ,调变催化剂的表面性质 ,可控制反应物苯及目的产物苯酚与Al Ti MCM 41催化活性中心接近的程度 ,从而可实现对芳烃羟化反应化学选择性的控制 .介质极性对芳烃的化学亲和选择性也有影响 ,只有富含供电子氧原子且其极性大于苯的介质才有利于芳烃的羟化反应     

纳米孔炭负载 MnOx 催化剂上苯甲醇氧化反应性能

 以纳米孔炭 (NC) 为载体, 采用浸渍法制备了一系列 MnOx/NC 催化剂, 并用于以空气为氧源的苯甲醇液相氧化反应. 通过 X 射线衍射、X 射线光电子能谱、N2 吸附-脱附和 H2-程序升温还原等手段对催化剂进行了表征, 考察了催化剂中 Mn 负载量和焙烧温度, 以及反应条件等对反应性能的影响. 结果表明, 10%MnOx/NC 催化剂的活性较高, 反应 4 h 后苯甲醇转化率可达 80.4%; 明显高于活性炭负载的 MnOx 催化剂. 这主要归因于其表面存在大量高分散、且易于还原的 Mn 物种.     

4.4′-二碘苯磺酰替苯胺的合成及表征

以4,4'-二氨基苯磺酰替苯胺(DASA)、KI为原料,通过重氮化、取代反应制备了4,4'-二碘苯磺酰替苯胺.考察了反应温度、时间、原料配比及pH等因素对反应的影响。结果表明最佳反应条件为:反应温度为5℃、反应时间为3 h、pH为2、原料物质的量之比DASA∶NaN O_2∶H_2SO_4∶KI为1∶2.5∶2.8∶2.5.利用IR、MS、~1H NMR及元素分析对产物结构进行了表征.     

Co-ZSM-5催化剂上乙烯选择性催化还原Nox表面中间物种的组成

 采用预处理-瞬态反应产物分析方法定量研究了Co-ZSM-5催化剂上乙烯选择性催化还原氮氧化物反应过程中表面中间物种的组成. 催化剂在275 ℃经0.1%NO-0.05%C2H4-10%O2/Ar混合气处理后生成了表面中间物种NCaObHc, 该物种与NO/O2/Ar混合气反应比与单独的NO或O2反应生成更多的N2. 通过质谱、红外吸收四组分 (CO2, CO, CH4和N2O)分析仪及气相色谱-质谱联用等技术分析了表面中间物种与NO/O2/Ar混合气反应的产物,确定了表面中间物种中三种元素N, C和H的平均原子数之比为1.0∶1.8∶5.0 (氧物种由于实验原因很难确定).     

挥发性有机物的气相光解及光催化降解研究

研究了三氯乙烯、丙酮、苯、甲苯、二氯甲烷、三氯甲烷、四氯化碳的气相光解及光催化反应,对反应过程中反应物及CO2的浓度进行了定量监测。结果表明,在253.7nm的紫外灯光照射下,三氯乙烯可迅速被光解,反应产生CO2;甲苯和丙酮蒸气也可以被光解,但不产生CO2;在空气介质中,除CCl4外,其它几种有机物均可被光催化降解。     

Synthesis and characterization of phosphorized polyaniline doped with phytic acid and its anticorrosion properties for Mg-Li alloy

A phosphorized polyaniline (PANI) doped with phytic acid (PhA) was synthesized by the chemical oxide method with PhA as a dopant and applied to improve the anticorrosion properties of magnesium-lithium (Mg-Li) alloys after blending with eco-friendly silane sol. The chemical structures and morphologies of PANI samples were evaluated by FTIR spectroscopy, UV-Vis-NIR spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). All characterizations indicate that the as-synthesized phosphorized PANI (PANI-PhA) exists in doped emeraldine salt state with net-like structures crosslinked by phosphate carboxyl groups. The conductivity and thermostability of PANI-PhA were better than those of PANI doped with phosphoric acid (PANI-H₃PO₄) and undoped PANI. The anticorrosion properties of PANI/silane sol composite coatings for Mg-Li alloy were tested by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The results prove that the anticorrosion ability of PANI-PhA is the best among the three PANI samples, as shown by a low corrosion current (1.28 × 10^?7 A·cm^?2) and high impedance (5.62 × 10⁶ Ω·cm²). The possible anticorrosion mechanism was proposed based on procedure analysis.     

Preparation of Mg-Li alloys by electrolysis in molten salt at low temperature

A new technology for preparation of low cost Mg-Li alloys was studied. The alloys were prepared by electrolysis in molten LiCl-KCl (weight ratio is 1:1) electrolyte with Mg rod severing as the consumed cathode. Main factors that affect current efficiency were investigated, and optimal electrolysis parameters were obtained. Mg-Li alloys with low lithium content (about 25%) were prepared by the unique method of a higher post-thermal treatment temperature after electrolysis at low temperature. The results showed that the electrolysis can be carried out at low temperature, which resulted in reducing preparation cost due to energy saving.The new technology for the preparation of Mg-Li alloy by electrolysis in molten salt was proved to be feasible.     

硅烷改性纳米ZrO2对镁锂合金表面环氧树脂涂层耐蚀性能的影响

采用涂覆法在镁锂合金表面制备了含双-[3-(三乙氧基硅)丙基]四硫化物(KH-69硅烷)改性纳米ZrO₂的环氧树脂涂层. 通过傅里叶变换红外光谱(FTIR)、 扫描电子显微镜(SEM)和电化学阻抗谱(EIS)等手段表征了该涂层. 考察了KH-69硅烷改性纳米ZrO₂浓度对环氧树脂涂层耐蚀性能的影响. 结果表明, KH-69硅烷改性纳米ZrO₂能显著提高镁锂合金表面环氧树脂涂层的耐腐蚀性能, 其中1.0%(质量分数) KH-69硅烷改性纳米ZrO₂环氧树脂涂层具有较好的耐蚀性能. 在NaCl溶液中浸渍528 h后的低频阻抗值为1.6×10⁹ Ω·cm², 相比在NaCl溶液中浸渍240 h的纯环氧树脂涂层提高约5个数量级.     

Conversion of Mg-Li Bimetallic Alloys to Magnesium Alkoxide and Magnesium Oxide Ceramic Nanowires

Technologically important composites with enhanced thermal and mechanical properties rely on the reinforcement by the high specific strength ceramic nanofibers or nanowires (NWs) with high aspect ratios. However, conventional synthesis routes to produce such ceramic NWs have prohibitively high cost. Now, direct transformation of bulk Mg-Li alloys into Mg alkoxide NWs is demonstrated without the use of catalysts, templates, expensive or toxic chemicals, or any external stimuli. This mechanism proceeds through the minimization of strain energy at the boundary of phase transformation front leading to the formation of ultra-long NWs with tunable dimensions. Such alkoxide NWs can be easily converted in air into ceramic MgO NWs with similar dimensions. The impact of the alloy grain size and Li content, synthesis temperature, inductive and steric effects of alkoxide groups on the diameter, length, composition, ductility, and oxidation of the produced NWs is discussed.     

压电晶体传感器阵列用于混合有机溶剂蒸气中官能团的识别

为模拟生物化学传感体系, 提出了可用于识别有机官能团的传感器阵列, 用作人工气味识别系统。该阵列由八个压电晶体传感器组成, 每个传感器涂以具有广谱响应性能的不同吸附活性材料, 阵列对常见小分子有机溶剂混合蒸气的响应频移数据采用逐步判别分析(SDA)处理, 选出五个供信能力最佳的判别变量, 以此构成的阵列用于小分子有机溶剂混合蒸气中醇羟基、羰基与其它官能团的识别, 并采用主成分分析(PCA)法降维投影, 在二维空间含相同官能团的物质聚为一类; 阵列可用于酒类、软饮料的识别。     

Surface Modification of Graphene Oxides by Plasma Techniques and Their Application for Environmental Pollution Cleanup

Graphene oxides (GOs) have come under intense multidisciplinary study because of their unique physicochemical properties and possible applications. The large amount of oxygen‐containing functional groups on GOs leads to a high sorption capacity for the removal of various kinds of organic and inorganic pollutants from aqueous solutions in environmental pollution cleanup. However, the lack of selectivity results in difficulty in the selective removal of target pollutants from aqueous solutions in the presence of other coexisting pollutants. Herein, the surface grafting of GOs with special oxygen‐containing functional groups using low‐temperature plasma techniques and the application of the surface‐modified GOs for the efficient removal of organic and inorganic pollutants in environmental pollution are reviewed. This paper gives an account of our research on the application of GO‐based nanomaterials in environmental pollution cleanup, including: (1) the synthesis and surface grafting of functional groups on GOs, summarizing various types of low‐temperature plasma techniques for the synthesis of graphene/GOs; and (2) the application of graphene/GOs and their composites for the efficient removal of organic and inorganic pollutants from aqueous solutions, including the interaction mechanism according to recently published results.     

Static SIMS studies of fatty alcohols,amines and esters on gold and aluminium–magnesium alloy surfaces

Static secondary ion mass spectrometry was used to study the chemical reactions and lateral distributions of fatty amines, alcohols and esters spin coated onto gold surfaces and commercial aluminium–magnesium (Al–Mg) alloy surfaces, cleaned using UV–ozone. The aim of this study is to develop an understanding of the interactions of model lubricants with metal surfaces, such as gold and aluminium. This static SIMS study of organic thin films has been able to identify specific reaction products on the aluminium surface for each functional group. This work demonstrates that organic molecules with alcohol, ester and amine functional groups undergo specific chemical reactions with oxidized Al–Mg alloy surfaces. For example, films composed of the fatty alcohol dodecanol were observed to emit monomers, dimers and trimers with discrete distributions. In addition, negative secondary ion mass spectra indicate that a surface carboxylate is formed from the alcohol. The formation of carboxylate reaction products was confirmed by Fourier transform infrared spectroscopy. On Al–Mg alloy surfaces, a direct interaction with the amine and aluminium oxide surface is observed by the detection of a molecular ion that corresponds to the mass of dodecylamine and AlO^?, characteristic of aluminium oxide. Ethyl laurate was shown to eliminate the ethyl group, leaving the laurate anion. This study demonstrates the ability of time‐of‐flight (ToF) SIMS to discriminate and detect chemical reaction products formed between model lubricant molecules and metal surfaces. As a result of this study, the use of ToF‐SIMS to identify reaction products of model lubricants can be extended to provide a better understanding of the interactions of lubricants and metal surfaces at high temperatures and pressures that more closely resemble the conditions encountered in industrial rolling processes. Copyright © 2005 John Wiley & Sons, Ltd.     

Controlling adsorption and release of drug and small molecules by organic functionalization of mesoporous materials

A series of mesoporous nanosphere materials that are functionalized with various terminal and bridging organic groups were synthesized. They have improved adsorption capacity and different release properties for drug and small molecules. The materials contained terminal vinyl, 3-mercaptopropyl, 3-aminopropyl, and secondary amine functional groups and bridging ethane, ethene, and benzene groups within their mesopore channel walls. The samples containing mercaptopropyl and vinyl groups showed greater adsorption capacity and better controlled release behavior for rhodamine 6G molecules. On the other hand, mesoporous matrices containing amine functional groups showed higher adsorption capacity and better release properties for ibuprofen molecules. Further studies revealed that the bridging organic groups in the mesopore channel walls also improved the adsorption capacity and release properties of the materials compared to the corresponding samples containing no bridging organic groups. Such improved adsorption and controlled release properties of molecules by simple changes of functional groups on mesoporous materials are important for the development of nanomaterial drug delivery vehicles and for controlled release of drugs over long time periods at specific targeted sites in the body. By judicious choice of organic groups and by systematic design and synthetic approaches, nanoporous materials having different adsorption capacity and release properties for many other drug molecules can also be achieved.     

Hypercrosslinked Phenolic Polymers with Well‐Developed Mesoporous Frameworks

A soft chemistry synthetic strategy based on a Friedel–Crafts alkylation reaction is developed for the textural engineering of phenolic resin (PR) with a robust mesoporous framework to avoid serious framework shrinkage and maximize retention of organic functional moieties. By taking advantage of the structural benefits of molecular bridges, the resultant sample maintains a bimodal micro‐mesoporous architecture with well‐preserved organic functional groups, which is effective for carbon capture. Moreover, this soft chemistry synthetic protocol can be further extended to nanotexture other arene‐based polymers with robust frameworks.     

Chemical derivatization techniques in the determination of functional groups by X-ray photoelectron spectroscopy

The fundamentals of chemical derivatization techniques as applied to the quantitative analysis of ultrathin surface layers of various organic compounds via functional groups were considered. Using X-ray photoelectron spectroscopy as an example of the most informative and almost nondestructive technique for characterization of thin layers, the general requirements imposed on the selective chemical reactions and possible artifacts were discussed. The validity of the technique was illustrated by the examples of analyses of surface layers of organic polymers with known concentrations of surface functional groups, plasma-modified polymers, and carbon fibers. It was noted that selective chemical reactions are successfully used in other techniques for studying material surfaces. The surface analysis of organic materials via functional groups can be performed with a simultaneous increase in the sensitivity of the corresponding spectral technique.