三氟三氯乙烷加氢脱氯Pd-Cu催化剂失活分析

以活性炭为催化剂载体,采用浸渍法制备Pd、Cu、Pd-Cu三种催化剂,将催化剂应用于三氟三氯乙烷(CFC-113)加氢脱氯制三氟氯乙烯(CTFE)的反应,考察Cu的引入对Pd催化剂性能的影响。对反应前后及再生的Pd-Cu催化剂进行X射线衍射(XRD)、X射线光电子能谱(XPS)、氮气吸附-脱附(BET)、氢气程序升温还原(H₂-TPR)、热重(TG)、氨气程序升温脱附(NH₃-TPD)等表征分析。研究表明,Pd催化剂具有较高的加氢脱氯性能,其主要产物为三氟乙烷,Cu的加入有利于提高CTFE的选择性。这应与Cu、Pd之间存在相互作用并形成合金,抑制了Pd的脱氯性能有关。反应后的催化剂存在表面结焦、反应过程中吸附Cl以及金属Cu价态变化和迁移等现象,其中表面高沸物的形成、卤元素吸附导致的金属迁移和Cu-Pd相互作用的改变是Pd-Cu催化剂失活的主要原因。     

蒸气浸渍法制备完全无氯CuY催化剂及其氧化羰基化性能

以具有升华性质且易分解的乙酰丙酮铜为铜源,NH₄Y分子筛为载体,采用蒸气浸渍法制备了CuY催化剂,考察了其对甲醇氧化羰基化合成碳酸二甲酯的催化性能,并采用XRD、H₂-TPR和NH₃-TPD等表征手段研究了催化剂上铜物种的分散状态、催化活性中心的含量及催化剂的酸强度和浓度,发现铜物种在Y分子筛载体上高度分散,且Y分子筛载体的晶体结构保持完好。在N₂∶H₂=12∶1的气氛中,250℃还原得到的催化剂CuY/250催化活性中心含量最高,催化活性也达到了最佳,其甲醇转化率为11.1%,碳酸二甲酯的时空收率和选择性分别为200.5mg/(g·h)和60.3%。     

异辛醇胺化合成三异辛胺镍铜基催化剂的研究

采用浸渍法制备了不同镍铜比的镍基催化剂。采用氢气程序升温还原(H₂-TPR)、氨气程序升温脱附(NH₃-TPD)、X射线粉末衍射(XRD)对催化剂进行表征,并考查其催化异辛醇氨化合成三异辛胺的活性。结果表明,还原态催化剂表面检测出明显的Cu衍射峰,Ni的衍射峰较弱,说明Ni物种更为分散。H₂-TPR表征显示,铜的添加促进了镍的还原,使得催化剂表面还原态Ni和Cu物种增多,增加了催化剂加氢、脱氢能力;NH₃-TPD显示,镍对NH₃有更好的吸附活化作用,铜与镍对NH₃形成了协同吸附。Cu_1.5Ni₁/A300催化剂体现出较好的催化活性,胺化反应4 h,异辛醇转化率达82.69%,三异辛胺选择性达到63.28%。     

铜源阴离子对CuY催化剂性能的影响

利用NH_4Y分子筛与铜源间的固相反应制备CuY催化剂,选用5种铜源调控CuY的织构特点及催化剂上铜物种的化学状态,并考察了CuY在甲醇氧化羰基化合成碳酸二甲酯过程中的催化性能。利用XRD、H_2-TPR和NH_3-TPD等表征手段对CuY进行分析。结果表明,以Cu(NO_3)_2为铜源制备得到的CuY-N上,碳酸二甲酯的时空收率(STY_(DMC))为137.4 mg/(g·h);以CuCl_2为铜源制备的CuY-C上无CuO_x物种,其催化活性比CuY-N差;以Cu(COOCH_3)_2为铜源制备得到的CuY-AC催化活性更差;以CuSO_4为铜源制备的CuY-S几乎没有催化活性;而以Cu(acac)2为铜源制备的CuY-acac活性最佳,STY_(DMC)达到267.3 mg/(g·h)。     

磁性CuO-Bi2O3/Fe3O4-SiO2-MgO催化剂的制备及甲醛乙炔化性能

采用浸渍法和共沉淀法制备了一系列不同Cu含量的超顺磁CuO-Bi₂O₃/Fe₃O₄-SiO₂-MgO催化剂。使用电感耦合等离子体发射光谱仪(ICP-AES)、低温N₂物理吸-脱附、X射线衍射(XRD)、H₂程序升温还原(H₂-TPR)、振动样品磁强计(VSM)对催化剂的组成、结构、织构及磁性能进行表征, 评价了该催化剂催化甲醛乙炔化合成1, 4-丁炔二醇的催化活性。结果表明, 制备方法对催化剂中活性组分CuO的存在状态及炔化性能有较大影响, 采用共沉淀法较浸渍法制备的催化剂具有更高的比表面积、CuO分散度与较好的还原能力, 表现出较高的炔化性能;Cu含量是影响催化剂炔化性能的另一重要因素, 随Cu含量的增加, 催化剂活性逐渐增加, 在本研究考察范围内, 以共沉淀法制备的Cu质量分数为30%的催化剂表现出最佳的甲醛乙炔化性能。同时, 该催化剂具有良好的超顺磁性, 可以在外加磁场的作用下迅速分离回收, 循环使用6次后, 其催化活性明显高于非磁性催化剂。     

基于CuAl-LDH载体制备高分散Cu/ZnO/Al2O3催化剂及其催化性能

通过沉积沉淀法制备了以层状CuAl-LDH为载体负载不同Cu/Zn比例的前体,经热处理得到CuZnAl-LDO复合催化剂,应用于合成气制甲醇反应。采用电感耦合等离子体发射光谱（ICP）、X射线衍射（XRD）、H₂程序升温还原（H₂-TPR）、N₂O化学吸附、N₂吸脱附、透射电镜（TEM）和X射线光电子能谱技术（XPS）等手段对前体及催化剂进行表征,考察了水滑石的限域效应和金属-载体相互作用对催化剂活性及稳定性的影响。结果发现：由于水滑石特殊的层状结构,具有较大比表面积和丰富孔道结构,促进了Cu物种的分散,有利于催化剂表面对CO和H₂的吸附,增加了Cu、Zn之间的相互作用,提高了催化剂的催化活性。在水滑石前体拓扑转变过程中,层板羟基和水脱除后形成的粗糙表面对所负载的Cu活性物种起到限域作用,抑制了Cu的迁移和团聚。其中,Cu_0.6Zn_0.3Al_0.1-LDO催化剂催化合成甲醇的时空收率达到883mg/(g?h),且反应120h后仅下降2.8%,较共沉淀制备催化剂失活速率降低了81%,表现出较好的催化活性及稳定性。     

有序介孔CuCoZr催化剂的制备及其催化合成气制乙醇及高级醇性能

改性费托合成催化剂(尤其是CuCo催化剂)在合成气制乙醇及高级醇反应中具有高的催化活性和总醇选择性,被认为是潜在的工业催化剂。采用蒸发诱导自组装(EISA)法和共沉淀(CP)法制备了一系列CuCoZr催化剂,考察了制备方法及EISA法制备的催化剂Cu/Co原子比对合成气制乙醇及高级醇性能的影响。采用N₂物理吸附-脱附、小角X射线衍射(XRD)、原位XRD、透射电镜(TEM)、H₂-程序升温还原(TPR)、CO-程序升温脱附(TPD)和原位红外漫反射光谱(DRIFT)对催化剂进行表征,分析了合成气在Cu/Co原子比为3∶1的Cu₃Co₁Zr催化剂表面的反应路径。结果表明,EISA法制备的Cu Co Zr催化剂为有序介孔结构,比表面积随Cu/Co原子比的增加先增大后减小,其中Cu₃Co₁Zr催化剂比表面积和CO吸附量均为最大,分别为143m²/g和0.33mmol/g,催化剂的Cu晶粒尺寸仅为9.1nm。在催化合成气制醇的反应中CO转化率...     

低温深度脱除液相丙烯中微量CO的CuO(y)/CuxCe1-xOδ催化剂表征分析及性能实验

采用柠檬酸络合-浸渍的方法制备了CuO(y)/Cu_xCe_1-xO_δ催化剂,重点研究了CuO的载体掺杂和表面负载对催化剂结构性质、氧化还原性能、吸附性能及CO净化性能等的影响,旨在指导催化剂进一步改性,实现低温下深度脱除液相丙烯中微量CO的工业化应用。采用X射线衍射（XRD）、透射电镜（TEM）、X射线光电子能谱分析仪（XPS）、拉曼光谱仪（Raman）和程序升温化学吸附仪（H₂-TPR、CO-TPD）等手段表征了催化剂的结构和性质,结果显示,CuO掺杂的载体,Cu进入CeO₂晶体形成固溶体,有利于催化剂氧化还原性能;浸渍法负载CuO制得的催化剂,表面具有更多的还原态、高分散的Cu物种,有利于表面对CO吸附性能;两者协同作用共同促进了CO催化氧化性能的提升。CuO(0.40)/Cu_0.1Ce_0.9O_δ催化剂具有优异的CO净化性能,在50℃、3.0MPa的工况条件下,可将液相丙烯中CO体积分数从1×10^-5脱除至2.65±0.27×10^-8,达到聚合级烯烃对CO脱除深度的要求,稳定性能良好。     

Ti/Sn掺杂CeMn基催化剂的低温脱硝活性及抗水性能

采用共沉淀法制备了Ti/Sn掺杂的CeMn基复合金属氧化物催化剂,研究了Ti/Sn改性对CeMnO_x催化剂的脱硝性能和抗水性能的影响,并通过物化性能表征对催化剂的微观结构、吸附氨状态、氧化还原能力以及表面元素价态进行了分析。结果表明,Ti和Sn元素的引入均可以提升CeMnO_x催化剂低温NO_x转化活性和抗水性能,并且Ti的提升效果更加显著,在150～250℃,CeMnTiO_x脱硝效率接近100%,在200℃、10vol%H₂O条件下,脱硝效率维持在95%以上。H₂程序升温还原、NH₃程序升温脱附及X射线光电子能谱等检测结果表明催化剂表面Ce-O-Ti和Mn-O-Ti结构的形成提升了催化剂的氧化还原性能,增多了催化剂表面弱酸位、中强酸位数量,同时形成了更多的氧空位,从而使催化剂获得了良好的低温NO_x转化活性。     

甘油氢解用固体超强碱负载的铜催化剂

用浸渍-燃烧法制备了固体超强碱MgO-CaO和MgO-SrO负载的高分散铜基催化剂,并将其用于甘油氢解制备1,2-丙二醇的反应。N₂吸附、X射线衍射、透射电子显微镜、H₂程序升温还原和N₂O氧化吸附及CO₂程序升温脱附等表征实验结果显示:Cu粒子均分散于Cu/MgO-CaO(或者Cu/MgO-SrO)催化剂的表面;与Cu/MgO相比,Cu/MgO-CaO和Cu/MgO-SrO具有更强的碱性,可以加速甘油的转化。上述结果表明,甘油氢解反应中铜催化剂的活性随碱性的增强而增加。     

Conducting polymer coated carbon surfaces and biosensor applications

This review article focuses on several approaches in the characterization and modification of carbon surfaces with electrocoated thin films which has been realized by recent progress in experimental methods. Electropolymerization and electrocopolymerization of π-conjugated polymers (pyrrole, carbazole, N-vinylcarbazole and aniline) onto carbon surfaces are reviewed with 348 references. Particular emphasis is placed on the recent nanoscale surface characterization techniques applied to the resulting electrocoated polymers onto carbon fibers (i.e., scanning electron microscopy (SEM), cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), focused ion beam-secondary ion mass spectroscopy (FIB-SIMS), Fourier transformed infrared spectroscopy (reflectance-FTIR), and Raman spectroscopic measurements).     

Changes of copper location in CuY zeolites induced by preparation methods

The location of transition ions in copper- and copper-zinc-loaded Y type zeolites prepared by different procedures has been studied by temperature-programmed reduction, infrared spectroscopy of CO adsorbed on pretreated samples and X-ray photoelectron spectroscopy. Samples outgassed at 673 K showed Cu⁺ species due likely to reduction of Cu²⁺ ions under vacuum. Over exchanged CuY zeolites copper species in exchange sites were detected, while an impregnated sample exhibited bands of CO adsorbed on both Cu²⁺ and Cu⁺ ions developed at the surface of CuO crystals, and small proportions of Cu⁺ ions located in accessible exchange sites S_II and Sn_II. Similar findings were observed in Zn- and Cu-exchanged zeolites although the relative proportion of Cu in S_I positions was decreased due to competition between Cu²⁺ and Zn²⁺ ions. Samples reduced in hydrogen at 523 K showed the appearance of Cu⁰ species in impregnated samples, whereas Cu⁺ dominated in the exchanged counterparts. Reduction at 598 K led to substantial changes in Cu-exchanged samples in water. The proportion of Cu⁺ species decreased by reduction to Cu⁰ and simultaneously migration to Cu⁺ to S_II sites occurred. While Cu²⁺ or Cu⁺ were found on outgassed samples, only Cu⁰ and intrazeolite Cu⁺ were observed after H₂-reduction at 623 K. Changes in copper exposure as a function of sample pretreatments were also revealed by X-ray photoelectron spectroscopy.     

Studies on the adhesion of polyimide coatings on copper foil

The peel strength and the color of the copper foil peeled at 90 degrees from five different polyimide films were studied. The interfacial surfaces of copper foil and polyimide were examined by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and energy dispersion analysis by X-ray (EDAX). There is a correlation between peel strength, and the color of the interfacial side copper caused by oxygen diffusion. Study of the imidization process carried out in vacuum indicates that the geometric arrangements of the atoms of polyimide also play a very important role in peel strength.     

Self-assembly on copper surface by using imidazole derivative for corrosion protection

This paper presents the self-assembly of 1-(3-aminopropyl) imidazole (API) monolayer on the copper surface to study the inhibition effect of the API against copper corrosion in 3% NaCl solution. The optimum concentration and assembling time for the assembly of API on copper were ascertained using electrochemical impedance spectroscopy (EIS). It was found that the API self-assembled monolayer (SAM) was formed with the concentration of 1.0 mM of API at 24 h assembling time and the maximum inhibition efficiency that could be achieved was 93.10%. The API SAM on copper was characterized by Fourier transform infrared spectroscopy (FT-IR), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and water contact angle measurement (WCA). The presence of N and C signals in the XPS and EDX, show that the API molecules successfully anchor on the copper surface which demonstrates formation of API SAM on the copper surface. Corrosion protection capability of the copper modified with API was evaluated by the electrochemical polarization study (EPS) and scanning electron microscopy (SEM). The results of electrochemical and SEM analysis revealed that the API modified copper showed better corrosion protection in 3% NaCl solution.     

Characterisation of active phases of a copper catalyst for methanol oxidation under reaction conditions: an in situ X-ray absorption spectroscopy study in the soft energy range

The oxidation of methanol over copper is investigated by X-ray absorption spectroscopy in the soft X-ray range under reaction conditions. This in situ method allows the surface electronic structure of the catalyst to be correlated with its performance. The correlation reveals information about the catalytic function of various oxygen species on the surface. Oxide and metastable suboxide species affect in distinctly different ways the multiple action of copper as selective or unselective heterogeneous catalyst.     

Synthesis,characterization and corrosion protection of poly-4-methyl-3-mercapto-1,2,4-triazole/TiO2 composite on copper

The present work deals with the electrochemical synthesis of poly-4-methyl-3-mercapto-1,2,4-triazole (p-MMTA)/TiO₂ composite on metallic copper to evaluate its corrosion protection. The composite was characterized by FT-IR, cyclic voltammetry, X-ray diffraction and energy dispersive X-ray analysis. The distribution of inorganic particles in the polymeric matrix was evidenced from the scanning electron microscopic studies. The corrosion performance of composite coating was evaluated by electrochemical impedance spectroscopy and Tafel polarization measurements in 3.5 % NaCl medium. The p-MMTA/TiO₂ composite showed an excellent corrosion protection ability, which was evidenced from the results of electrochemical measurements. The enhanced ability could be due to the barrier effect of composite coatings against corrosive species and also due to the synergistic effect between organic polymer and inorganic particles.     

Probing the electronic structure of an active catalyst surface under high-pressure reaction conditions: the oxidation of methanol over copper

The active phase of a bulk metallic copper catalyst is investigated by surface sensitive X-ray absorption spectroscopy at the oxygen K-edge and the Cu L-edges in the total electron yield mode under practical steady state flow-through conditions. The active catalyst surface contains oxygen atoms revealing significant spectral differences compared to those of known copper oxides. The partial oxidation of methanol to formaldehyde is correlated to the abundance of this copper suboxide. These oxygen atoms probe defects of the copper lattice, which represent catalytically active sites. The suboxide is undetectable under UHV conditions. The total oxidation of methanol is catalysed by a conventional copper(I) oxide species and the abundance of carbon dioxide in the gas phase is increasing with decreasing integrated intensity of the oxide species. This revised version was published online in July 2006 with corrections to the Cover Date.     

梯度电流密度下电沉积制备铜-镍-钼合金电极及其性能研究

采用梯度电沉积法制备铜基Cu–Ni–Mo合金电极,电流密度参数为:10 mA/cm^2×5 min+30 mA/cm^2×40 min+50 mA/cm^2×5 min。通过扫描电子显微镜(SEM)、能谱仪(EDS)、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)分析了Cu–Ni–Mo合金镀层的表面形貌、元素组成、相结构和各元素的化学价态,并通过线性扫描伏安曲线(LSV)、电化学阻抗谱(EIS)和计时电流法对比了Cu–Ni和Cu–Ni–Mo合金电极在1 mol/L KOH溶液中的析氢性能和稳定性。结果表明,所得Cu–Ni–Mo合金镀层是呈花椰菜多孔形貌的非晶态结构。与Cu–Ni合金电极相比,Cu–Ni–Mo合金电极具有更大的比表面积,可为析氢反应提供更多活性位点,表现出更好的析氢性能,稳定性也更好。     

Carbon Nanomaterial–Reinforced Epoxy Composites: A Review

Conducting fillers such as graphite, carbon nanotubes, and carbon nanofibers are used as reinforcing agents for enabling the conducting behavior of epoxy resin. The present review focused on the work related to epoxy composite with reinforcement of various nanofillers. Different methods of preparation for epoxy-based conducting nanocomposites are summarized. Various characterization techniques of epoxy composites such as Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy are discussed. Important properties of epoxy-based nanocomposites are explained with different applications of epoxy-based conducting polymers.