碱性CeO2载体对Ru/CeO2催化剂氨合成活性的影响

钌基催化剂因其在低温低压下具有比常规的铁基催化剂更具活性的特点成为合成氨催化剂的理想选择.我们研究了CeO₂载体表面碱性对Ru基合成氨催化剂的影响.通过调节KOH沉淀剂的量来制备具有不同碱性位点的CeO₂载体（pH=10/11/12）,证明了催化剂适当碱性位点密度提高了合成氨催化活性.催化性能测试结果表明,1.25% Ru/CeO₂-11催化剂在3.8 MPa,450℃,H₂/N₂=3（60 mL·min^-1）下表现出优异的氨合成活性（7040 μmol·g^-1·h^-1）.CeO₂-11的碱性位点增强了载体的电子给予能力,这有利于电子向活性金属Ru转移,从而促进了N₂的活化.碱金属和碱土金属的引入提高了活性金属Ru的还原能力.4% Cs-1.25% Ru/CeO₂-11（12 000 μmol·g^-1·h^-1）催化剂具有更多的氧空位,这增加了Ru周围的电子密度并促进了N≡N的裂解.通过XRD,BET,SEM,CO₂-TPD,H₂-TPR和XPS分析了不同碱性CeO₂载体对合成氨催化反应的影响.     

Ru 前驱体对 Ru/MgO-CeO2 氨合成催化剂性能的影响

 分别以 K₂RuO₄, Ru(Ac)₃ 和 RuCl₃ 为 Ru 前驱体, 制备了 Ru/MgO-CeO₂ 催化剂, 并运用 X 射线衍射、X 射线荧光光谱, CO 吸附、N₂ 物理吸附和 H₂程序升温还原等技术对催化剂进行了表征, 考察了 Ru 前驱体对 Ru/MgO-CeO₂ 催化剂氨合成性能的影响. 结果表明, Ru 前驱体对载体 MgO-CeO₂ 和 Ru 的还原性能、氯残留量和催化剂比表面积的影响都很大, 从而导致催化剂的氨合成性能的不同. 其中以 K₂RuO₄ 为 Ru 前驱体制备的催化剂的载体和 Ru 容易还原, 无氯离子, 且比表面积较高, 因而催化剂活性和氨合成转换频率较高. 在 10 MPa, 425 °C, 10 000 h^-1 条件下, K₂RuO₄, Ru(Ac)₃ 和 RuCl₃ 作前驱体制备的催化剂上氨合成转换频率比为 1.33:1.05:1.     

Fe2O3/Al2O3二元气凝胶合成高质量单壁纳米碳管

通过溶胶和超临界干燥方法制得了Fe₂O₃/Al₂O₃二元气凝胶，其比表面积和孔隙体积分别为246 m²·g^-1和1.89 cm³·g^-1，并具有较宽的孔径分布。以Fe₂O₃/Al₂O₃二元气凝胶作催化剂，通过甲烷催化裂解成功地合成了高质量的单壁纳米碳管。利用FESEM、TEM和HRTEM、Raman光谱等分析手段研究了反应温度对单壁纳米碳管生长的影响。结果表明在900 ℃时合成单壁纳米碳管的质量较高，并且合成的炭产物为毡状，该炭产物主要为高质量的单壁纳米碳管。     

CeZrYLaO对Fe基整体式稀薄甲烷催化燃烧性能的影响

采用共沉淀法制备了高性能低铈储氧材料Ce_0.35Zr_0.55Y_0.07La_0.03O_1.95(OSM,储氧材料)和胶溶法制备了耐高温、高比表面的La-Al₂O₃并以它们为载体,制备了一系列整体式铁基催化剂。考察了该系列催化剂对甲烷稀薄燃烧的催化性能,并用低温N₂吸附-脱附,储氧能力(oxygen storage capacity,OSC),XRD,XPS和H₂-TPR等测试手段对载体和催化剂进行了表征。活性测试结果表明所制得的整体式催化剂Fe/OSM+La-Al₂O₃可在50 000 h^-1的高空速条件下使含量为1%的甲烷在474 ℃起燃,565 ℃完全转化;低温氮吸附-脱附测试结果表明,所制得的Ce_0.35Zr_0.55Y_0.07La_0.03O_1.95经1 050 ℃焙烧5 h后的BET比表面积达33 m²·g^-1,孔容为0.14 mL·g^-1;La-Al₂O₃经1 050 ℃焙烧5 h后的BET比表面积达125 m²·g^-1,孔容为0.46 mL·g^-1,是优良的催化剂载体;OSC测试结果表明,加入储氧材料(oxygen storage material(OSM))能增加催化剂的储氧性能,有利于催化活性的提高;XRD测试结果表明,OSM以均一固溶体存在;XPS测试结果表明,Fe₂O₃与OSM载体之间的相互作用最强;H₂-TPR测试结果表明,加入OSM能增加催化剂的还原性能,从而提高了催化活性。     

介孔炭的孔结构对其负载的Ru基氨合成催化剂性能的影响

采用模板法合成了介孔炭(MC),研究了其孔结构对其负载的Ru基氨合成催化剂Ba-Ru-K/MC性能的影响,采用N₂吸附脱附、扫描电镜和透射电镜等手段对介孔炭的孔结构进行了表征.研究发现,介孔炭载体的孔结构取决于模板剂的用量,当SiO₂/C质量比为1.0时,所制介孔炭比表面积最大.介孔炭负载的Ba-Ru-K催化剂活性与其介孔比表面积相关.在425℃,10MPa和10000h^-1条件下,合成氨的反应速率为139mmol/(g_cat·h).     

CuPd/MgO室温高效催化甲醛溶液产氢

采用浸渍还原法制备了MgO负载纳米CuPd合金的复合催化剂(CuPd/MgO)。该催化剂在室温催化甲醛溶液重整产氢过程中表现出优异的催化性能,转换频率(TOF)高达812.6h^-1,分别是相同条件下Cu/MgO(TOF=356.7h^-1)和Pd/MgO(TOF=34.8h^-1)的2.3倍和23倍。基于实验测试和表征结果,发现CuPd/MgO催化剂中纳米CuPd合金与表面富集缺陷的MgO载体之间存在金属-载体强相互作用。这种相互作用能够促进氧气在催化剂表面吸附活化并生成活性氧物种(超氧阴离子自由基,·O₂^-),·O₂^-先后促进甲醛中的C—H键断裂和水分子的解离,随后与反应体系中生成的质子及氢自由基(·H)依次结合,最终实现氢气的析出与氧气的再生。     

沉淀剂和Ag含量变化对甲醛降解性能的影响

采用不同沉淀剂制备CeO₂-Co₃O₄复合金属氧化物载体,通过浸渍负载不同含量Ag获得Ag/CeO₂-Co₃O₄催化剂.借助氮气物理吸附、XRD、Raman和H₂-TPR等手段研究了催化剂的物理化学性质.结果表明：当WHSV=30 000 mL·g^-1·h^-1时,催化剂能表现出良好的催化氧化甲醛性能,在≤ 90℃时实现甲醛的完全转化.草酸沉淀能有效降低Ce-Co氧化物的结晶度,使得Co²⁺含量增加,提供更多的氧空位,促进了氧分子的活化与迁移,从而提高了催化活性.随着Ag含量增加,使得由草酸沉淀制备的Ag/CeO₂-Co₃O₄催化剂的活性增强,且金属与载体间的相互作用也增强,当Ag负载量为1%（重量百分比）时活性最佳.     

碳载体预处理对CoTMPP/BP电催化剂氧还原性能的影响

采用微波加热合成法制备了CoTMPP/BP电化学氧还原催化剂。采用旋转圆盘电极(RDE)研究了BP2000碳载体经30% H₂O₂或6 mol·L^-1 HNO₃化学预处理后对催化剂氧还原催化活性的影响，并且在PEM燃料电池工作站上测试了不同CoTMPP/BP催化剂的燃料电池单电池性能。结果表明，碳载体经过化学预处理后催化剂性能有显著的提高，并且30% H₂O₂处理效果更好。采用IR、XRD和XPS进一步分析了载体化学预处理对催化剂活性影响的机理：IR结果表明预处理后载体表面羟基(-OH)等含氧基团增多；XRD分析表明900℃热处理后催化剂中有Co₃C(101)和金属态Co(111)结构出现；XPS分析表明碳载体预处理后N原子表面浓度以及组分N1和Co^Ⅲ相对比例升高，有利于Co-N4-C活性位的形成，然而组分N1，O1s Co^Ⅲ和Co^Ⅱ的结合能(BE)有所下降。     

酸处理对CuY催化剂孔结构及氧化羰基化性能的影响

对NaY分子筛(n_Si/n_Al=2.65)进行了草酸脱铝处理并作为载体采用液相离子交换法制备CuY催化剂,应用于常压甲醇氧化羰基化合成碳酸二甲酯(DMC)反应。NaY分子筛及其CuY催化剂通过N₂低温吸附-脱附、透射电子显微镜、X射线衍射、²⁹Si固体核磁共振、NH₃吸附程序升温脱附、吡啶吸附红外光谱、H₂程序升温还原、原子吸收等方法进行表征。研究结果表明,酸处理NaY分子筛后,骨架铝被脱除,导致骨架n_Si/n_Al比增加、相对结晶度降低并产生介孔,有利于产物分子的扩散,从而影响催化活性。采用4 h、2 mol·L^-1草酸处理NaY分子筛作为载体制备的CuY催化剂显示出较高的催化性能,DMC时空收率和甲醇转化率分别从103.6 mg·g^-1·h^-1和6.3%增加到184.9 mg·g^-1·h^-1和10.2%。产生的介孔能够促进催化剂中铜活性位的可接近性及反应物分子和产物分子的扩散。     

高比表面CexZr1-xO2复合氧化物的制备及表征

分别采用共沉淀法和阴离子表面活性剂模板法制备了Ce_xZr_1-xO₂复合氧化物。采用XRD、AFM、FTIR以及N₂吸附-脱附等方法对样品进行了表征。结果表明，共沉淀法合成的样品在500 ℃煅烧2 h后，生成了立方相Ce_0.75Zr_0.25O₂和四方相Ce_0.5Zr_0.5O₂固溶体，比表面积为62.1 m²·g^-1，孔体积为0.097 cm³·g^-1；以阴离子表面活性剂十二烷基苯磺酸钠(SDBS)为模板剂，乙二胺为助模板剂合成的样品在500 ℃煅烧2 h后，生成了纯四方相Ce_0.5Zr_0.5O₂固溶体，比表面积为180 m²·g^-1，孔体积为0.182 cm³·g^-1。结果表明，以阴离子表面活性剂SDBS为模板剂，可以合成高比表面积且具有介孔结构的Ce_0.5Zr_0.5O₂复合氧化物；加入乙二胺作为助模板剂可明显的提高比表面积和孔体积。     

Methods for sorption purification of underground water to remove uranium

Possibility was examined of using sorption purification of underground water containing 246 μg dm^–3 of uranium to remove this component with zeolite and shungite of natural origin, technogenic phosphogypsum, and products of their modification under static and dynamic sorption conditions. Copper(II), nickel, and zinc hydroxides served as modifying agents. It was shown that the modified sorbents enable a substantially higher extraction of uranium into the sorbent under static and dynamic sorption conditions. The water purification reached the level satisfying the requirements of hygienic regulation GN 2.1.5.1315–03 (maximum permissible concentration of chemical substances in water of household and cultural water bodies), imposed on technical-grade water used for industrial purposes.     

Modification of Synthesis of 3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone(MX)

Addition of chlorine to methyl 3-(dichloromethyl)-4,4-dichlorocrotonate (1), a critical procedure in the total synthesis of the title compound MX, was modified by using novel catalysts. A minor modification in the purification of MX was also described.     

Chemical Modification of Ethyl Cellulose-Based Highly Porous Membrane for the Purification of Immunoglobulin G

The chemical modification of developed ethyl cellulose-based membrane was carried out to make it suitable for bioseparation. The different reagents were used for the modification of membrane to couple protein A (PA) to study the purification of immunoglobulin G (IgG) from blood. The chemical modification was carried out using relatively simple and mild reaction conditions. The attenuated total reflectance Fourier transform infrared analysis of chemically modified membrane showed new peak at 1,596.06 and 1,716.49 cm^?1. The scanning electron microscopy of PA-coupled membrane, which was used for IgG purification showed open pores and 950?±?21.5 LMH (L?m^?2?h^?1) operational flux at 0.5-bar out pressure. The flux of unmodified membrane was 1,746?±?18.5 LMH at 0.5-bar out pressure. The equilibrium adsorption concentration (318.5?±?5.9 μg?cm^?2) was obtained at 3 h. The adsorption character of PA-coupled membrane was consistent with the Langmuir adsorption model and the non-specific binding was 67.08?±?1.3 μg?cm^?2. The sodium dodecyl sulfate polyacrylamide gel electrophoresis analysis showed similar purification pattern for purified IgG from human serum and commercial preparation of IgG. All the results have suggested a high potential of PA-coupled ethyl cellulose-based membrane for large-scale purification of IgG.     

Characterization of maleuric acid derivatives on transgenic human monoclonal antibody due to post-secretional modifications in goat milk

A fully human antibody to tumor necrosis factor-alpha was expressed in the mammary glands of transgenic goats. The goat expressed antibody (gAb) is heterogeneous and has several isoforms due to typical cellular post-translational modifications. In addition, one post-secretional modification on gAb was discovered by high-resolution cation exchange chromatography (CIEX). The presence of these variants in the final product was shown to be dependent upon the initial milk storage and traditional purification methodologies used. These observations allow for the development of new sample recovery and purification processes to eliminate these variants. Various enzymatic treatments were used to characterize different gAb heavy chain C-terminal lysine and sialic acid variants. In addition, an unknown derivative with the additional mass of 140 Da was found in transgenic gAb using mass spectrometry (MS). The modification sites were identified as the N-termini of gAb light chains and heavy chains using Q-TOF MS. Characterization of transgenic gAb isoforms was facilitated by utilizing different enzymes, CIEX and MS techniques. A maleuric acid modification on the N-terminal portion of gAb was shown to be consistent with the available data characterizing this new derivative of transgenic gAb isoforms in goat milk.     

New downstream processing strategy for the purification of monoclonal antibodies from transgenic tobacco plants

Affinity chromatography on immobilized Protein A is the current method of choice for the purification of monoclonal antibodies (mAbs). Despite its widespread use it presents certain drawbacks, such as ligand instability, leaching, toxicity and high cost. In the present work, we report a new procedure for the purification of two human monoclonal anti-HIV (human immunodeficiency virus) antibodies (mAbs 2G12 and 4E10) from transgenic tobacco plants using stable and low cost chromatographic materials. The first step of the mAb 2G12 purification procedure is comprised of an aqueous two-phase partition system (ATPS) for the removal of polyphenols while providing an essential initial purification boost (2.01-fold purification). In the second step, mAb 2G12 was purified using cation-exchange chromatography (CEX) on S-Sepharose FF, by elution with 20mM sodium phosphate buffer pH 7.5, containing 0.1M NaCl. The eluted mAb was directly loaded onto an immobilized metal affinity chromatography column (IMAC, Zn(2+)-iminodiacetic acid-Sepharose 6B) and eluted by stepwise pH gradient. The proposed method offered 162-fold purification with 97.2% purity and 63% yield. Analysis of the antibody preparation by sodium dodecyl sulphate-polyacrylamide gel electrophoresis (SDS-PAGE), enzyme immunosorbent assay (ELISA) and western blot showed that the mAb 2G12 was fully active and free of degraded variants, polyphenols and alkaloids. The effectiveness of the present purification protocol was evaluated by using a second transgenic human monoclonal anti-HIV mAb 4E10. The results showed that the same procedure can be successfully used for the purification of mAb 4E10. In the case of mAb 4E10, the proposed method offered 148-fold purification with 96.2% purity and 36% yield. Therefore, the proposed protocol may be of generic use for the purification of mAbs from transgenic tobacco plants.     

Synthesis of Carbon Nanotubes by Catalytic Chemical Vapor Deposition Using Hydrogen Storage Alloy as A Catalyst

Carbon nanotubes, which was discovered by Iijima1 in 1991, is the most typical one-dimensional nano-material with the micrometers order in length and nanometers order in diameter. CNTs are composed of graphitic sheets rolled into closed concentric cylinders, and classed into single wall nanotubes and multi-wall nanotubes. CNTs can offer many significant advantages over most existing materials. Since its discovery, unprecedented interest has been stimulated because of its significance both in…     

Rapid analysis of alpha-dicarbonyl compounds by laser desorption/ionization mass spectrometry using 9-(3,4-diaminophenyl)acridine (DAA) as a reactive matrix

A rapid, sensitive and selective method has been developed for the analysis of alpha-dicarbonyls using a readily ionizable compound, 9-(3,4-diaminophenyl)acridine (DAA), as a reactive matrix (derivatizing agent and ionization efficiency enhancer), by reactive matrix laser desorption/ionization time-of-flight mass spectrometry (RM-LDI-TOF MS). The reaction between the DAA and alpha-dicarbonyls resulted exclusively in formation of vacuum-stable dicarbonyl-quinoxaline acridine derivatives that were found to possess excellent ionization efficiency in positive ion mode, without the need to use an additional matrix. The alpha-dicarbonyls used as test compounds included methylglyoxal, dimethylglyoxal, and diphenylglyoxal. Both one-pot and rapid on-plate chemical modification approaches were employed with no extraction or purification necessary. The approach is particularly suitable for high-throughput analysis. The method was found to be selective and specific, with alpha-dicarbonyls unequivocally identified, even in complex matrices, e.g. beer. The figures of merit: relative standard deviation (RSD) 6.9-17%, (n = 4); limit of detection (LOD) < or =0.3 ng mL(-1) for the three standards tested using the one-pot derivatization method; and a good linear calibration curve using an internal standard derivatized in situ (R(2) > or = 0.979), demonstrate the applicability of the technique and its utility in improving the sensitivity and precision of the LDI analysis of small molecules.     

金属-ZSM-5/堇青石整体式催化剂上稀燃汽车尾气的净化

 在原位合成的ZSM-5/堇青石整体式样品基础上制备了几种金属(Cu, In或Ag)改性的ZSM-5/堇青石催化剂,并将其应用于稀燃发动机尾气的净化. 结果表明, Cu-ZSM-5/堇青石催化性能最好,尾气中的三种主要污染物NOx, CO和HC可以同时得到净化. 用微量(0.02%)贵金属(Pd, Rh或Ir)对Cu-ZSM-5/堇青石进一步改性,所得催化剂对CO的净化能力大大增强,保持高NOx转化率的温度窗口也大大加宽,因而该催化剂在稀燃汽车尾气净化方面具有潜在的应用前景. 微量贵金属对Cu-ZSM-5/堇青石催化剂的改性作用也在文中进行了讨论.     

Separation and purification of fructooligosaccharides on a zeolite fixed‐bed column

Fructooligosaccharides (FOS), a well‐known prebiotic product, are obtained by enzymatic synthesis and consist of a mixture of mono‐ and disaccharides. In this work, a methodology for their separation and purification was developed using a zeolite fixed‐bed column. The effects of column temperature (40–60°C), eluent flow rate (0.10–0.14 mL/min), injected to bed volume percent ratio (2.6–5.1%), and ethanol concentration in the eluent (40–60%, v/v) were investigated using a fractionary factorial design (2^4–1), having the separation efficiency and purity as target responses. Additional experiments were performed as well, where the temperature and ethanol concentration were studied in a central composite design (2²). In this work, the zeolite fixed‐bed column was shown to be a good alternative for FOS purification, allowing a FOS purity of 90% and separation efficiency of 6.86 between FOS and glucose, using an eluent at 45°C with 60% ethanol concentration.