Catalytic activity in the oxidative dehydrogenation of ethane over Ni and/or Co molybdate catalysts: Synthesis and characterization

Ni and/or Co molybdate based catalysts were synthetized by co-precipitation for the oxidative dehydrogenation of ethane reaction. The catalysts were characterized by several techniques such TGA-DTA, HT-XRD, XRD, LRS, N₂ adsorption, XPS and TPR. The results showed that the addition of Ni or Co to MMoO₄matrices (M=Ni or Co) led to a high dispersion of additives into the molybdenum matrix without the formation of a significant amount of other bulk metal oxides. Compared to the pure MMoO₄, the modified molybdenum (Ni_0.5Co_0.5MoO₄) presents a higher thermal stability (up to 1000 °C). It has a lower BET surface area and higher reduction temperature compared to those of the NiMoO₄ sample. In the ODH of ethane, Ni_0.5Co_0.5MoO₄ shows a lower catalytic activity compared to that of MMoO₄ samples; however, the ethylene selectivity is enhanced (exceeding 90%). As a result, these series of catalysts show improved efficiency for ethylene production in the ethane ODH reaction.     

TiO_2-Al_2O_3载体的制备方法对其负载的磷化镍催化剂加氢脱氮反应性能的影响

采用共沉淀法和原位溶胶-凝胶法制备了TiO2-Al2O3复合载体,其负载的磷化镍催化剂采用等体积浸渍法和H2原位还原法制备.通过N2吸附(BET)、X射线衍射(XRD)、透射电镜(TEM)、程序升温还原(TPR),X射线光电子能谱(XPS)和等离子体发射光谱(ICP-AES)表征技术对催化剂进行了表征,并通过喹啉的加氢脱氮反应评价了催化剂的加氢脱氮性能.结果表明,原位溶胶-凝胶法制成的复合载体基本保留了原有的γ-Al2O3的孔特征,具有较大的比表面积和较宽的孔分布,TiO2主要以表面富集的形式分散在管状的γ-Al2O3表面,其负载的磷化镍催化剂还原后所形成的活性相为Ni2P和Ni12P5;而共沉淀法制成的复合载体比表面积较小,孔径分布更加集中,TiO2趋于在块状的Al2O3表面均匀分散,其负载的磷化镍催化剂具有更好的可还原性,还原后所形成的活性相为Ni2P.不同的载体制备方法和不同的钛铝比对催化剂加氢脱氮性能影响较大,当n(Ti)/n(Al)=1/8时,共沉淀法载体负载的催化剂表现出最佳的加氢脱氮性能,在340℃,3 MPa,氢油体积比500,液时空速3 h-1的反应条件下,喹啉的脱氮率可以达到91.3%.     

选择性刻蚀制备铜锰复合氧化物及其CO催化氧化性能

由于在工业、环保和能源等诸多领域的潜在应用,低温CO催化氧化催化剂的研发引起了广泛关注.尽管贵金属表现出优越的CO氧化活性和稳定性,但是其有限储量和高昂价格一直限制着它们的实际应用.铜锰氧化物是著名的霍加拉特催化剂的主组分,价格低廉,催化氧化CO活性高,可高效替代贵金属催化剂.大量研究已证实, CO在铜锰氧化物上的氧化遵循氧化-还原机理,因此调变铜锰氧化物催化剂的氧化-还原性能对于改善其CO氧化活性至关重要.本文报道了一种简单的选择性刻蚀技术,即在铜、锰前驱物共沉淀过程中引入氨水作为刻蚀剂,利用氨水与铜离子的强络合作用选择性刻蚀铜组分,调变铜锰氧化物的铜锰比,有效改善了铜锰氧化物的氧化-还原特性,从而提高了其CO氧化性能. X射线粉末衍射(XRD)测试结果表明,初始制备的样品结晶弱,主要物相包含铜锰复合氧化物和氧化锰,此外还存在少量碳酸锰.不同浓度氨水刻蚀几乎未改变铜锰氧化物的物相组成.透射电子显微(TEM)照片中几乎没有发现晶格相,进一步证实这些铜锰氧化物的弱结晶本质.扫描电子显微(SEM)照片显示初始制备的铜锰复合氧化物主要由1.5?m左右的球形颗粒堆积而成,氨水刻蚀后颗粒形状变得不规则,表面更加粗糙,样品比表面积也从刻蚀前的85 m2/g增加到139 m2/g.理论上,氨水与铜的络合作用更强,样品主体和表面组成分析结果显示,随着氨刻蚀量增加,铜含量逐步降低,这清晰证实了氨有效地选择性刻蚀了铜组分. 进一步运用X射线光电子能谱(XPS)、氢程序升温还原(H2-TPR)、CO程序升温还原(CO-TPR)和氧程序升温脱附(O2-TPD)等测试手段表征了铜锰氧化物的氧化和还原特性,特别是氨刻蚀后催化剂氧化-还原性能. XPS分析显示铜锰氧化物中铜和锰物种的氧化态分别为+2和+3,氨刻蚀并没有改变两物种的氧化态. H2-TPR和CO-TPR证实氨刻蚀有效促进了铜锰氧化物中晶格氧从锰到铜物种的迁移,氨刻蚀同时还增强了与铜和锰键合的晶格氧物种的反应活性. O2-TPD结果进一步表明,氨刻蚀显著改善了铜锰氧化物中与铜键合晶格氧的释放.综合来看,氨刻蚀可有效促进铜锰氧化物的晶格氧迁移、释放和反应等氧化-还原特性. CO氧化反应研究显示,氨刻蚀大幅度促进了铜锰氧化物的催化活性.当反应温度在30?C时,相比于初始制备的铜锰氧化物催化剂,氨水刻蚀的样品上CO转化率提高了30%,达到90%转化率时的温度降低了20?C.关联催化剂结构表征和CO氧化性能数据发现,以表面Cu量归一化的CO氧化反应速率与催化剂的氧化-还原性能正相关.这一结果清晰证实氨刻蚀能显著改善铜锰氧化物的氧化-还原特性,进而有效促进其CO氧化活性.     

磁性纳米复合氧化物固体酸催化剂的制备及酯化性能

固体酸催化剂的无腐蚀、环境友好和可循环使用等特点使其成为无机液体酸的最佳替代物.磁性纳米固体酸具有优于常规固体酸催化剂的催化活性及分离简单的特性.用共沉淀法分别合成了一系列三组分TiO2-Al2O3-Fe3O4(TAF)和CeO2-Al2O3-Fe3O4(CAF)及四组分ZrO2--Al2O3-Fe3O4(ZACF)磁性纳米复合氧化物固体酸催化剂,通过电感耦合等离子体原子发射光谱、比表面积测定、X射线衍射、透射电镜、热重分析和红外光谱等对其进行了表征,并利用酯化反应作为探针反应评价了其催化性能.结果表明,合成的磁性纳米固体酸催化剂在酯化反应中表现出很好的催化活性.     

Electrospinning fabrication of rime-like NiO nanowires/nanofibers hierarchical architectures and their photocatalytic properties

Rime-like NiO Nanowires/nanofibers hierarchical architectures have been fabricated employing a co-precipitation reaction and electrospinning method. The synthesized hierarchical structure was characterized using SEM, XRD and BET analysis methods. The effects of growth temperature and reaction time on the morphologies of the as-prepared structures were investigated by SEM characterization and a possible mechanism for the formation of NiO hierarchical structures is proposed. Based on the nitrogen adsorption and desorption measurements, the BET surface area of the as-obtained sample is 61.0 m²/g and the pore sizes of ca. 5.0 nm. The catalytic efficiency of the NiO nanomaterials developed was evaluated by the photocatalytic degradation of acetaldehyde. In comparison with sphere-like and fiber-like structures, the NiO hierarchical structures show an excellent ability to rapidly acetaldehyde pollutant, which may be attributed to its unique hierarchical and porous surface structures.     

共沉淀法合成Sm3+掺杂的Sr2CeO4的荧光光谱

以（NH4）2C2O4为沉淀剂，用Sr，Ce和Sm的硝酸盐为反应物，制备了Sr2CeO4：Sm的前驱体。将此前驱体烧结后，得到了Sm掺杂的Sr2CeO4白色荧光材料。其荧光光谱强度与烧结温度和Sm^3＋的掺杂浓度密切相关，当烧结温度为1050℃以及Sm^3＋的掺杂浓度为1mol％时，峰值为470nm的宽带以及Sm^3＋在608和654nm的线谱发射最强。同直接在高温固相反应下得到的样品进行比较，其发射光谱强度大大提高。     

Investigation of structural,optical and photoluminescence properties of non-essential amino acid capped zinc sulfide nanoparticles for optoelectronic applications

The objective of the study is to synthesize Zinc Sulphide nanoparticles (ZnS) with different amino acid capping agents in aqueous solution by a simple and cost effective facile chemical co precipitation method and analyze their optoelectronic features. Bio compatibility with less toxic amino acids such as l-Glutamic acid, l-Alanine and l-Asparagine were used as capping agents. These amino acids are from Non-essential amino acid group and its capping behavior suitable for semiconducting nanoparticles like ZnS. The role of non essential amino acids were to stabilize the nanoparticle against agglomeration and also to provide chemical passivation that leads to a significant influence on the improved structural, optical and photoluminescence properties of ZnS nanoparticles. The detailed structural analysis of Zinc Sulphide nano particles revealed by X-ray diffraction method (XRD). From this analysis observed the formation of Cubic ZnS nanoparticles with an average crystallite size in the range of 2.08–2.22 nm.The morphology of the nano particles studied by Field emission scanning electron microscope (FESEM). Particle size examined by Dynamic Light scattering studies (DLS) and which revealed that particle size ranges are below 50 nm. The functional groups of nanoparticles were identified by Fourier transform Infrared spectroscopy (FT-IR) studies. Photoluminescence studies attributed that the considerable emission bands. The UV–Vis analysis disclosed the optical band gap range from 3.77 eV to 3.95 eV.     

Synthesis and characterization of nano silver ferrite composite

We report the synthesis of nano sized silver ferrite composite having the empirical formula AgFeO₂ by a co-precipitation method. The resulting powders are thin platelets, transparent and a rich ruby red in color in transmission. The X-ray diffraction (XRD) powder data consisted of only nine reflections, and the analysis showed the unit cell to be rhombohedral. The powders showed extensive XRD line broadening and the sizes of the crystals are calculated to be in the range 4-36.5 nm. The morphology of the silver ferrite composite studied using scanning electron microscope showed nano sized particles. The particle size is found to increase with increase in annealing temperature. The magnetic behavior, measured using a vibrating sample magnetometer, indicated a change from paramagnetic to ferromagnetic with increase in particle size.     

Effect of Pb on structural and magnetic properties of Ba-hexaferrite

Lead was doped in barium hexaferrite by co-precipitation method and the Pb-doped Ba-hexaferrite with compositions of Ba_1−xPb_xFe₁₂O₁₉ was investigated for the first time at x=0.0, 0.2, 0.4, 0.6, 0.8, 1.0. The molar ratio (Fe³⁺/Ba²⁺) of the solutions was kept 12 while pH was maintained at 13 by using NaOH (M=5) as precipitating agent. Prepared samples were sintered at 965±5 °C for three hours. Structural and morphological studies were done by X-ray diffractometer (XRD) and the scanning electron microscope (SEM). SEM micrographs confirmed the formation of hexagonal plate like structures and particle size was observed to be increased with the increase in Pb concentration. The hysteresis loops obtained from the magnetometer showed that with the increase in Pb concentration, the coercivity decreased while magnetic induction and remanence increased, which in turn increased the maximum energy product (BH)_max. Lower coercivity and the moderate increase in saturation magnetization obtained from Pb doping makes the material useful for magnetic recording media and other frequency based applications.     

Synthesis of ferromagnetic semiconductor 0.67FeTiO3-0.33Fe2O3 powder by chemical co-precipitation

0.67FeTiO₃-0.33Fe₂O₃ (IH33) solid solution powder was successfully synthesized by a chemical co-precipitation method using a mixture of ferrous and ferric salts as start material. Single phase of IH33 was obtained when the preparation was performed in argon atmosphere in order to protect Fe²⁺ ions from oxidization. Investigation of X-ray photoelectron spectroscopy confirmed the presence of Fe²⁺ ions in the IH33 powder. Magnetic measurement showed that the IH33 powder exhibited room-temperature ferromagnetism with a coercivity of 160 Oe.