焙烧温度对橄榄石催化甲苯裂解性能的影响

以橄榄石为催化剂,通过N2物理吸附、XRD、H₂-TPR和TEM等手段研究了焙烧温度对催化剂的结构、物相、还原性能以及甲苯裂解反应活性的影响。结果表明,焙烧温度对催化剂结构和活性影响显著,低温焙烧时主要存在Mg₂SiO₄和Fe₂O₃的晶相衍射峰,随着焙烧温度的升高,Fe₂O₃的晶相衍射峰逐渐消失,随之出现了非常明显的 (Fe, Mg)SiO₃的衍射峰。选择适中的焙烧温度可以增加表面上可还原Fe₂O₃的量,从而拥有较高的甲苯裂解活性位。在实验考察范围内,900℃焙烧的橄榄石表现了最高的甲苯裂解活性。TG结果表明,该温度焙烧的橄榄石具有较好的抗积炭性能。     

助催化剂对Fe1-xO基氨合成催化剂热稳定性的影响

采用梯级升温耐热和层叠添加助催化剂技术,运用XRD、BET和SEM表征方法,研究助催化剂对Fe_1-xO基氨合成催化剂热稳定性的影响。结果表明,多助剂的Fe_1-xO基氨合成催化剂晶粒随温度升高而长大,比Fe₃O₄基催化剂晶粒小且长大缓慢;孔径和孔容随温度升高而减小。K2O和CaO能提高催化剂活性,但不利于热稳定性,CaO和Al₂O₃能均匀分散催化剂晶粒,M既能提高催化剂活性,又能增强其耐热性。     

Fe2O3对高变质程度脱灰煤热解反应性与半焦结构的影响

利用热天平研究了共混合法负载Fe₂O₃高变质程度脱灰煤的热解反应性,结果表明煤粉负载Fe₂O₃后热解反应性高于无负载的热解反应性。负载Fe₂O₃煤样在程序升温加热的马弗炉中制备出半焦,利用FTIR、XRD和RAMAN 等分析了半焦结构。由TG和FTIR可知,负载Fe₂O₃煤样热解时,热解转化率增加,热解后自由基增加。由XRD可知,Fe₂O₃没有使得煤样半焦的002峰衍射角发生明显变化,但使L_a和L_c参数明显降低,说明半焦的微晶结构石墨化程度降低。另外,在XRD分析谱图中发现部分Fe₂O₃被还原成FeO。由RAMAN可知,Fe₂O₃使半焦的G峰峰面积降低,D峰峰面积增加,说明半焦的有机结构有序化程度降低。     

化学气相沉积法制备碳纳米管过程中NH3对其微观结构和石墨化程度的影响

以二茂铁为催化剂前驱体,C₂H₂为碳源,在NH₃和N₂气氛中在Al₂O₃多孔基体上化学气相沉积制备出了一致取向的碳纳米管阵列.采用拉曼散射、扫描电子显微镜、高分辨电子显微镜、X射线衍射和元素分析等技术对产物进行表征.实验结果表明,以NH₃为载气时,所制备的碳纳米管为竹节形结构,并且有一定量的N掺杂在其中,其质量含量大约在3.46%,碳纳米管的石墨层间距在0.384 nm左右,实验产物中有Fe₃C和Fe₂N或Fe₃N的生成,NH₃在催化剂表面的吸附导致催化剂的表面性质的改变以及N的掺杂使生成的碳纳米管结构有一些缺陷,石墨化程度有所降低.碳纳米管的管径随着反应温度的增加而增大.     

Fe2O3对高变质程度脱灰煤热解反应性与半焦结构的影响

利用热天平研究了共混合法负载Fe₂O₃高变质程度脱灰煤的热解反应性，结果表明煤粉负载Fe₂O₃后热解反应性高于无负载的热解反应性。负载Fe₂O₃煤样在程序升温加热的马弗炉中制备出半焦，利用FTIR、XRD和RAMAN 等分析了半焦结构。由TG和FTIR可知，负载Fe₂O₃煤样热解时，热解转化率增加，热解后自由基增加。由XRD可知，Fe₂O₃没有使得煤样半焦的002峰衍射角发生明显变化，但使L_a和L_c参数明显降低，说明半焦的微晶结构石墨化程度降低。另外，在XRD分析谱图中发现部分Fe₂O₃被还原成FeO。由RAMAN可知，Fe₂O₃使半焦的G峰峰面积降低，D峰峰面积增加，说明半焦的有机结构有序化程度降低。     

流化床焚烧处理有机浓缩废液的结焦结渣特性

温度是有机废液焚烧的重要参数,也是影响焚烧炉结焦结渣的重要因素.实验研究分析了采用流化床焚烧处理有机浓缩废液时,焚烧温度对结焦结渣的影响.研究表明：随着焚烧温度的升高,焚烧炉的结焦结渣程度逐渐加大,渣样晶相由以Na₂SO₄、NaCl等为主转变为以Na₂SO₄、Na₂Si₃O₇等为主,且Na₂Si₃O₇在渣样中的比重随着焚烧温度的升高而升高;向焚烧炉添加石灰石、Fe₂O₃粉末、高岭黏土等添加剂能够较好地抑制焚烧炉的结焦结渣.     

焚烧含盐有机废液添加剂对流化床床料烧结的影响

研究分别以砂子和煤灰为床料,含盐废液在流化床中焚烧,添加剂CaO、Fe₂O₃、A1₂O₃对阻止床料结焦的作用机理.结果表明,当砂子或煤灰中形成Na₂CO₃时,CaO、Fe₂O₃能够解决床料的结焦问题,而Al₂O₃却促进砂子的结焦.当砂子中含有NaCl时,A1₂O₃能很好地解决砂子的结焦问题,而CaO、Fe₂O₃虽然对防止结焦有效果,但不能根本解决砂子的结焦问题.当煤灰中含有NaCl时,CaO、Fe₂O₃对于防止床料的结焦效果较好,而A1₂O₃反而造成严重结焦.研究结果为含盐有机废液在流化床中焚烧时防止床料结焦选择合适的添加剂提供理论依据.     

SO2－4/Fe2O3-γ-Al2O3固体超强酸催化剂的制备

通过浸渍法制备SO^2－₄/Fe₂O₃(SF)固体超强酸，将γ-Al₂O₃纳米纤维通过粘附的方法负载到固体超强酸SO^2－₄/ Fe₂O₃上，制得SO^2－₄/Fe₂O₃-γ-Al₂O₃(SFA)固体超强酸催化剂,并选用乙酸和丁醇的酯化反应来测试SO^2－₄／Fe₂O₃-γ-Al₂O₃(SFA)固体超强酸催化剂的催化性能，在不同催化剂种类、不同γ-Al₂O₃加入量、不同焙烧温度和时间以及不同浸渍液种类和浓度的条件下，对催化活性进行了分析和讨论。     

固体超强酸催化剂S2O2-8/Fe2O3-Al2O3的制备及其酯化性能

以硝酸铁为铁源、硝酸铝为铝源,通过共沉淀法制备固体超强酸催化剂S₂O^2-₈/Fe₂O₃-Al₂O₃。通过催化剂样品的FT-IR谱图、不同焙烧温度催化剂样品的XRD谱图、不同陈化温度的N2吸附-脱附曲线以及催化剂样品的SEM照片,研究了其晶体的形成过程。催化剂样品红外谱图表明,催化剂中的S=O有较强的共价双键特征,诱导催化剂形成超强酸性;在XRD谱图中既无Al₂O₃的晶相峰,也无Fe₂(SO₄)₃晶相峰,说明Al₂O₃与Fe₂O₃ 在催化剂样品的表面形成了Al₂O₃-Fe₂O₃ 共价键的复杂结构。采用BET方程和BJH模型计算催化剂样品的比表面积和孔径分布,经冰水陈化的催化剂样品平均孔径为9.1 nm,最可几孔径为7.5 nm,比表面积为78.9 m²·g^-1,孔容0.149 cm³·g^-1。研究了催化剂的铁与铝物质的量比、(NH₄)₂S₂O₈浸渍浓度和不同焙烧温度对硬脂酸正丁酯酯化率的影响。在反应温度85 ℃、催化剂用量0.2 g (为反应物总质量的2%)和回流反应150 min的条件下,酯化率可达84.5%。     

多孔氧化铝模板电化学沉积铁纳米线结构及磁性能

以硫酸溶液为电解质,采用两步电化学阳极氧化法制备了氧化铝有序多孔膜,孔径为20nln,孔间距为50nm左右,孔洞密度为4.5×1010个/cm2.以此多孔膜为模板,脉冲电压电化学沉积制备金属Fe纳米线阵列,单根纳米线直径为20 nm,Rietveld拟合表明纳米线择优取向为Fe(110)晶面,择优取向因子为0.30.磁滞回线结果表明,垂直于膜面的方向为易磁化方向,当磁场垂直于膜面时,矩形比高达0.914,矫顽力为1 656 Oe.     

Ordered CoFe2O4 nanowire arrays with preferred crystal orientation and magnetic anisotropy

CoFe₂O₄ nanowire arrays were fabricated by electrodeposition of Fe²⁺ and Co²⁺ into anodic aluminum oxide (AAO) templates and further oxidization. The phase structure of the nanowires is cubic spinel-type, and the XRD result exhibits perfect preferred crystallite orientation along the nanowire axes. Compared with CoFe₂O₄ nanowire arrays synthesized by other methods, the magnetic hysteresis loops demonstrate that the arrays of nanowires exhibit uniaxial magnetic anisotropy with easy magnetization direction along the nanowire axes owing to the large shape anisotropy. This approach provides a facile technology to fabricate oxide nanowires with uniaxial magnetic anisotropy.     

直流电沉积二元合金Co55Ni45纳米棒阵列及其表征

引言 一维金属及合金纳米材料由于其纳米尺寸产生的小尺寸效应、表面效应、量子尺寸效应及宏观量子隧道效应导致与常规金属及合金材料迥然不同的热、磁、光、电、敏感特性和表面稳定性,有望在纳机电系统(NEMS)、光吸收过滤器和调制器、垂直磁记录材料和巨磁阻材料、催化剂等领域取得重大突破.人们采取许多种方法进行一维金属及合金纳米材料的合成及性能研究.很多研究者以含有纳米微孔的聚碳酸酯过滤膜或多孔氧化铝膜为模板合成了Au[1]、Cu[2]、Pd[2]、Ag[3]、Fe[4]、Co[5]、CoFe[5]、Ni[6]等一维纳米线,Liu[7]在钼网上气相沉积了Cu纳米棒和纳米线,Xiong等[8]利用二茂铁的夹层结构,还原制备了银纳米线,Yen[9]利用氯化亚铜与二甲基硅氧烷聚合物胶囊材料合成了铜纳米线等,姚素薇等[10]在单晶硅上脉冲电沉积制备了Cu/Co纳米多层膜.相对于单一金属而言,合金由两种及两种以上金属组成而具有多种金属复合性能,因此更具有研究与应用价值,但目前对合金类一维纳米材料的研究还较少.本文以聚碳酸酯膜为模板,利用直流电沉积的方法制备出二元合金Co55Ni45纳米棒阵列结构材料,实验在双电极体系下进行,方法简单,所制备的Co55Ni45合金纳米棒阵列呈锥状结构且整齐排列,可用作垂直磁记录材料及原子力显微镜探针材料.     

Synthesis and magneto-transport properties of single PEDOT/Ni and PEDOT/Ni30Fe70 core/shell nanowires

Single polyethylenedioxythiophene (PEDOT) nanowires bridging pairs of electrodes were utilized as positive templates to create PEDOT/Ni and PEDOT/Ni₃₀Fe₇₀ core/shell nanowires by electrodepositing ferromagnetic material (i.e., Ni and Ni₃₀Fe₇₀) on the entire assembly, including both the electrodes and nanowire. The temperature dependence of the electrical resistance indicated that electrons are transported predominately through the ferromagnetic shell. The magnetoresistive (MR) behavior of the core/shell nanowires was investigated as a function of temperature, magnetic field orientation, shell thickness, and composition. The MR behavior of the PEDOT/Ni core/shell nanowires was anomalous for low applied magnetic fields, deviating from expected anisotropic magnetoresistance, with positive ΔR/R_O values for all field orientations. PEDOT/Ni₃₀Fe₇₀ core/shell nanowires displayed the opposite behavior, with negative ΔR/R_O for both longitudinal and transverse field orientations. The origin of this magnetoresistive behavior is postulated to be a geometry induced domain wall effect.     

Structure and magnetic properties of Fe1−xCox nanowires in self-assembled arrays

Fe_1−xCo_x nanowires in self-assembled arrays with varying compositions were produced by the template-assisted pulsed electrochemical deposition method. The structural and magnetic properties of the arrays were investigated using several experimental techniques. TEM analyses indicated that the nanowires were regular, uniform, 8 μm in length and 50 nm in diameter. The results of X-ray diffraction indicated that the body-centered-cubic (bcc) (α), face-centered-cubic (fcc) (γ), and hexagonal-close-packed (hcp) () Fe–Co phases appeared in different compositions. Magnetic measurements showed that the coercivity and squareness of the hysteresis loops of the Fe_1−xCo_x changed with their compositions, which may be attributable to shape anisotropy. The room temperature ⁵⁷Fe Mössbauer spectra of the arrays of the Fe_1−xCo_x nanowires revealed strong shape anisotropy.     

Ni纳米线阵列的电化学组装及磁性能研究

利用二次氧化法制备了多孔阳极氧化铝(AAO)模板,通过恒电位沉积法在模板内组装了Ni纳米线阵列。采用SEM、TEM、SAED、EDS和VSM等检测技术对填孔过程、阵列形貌、结构和磁性能进行了分析和表征。结果表明,Ni纳米线在纳米孔中的生长过程经历四个阶段,填孔终止时间控制在第三阶段。适宜AAO模板中Ni纳米线沉积的电位为-0.9 V,pH为3.5。Ni纳米线是沿着(111)方向生长的单晶结构。当外磁场平行或垂直Ni纳米线阵列时,在磁场强度周期变化下,测量纳米线阵列磁滞现象的闭合磁化曲线,Ni纳米线阵列在平行和垂直两个方向的磁性不同,剩余磁化强度Mr与饱和磁化强度Ms之比分别为0.282和0.055,其矫顽力是293 Oe、100 Oe。     

氧化钛纳米线阵列的溶胶凝胶模板合成与表征

采用二次阳极氧化工艺制备了高度规则排列的多孔氧化铝（PAA）模板,并利用模板法与溶胶-凝胶法结合的模板组装技术制备了氧化钛纳米线阵列,得到了直径在50 nm左右,线间距约为50 nm的纳米线阵列.研究了模板组装过程不同压力条件对溶胶向模板孔洞中填充度的影响,发现在一定的负压条件下,有利于PAA孔中气体的排出,得到高的溶胶填充度,进而制备出高质量的纳米线阵列.分别通过SEM及XRD技术表征了PAA模板及纳米线的形貌及相结构.SEM观察发现纳米线彼此平行,表面光洁,不存在龟裂,纳米线的长度和直径与所使用模板的厚度和直径一致,表明纳米线的生长受控于模板;XRD分析表明模板为单一的θ-Al₂O₃晶型,纳米线为锐钛矿型TiO₂.     

用多孔氧化铝膜为模板制备Fe磁性纳米线

铝在0．3mol／L草酸或硫酸介质中经过阳极氧化,得到不同孔径的多孔氧化铝模板,在此模板中电解沉积的Fe纳米线排布规则、有序,长径比约为150。根据测量的磁滞回线,可以看到制备的铁纳米线具有较大的磁各向异性,其垂直方向具有较高的矫顽力。     

Tunable Magnetic Properties of Heterogeneous Nanobrush: From Nanowire to Nanofilm

With a bottom-up assemble technology, heterogeneous magnetic nanobrushes, consisting of Co nanowire arrays and ferromagnetic Fe₇₀Co₃₀ nanofilm, have been fabricated using an anodic aluminum oxide template method combining with sputtering technology. Magnetic measurement suggests that the magnetic anisotropy of nanobrush depends on the thickness of Fe₇₀Co₃₀ layer, and its total anisotropy originates from the competition between the shape anisotropy of nanowire arrays and nanofilm. Micromagnetic simulation result indicates that the switching field of nanobrush is 1900 Oe, while that of nanowire array is 2700 Oe. These suggest that the nanobrush film can promote the magnetization reversal processes of nanowire arrays in nanobrush.     

Hierarchical Cd4SiS6/SiO2 Heterostructure Nanowire Arrays

Novel hierarchical Cd₄SiS₆/SiO₂ based heterostructure nanowire arrays were fabricated on silicon substrates by a one-step thermal evaporation of CdS powder. The as-grown products were characterized using scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. Studies reveal that a typical hierarchical Cd₄SiS₆/SiO₂ heterostructure nanowire is composed of a single crystalline Cd₄SiS₆ nanowire core sheathed with amorphous SiO₂ sheath. Furthermore, secondary nanostructures of SiO₂ nanowires are highly dense grown on the primary Cd₄SiS₆ core-SiO₂ sheath nanowires and formed hierarchical Cd₄SiS₆/SiO₂ based heterostructure nanowire arrays which stand vertically on silicon substrates. The possible growth mechanism of hierarchical Cd₄SiS₆/SiO₂ heterostructure nanowire arrays is proposed. The optical properties of hierarchical Cd₄SiS₆/SiO₂ heterostructure nanowire arrays are investigated using Raman and Photoluminescence spectroscopy.     

Low temperature sintering of magnetic Ni0.5Co0.5Fe2O4 ceramics prepared from mechanochemically synthesized nanopowders

The effect of mechanochemichally synthesized nanoceramics Ni_0.5Co_0.5Fe₂O₄ (NCF) on the sintering process was studied. After 60?h of mechanochemichal treatment, the amount of formed ferrite phase reaches to about 70?vol%. From 60–100?h 10% increase in volume fraction of synthesized magnetic phase can be observed. Further increment in process time had no remarkable effect on the NCF phase formation. After 60?h, ceramic nanoparticle formation is directly reflected by TEM image and specific surface area (28?m²/g equivalent to 40?nm in diameter). The coercivity (Hc) shows a drastic diminution from 1996 to about 159?Oe by 60?h process time. Further milling treatment has no observable effect on the values of Hc. Additionally, the magnetization saturation (Ms) increases up to ~13?emu/g by 60?h mechanical milling of powders mixture. Thereafter from 60?h to 100?h, the Ms rapidly increased from 13 to 32?Oe. Finally, with continuing mechanochemichal process up to 130?h the Ms slightly diminished (~29?emu/g). Additionally, compared to synthesized powders the higher values of M_S (65?emu/g) and lower values of H_C (140?Oe) for sintered ceramic were detected. The low sintering temperature (1300?°C) for magnetic NCF sample prepared from nanoparticles may be caused by the high activity of nanoceramics.