γ-Al2O3对SCR脱硝催化剂V2O5-WO3/TiO2的改性研究

采用溶胶凝胶法制备了不同γ-Al₂O₃含量的钛铝复合载体,以此为载体采用浸渍法负载V₂O₅和WO₃制备了一系列催化剂。采用X射线衍射(XRD)、比表面积测定(BET)、程序升温还原(H₂-TPR)、高分辨率透射电子显微镜(HRTEM)等表征技术对催化剂表面形态进行分析,同时在模拟氨气选择性催化还原NO(NH₃-SCR)的反应条件下,对催化剂的脱硝反应活性和SO₂抗中毒进行考察。结果发现,TiO₂和γ-Al₂O₃之间的协同作用使得V₂O₅-WO₃/TiO₂-γ-Al₂O₃催化剂的脱硝效率及活性窗口明显优于单一载体制备的催化剂,表现出了良好的热稳定性和抗SO₂毒化能力,特别是V₂O₅-WO₃/TiO₂-15% γ-Al₂O₃在310~460 ℃,NO的转化率均在80%以上,反应窗口最宽。各种表征结果表明,TiO₂-γ-Al₂O₃复合载体中γ-Al₂O₃高度分散在TiO₂上,复合载体具有较大的比表面积,同时具有较强的还原能力。     

TiO2对Ni/Al2O3催化剂CO甲烷化性能的影响

采用溶胶凝胶法制备了一系列不同TiO₂含量的TiO₂-Al₂O₃复合载体,并通过浸渍法制备了NiO/TiO₂-Al₂O₃催化剂。分别考察了不同TiO₂含量的NiO/TiO₂-Al₂O₃催化剂及反应温度对CO甲烷化催化性能的影响。实验结果表明,当复合载体中TiO₂质量分数为30%,反应温度为350～450 ℃时,催化剂催化活性较高。利用N₂吸附-脱附(BET)、X射线衍射(XRD)及H₂程序升温还原(H₂-TPR)等手段对催化剂物化性能进行了表征。结果表明,加入适量的TiO₂能抑制镍铝尖晶石NiAl₂O₄物种的生成,改善NiO的表面分散性能,避免大晶粒NiO的形成,也改善了催化剂的还原性能,从而提高催化剂的CO甲烷化活性。     

复合载体TiO2-Al2O3的制备及其对Ni-Mo-S负载型催化剂加氢脱氧性能的影响

采用共沉淀法制备出复合载体TiO₂-Al₂O₃,用N₂-吸附、XRD和吡啶吸附红外光谱等手段进行表征。采用原位硫化法制备Ni-Mo-S/TiO₂-Al₂O₃负载型催化剂,以苯酚为模型化合物研究其加氢脱氧催化性能。主要研究铝源和沉淀剂对TiO₂-Al₂O₃复合载体性能的影响以及其作为载体对Ni-Mo-S/TiO₂-Al₂O₃催化苯酚加氢脱氧反应的影响。结果表明,以氯化铝为铝源制备的复合载体具有较大的孔容和孔径,孔容达1.12cm³/g,孔径达18.0nm;以硫酸铝为铝源和以碳酸氢铵为沉淀剂制备的复合载体具有较大的比表面积,高达295m²/g;氨水沉淀制备的复合载体具有较多的L酸;以硫酸铝为铝源制备的复合载体形成少量的B酸。TiO₂-Al₂O₃作为载体影响Ni-Mo-S/TiO₂-Al₂O₃负载型催化剂加氢脱氧性能的主要因素是载体的酸性和载体的比表面积。在300℃,4.0MPa条件下Ni-Mo-S/TiO₂-Al₂O₃催化苯酚的转化率达81.9%,产物中无氧化合物的总选择性达100%,脱氧率达79.4%。     

V2O5-CuO/TiO2催化剂中低温选择性催化NOx还原研究

浸渍法制备了一系列V₂O₅-CuO/TiO₂催化剂,考察中低温(200~300℃)条件下,以氨为还原剂选择性催化还原NO_x的活性,并利用比表面积及微孔孔隙分析仪(BET)、X射线衍射(XRD)对催化剂进行微观表征和分析。结果表明,500℃焙烧的2V16Cu/TiO₂催化剂展示了最佳的中低温催化活性和较宽的活性温度范围,在空速6.0×10⁴ h^-1、225℃条件下,NO_x转化率达97.3%,250℃时达到100%,温度升至300℃,催化活性仍保持在100%。XRD结果表明,随着Cu负载量的增加,逐渐显现CuO的特征峰。结合活性评价数据说明,CuO是VCu/TiO₂催化剂的主要活性组分之一,是降低SCR催化反应温度的重要因素。BET结果表明,CuO的负载对钒钛催化剂的表面结构有较大影响。耐硫性实验结果表明,添加钒氧化物制备的2V16Cu/TiO₂催化剂的抗硫性能有所改善。     

电镀法制备Pt/TiO2纳米管电极及其电催化析氢性能

采用阳极氧化法制备得到锐钛矿型二氧化钛(TiO₂)纳米管阵列,在其表面通过电镀法沉积Pt,得到了低铂的Pt/TiO₂纳米管电极(Pt/TiO₂?NTs)。通过扫描电子显微镜和透射电子显微镜对其进行形貌表征后发现,Pt较为均匀地分布于TiO₂纳米管阵列中。进一步的电催化析氢结果表明,Pb/TiO₂?NTs在10 mA·cm^-2时,过电位为0.079 V,塔菲尔斜率为42.7 mV·dec-1,较Pt/TiO₂致密膜电极(Pt/TiO₂?F)以及商业Pt/C催化剂显示了更为优异的催化活性。同时,在长循环稳定性测试(3000个周期)中,Pb/TiO₂?NTs相较于上述2种对比电极显示了更为优异的稳定性。     

C/Cr2O3/TiO2复合材料的制备及其光催化性能研究

本文以制革含铬革屑为原材料,基于矿物鞣剂复鞣的原理,将Ti(IV)均匀、稳定地负载到含铬革屑上,在氮气氛围下,经高温热解制备得到C/Cr₂O₃/TiO₂光催化剂,并研究了其对四环素(TC)的光催化降解效果及机理。结果表明,C/Cr₂O₃/TiO₂光催化剂具有明显的介孔结构,比表面积较大,为277.47 m²·g^-1,Cr₂O₃和TiO₂已实现复合并负载在生物炭(C)上。通过光催化降解发现,在模拟自然光照下,当催化剂用量为0.04 g,TC初始浓度为50 mg·L^-1,溶液pH为2时,TC的去除率可高达99.99%。结合自由基捕获实验发现,C/Cr₂O₃/TiO₂光催化剂对TC的降解作用主要依靠反应体系中产生的大量·O₂^-,·OH和h⁺。     

Pt/H-TiO2催化剂制备及其甲醇电催化氧化性能

以四氯化钛为前驱体,采用水热法合成二氧化钛纳米棒（TiO₂,白色）,在纯H₂气氛,将其550 ^oC热处理2 h,即得有氧缺陷和Ti³⁺填隙原子的二氧化钛纳米棒（H-TiO₂,灰黑色）. 将Pt纳米粒子（~ 1.9 nm）负载于此两种二氧化钛纳米棒上,制得Pt/TiO₂和Pt/H-TiO₂催化剂. XRD和XPS测试表明,氢处理TiO₂晶型没有变化,仍属金红石型,但增加了Ti-OH表面物种. 电化学测试表明,H-TiO₂载体能够增强氧在Pt表面的吸脱附能力,从而提高其甲醇电催化氧化活性,Pt/H-TiO₂电极甲醇氧化峰电流密度为Pt/TiO₂电极的1.6倍、Pt/C电极的2.1倍.     

V2O5-Sb2O3-TiO2催化剂 低温NH3还原NO及其抗H2O和SO2毒化性能

浸渍法制备了催化剂V₂O₅-Sb₂O₃-TiO₂,考察了V₂O₅、Sb₂O₃负载量、pH值和焙烧温度对催化剂V₂O₅- Sb₂O₃-TiO₂低温氨选择性催化还原(SCR)NO活性的影响;同时,考察了催化剂V₂O₅-Sb₂O₃-TiO₂抗H₂O和SO₂毒化性能。结果表明,V₂O₅和Sb₂O₃负载量分别为5%和2%、焙烧温度为400℃、pH值为4时,催化剂SCR活性最好,反应温度220℃时,可达97%。Sb₂O₃的加入不仅能增强V₂O₅/TiO₂的催化活性,而且能明显提高催化剂的抗H₂O和SO₂毒化性能。SO₂、NO吸附暂态反应和TG-DTG测试表明,Sb₂O₃的促进机制主要是促进了催化剂在SO₂存在条件下对NO的吸附,同时,减弱了硫酸铵盐与催化剂之间的相互作用,硫酸铵盐更容易分解。     

OMS-2/Al2O3/堇青石整体式催化剂的制备及其催化性能研究

以Al₂O₃/堇青石蜂窝陶瓷为载体,氧化锰八面体分子筛(OMS-2)为活性组分,采用涂覆法制备了系列整体式催化剂。考察了黏合剂种类和活性组分涂覆次数对二甲醚(DME)催化燃烧性能的影响,并对催化剂进行XRD、BET、SEM、H₂-TPR、O₂-TPD等表征。结果表明,以甲氧基聚乙二醇为黏合剂经一次涂覆制备的整体式催化剂的性能最佳,活性组分OMS-2以相互交织的簇体均匀分布在载体上,并与Al₂O₃之间存在较强的相互作用。涂层的添加有效增加了催化剂的比表面积,提高了催化剂的性能,最佳催化活性t₉₀为257 ℃。     

不同前驱物制备的MnOx/TiO2联合O3催化氧化NO性能

分别以乙酸锰（MnAc）、氯化锰（MnCl₂）和硝酸锰（Mn（NO₃）₂）为前驱物,采用浸渍法制备MnAc/TiO₂、MnCl/TiO₂和MnN/TiO₂三种催化剂,并采用氮吸附、SEM、H₂-TPR、O₂-TPD、XRD和XPS进行表征。在固定床反应器上研究了三种催化剂的联合臭氧催化氧化NO性能。结果表明,以乙酸锰为前驱物制备的MnAc/TiO₂催化剂联合臭氧催化氧化NO活性最高;MnAc/TiO₂催化剂颗粒分散性好,比表面积相对较大,催化剂表面Mn³⁺较多,因而具有较高的催化活性。     

Sc2MgGa2 and Y2MgGa2

Scandium magnesium gallide, Sc₂MgGa₂, and yttrium magnesium gallide, Y₂MgGa₂, were synthesized from the corresponding elements by heating under an argon atmosphere in an induction furnace. These intermetallic compounds crystallize in the tetragonal Mo₂FeB₂‐type structure. All three crystallographically unique atoms occupy special positions and the site symmetries of (Sc/Y, Ga) and Mg are m2m and 4/m, respectively. The coordinations around Sc/Y, Mg and Ga are pentagonal (Sc/Y), tetragonal (Mg) and triangular (Ga) prisms, with four (Mg) or three (Ga) additional capping atoms leading to the coordination numbers [10], [8+4] and [6+3], respectively. The crystal structure of Sc₂MgGa₂ was determined from single‐crystal diffraction intensities and the isostructural Y₂MgGa₂ was identified from powder diffraction data.     

Zur Kenntnis der Dialkalimetalldichalkogenide β-Na2S2, K2S2, α-Rb2S2, β-Rb2S2, K2Se2, Rb2Se2, α-K2Te2, β-K2Te2 und Rb2Te2

On Dialkali Metal Dichalcogenides β-Na₂S₂, K₂S₂, α-Rb₂S₂, β-Rb₂S₂, K₂Se₂, Rb₂Se₂, α-K₂Te₂, β-K₂Te₂ and Rb₂Te₂ The first presentation of pure samples of α- and β-Rb₂S₂, α- and β-K₂Te₂, and Rb₂Te₂ is described. Using single crystals of K₂S₂ and K₂Se₂, received by ammonothermal synthesis, the structure of the Na₂O₂ type and by using single crystals of β-Na₂S₂ and β-K₂Te₂ the Li₂O₂ type structure will be refined. By combined investigations with temperature-dependent Guinier-, neutron diffraction-, thermal analysis, and Raman-spectroscopy the nature of the monotropic phase transition from the Na₂O₂ type to the Li₂O₂ type will be explained by means of the examples α-/β-Na₂S₂ and α-/β-K₂Te₂. A further case of dimorphic condition as well as the monotropic phase transition of α- and β-Rb₂S₂ is presented. The existing areas of the structure fields of the dialkali metal dichalcogenides are limited by the model of the polar covalence.     

The alkali hypophosphites KH2PO2, RbH2PO2 and CsH2PO2

The structures of the hypophosphites KH₂PO₂ (potassium hypophosphite), RbH₂PO₂ (rubidium hypophosphite) and CsH₂PO₂ (caesium hypophosphite) have been determined by single‐crystal X‐ray diffraction. The structures consist of layers of alkali cations and hypophosphite anions, with the latter bridging four cations within the same layer. The Rb and Cs hypophosphites are isomorphous.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

Formal [(2+2)+2] and [(2+2)+(2+2)] nonconjugated dienediyne cascade cycloadditions

[reaction: see text] Fluoranthene 2 and heptacycle 3 are easily accessible from the reaction of diyne 1 and norbornadiene (NBD) in the presence of the rhodium catalyst. The unusual [(2+2)+(2+2)] adduct 3 was confirmed by the X-ray crystal structure analysis.     

Thermal decomposition of Me3SnO2PCl2, Me2Sn(O2PCl2)2 and Ph3SnO2PCl2

TG and DTA studies on Me₃SnO₂PCl₂, Me₂Sn(O₂PCl₂)₂ and Ph₃SnO₂PCl₂ were carried out under dynamic argon atmosphere. The results show that the decomposition proceeds in different stages leading to the formation of Sn₃(PO₄)₂ as a stable product. This compound was characterized by IR spectroscopy. Decomposition schemes involving reductive elimination reactions were proposed.     

The bivalent metal hypophosphites Sr(H2PO2)2, Pb(H2PO2)2 and Ba(H2PO2)2

The structures of isomorphous monoclinic strontium and lead bis­(di­hydrogenphosphate), Sr(H₂PO₂)₂ and Pb(H₂PO₂)₂, and orthorhombic barium bis­(di­hydrogen­phos­phate), Ba(H₂PO₂)₂, consist of layers of hypophosphite anions and metal cations exhibiting square antiprismatic coordination by O atoms. The Sr and Pb atoms are located on sites with point symmetry 2, and the Ba atoms are on sites with point symmetry 222. Within the layers, each anion bridges four metal cations.