固体酸ZrO2-Ce2O3／SO4^2-催化合成丙二酸二丁酯

以含铈固体超强酸ZrO2-Ce2O3／SO4^2-为催化剂，丙二酸和正丁醇为原料合成了丙二酸二丁酯。最佳反应条件为：催化剂活化温度500℃，丙二酸100mmol，n(酸)：n(醇)=1．0：2．5，催化剂用量1g,反应时间2h，酯化率达95．8％。结果表明，加入铈有助于提高固体超强酸的使用寿命。     

纳米固体超强酸SO2-4/Fe2O3催化合成尼泊金酸乙酯

以纳米固体超强酸SO2-4/Fe2O3催化尼泊金酸与乙醇的酯化反应合成了尼泊金酸乙酯.较适宜的反应条件为:尼泊金酸25 mmol,n(尼泊金酸):n(乙醇)=1:4,ω(催化剂)=3.73%,甲苯15 mL,于84℃～86℃反应3 h,产率达到93.3%.     

固体超强酸SO2-4/SnO2-TiO2-Al2O3催化合成PEG6000双山嵛酸酯

以自制的固体超强酸5O2-/SnO2-TiO2-Al2O3催化山嵛酸与聚乙二醇6000(PEG6000)的酯化反应,合成了PEG6000双山嵛酸酯(DB6000),其结构经IR确证.较适宜的反应条件为:PEG6000 80 mmol,n(山嵛酸)∶n(PEG6000) =2.2∶1.0,催化剂用量为总反应物质量的0.8％,氮气保护下于210℃反应6h,酯佗率高于99％.     

固体超强酸ZrO_2/S2O_8~(2-)催化合成肉桂酸甲酯

研究了在固体超强酸ZrO2/S2O2-8催化下,肉桂酸与甲醇作用合成肉桂酸甲酯的工艺.考查了催化剂的用量、酸醇摩尔比、反应时间及催化剂的性能对反应的影响.最佳反应条件为∶n(肉桂酸)∶n(甲醇)=1∶10,m(肉桂酸)∶m(催化剂)=3∶1,反应温度90～95℃,反应时间5h,酯化率为95.7%.     

La(OTf)_3催化合成1,3-二噁烷-4,6-二酮化合物的研究

研究了在La(OTf)3的催化条件下,以丙二酸和酮为原料,缩合反应合成了3种1,3-二噁烷-4,6-二酮化合物.考察了酸酮物质的量之比、反应温度、反应时间、催化剂用量及催化剂的稳定性等因素对反应的影响.确定了其最佳反应条件为:取0.1mol丙二酸,n(丙二酸)∶n(酮)=1.0∶1.1,催化剂用量为0.3mol%,反应温度30℃,反应时间为3.0h,在上述反应条件下,产品收率可达62.3%～77.5%.     

纳米复合固体超强酸S_2O_8~(2-)/CoFe_2O_4催化合成癸二酸二乙酯

将硫酸钴、硫酸亚铁在NaOH溶液中与NaHCO3反应制得碱式碳酸盐前驱体 ,后者用 (NH4 ) 2 S2 O8浸渍、干燥 ,再经 5 0 0℃焙烧得到固体超强酸催化剂S2 O2 -8/CoFe2 O4 。产物经XRD、TEM、BET、TG DTA及化学法等检测 ,含硫量 4 5 2 % ,粒径为 4 2nm ,比表面积为 1 4 6m2 /g ,粒度均匀。催化剂的酸强度处于 -1 6 0 2和-1 4 5 2之间。以该固体酸为催化剂 ,由癸二酸和无水乙醇合成了癸二酸二乙酯。最佳反应条件为 :n(醇 )∶n(酸 ) =4 0∶1 0 ,癸二酸 0 1mol,催化剂 1 0 g ,反应时间 2 5h。在此反应条件下 ,酯化率可达 93 6%。     

固体超强酸SO2-4/TiO2-SnO2的制备、表征及催化合成D, L-丙交酯

采用沉淀法在不同工艺条件下制备了稀土改性的新型固体超强酸SO2-4/TiO2-SnO2催化剂, 考察了其对D, L-乳酸合成D, L-丙交酯的催化活性, 并通过Hammett指示剂法测定了催化剂的酸强度, 用FT-IR和FT-Raman技术考察了焙烧温度、硫酸浸渍液浓度和浸渍时间以及La2O3的负载量对该固体超强酸结构和性能的影响. 研究结果表明: SnO2的存在促进了金红石相TiO2的形成, 在600 ℃焙烧3 h、 3.0 mol/L H2SO4溶液浸渍12 h、 n(Ti4+): n(Sn4+): n(La3+)=1:1:0.05条件下制备的SO2-4/TiO2-SnO2的酸强度最大, 达-13.75以上, 催化合成丙交酯的产率最高(78.4%). 并且考察了催化剂用量对D, L-丙交酯粗产率的影响和催化剂重复使用的性能.     

固体酸催化剂对二甲醚水蒸气重整制氢过程的影响

将 HZSM-5 (n(SiO2)/n(Al2O3) = 25, 38, 50 和 93.5), HM, Hβ, HY 和γ-Al2O3 等多种固体酸催化剂用于二甲醚(DME)水解, 并将其分别同自制的 CuO/ZnO/Al2O3 催化剂进行机械混合, 制备双功能催化剂并用于 DME 水蒸气重整制氢反应. 结合 NH3 程序升温脱附表征手段, 考察了固体酸催化剂酸性位的强度、酸量及种类对 DME 水解和重整反应的影响;结合热重-差热扫描量热分析表征手段, 研究了 HZSM-5(93.5)和γ-Al2O3 在 DME 水解过程中的稳定性. 在此基础上, 进一步研究了固体酸催化剂对 DME 重整制氢反应中 DME 转化率、H2 摩尔产率以及含碳气体产物选择性的影响. 结果表明, 固体酸催化剂的酸性位的强度和酸量对 DME 重整制氢过程具有显著的影响, 强酸度和高酸量无益于 DME 水蒸气重整制氢;以 HZSM-5 为固体酸的双功能催化剂具有较好的低温活性, 而以γ-Al2O3 为固体酸的双功能催化剂在高温下具有较高的 H2 产率.     

固体超强酸SO42-/SnO2-TiO2-Al2O3催化合成PEG6000双山嵛酸酯

以自制的固体超强酸SO42-/SnO2-TiO2-Al2O3催化山嵛酸与聚乙二醇6000(PEG6000)的酯化反应,合成了PEG6000双山嵛酸酯(DB6000),其结构经IR确证。较适宜的反应条件为:PEG6000 80 mmol,n(山嵛酸):n(PEG6000)=2.2:1.0,催化剂用量为总反应物质量的0.8%,氮气保护下于210℃反应6 h,酯化率高于99%。     

SO42-/ZrO2-TiO2催化苯与1-十二烯烷基化合成十二烷基苯

利用沉淀-浸渍法制备了SO42-/ZrO2-TiO2固体酸催化剂,优化了SO42-/ZrO2-TiO2催化苯与1-十二烯烷基化合成十二烷基苯的工艺条件,并通过IR及GC/MS对产物的结构进行了表征.结果表明: SO42-/ZrO2-TiO2对苯与1-十二烯的烷基化反应具有良好的催化性能,其催化中心主要为B酸中心.0.12g催化剂/ mL1-十二烯、n(苯)/n(烯)=6:1、反应时间3 h等优化条件下1-十二烯转化率100%,LAB与2-LAB选择性分别达到90.3%和88.6%.使用后的催化剂可以通过H2SO4浸渍500 ℃焙烧再生.GC/MS分析表明产物主要包括2～6-LAB及少量二烷基苯.     

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.