SO_4~(2-)/SiO_2表面酸性的红外光谱和密度泛函理论研究

对介孔SiO2及硫酸根促进的SiO2样品进行了原位吡啶吸附红外光谱测试,分别建立了硫酸根促进前后的SiO2表面原子簇模型,用密度泛函理论对其吡啶吸附行为进行了计算,分析了SO42-/SiO2表面酸性产生的机理.实验和计算结果表明,SO42-/SiO2表面不存在Lewis酸中心,原位红外谱图中表征Lewis酸性的特征峰对应于氢键吸附吡啶的环振动,这种氢键作用因SiO2表面的硫酸根促进而得到加强.HSO4-螯合结构为SO42-/SiO2表面Brφnsted酸中心,其酸强度强于表面磺酸基团修饰的介孔SiO2材料SO3H-MSU,而弱于HZSM-5.SO42-/SiO2的酸催化活性源于其表面的Brφnsted酸性.     

硫酸根促进的纯硅MCM-41催化假性紫罗兰酮环化合成紫罗兰酮的性能

 分别采用硫酸和硫酸铵溶液作为促进剂,对MCM-41进行表面硫酸根促进,并在不同温度下焙烧制得一系列硫酸根促进的纯硅MCM-41样品SM和ASM. 采用氮吸附-脱附、吸附氨的程序升温脱附(NH3-TPD)、 热重分析(TG-DTG)、 元素分析和红外光谱(FT-IR)等表征方法对两类样品的介孔结构、硫酸根促进过程和表面酸性进行了考察,并通过环化合成紫罗兰酮这一典型的液体酸催化反应评价其催化活性. 结果表明,经450 ℃焙烧的样品(SM-450和ASM-450)中促进剂完全分解,不存在作为原始促进剂或分解中间产物的游离硫酸分子,硫酸根以双齿螯合配位结构存在于SiO2表面. 原位吡啶吸附红外光谱显示ASM-450表面同时存在L酸和B酸中心, NH3-TPD测试结果表明其酸强度较弱. SM-450和ASM-450具有与商品化氢型酸性树脂Amberlyst-15相当的催化性能,其催化作用来源于一般被认为不具备酸活性的SO2-4/SiO2表面螯合结构. 在较低反应温度下, ASM-450具有优于Amberlyst-15的催化性能,并在循环使用5次后仍保持较高的催化活性.     

硫酸改性MCM-41分子筛催化剂的制备及其在甘油脱水制备丙烯醛中的应用

以MCM-41介孔分子筛作为载体,采用等体积浸渍法负载硫酸制得H2SO4/MCM-41催化剂,其结构和性能经吡啶红外,XRD,N2吸附-脱附和NH3-TPD表征。并研究了其对甘油脱水制备丙烯醛的催化性能。结果表明:硫酸负载量为10%时,丙烯醛产率最高(85.5%),改性后催化剂保持介孔结构,且酸性增强,Brnsted酸比例增加。     

F127辅助制备介孔Fe/TiO2催化剂用于中温NH3选择性催化还原反应

NOx是大气污染物的重要组成部分,能够造成酸雨、光化学烟雾和臭氧层破坏等一系列环境问题,严重危害人类健康.选择性催化还原(SCR)是控制NOx排放的主要技术,当前工业上普遍采用的是钒钛催化剂,然而该催化剂活性温度窗口较窄(300-400oC),N2选择性较低,而且钒物种本身有毒.因此开发新型SCR催化剂成为研究热点.Fe/TiO2催化剂具有稳定的化学性质,环境污染少且价格低廉,近年来受到广泛关注.为了提高Fe/TiO2催化活性,人们采用了各种不同的制备方法.本文以F127作为结构导向剂,结合溶胶-凝胶法原位合成了具有介孔结构、工作温度在150-300 oC的Fe/TiO2脱硝催化剂,并与普通浸渍法和共沉淀法制备的催化剂进行了对比.利用N2吸附脱附、紫外-可见光谱、X射线电子能谱、NH3程序升温脱附和原位红外光谱等技术研究了制备方法对Fe/TiO2催化剂物理结构及脱硝性能的影响.结果表明,相较于浸渍法和共沉淀法,模板法制备的催化剂具有较高的脱硝效率和抗H2O和SO2性能.作为结构导向剂,F127能够诱导催化剂形成均匀的介孔结构,有利于提高催化剂比表面积,促进反应物分子的扩散和转移,从而提高催化剂脱硝效率.进一步研究发现,模板法能够明显促进活性组分Fe物种的分散和NH3吸附,载体与活性组分具有较强的相互作用,因而有利于催化剂产生较多的活性位.结合XPS结果,较多的活性位点有利于表面吸附氧(Oα)在催化剂表面的吸附.Oα有利于NO到NO2的转化,从而促进快速SCR反应:NO+NO2+2NH3→2N2+3H2O.通过原位红外机理分析证明,吸附在模板法制备的催化剂表面的NO物种具有较强的稳定性,当温度超过200 oC时,仍然保持一定的吸附强度;吸附NH3红外结果表明,Lewis酸性位比Br?nsted酸性位具有更强的稳定性,当温度超过150oC仍然具有较强的Lewis酸吸附.催化剂表面稳定的NO物种和Lewis酸位上强的NH3吸附是催化剂催化活性增加的重要原因.     

载体对Rh基催化剂上甲烷解离活性的影响

采用脉冲反应技术、原位CO吸附和吡啶吸附红外光谱,考察了Al2O3和SiO2负载的Rh基催化剂上Rh-CeO2相互作用和CH4解离活性.结果表明,载体酸性对Rh-CeO2相互作用有显著影响.Rh/Al2O3催化剂中添加CeO2增加了载体Al2O3的Lewis酸位,使Al2O3接受电子的能力增强,从而降低Rh的电子密度,有利于CH4解离活化.相反,Rh/SiO2催化剂中添加CeO2减少了载体SiO2的Lewis酸位和酸强度,使SiO2难于接受电子,导致Rh的电子密度增加,不利于CH4解离活化.     

双酸位SO_4~(2-)/ZrO_2-SiO_2固载离子液体催化剂的构筑及性能

采用一步共缩合-水热法合成酸性载体SO_4~(2-)/ZrO_2-SiO_2,化学法接枝酸性离子液体磺酸功能化咪唑硫酸氢盐([Ps-im]HSO4),构筑拥有Br觟nsted与Lewis双酸位的离子液体固载型催化剂SO_4~(2-)/ZrO_2-SiO_2-IL。采用X射线衍射、傅里叶红外、N2吸附-脱附、X射线光电子能谱、热重以及透射电镜对催化剂的结构进行表征,结果表明:锆原子和酸性结构SO42-被成功引入纯硅材料,所合成的载体具有一定酸性;离子液体成功固载于酸性介孔材料SO_4~(2-)/ZrO_2-SiO_2,且固载后的催化剂保持其介孔结构。以大豆油和甲醇的酯交换反应为探针,考察了SO_4~(2-)/ZrO_2-SiO_2-IL催化剂的催化性能。在反应温度为150℃、反应时间为4 h、催化剂量5%(w/w)、醇油物质的量之比为24∶1的反应条件下,生物柴油的收率超过92%,且回收利用5次后,生物柴油的收率仍达86%。     

Nb2O5在t-ZrO2表面的分散状态与Br(φ)nsted酸特征

以草酸铌为前驱物,四方相氧化锆(t-ZrO2)为载体,通过浸渍法制备不同负载量的Nb2O5/t-ZrO2催化剂.采用粉末X射线衍射(XRD)、激光拉曼光谱(LRS)、紫外-可见漫反射光谱(UV-Vis DRS)等技术对t-ZrO2表面Nb2O5分散状态进行表征;采用异丁烯(IB)与异丁醛(IBA)缩合生成2,5-二甲基-2,4-己二烯(DMHD)反应评价不同负载量的Nb2O5/t-ZrO2的催化性能,采用吡啶吸附红外(Py-IR)光谱表征催化剂Br(φ)nsted酸中心特征.结果表明,由XRD定量相分析方法测定的Nb2O5在t-ZrO2表面单层分散容量与“嵌入模型”预测值接近.Nb2O5/t-ZrO2表面Br(φ)nsted酸中心特征与Nb2O5聚集状态密切相关.     

F127辅助制备介孔Fe/TiO_2催化剂用于中温NH_3选择性催化还原反应（英文）

NOx是大气污染物的重要组成部分,能够造成酸雨、光化学烟雾和臭氧层破坏等一系列环境问题,严重危害人类健康.选择性催化还原(SCR)是控制NOx排放的主要技术,当前工业上普遍采用的是钒钛催化剂,然而该催化剂活性温度窗口较窄(300-400 ℃),N_2选择性较低,而且钒物种本身有毒.因此开发新型SCR催化剂成为研究热点.Fe/TiO_2催化剂具有稳定的化学性质,环境污染少且价格低廉,近年来受到广泛关注.为了提高Fe/TiO_2催化活性,人们采用了各种不同的制备方法.本文以F127作为结构导向剂,结合溶胶-凝胶法原位合成了具有介孔结构、工作温度在150-300 ℃的Fe/TiO_2脱硝催化剂,并与普通浸渍法和共沉淀法制备的催化剂进行了对比.利用N_2吸附脱附、紫外-可见光谱、X射线电子能谱、NH_3程序升温脱附和原位红外光谱等技术研究了制备方法对Fe/TiO_2催化剂物理结构及脱硝性能的影响.结果表明,相较于浸渍法和共沉淀法,模板法制备的催化剂具有较高的脱硝效率和抗H_2O和SO_2性能.作为结构导向剂,F127能够诱导催化剂形成均匀的介孔结构,有利于提高催化剂比表面积,促进反应物分子的扩散和转移,从而提高催化剂脱硝效率.进一步研究发现,模板法能够明显促进活性组分Fe物种的分散和NH_3吸附,载体与活性组分具有较强的相互作用,因而有利于催化剂产生较多的活性位.结合XPS结果,较多的活性位点有利于表面吸附氧(O_α)在催化剂表面的吸附.Oα有利于NO到NO_2的转化,从而促进快速SCR反应:NO+NO_2+2NH_3→2N_2+3H_2O.通过原位红外机理分析证明,吸附在模板法制备的催化剂表面的NO物种具有较强的稳定性,当温度超过200 ℃时,仍然保持一定的吸附强度;吸附NH_3红外结果表明,Lewis酸性位比Br?nsted酸性位具有更强的稳定性,当温度超过150℃仍然具有较强的Lewis酸吸附.催化剂表面稳定的NO物种和Lewis酸位上强的NH_3吸附是催化剂催化活性增加的重要原因.     

介孔ZSM-5沸石微球催化剂上萘的苄基化反应

以有机硅烷化的二氧化硅为硅源,制备了由纳米粒子聚集而成的、具有晶间和晶内介孔的微球状ZSM-5(MMZ-5)沸石.通过吡啶(Py)和2,6-二叔丁基吡啶(DTBPy)在介孔沸石表面吸附的原位红外测试,对其酸性进行了表征.与微孔ZSM-5沸石相比,MMZ-5沸石上的Lewis酸位和总酸位增加,特别是探针大分子DTBPy(动力学直径约为1.05 nm)可及的Br?nsted酸位显著提高.萘在MMZ-5沸石上的苄基化催化结果表明,反应发生在拥有大量活性位的沸石外表面,大的沸石外表面为该催化反应提供了作用空间,从而提高了沸石活性位的有效利用率,使MMZ-5沸石上萘的苄基化反应活性显著提高,能够生成大分子产物一苄基萘和二苄基萘;其中,一苄基萘的选择性约为79%,且随着反应时间的延长,MMZ-5沸石大的晶内介孔(3-5 nm)为反应提供了有效反应空间,促进一苄基萘向二苄基萘转化.异构体α-一苄基萘和β-一苄基萘的摩尔比值约为83:17,该值不随着温度和转化率的变化而改变.     

磺酸基团功能化的碳-硅介孔复合材料的制备及其在生物柴油绿色合成中的应用(英文)

利用化学浸渍法将蔗糖负载到 SBA-15 介孔材料孔道内部, 高温炭化形成的多聚苯环经发烟硫酸气相磺化处理后, 得到磺酸基团功能化的新型碳-硅介孔复合材料. 发烟硫酸气相磺化处理是该材料合成的关键步骤. X 射线衍射、扫描电镜和氮气吸附结果表明, 碳-硅介孔复合材料经磺酸化处理保持了高度有序的介孔结构. 热重、傅里叶变换的红外光谱及吡啶吸附红外光谱结果证明, 磺酸功能基团成功的嫁接于碳-硅介孔复合材料孔道的内表面, 反应活性中心为 Br?nsted 酸, 酸密度在 0.09~0.70 mmol/g 可以有效调变. 当碳负载量为 35% 时, 该复合材料在生物柴油的绿色合成中显示出最优的催化性能, 且可重复使用 3 次以上.     

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.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

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 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.