碱金属和氯离子对Mn_2O_3－Na_2WO_4／SiO_2催化剂甲烷氧化偶联反

本文考察了碱金属和氯离子对Ｍｎ２Ｏ３－Ｎａ２ＷＯ４／ＳｉＯ２催化剂甲烷氧化偶联反应性能的影响，结果表明，只有在氯离子和碱金属的共同作用下才能有效地提高Ｃ２烃的收率及其选择性．催化剂经ＮａＣｌ改性后，Ｃ２烃收率为２２％，并可获较高的烯烷比．在考察范围内增加接触时间（Ｗ／Ｆ），催化剂选择性保持不变，但乙烯的选择性呈上升趋势．钠盐Ｎａ２ＷＯ４、Ｎａ４Ｐ２Ｏ７、Ｎａ２ＳＯ４、Ｎａ２ＣＯ３及Ｎａ２Ｂ４Ｏ７对稳定催化剂的贡献按上述顺序逐渐减小．对ＮａＣｌ－Ｍｎ２Ｏ３－Ｎａ２ＷＯ４／ＳｉＯ２催化剂进行了稳定性考察，使用ＸＰＳ、ＸＲＤ和红外光谱对经历不同反应时间的催化剂进行了表征．     

La-Ba-Sn(Sm,Ce)体系催化剂上的甲烷氧化偶联

报道了Ｌａ－Ｂａ－Ｓｎ（Ｓｍ，Ｃｅ）体系催化剂上甲烷氧化偶联反应（ＯＣＭ）的催化性能．实验结果表明：第三组分Ｓｎ、Ｓｍ、Ｃｅ的添加显著提高了ＯＣＭ催化活性和Ｃ２烃选择性．不同催化剂制备方法对催化活性的影响不同，混浆法低温焙烧有利于低温ＯＣＭ反应；干混法高温焙烧能在最佳ＯＣＭ反应条件下获得较高的Ｃ２烃收率和选择性．     

甲烷部分氧化制合成气反应Pt/Al_2O_3和Pt/CeO2/Al_2O_3催化剂的研究(英文)

研究了Ｐｔ／Ａｌ２Ｏ３和Ｐｔ／ＣｅＯ２／Ａｌ２Ｏ３催化剂对甲烷部分氧化制合成气反应的催化活性，发现Ｐｔ／ＣｅＯ２／Ａｌ２Ｏ３显示了比Ｐｔ／Ａｌ２Ｏ３更高的甲烷转化率和合成气选择性。用Ｈ２ＴＰＲ，Ｈ２ＴＰＤ，ＳＥＭ和ＸＲＤ等手段和技术对催化剂进行了表征。ＣｅＯ２与Ｐｔ之间存在较强的相互作用（ＳＭＳＩ），这种作用促进了Ｐｔ在催化剂表面的分散，抑制了Ｐｔ在催化剂表面的迁移，大大降低了催化剂在反应中的完全燃烧活性，提高了催化剂的部分氧化活性和选择性，避免了因催化剂床层局部温度过高而导致催化剂活性下降或失活，提高了催化剂的稳定性。同时，在反应过程中，ＣｅＯ２通过促进水蒸气变换反应（ＷＧＳＲ）的进行使反应体系迅速达到平衡，提高了催化剂对Ｈ２的选择性。     

环状配合物Me_2Si［η~5－C_5H_4Fe（CO）_2］_2SnR_2的合

通过ＳｎＣｌ_２对化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）］_２（μ－ＣＯ）_２（Ⅰ）中Ｆｅ－Ｆｅ键的插入反应以及Ⅰ被Ｎａ－Ｈｇ齐还原所生成的相应双铁负离子｛Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２｝~（２－）与ＳｎＲ_２Ｃｌ_２（Ｒ＝Ｍｅ，Ｐｈ）的亲核反应，合成了环状化合物Ｍｅ_２Ｓｉ［η~５－Ｃ_５Ｈ_４Ｆｅ（ＣＯ）_２］_２ＳｎＲ_２［Ｒ＝Ｃｌ（１），Ｍｅ（２），Ｐｈ（３）］。以元素分析、ＩＲ和~１ＨＮＭＲ谱表征了它们的结构，并用Ｘ射线衍射测定了配合物３的晶体结构。３为单斜晶系，空间群Ｐ２_１／ｎ，ａ＝１．０３８４（３）ｎｍ，ｂ＝１．６３８４（１）ｎｍ，ｃ＝１．５７６２（５）ｎｍ，β＝９７．９３（２）°，Ｖ＝２．６５６（２）ｎｍ~３，Ｚ＝４，Ｄｘ＝１．７１ｇ／ｍＬ。     

超高比表面炭载钼煤气甲烷化催化剂

以沥青中间相为原料，氢氧化钾直接活化，获得了比表面达２３６３ｍ￣２／ｇ的超高比表面炭分子筛（ＣＭＳ）。分别以ＣＭＳ、ＳｉＯ＿２、活性炭和θ－Ａｌ＿２Ｏ＿３为担体，制备了负载钼催化剂，并研究其加压甲烷化反应性能，发现活性依下面顺序增加：θ－Ａｌ＿２Ｏ＿３＜ＳｉＯ＿２＜活性炭（ＡＣ）＜ＣＭＳ。还分别以钼酸铵和磷钼酸（ＨＰＭｏ）为前驱体，制备了ＣＭＳ负载钼催化剂，并考察了其煤气甲烷化活性，发现不同的催化剂前驱体对催化剂反应活性影响很大。根据产物中ＣＨ＿４／ＣＯ＿２的变化，推测ＣＯ在钼催化剂上的甲烷化反应包括如下两个步骤：（１）３Ｈ＿２＋ＣＯ→ＣＨ＿４＋Ｈ＿２Ｏ，（２）ＣＯ＋Ｈ＿２Ｏ→ＣＯ＿２＋Ｈ＿２。     

（四甲基二硅撑）双（3—三甲硅基环戊二烯基）—四羰基二铁…

标题化合物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２〕２／（μ－ＣＯ）２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ２Ｃｌ、ＣｌＣＨ２ＣＯＯＣ２Ｈ５和Ｐｈ３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ２ＳｉＳｉＭｅ２）〔η＾５－（３－Ｍｅ３ＳｉＣ５Ｈ３）Ｆｅ（ＣＯ）２Ｒ〕２（Ｒ：Ｍ     

（四甲基二硅撑）双（3－三甲硅基环戊二烯基）－四羰基二铁的反应性

标题化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２／（μ－ＣＯ）_２（Ａ）分子中的Ｆｅ－Ｆｅ键被钠汞齐还原断裂，生成相应的双铁负离子，分别与ＭｅＣＯＣｌ、ＰｈＣＯＣｌ、ＰｈＣＨ_２Ｃｌ、ＣｌＣＨ_２ＣＯＯＣ_２Ｈ_５和Ｐｈ_３ＳｎＣｌ进行亲核取代反应，生成在铁原子上引入相应取代基的产物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２Ｒ］_２（Ｒ：ＭｅＣＯ（１），ＰｈＣＯ（２），ＰｈＣＨ_２（３），ＣＨ_２ＣＯＯＣ_２Ｈ_５（４），Ｐｈ_３Ｓｎ（５），Ｉ（６））。Ａ在氯仿中与碘反应，得到Ｆｅ－Ｆｅ断裂的双铁碘化物，但在苯中与过量碘反应，则得到Ｆｅ－Ｉ－Ｆｅ桥联的离子型化合物（Ｍｅ_２ＳｉＳｉＭｅ_２）［η￣５－（３－Ｍｅ_３ＳｉＣ_５Ｈ_３）Ｆｅ（ＣＯ）_２］_２Ｉ·Ｉ（７）。化合物６的晶体和分子结构经Ｘ射线衍射测定，６属单斜晶系，Ｐ２１／ｃ空间群，ａ＝１．７２１７（４）ｎｍ，ｂ＝０．７７５３（２）ｎｍ，Ｃ＝１．３６２９（７）ｎｍ，β＝１０３．８０（３）°，Ｖ＝１．７６７（２）ｎｍ３，Ｚ＝４，Ｄｃ＝１．６２９９·ｃｍ－１，最终偏差因子Ｒ＝０．０５４。     

甲烷部分氧化制合成气Ⅱ．镍系催化剂的反应性能

主要用第四周期金属元素的氧化物与Ａｌ２Ｏ３的复合氧化物催化剂上甲烷氧化的结果证实了催化剂设计中的预测：（１）催化剂首先应能解离活化甲烷，（２）催化剂要能较快地活化Ｏ２分子．只有同时满足这两个条件，催化剂才可能有较好的甲烷部分氧化活性．第四周期元素中只有镍具有这样的性质．Ｃｕ，Ｍｎ，Ｃｒ，Ｌａ，Ｃａ，Ｚｎ等氧化物的添加可明显提高Ｎｉ－Ａｌ２Ｏ３催化剂的甲烷部分氧化性能，其中Ｃｕ的助催化性能最好．催化剂ＮｉＯ－ＣｕＯ－Ａｌ２Ｏ３，ＮｉＯ－ＭｎＯ－Ａｌ２Ｏ３，ＮｉＯ－Ｃｒ２Ｏ３－Ａｌ２Ｏ３的反应活性和选择性顺序，与金属Ｃｕ，Ｍｎ，Ｃｒ上ＣＯ和Ｈ２脱附的顺序是一致的     

柄型金属有机化合物（Ⅰ）──硅桥联二（1－茚基）和四氢茚基钛化合物的合成及结构

通过１，３－二（１－茚基）四甲基二硅氧烷的双锂盐与ＴｉＣｌ４·２ＴＨＦ反应制得硅桥联二（１－茚基）钛化合物（Ｍｅ２ＳｉＯＳｉＭｅ２）［Ｉｎｄ］２ＴｉＣｌ２（１），对其催化氢化得到相应的四氢茚基化合物（Ｍｅ２ＳｉＯＳｉＭｅ２）［ＩｎｄＨ４］２ＴｉＣｌ２（２）。对化合物１和２的单晶进行了Ｘ射线衍射结构分析，它们的晶体都属单斜晶系，Ｐ２１／ｎ空间群。     

金属键有机化合物的研究──非对称型η~5－取代环戊二烯基三羰基钼（钨）金属单键化合物的合成及表征

通过η５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭＮａ（Ｍ＝Ｍｏ，Ｗ）以及η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）＿３ＭｏＮａ与η~５－Ｒ~２Ｃ＿５Ｈ＿４（ＣＯ）＿３ＷＮａ在Ｆｅ＿２（ＳＯ＿４）＿３醋酸水溶液作用下的交叉氧化偶联反应，合成了７个新的非对称型金属单键化合物η~５－Ｒ~１Ｃ＿５Ｈ＿４（ＣＯ）－３Ｍｏ─Ｍｏ（ＣＯ）＿３Ｃ＿５Ｈ＿４Ｒ~２－η~５（Ｒ~１，Ｒ~２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ），η５－Ｒ１Ｃ５Ｎ４（ＣＯ）３Ｗ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，ＣＯ２Ｅｔ；Ｈ，ＣＯ２Ｅｔ）和η５－Ｒ１Ｃ５Ｈ４（ＣＯ）３Ｍｏ─Ｗ（ＣＯ）３Ｃ５Ｈ４Ｒ２－η５（Ｒ１，Ｒ２：Ｃ（Ｏ）Ｍｅ，Ｈ；Ｅｔ，Ｃ（Ｏ）Ｍｅ；Ｃ（Ｏ）Ｍｅ，ｎ－Ｂｕ；ＣＯ２Ｍｅ，ｎ－Ｂｕ）．用Ｃ／Ｎ分析、ＩＲ、１ＨＮＭＲ和ＭＳ表征了它们的结构，并对该氧化偶联反应的特点进行了讨论．     

Low temperature catalytic conversion of methane to methanol by barium sulfate nanotubes supporting sulfates: Pt(SO4)2, HgSO4, Ce(SO4)2 and Pb(SO4)2

Barium sulfate nanotubes perform excellently in supporting sulfates (Pt(SO4)2, HgSO4, Ce(SO4)2 and Pb(SO4)2) for low temperature catalytic conversion of methane to methanol under strongly acidic conditions in a conventional gas-phase reactor.     

间接电氧化法合成甘油醛

通过电化学合成前驱体和溶胶-凝胶法在Ti表面修饰一层纳米TiO2膜，在纳米Ti02膜上电沉积分散的Pt微粒制成钛基纳米TiO2-Pt(Ti/nano-TiO2-pt)修饰电极。采用循环伏安法、间接电氧化法研究了纳米Ti02-Pt修饰电极的电催化活性以及Mn^3 ／Mn^2 媒质氧化甘油为甘油醛的过程。结果表明，纳米Ti02-Pt修饰电极对Mn^2 的电氧化具有高催化活性，电流效率可达90％以上，非均相电解得到的Mn^3 可一步氧化甘油为甘油醛，收率为91％。     

CODCr测量方法优化及其受营养盐胁迫研究

基于CODCr的K2 Cr2O7滴定法和HACH(哈希公司)DR6000,结合design-expert拟合分析,得到CODCr精确测量的最佳方案:消解液加入量为3 mL,K2 Cr2O7与H2 SO4-Ag2 SO4的加入比为1:5(V/V),K2Cr2O7溶液0.046 g/mL、H2SO4-Ag2SO4溶液3 g/L、HgSO40.038 g/支,恒温120℃消解2 h。同时,基于拟定的最佳方案分析了营养盐类对CODCr测定结果的影响,发现氨氮和亚硝态氮对测定结果有明显影响,而磷酸盐和偏磷酸盐对测定结果的影响较小。     

金属锰Corrole的脱金属研究

合成了中位带有不同取代基的锰corrole配合物1-Mn, 2-Mn, 3-Mn, 4-Mn,并研究了其酸解和还原脱金属特性。结果表明取代基的性质对脱金属产率有很大的影响。缺电子金属锰corrole的酸解脱金属产率比富电子金属锰corrole高,而还原脱金属产率的顺序则正好相反。     

以硫酸锰作催化剂无汞快速测定COD

在硫酸、磷酸混合液中以MnSO4作催化剂无汞快速测定水的化学需氧量(COD)。通过实验,该法的最佳测定条件为:MnSO4 0.2 g,H2SO4-H3PO4 20 mL(H2SO4∶H3PO4= 5∶1体积比),回流时间15 min。     

Template synthesis of lanthanide (Pr, Nd, Gd) coordination polymers with 2-hydroxynicotinic acid exhibiting ferro-/antiferromagnetic interaction

Lanthanide coordination polymers were synthesized from Pr(III), Nd(III), and Gd(III) salts; 2-hydroxynicotinic acid (Hnica); and MnSO 4.H 2O under hydrothermal conditions. In the absence of (CH 3) 3CCOONa, 1D polymers with an infinite Ln(III)-O-Ln(III) chain structure, [Pr(Hnica)(H 2O) 2SO 4] n ( 1), [Nd(Hnica)(H 2O) 2SO 4] n ( 2), and [Gd(Hnica)(H 2O) 2SO 4] n ( 3), were generated. When (CH 3) 3CCOONa was added to the synthetic systems, 2D coordination polymers {[Pr 3(Hnica) 6(H 2O) 9].3H 2O.SO 4.NO 3} n ( 4), {[Nd 3(Hnica) 6(H 2O) 9].3H 2O.SO 4.NO 3} n ( 5), and {[Gd(Hnica) 2(H 2O) 2]ClO 4.H 2O} n ( 6) were obtained. Complexes 4 and 5 both exhibit Kagome lattice structure, while 6 displays a rhombic grid structure. All complexes were characterized by elemental analysis, IR spectra, UV-vis spectra, and X-ray single-crystal diffraction. The variable-temperature magnetic susceptibility studies reveal ferromagnetic interactions between gadolinium(III) ions in 3 and 6 and antiferromagnetic interactions in 1, 2, 4, and 5.     

Amine-controlled assembly of metal-sulfite architecture from 1D chains to 3D framework

Whereas open-framework materials have been made in a variety of chemical compositions, few are known in which 3-connected SO3(2)- anions serve as basic building units. Here, we report four new metal-sulfite polymeric structures, (ZnSO3)Py (1, py = pyridine), (ZnSO3)2(2,2'-bipy)H2O (2, 2,2'-bipy = 2,2'-bipyridine), (ZnSO3)2(TMDPy) (3, TMDPy = 4,4'-trimethylenedipyridine), and (MnSO3)2en (4, en = ethylenediamine) that have been synthesized hydrothermally and structurally characterized. In these compounds, low-dimensional 1D and 2D inorganic subunits are assembled into higher 2D or 3D covalent frameworks by organic ligands. In addition to the structure-directing effect of organic ligands, the flexible coordination chemistry of Zn2+ and SO3(2)- also contributes to the observed structural diversity. In compounds 1-3, Zn2+ sites alternate with trigonal pyramidal SO3(2)- anions to form three types of [ZnSO3]n chains, whereas in compound 4, a 2D-corrugated [MnSO3]n layer is present. Compound 1 features a rail-like chain with pendant pyridine rings. The pi-pi interaction between 2,2'-bipy ligands is found between adjacent chains in compound 2, resulting in 2D sheets that are further stacked through interlayer hydrogen bonds. Compound 3 exhibits a very interesting inorganic [(ZnSO3)2]n chain constructed from two chairlike subunits, and such chains are bridged by TMDPy ligands into a 2D sheet. In compound 4, side-by-side helical chains permeate through 2D-corrugated [MnSO3]n layers, which are pillared by neutral ethylenediamine molecules into a 3D framework that can be topologically represented as a (3,6)-connected net. The results presented here illustrate the rich structural chemistry of metal-sulfites and the potential of sulfite anions as a unique structural building block for the construction of novel open-framework materials, in particular, those containing polymeric inorganic subunits that may have interesting physical properties such as low-dimensional magnetism or electronic properties.     

Methyl Tin(IV) derivatives of HOTeF(5) and HN(SO(2)CF(3))(2): a solution multinuclear NMR study and the X-ray crystal structures of (CH(3))(2)SnCl(OTeF(5)) and [(CH(3))(3)Sn(H(2)O)(2)][N(SO(2)CF(3))(2)

The new tin(IV) species (CH(3))(2)SnCl(OTeF(5)) was prepared via either the solvolysis of (CH(3))(3)SnCl in HOTeF(5) or the reaction of (CH(3))(3)SnCl with ClOTeF(5). It was characterized by NMR and vibrational spectroscopy, mass spectrometry, and single crystal X-ray diffraction. (CH(3))(2)SnCl(OTeF(5)) crystallizes in the monoclinic space group P2(1)/n (a = 5.8204(8) A, b =10.782(1) A, c =15.493(2) A, beta = 91.958(2) degrees, V = 971.7(2) A(3), Z = 4). NMR spectroscopy of (CH(3))(3)SnX, prepared from excess Sn(CH(3))(4) and HX (X = OTeF(5) or N(SO(2)CF(3))(2)), revealed a tetracoordinate tin environment using (CH(3))(3)SnX as a neat liquid or in dichloromethane-d(2) (CD(2)Cl(2)) solutions. In acetone-d(6) and acetonitrile-d(3) (CD(3)CN) solutions, the tin atom in (CH(3))(3)SnOTeF(5) was found to extend its coordination number to five by adding one solvent molecule. In the strong donor solvent DMSO, the Sn-OTeF(5) bond is broken and the (CH(3))(3)Sn(O=S(CH(3))(2))(2)(+) cation and the OTeF(5)(-) anion are formed. (CH(3))(3)SnOTeF(5) and (CH(3))(3)SnN(SO(2)CF(3))(2) react differently with water. While the Te-F bonds in the OTeF(5) group of (CH(3))(3)SnOTeF(5) undergo complete hydrolysis that results in the formation of [(CH(3))(3)Sn(H(2)O)(2)](2)SiF(6), (CH(3))(3)SnN(SO(2)CF(3))(2) forms the stable hydrate salt [(CH(3))(3)Sn(H(2)O)(2)][N(SO(2)CF(3))(2)]. This salt crystallizes in the monoclinic space group P2(1)/c (a = 7.3072(1) A, b =13.4649(2) A, c =16.821(2) A, beta = 98.705(1) degrees, V = 1636.00(3) A(3), Z = 4) and was also characterized by NMR and vibrational spectroscopy.     

氧化锡基甲烷催化燃烧催化剂的硫中毒反应机理

测定了几种活性较高的氧化锡基甲烷燃烧催化剂在200×10－6（φ）SO2存在下的催化活性.结果发现,SnCrO样品具有很好的抗硫性能,而SnCuO及SnCoO样品在SO2存在时的活性大大降低.用XRD、BET、XPS、FT-IR及DTA-TG等技术对反应前后的样品进行了表征,结果表明,硫酸盐的热稳定性对催化剂在SO2处理过程中的变化起决定作用.在实验的温度下（500 ℃）,Co2(SO4)3和CuSO4均能稳定存在,而Cr2(SO4)3会分解.SnCrO样品在SO2存在下反应时只是表面吸附少量硫酸根,因此其催化活性基本保持不变.这是SnCrO样品具有良好抗硫性能的原因.     

异丁烷-丁烯烷基化反应催化剂的研究

固体强酸;异丁烷-丁烯烷基化反应催化剂的研究