大环化合物合成中金属的模板效应

经非模板和模板反应合成了一系列二苯并四氮杂￣［１４］轮烯（Ｈ＿２ＴＡＡ，ｌａ；ＨＨ＿２ＤＮＴＡＡ，２ａ和Ｈ＿２ＴＭＴＡＡ，３ａ）及其对应的二价金属络合物［ＴＡＡ·Ｍ，Ｍ＝Ｃｏ（Ⅱ），ｌｃ；Ｎｉ（Ⅱ），ｌｄ；Ｃｕ（Ⅱ），ｌｄ和ＴＡＡ·Ｍ，Ｍ＝Ｎｉ（Ⅱ），３ｂ，Ｃｕ（Ⅱ），３ｃ〕，结果表明：借助于使用金属离子即金属离子的模板效应提高了环状产物得率，讨论了反应中间体的种类和金属离子半径大小对模板反应的影响作用。     

有机锡试剂与芳卤化合物在Pd(Ⅱ)/γ-Al_2O_3催化下的偶联反应

制备了有机锡试剂Ｂｕ３ＳｎＰｈ、Ｂｕ３ＳｎＣＨ２Ｐｈ及催化剂Ｐｄ（Ⅱ）／γＡｌ２Ｏ３,催化剂对有机锡试剂与芳卤化合物的偶联反应有较高的活性。该反应条件温和,催化剂可重复使用,产率较高     

有机锡试剂与芳卤化合物在Pd（Ⅱ）／γ—Al2O3催化下的偶联反应

制备了有机锡试剂Ｂｕ３ＳｎＰｈ,Ｂｕ３ＳｎＣＨ２Ｐｈ及催化剂Ｐｄ（Ⅱ）／γ－Ａｌ２Ｏ３催化剂对有机锡试剂与芳卤化合物的偶联反应有较高的活性。该反应条件温和,催化剂可重复使用,产率较高。     

1，3－取代方酸衍生物的光谱研究及二聚体、簇集体的形成

本文合成了１，３－取代方酸衍生物：１，３－双［４－二甲胺苯基］－２，４二羟基环丁二烯氢氧双内盐（ＤＭＣＳ），１，３－双［４－双十六烷胺苯基］－２，４二羟基环丁二烯氢氧双内盐（ＤＨＣＳ）。研究了ＤＭＣＳ和ＤＨＣＳ在不同溶剂中的光物理行为，估算了ＤＭＣＳ、ＤＨＣＳ的基态与激发态之间偶极矩差值。在ＣＴＡＢ胶束中，除ＤＭＣＳ单体分子外，ＤＭＣＳ形成了二聚体。在二氧六环－水体系中，研究了ＤＨＣＳ的簇集行为，并测定了ＤＨＣＳ的临界簇集组成（Ｃ＿ψ）及临界簇集浓度（Ｃ＿Ａ）     

合成二氧化氯的催化剂

在高活性且低失活速率催化剂的存在下，可由亚氯酸钠溶液制备二氧化氯。适宜催化剂为含Ｌａ２Ｏ３和Ｎｄ２Ｏ３的Ｐｄ／Ａｌ２Ｏ３或钯和其它铂族金属（例如Ｐｄ＋Ｐｔ／Ａｌ２Ｏ３）或钯和ＩＢ族金属（例如Ｐｄ＋Ａｕ／Ａｌ２Ｏ３）催化剂。     

具有生物活性的含硅有机锡化合物研究

作者合成了一系列含硅有机锡化合物，对其结构进行了表征。化台物的生物选择性主要取决于硅原子上的取代基（Ｍｅ和／或Ｐｈ）．生物活性实验表明其规律为：（Ｍｅ＿３ＳｏＣＨ＿２）＿３ＳｎＹ＞（ＰｈＭｅ＿２ＳｉＣＨ＿２）＿３ＳｎＹ＞＞（Ｐｈ＿２ＭｅＳｉＣＨ＿２）＿３ＳｎＹ并且不受阴离子Ｙ的影响。     

MgO对C_4A_3S水化性能的影响

用ＸＲＤ，ＩＲ和化学分析法研究了ＭｇＯ对Ｃ＿４Ａ＿３Ｓ晶体水化性能的影响。结果大明，ＭｇＯ的引不影响Ｃ＿４＿３的晶体形态和晶格尺寸，Ｍｇ￣（２＋）以间隙方式固溶入Ｃ＿４Ａ＿３晶体的晶格空隙中。用微量热仪和浆体的线性膨胀率探讨了ＭｇＯ对Ｃ＿４Ａ＿３水化性能的影响。结果表明，ＭｇＯ能延缓Ｃ＿４Ａ＿３的早期水化，降低其线性膨胀率，冈而体积稳定性得到提高。     

新试剂2-[2''''-(6''''-取代苯并噻唑)偶氮]-5-二甲氨基苯甲酸的合成及其光度特性的研究

合成了６种２－［２＇－（６’－取代苯并噻唑）偶氮］－５－二甲氨基苯甲酸（６－Ｒ－ＢＴＡＭＢ，其中Ｒ＝ＣＨ３，ＯＣＨ３，Ｃｌ，Ｂｒ，ＣＨ３ＳＯ２，ＮＯ２）新试齐４。初步研究了６－ＣＨ３－ＢＴＡＭＢ与Ｆｅ（Ⅱ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）和Ｐｄ（Ⅱ）等离子的络合显色反应的光度特性。     

直接法合成甲基（氢）二氯硅烷新工艺研究

本文通过催化作用原理研究，提出了以Ｓｉ、ＣＨ＿３Ｃｌ为原料，直接法合成ＣＨ＿３ＳｉＨＣｌ＿２的新工艺．采用ＣｕＣｌ－Ｎｉ－Ｚｎ催化体系不但能使ＣＨ＿３Ｃｌ适量分解产生ＨＣｌ．而且还能促进ＨＣｌ与Ｓｉ、ＣＨ＿３Ｃｌ反应并有效地转化为目的产物ＣＨ＿３ＳｉＨＣｌ＿２，由小试和４００ｍｍ流化床中试所得的混合单体中，ＣＨ＿３ＳｉＨＣｌ＿２含量＞１５％，（ＣＨ＿３）＿２ＳｉＣｌ＿２＞５０％，为工业化生产有机硅含氢单体开辟了新的途径。     

化学镀Ni－Mo－P合金阳极溶解行为的XPS研究

利用ＸＰＳ等手段研究了化学镀Ｎｉ－Ｍｏ－Ｐ合金在Ｈ＿２ＳＯ＿４溶液中的阳极溶解行为。结果显示，稳定电位下阳极形成稳定致密的钝化膜，其主要成分为Ｎｉ（ＯＨ）＿２，其余为Ｎｉ（ＰＯ＿４）＿２、ＭｏＯ＿２及部分结合水。阳极电位正移，阳极表面膜厚度增加，结合水减少，在０．２Ｖ左右，阳极溶解电流剧增，局部腐蚀严重。此时，表面膜的主要成分为Ｎｉ＿３（ＰＯ＿４）＿２，其余为Ｎｉ（ＯＨ）＿２及ＭｏＯ＿２。合金在阳极溶解过程中出现磷（钼）在合金的富集。     

Investigation of the preparation methodologies of Pd-Cu single atom alloy catalysts for selective hydrogenation of acetylene

Galvanic replacement, co-impregnation and sequential impregnation have been employed to prepare Pd-Cu bimetallic catalysts with less than 1 wt-% Cu and ca. 0.03 wt-% Pd for selective hydrogenation of acetylene in excess ethylene. High angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) and H₂ chemisorption results confirmed that Pd-Cu single-atom alloy structures were constructed in all three bimetallic catalysts. Catalytic tests indicated that when the conversion of acetylene was above 99%, the selectivity of ethylene of these three single atom alloy catalysts was still more than 73%. Furthermore, the single atom alloy catalyst prepared by sequential incipient wetness impregnation was found to have the best stability among the three procedures used.     

Pd-Cu/凹凸棒石黏土催化剂催化CO氧化性能

以凹凸棒石黏土(APT)作载体,采用浸渍法制备双金属催化剂Pd-Cu/APT、单金属催化剂Pd/APT和Cu/APT,在连续流动微反装置上考察催化剂的CO催化氧化活性,采用N_2物理吸附/脱附、X射线粉末衍射和程序升温还原/脱附等手段对催化剂进行表征。结果表明,Pd-Cu/APT催化剂中Cu主要以CuCl形式存在,Pd高度分散与Cu之间产生了明显的相互作用,使Cu物种的还原温度大幅降低;经水蒸汽预处理增强了Pd-Cu/APT催化剂表面酸性,促进了催化活性的提高。在CO体积分数为0.5%、水蒸汽体积分数3.3%、空速6 000h^(-1)和常温反应条件下,CO转化率可达90%以上。     

三氟三氯乙烷加氢脱氯Pd-Cu催化剂失活分析

以活性炭为催化剂载体,采用浸渍法制备Pd、Cu、Pd-Cu三种催化剂,将催化剂应用于三氟三氯乙烷(CFC-113)加氢脱氯制三氟氯乙烯(CTFE)的反应,考察Cu的引入对Pd催化剂性能的影响。对反应前后及再生的Pd-Cu催化剂进行X射线衍射(XRD)、X射线光电子能谱(XPS)、氮气吸附-脱附(BET)、氢气程序升温还原(H₂-TPR)、热重(TG)、氨气程序升温脱附(NH₃-TPD)等表征分析。研究表明,Pd催化剂具有较高的加氢脱氯性能,其主要产物为三氟乙烷,Cu的加入有利于提高CTFE的选择性。这应与Cu、Pd之间存在相互作用并形成合金,抑制了Pd的脱氯性能有关。反应后的催化剂存在表面结焦、反应过程中吸附Cl以及金属Cu价态变化和迁移等现象,其中表面高沸物的形成、卤元素吸附导致的金属迁移和Cu-Pd相互作用的改变是Pd-Cu催化剂失活的主要原因。     

Pd-Cu/γ-Al_2O_3双金属催化剂脱除水中硝酸盐

采用分步浸渍法和共浸渍法制备系列Pd负载质量分数为1%的Pd-Cu/γ-Al2O3双金属催化剂,以氢气为还原剂研究其对水中硝酸盐催化脱除的性能。结果表明,催化剂中Cu与Pd物质的量比以及Cu、Pd的浸渍顺序对催化剂性能有重要影响,硝酸根转化率随着Cu与Pd物质的量比的增大而增大;硝酸根转化活性以Cu与Pd物质的量比为5∶1、先浸渍Pd再浸渍Cu所得催化剂较优;从氨氮选择性方面看,以先浸渍Cu后浸渍Pd制备的催化剂选择性较低,在Cu与Pd物质的量比为1∶1、先浸渍Cu再浸渍Pd所得催化剂较优。     

CuO含量对Pd/Al2O3催化剂乙醇氧化性能的影响

采用浸渍法制备了一系列具有不同CuO含量的Pd-CuO/Al₂O₃催化剂，并将其用于乙醇氧化反应，其结构与性质通过XRD、H₂-TPR和NH₃-TPD等手段进行分析。结果发现，催化剂的活性并不是随着CuO含量的增加而增强，Pd-1.0%CuO/Al₂O₃催化剂表现出最佳的活性，其点火温度和完全转化温度比Pd/Al₂O₃催化剂至少降低了50℃。与Pd/Al₂O₃催化剂相比，含CuO催化剂增强的衍射峰强度以及氢化钯分解峰的消失，说明Pd-Cu合金结构的形成有利于Pd、Cu物种之间的协同作用。对于Pd-1.0%CuO/Al₂O₃催化剂来说，还原峰向低温的移动以及还原峰面积的增大说明该催化剂上氧化性物质更易被还原且数量在增加，这对于氧化反应是十分有利的，新出现的还原峰表示Pd、Cu的相互作用生成了新物种。NH₃-TPD结果中更高含量的低温酸有利于高活性，而且新出现的脱附峰说明形成了新的酸性位点。     

微乳法制备Pd-Cu双金属催化剂

选择Cu为助剂,采用微乳法分别优选具有较好稳定性的Cu和Pd微乳液体系,并将Cu和Pd依次负载于Al_2O_3载体上,经干燥、活化和还原制备了Pd-Cu/Al_2O_3催化剂。采用原位IR、CO化学吸附和HRTEM等对催化剂进行表征,结果表明,与常规溶液负载法制备的Pd-Ag/Al_2O_3催化剂相比,采用微乳法降低了催化剂表面酸性,提高了活性组分Pd分散度,Pd粒径分布更为均匀。在750 mL加氢反应器中,采用C_2后加氢原料对催化剂性能进行评价,结果表明,与常规溶液负载法相比,微乳法制备的催化剂在反应温度低4℃条件下,乙炔转化率相当,选择性高9.9个百分点,绿油生成量较低。微乳法制备Pd-Cu双金属催化剂具有良好的工业应用前景。     

Pd-based bimetallic catalysts prepared by replacement reactions

Several Pd-based bimetallic catalysts, Pd/Co, Pd/Ni and Pd/Cu, were synthesized by replacement reactions. The catalysts were characterized by XRD and CO chemisorption and their catalytic properties were evaluated using cyclohexene self-hydrogenation. The results suggest that the high catalytic activity of Pd/Ni is most likely due to the monolayer-dispersion of Pd on the Ni surface. The results also suggest that Pd is monolayer-dispersed on the Co surface in Pd/Co, whereas Pd forms surface alloy or solid solution with Cu in Pd/Cu.     

助剂对Pd/AC催化剂催化三氟氯乙烯加氢脱氯的影响

采用等体积浸渍法制备了Cu-Pd/AC和K-Pd/AC催化剂,分别考察了Cu和K助剂添加量对三氟氯乙烯加氢脱氯生成三氟乙烯的反应性能的影响,并采用N_2-物理吸附、X射线粉末衍射(XRD)测试、透射电镜(TEM)和H_2-程序升温还原(TPR)等对催化剂进行表征。结果表明:加入助剂Cu,其与Pd形成Pd-Cu合金,抑制催化剂的加氢性能,从而降低催化剂反应活性;加入助剂K,其改变了Pd的电子结构,增强了Pd的电子云密度,使Pd活化H的能力增强,从而提高催化剂的活性。助剂K质量分数为3%的催化剂,在250℃下,具有较好的催化活性,三氟氯乙烯的转化率可达90%左右,三氟乙烯的选择性可达85%左右。     

Preparation and investigation of Pd doped Cu catalysts for selective hydrogenation of acetylene

A series of PdCu bimetallic catalysts with low Cu and Pd loadings and different Cu: Pd atomic ratios were prepared by conventionally sequential impregnation (CSI) and modified sequential impregnation (MSI) of Cu and Pd for selective hydrogenation of acetylene. Characterization indicates that the supported copper (II) nitrate in the PdCu bimetallic catalysts prepared by MSI can be directly reduced to Cu metal particles due to the hydrogen spillover from Pd to Cu(NO₃)₂ crystals. In addition, for the catalysts prepared by MSI, Pd atoms can form PdCu alloy on the surface of metal particles, however, for the catalysts prepared by CSI, Pd tends to migrate and exist below the surface layer of Cu. Reaction results indicate that compared with CSI, the MSI method enables samples to possess preferable stability as well as comparable reaction activity. This should be due to the MSI method in favor of the formation of PdCu alloy on the surface of metal particles. Moreover, even Pd loading is super low, <0.045 wt-% in this study, by through adjusting Cu loading to an appropriate value, attractive reactivity and selectivity still can be achieved.     

Hydrodenitrification with PdCu Catalysts: Catalyst Optimization by Experimental and Quantum Chemical Approaches

A continuous process for nitrate and nitrite abatement from drinking water by catalytic hydrogenation has been developed in our lab. We describe the experimental process development procedure, and support it with semiempirical quantum chemical methods. Comparisons of activated carbon (ACC) and silica glass fiber (GFC) cloths as supports for mono- and bimetallic Pd-Cu catalysts show the former to be 45-fold and 15-fold more active for nitrite and nitrate hydrogenation, respectively, than the latter. Catalysts prepared by selective deposition of Cu on Pd/ACC led to better activity for nitrate hydrogenation than catalysts prepared by co-impregnation or ion exchange methods. The optimal Cu:Pd atomic ratio was found to be 1:2. The computational results show the following: (i) The dispersion of Pd catalysts supported on ACC is much higher than that on GFC due to the larger surface area and higher density of adsorption sites, and that accounts for the higher activity of PdCu/ACC; (ii) Nanosized Pd particles supported on ACC have a semispherical shape and possess preferentially close-packed triangular surfaces, while Pd/GFC particles are extended in the direction parallel to the support surface and show both fcc (100) and (111) planes; (iii) The interaction of Cu atoms with both supports is stronger than that of Pd; adsorbed Cu atoms show a greater ability to form monometallic than bimetallic bonds and that should result in poor mixing of the metal upon co-impregnation, as was observed experimentally; (iv) Cu atoms in bimetallic PdCu particles admit a significant positive charge; the experimentally measured solubility of metal atoms correlates with their calculated charges. The best catalyst (2 wt%Pd-0.6 wt%Cu/ACC) was employed in a novel continuous flow reactor for nitrate hydrogenation in distilled and tap water. The advantages of the reactor investigated over a conventional packed bed reactor are discussed, suggesting a potential for further process intensification.