Synthesis of complex metal cluster and creation of new synergy

复杂金属团簇的合成及新协同效应的创造

基本信息

批准号：
06453099
负责人：
YAMADA Muneyoshi
金额：
$ 4.99万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1996
项目状态：
已结题

项目摘要

For the purpose of uncovering the cause of synergy at molecular level, creation of new synergy was attempted using a complex metal cluster synthesized from chelating agent, metal complex and metal ion. We found the promoting effect of nitrilotriacetic acid (NTA)on hydrodesulfrization (HDS) activity of cobalt-molybdenum/alumina (Co-Mo/Al_2O_3) catalyst. Selective synthesis of synergistic site (active site) was enhanced when Co-Mo/Al_2O_3 catalysts were prepared by an impregnation method using NTA as chelating agent. In this study it was found that EDTA and trans-1,2-cyclohexane diamine-N,N,N^1, N^1-tetra-acetic acid (CyDTA) shows higher promoting effect. HDS activity of Cy-DTA-Co-Mo/Al_2O_3 was 70% higher than that of Co-Mo/Al_2O_3. Incorporation of these chelated complex into zeolite cage nor synthesis of complex chelate cluster in the cage was not confirmed.In order to inverstigate the mechanism of activity promotion, IR spectra were measured to examine the behavior of adsorbed NO on … More the promoter and Mo sites. Mo K-edge EXAFS was also measured for clarify the local structure of active site. While HDS activity per CUS was increased, the effect of chelating agent vary greatly in dispersion of MoS2 cluster which is presumed to support the active site under reaction conditions, and in the number of coordinatively unsaturated site (CUS). It was suggested that highly dispersed cobalt is essential for formation of active site. Thus, it was demonstrated that dispersion of coblat is enhanced by chelating agent without changing local structure of active site.HDS activity of nickel-molybdenum/alumina (Ni-Mo/Al_2O_3) and nickel-tungsten/alumina (Ni-W/Al_2O_3) was compared with that of Co-Mo/Al_2O_3. While in the case of Ni-Mo/Al_2O_3, HDS activity was not influenced by NTA nor CyDTA addition, that of Cy-DTA-Ni-W/Al_2O_3 was 60% higher than that of Ni-W/Al_2O_3. The result shows that combination of metal ion is one of an important factor for the promotion effect of chelating agent. Less

为了发现分子水平的协同作用的目的，使用从螯合剂，金属复合物和金属离子合成的复杂金属簇尝试创建新协同作用。我们发现硝基三环酸（NTA）对钴 - 羟多氏菌/氧化铝（Co-Mo/al_2O_3）催化剂的氢再硫化（HDS）活性的促进作用。当使用NTA作为螯合剂的浸渍方法制备co-Mo/al_2O_3催化剂时，可以增强对协同位点（活动位点）的选择性合成。在这项研究中，发现EDTA和Trans-1,2-环己烷二氨酸-N，N，N^1，N^1-tetra-乙酸（CYDTA）显示出更高的促进效应。 CY-DTA-CO-MO/AL_2O_3的HDS活动比Co-Mo/Al_2O_3高70％。将这些化学复合物掺入沸石笼子中，也没有确认复杂樱桃簇的合成。为了倒置活性促进的机制，测量了IR光谱以检查IR光谱以检查启动子和MO位点的吸附no的行为。还测量了Mo K边缘EXAFS以阐明活性位点的局部结构。虽然每CUS的HDS活性增加了，但螯合剂的影响在MOS2簇的分散体方面差异很大，而MOS2簇的分散量则在反应条件下以及协调不饱和位点（CUS）的数量中提供了支持。有人提出，高度分散的钴对于形成活性位点至关重要。这就是证明钴的分散剂通过螯合剂增强而不会改变活性位点的局部结构。与co-mo/al_2o_3的镍 - 莫利布顿/铝（Ni-mo/al_2o_3）和镍丁香/氧化铝/氧化铝/氧化铝（Ni-Mo/al_2O_3）和镍汤斯坦/铝（Ni-W/Al_2o_3）的活性相比。在Ni-Mo/Al_2O_3的情况下，HDS活动不受NTA和CYDTA添加的影响，而CY-DTA-NI-W/AL_2O_3的添加比Ni-W/al_2o_3高60％。结果表明，金属离子的组合是螯合剂促进作用的重要因素之一。较少的