氨酸钾－碘化钾－铑（Ⅲ）－鲁米诺无机偶合化学发光反应测定痕量铑的研究

研究了Ｒｈ（Ⅲ）催化ＫＣｌＯ３－ＫＩ的反应与Ｉ２－Ｌｕｍｉｎｏｌ的化学发光反应相偶合，建立了测定痕量铑的化学发光新方法．对测定条件进行了优化，此方法具有较高的灵敏度，检测限达到３．８×１０－６μｇ／ｍＬＲｈ；线性浓度范围宽，为１×１０－５～１μｇ／ｍＬＲｈ．采用三正辛胺（ＴＯＡ）萃取色谱柱将铑（Ⅲ）分离出来，方法已用于测定贵金属离子混合液中的铑     

十二烷基苯磺酸钠存在下铑(Ⅲ)与5-Br-TAMB体系络合吸附波的研究

在表面活性剂存在下，研究了铑(Ⅲ)与2-(5-溴-2-噻唑偶氮)-5-二甲氨基苯甲酸络合物吸附波，结果表明，在pH=5．0的HAc-NaAc缓冲液中，Rh^3 -2-(5-溴-2-噻唑偶氮)-5-二甲氨基苯甲酸络合物有-较灵敏的极谱波，其峰电位Ep为-574mV(vs．SCE)，加入表面活性剂十二烷基苯磺酸钠使峰高增加3．7倍，峰电位负移到-584mV(vs．SCE)．铑质量浓度在0．15～6．0μg／L范围内与峰电流I′。有良好的线性关系，检出限为0．086μg／L．经多种电化学方法证明该波为络合物吸附波，其电极过程为不可逆过程，电子转移数为2．此外还试验了多种离子对峰电流I′p的影响，所拟方法已用于13X分子筛催化剂中痕量铑的测定。     

In situ time-resolved FTIR investigation on the reaction mechanism of partial oxidation of methane to syngas over supported Rh and Ru catalysts

In situ time-resolved FTIR spectroscopy was used to study the reaction mechanism of partial oxidation of methane (POM) to synthesis gas and the reaction of CH₄/O₂/He (2/1/45, molar ratio) gas mixture with adsorbed CO species over Rh/SiO₂, Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts at 500—600℃. It was found that CO is the primary product of POM reaction over reduced and working state Rh/SiO₂ catalysts. Direct oxidation of CH₄ is the main pathway of synthesis gas formation over Rh/SiO₂ catalyst. CO₂ is the primary product of POM over Ru/γ-Al₂O₃ and Ru/SiO₂ catalysts. The dominant reaction pathway for synthesis gas formation over Ru/γ-Al₂O₃ catalyst is via the reforming reactions of CH₄ with CO₂ and H₂O. For the POM reaction over Rh/SiO₂ and Ru/γ-Al₂O₃ catalysts, consecutive oxidation of surface CO species is an important pathway of CO₂ formation.     

丙烯氢甲酰化HRh（CO）（PPh3）3／SiO2催化剂的NMR研究

用固定床加压气相连续流动微反－气相色谱组合装置评价了ＳｉＯ２负载铑膦配合物催化剂上丙烯氢甲酰化反应．通过溶液（或液膜）３１Ｐ（１Ｈ）ＮＭＲ谱表征,发现配合物ＨＲｈ（ＣＯ）（ＰＰｈ３）３负载于硅胶载体上之后,原负载前驱苯溶液３１Ｐ（１Ｈ）ＮＭＲ谱在４１．１ｐｐｍ处的特征峰消失,但在化学位移为３７．０ｐｐｍ附近出现一新的宽峰,后者可能缘于配合物与载体表面发生相互作用．反应４ｈ后工作态催化剂的ＮＭＲ测试表明,在丙烯氢甲酰化反应条件下,铑的三膦配合物发生部分解络;工作态催化剂表面上主要的铑膦催化活性物种是含双膦的配合物物种,并暗示存在着含双羰基或羰、酰基的反应中间态;同时也观察到可归属于解络后的游离三苯基膦物种的相应谱峰．反应９０ｈ后催化剂的ＮＭＲ谱显示,铑配合物催化剂中膦配体含量已相当低;反应过程中膦配位体被氧化及铑、磷组份的流失是负载型催化剂活性下降乃至失活的主要原因．     

The Combinatorial Approach to Asymmetric Hydrogenation： More Miles out of Monophos

1 Introduction In custom manufacturing time-to-market is of overriding importance. Thus, asymmetric hydrogenation will be applied only if an appropriate catalyst can be found in a very short period of time. For this reason we have build up a full-scale capability for High Throughput Experimentation, encompassing several robot systems. As ligand synthesis was the last remaining barrier we have explored, together with the University of Groningen, the use of simple monodentate ligands, such as …     

铑-钨酸盐-番红花T缔合显色反应的研究及应用

在聚乙烯醇(PVA)存在下,铑(Ⅲ)与钨酸盐及番红花T(ST)形成的离子缔合物在480nm处产生最大吸收.据此建立了测定铑(Ⅲ)的光度分析方法,其表观摩尔吸光系数ε达108L·mol-1·cm-1数量级.方法的检测范围为0.15～1.5 ng/25ml.大量存在的常见离子对Rh(Ⅲ)的测定不干扰.用此方法测定了催化剂及工业产品中铑的含量,结果与标准方法(SnCl2法)一致.     

金属载体相互作用对铑催化剂上CO吸附态稳定性的影响

用程序升温脱附－红外光谱（ＴＰＤ－ＩＲ）动态方法，研究了铑与载互使用对铑催化剂上的ＣＯ孪生，线工和桥式吸附态稳定性的影响。结果表明，金属载体的非强相互作用（ＮＳＭＳＩ）能提高铑催化剂上３种ＣＯ吸附态的稳定性。其影响可用ＮＳＭＳＩ效应的酸－碱机制解释。     

甲醇气相羰基化合成醋酸非铑催化剂的筛选

本文对以甲醇气相羰基化合成醋酸非铑（Rh)催化剂作了初步筛选，在压条件下，筛选出活性较高的非Rh催化剂是，Ni-V、Ni-La、Ni-W等，其醋酸得率分别达到48．6％和48．31％。     

Synthesis and characterization of organometallic macrocyclic rhodium (Ⅲ) complex with pyrazine ligands

The synthesis and structure research of organometal-lic macrocyclic complexes has been a very active field of modern chemistry [1—3]. In this field, Pd2+, Pt2+ complexes were first used as the building block, connected by het-erocyclic ligands, to construct metal macrocyclic com-pound[4,5]. The fac-Re(CO)5X (X = Cl, Br) fragment, for example, was shown to be a versatile building block for the synthesis of metallamacrocycles[6]. Some of this kind of molecule have been found applications in…     

Rh-5-Br-TAMB 配合物形成条件的动力学研究

研究了铑(Ⅲ)和2-[2-(5-溴-噻唑)偶氮]-5-二甲氨基苯甲酸(5-Br-TAMB)之间配合反应的动力学规律.实验表明:该配合反应是一个按缔合交换机理进行的二级反应.采用动力学方法给出了该试剂测定微量铑(Ⅲ)的最佳反应条件为:pH4.5～6.5,试剂浓度2.5×10~(-4)mol·L~(-1)、反应温度100℃、反应时间5min.