甲醇合成催化剂Cu—Mn／Al2O3中锰的助催化作用

甲醇合成催化剂Ｃｕ－Ｍｎ／Ａｌ２Ｏ３中锰的助催化作用李基涛张伟德高利珍（厦门大学化学系物理化学研究所厦门３６１００５）林建毅陈华毅Ｋ．Ｌ．Ｔａｎ（国立新加坡大学物理系０５１１）关键词甲醇合成Ｍｎ的助催化作用活性表面态铜催化剂分类号Ｏ６４３．３２甲醇是...     

锂在甲烷氧化偶联催化剂中的助催化作用

自Lunsford等首次报道在Li/MgO催化剂上的甲烷氧化偶联(OCM)以来,许多研究者相继报道了添加碱金属对该反应的影响,其中以Li的添加最受关注。Li在OCM反应中对提高C_2烃选择性的作用最为明显,因而弄清Li在这一反应中的作用十分必要。本文讨论了Li在几个有代表性的碱土(CaO)及稀土(La_2O_3)中的存在形式与生成C_2产物的关系。     

Sm3+对甲醇电化学氧化反应的助催化作用

分别以相同面积的光滑Pt电极和吸附了Sm3+的铂电极作为工作电极,在酸性介质中采用循环伏安法对甲醇氧化进行测定.结果表明,吸附了Sm3+的Pt电极上产生了更大的氧化电流,表明Sm3+的加入对甲醇的电催化氧化起到了促进作用.这一研究结果在直接甲醇燃料电池(DMFC)阳极催化剂研制方面具有较大的应用潜力.     

含磷无机盐添加剂对甲醇羰基化反应的助催化作用研究

以Rh(OAc) 2 为催化剂,以钠、锌和铵的磷酸盐以及钠的磷钼酸盐和磷钨酸盐作为添加剂,在催化甲醇羰基化制乙酸的反应中系统考察了不同添加剂对反应的影响。实验表明,加入添加剂后可显著提高该反应体系的催化活性。其中磷酸盐系列以磷酸铵的助催化效果最好,该催化体系醋酸的时空收率能达到40mol (L·h)以上。磷钼酸钠催化体系在温度较高时醋酸的时空收率高于磷钨酸钠,达到3 5mol (L·h)以上。     

La2O3对Ni/γ-Al2O3甲烷化催化剂的助催化作用

我国将稀土作为助剂引入镍基甲烷化催化剂,大大提高了催化剂的活性和热稳定性,并已投入工业应用［1－3］．稀土对不同镍催化剂反应性能及其作用机理的研究已有一些报导［3－7］．谢有畅等观察到镍负载在经单层La2O3改性的γ－Al2O3表面,其晶粒要比没有La2O3时小得多．Rotgerink等认为添加La后反应速率的增加不只是由于几何效应,而是La对甲烷化本身有促进作用,单位镍表面的活性是随La含量不同而改变的,活性增加的同时表观活化能也增加［5］．作为助剂的La2O3在氢还原和反应过程中的变化及其作用的研究和讨论较少,目前一般认为添…     

富勒烯材料的催化作用研究进展

介绍了富勒烯材料（富勒烯和富勒烯衍生物）的催化作用研究进展,特别是催化有机反应方面,包括催化氢转移和硅氢化反应、烷烃裂解反应、氢氘互换反应、耦合和烷基转移反应等.这种新材料还可以催化产生单线态氧（1O2）的化学反应、催化非金属固氮反应、催化石墨合成金刚石的反应,同时还可催化高能燃料的燃烧过程,具有广泛的应用前景.     

稀土化合物对双烯合成的催化作用

研究了钕、钐、铕、铽、镥的乙酰丙酮化合物,铈、钕、钐、铕、铽、镝、钬、镥的水合氯化物及8-羟基喹啉化合物对环戊二烯与丙烯醛反应的立体化学影响,并比较了在均相反应和异相反应中这些稀土化合物对双烯合成产物的立体选择性的影响。     

几种酶催化作用的模拟

生物体内进行的化学反应最显著的特点是有着极高的效率和专一性。这种高效性和高选择性应当归功于生物催化剂——酶。酶催化反应的条件温和(在生物体所能承受的温度、压力     

直接反应法合成异丙醇钇中AlCl3的催化作用

在用直接反应法合成稀土金属醇盐的反应中,传统上一直以I2或Hg2 系列盐(如HgCl2,Hg(C2H3O2)2和HgI2等)或其混合物做催化剂.对某些金属合成反应会存在反应速率低、产率低的问题.通过以无水AlCl3做催化剂、金属钇薄片和异丙醇为原料,加热回流直接反应,成功地合成了异丙醇钇.反应中放出大量H2和红外吸收光谱分析结果证明产物确为异丙醇钇.实验证明以无水AlCl3做催化剂可以大大提高反应速率和产率.实验和理论分析揭示了无水AlCl3的催化机理:无水AlCl3与异丙醇作用生成了HCl和可表示为AlCl2(OPri).2AlCl3.PriOH的中间产物,使整个体系的酸性提高,从而加速了反应的进行.AlCl3催化机理完全不同于I2和Hg2 系列盐类,这里H 为氧化剂,起重要作用.使用无水AlCl3替代传统催化剂可以解决I2做催化剂对某些反应的效率低下问题,或Hg2 系列盐类的毒性问题.     

PdCOM+(M=Li,Na,K)体系中M+的助催化性能的成键能研究

本文采用成键能判据探讨了模型化合物ＰｄＣＯＭ＾＋分子轨道成键性质和原子间化学键强度，进而说明Ｍ＾＋的助催化性能，得到与文献［２］和实验［３］相符的结论。     

PdCO(OH)-体系中OH-助催化性能的成键能研究

本文使用相对论赝势从头计算方法和成键能判据[1 ] 研究了模型化合物 Pd CO(OH) -的电子结构 ,讨论了 OH-的助催化作用。得出 OH-对 Pd CO的助催化作用既可以通过其与金属 Pd形成化学键 (通过金属 )来实现 ,也可以通过空间电荷静电作用 (通过空间 )来实现。由分子轨道成键能分析指出 CO分子的强成键占据分子轨道 3σ和 1π的削弱是活化 CO的关键。     

COMPLEX SOLVENT DEPENDENCE OF PYRENEALDEHYDE FLUORESCENCE AS A MICELLAR POLARITY PROBE

Abstract— –Measurements on I-pyrenearboxaldehyde (PCHO) are repeated, extended and reinterpreted. Instead of a dependence on the dielectric constant of the solvent, a more complex solvent dependence is found. As a consequence. the use of PCHO as a micelle polarity probe is questioned.     

哌嗪-二氧化硫电荷转移复合物引发的甲基丙烯酸甲酯光聚合

本文研究了哌嗪 (PPZ)与二氧化硫 (SO2 )电荷转移复合物 (CTC)的制备及其作为光引发剂引发甲基丙烯酸甲酯 (MMA)的聚合 ,发现PPZ/SO2 摩尔比对聚合速率影响甚大 .当PPZ/SO2 为 1∶2时 ,形成了具有潜在引发能力的复合物 (Ⅰ ) .Ⅰ引发MMA光聚合的动力学关系式为Rp =Kp [Ⅰ ] 0 .34[MMA] 1.0 6 ,表观活化能为 2 3 7kJ/mol.并对引发机理进行了探讨     

含三重键有机小分子定域分子轨道的理论研究

为了能够应用定域分子轨道(LMO)模型计算链状有机大分子的光电子能谱,我们已做了一系列工作。本文是用STO-3G基组和Foster-Boys LMO程序,采用文中的计算方法,对含H、C、N和O原子及单,双和叁键的近20个有机小分子进行研究,得到了它们     

SYNTHESIS OF DIARYL ETHERS THROUGH PHASE TRANSFER CATALYSIS WITH POTASSIUN FLUORIDE COATED ALUMINA AS A STRONG BASE

Seven diaryl ethers were synthesized with potassium fluoride coated alumina as a strong base and the addition of catalytic amount of PTC.The yield of diaryl ethers with addition of PTC was much higher than that without PTC.A discussion of the catalysis mechanism was given in this paper.     

STUDY OF CARBONYLATION OF METHANOL TO ACETIC ACID AND ACETIC ANHYDRIDE OVER A BIDENTATE POLYMER BOUND CIS-DICARBONYLRHODIUM COMPLEX AS CATALYST

Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodiumused as a catalyst for carbonylation of methanol to acetic acid and anhydride has beenstudied. The structural characteristics of the copolymer ligand and complex, and the in-fluences of the reaction conditions on the carbonylation catalyzed by this polymer complexhave been investigated. In comparison with small molecule catalyst of Rh complex, thebidentate copolymer coordinated complex has better thermal stability. The reactionmechanism of the carbonylation reaction is also illustrated.     

A THEORETICAL STUDY OF EXCITONS IN CHLOROPHYLL a PHOTOSYSTEMS ON A PICOSECOND TIMESCALE

Abstract— The creation and decay of singlet excitons in structurally-explicit Chi a photosystems were investigated by numerical integration of the appropriate Master Equations. The antenna chlorophylls were excited by a simulated 6ps Gaussian light pulse. Positions and orientations for the antenna chlorophylls were randomly generated within regions whose size and shape were chosen to be appropriate for the particles observed in freeze-fractured photosynthetic membranes. Among the variables considered were chlorophyll concentration, depth of the trap (i.e. P680 or P700), and the R₀ parameter for Förster transfer. Among the properties considered were antenna fluorescence lifetime; detrapping rates; the instantaneous and integrated quantum yields for antenna fluorescence and intersystem crossing; and the instantaneous and integrated quantum yields for trap fluorescence, intersystem crossing, and photochemistry. A variety of experimental evidence was used as input to the computational model.     

CATION/ANION MODIFIED CERIA-ZIRCONIA SOLID SOLUTIONS PROMOTED BY Pt AS CATALYSTS OF METHANE OXIDATION INTO SYNGAS BY WATER IN REVERSIBLE REDOX CYCLES

Ca and/or F-modified fluorite-like Ce-Zr-mixed oxides have been prepared by Pechinis method. The bulk structure of samples was characterized by XRD, EXAFS and FTIRS of the lattice modes. The surface properties were studied by SIMS and FTIRS of adsorbed CO and surface hydroxyls. The specific reactivity of the surface oxygen, its amount, coefficients of bulk and near-surface diffusion, as dependent upon the sample composition and temperature, were estimated using sample reduction by CO in the pulse/flow mode. Insertion of fluorine into the lattice results in decreasing the degree of oxygen polyhedra distortion, thus decreasing the amount of reactive oxygen and diffusion coefficients. Calcium and Pt addition counteracts this effect. At 500^oC for Pt-supported Ce-Zr-O samples including those modified by Ca and F, the lattice oxygen is easily removed by methane generating CO and hydrogen with high selectivity. Reoxidation of reduced samples by water or carbon dioxide at the same temperature restores the oxygen capacity producing more hydrogen or carbon monoxide.     

CO~2(CO)~8/吡啶络合催化苯乙烯氢羧化反应的研究

在苯乙烯氢羧化反应(Hydrocarboxylation)中,Co_2(CO)_8的催化活性很低,吡啶的加入可显著提高催化活性,Co_2(CO)_8与吡啶的配比不同时,对反应活性、收率和正、异构产物的比例均有影响,而且与反应温度有关。此外,还观察了各种吡啶衍生物对氢羧化反应的影响。