钯催化Heck反应的研究进展

钯催化的Heck反应是一类构建新的C—C键的偶联反应,也是卤代芳烃烯基化的重要手段.近年来,Heck反应已成为催化领域和有机合成化学方面的研究热点之一,并已取得了很好的研究成果.本文综述了近几年新发现的均相和非均相体系中Heck反应的研究进展,其中均相催化体系按参与的配体不同,可分为含膦、氮、硫及含NHC配体的钯催化体系;非均相催化体系按固相载体的不同,可分为活性炭、金属氧化物、介孔材料、二氧化硅等负载型钯催化体系.     

交叉脱氢偶联反应研究进展

交叉脱氢偶联(CDC反应)是在氧化条件下直接通过两分子反应底物C—H键的断裂而形成C—C键的一种高效率、高原子经济性的直线合成方法.本文按照以下分类,含有胺N原子α-C—H键底物的CDC反应;含有醚O原子α-C—H键底物的CDC反应;烯丙基和苄基底物进行的CDC反应;烷烃的CDC反应,详细综述了近年来该领域的一些研究进展.     

金催化剂的研究进展及在环保催化中的应用

综合评述了负载型金催化剂的研究进展,及其在环保催化方面的应用,涉及的反应包括CO氧化、挥发性有机化合物的氧化、NO x 的分解与还原、臭氧分解等.     

纳米金催化剂低温催化氧化甲醛和一氧化碳的研究

采用均相沉积沉淀法制备了Au/CeO2催化剂,考察了不同焙烧条件对金催化剂催化HCHO和CO氧化两个反应的活性变化规律,并对活性机理进行了研究。实验结果显示,该催化剂具有优异的低温催化HCHO和CO氧化的活性。其中经500?℃焙烧的催化剂在50?℃、体积空速为5000h-1下可以实现甲醛的完全催化氧化;经300?℃焙烧的催化剂在0?℃、体积空速为450000h-1下可以实现对CO70%的转化。发射扫描透射电镜、X射线粉末衍射的表征结果显示：对于催化CO氧化来说,粒径越小活性越高,而对于催化HCHO氧化来说,则呈高斯曲线型,粒径较低时,粒径的大小和活性是呈正比的。X射线光电子能谱表征结果显示：催化CO氧化体系中,Auδ+和Au0共同作为活性组分,而催化HCHO氧化体系中,则是Au0为主要的活性组分。     

等离子体催化转化甲烷合成C2烃的研究进展

甲烷是天然气的主要成份,由于其化学性质稳定。因而将甲烷直接转化合成C2烃难度很大。本文论述了利用等离子体活化及等离子体与催化剂协同活化甲烷转化的国内外研究进展。同时对其反应机理进行了讨论,分析了当前利用等离子体活化甲烷所存在的问题。并提出了今后的研究方向。     

光驱动低碳小分子碳氢活化与碳碳偶联的研究进展

资源含量丰富的低碳烷烃和价廉易得的低碳醇的高效转化利用是化学领域十分重要而又富有挑战性的研究课题.光催化为温和条件下低碳烷烃和低碳醇的催化选择转化制高值化学品带来了新的机遇.本文针对低碳烷烃(甲烷、乙烷、丙烷)和低碳醇(甲醇、乙醇、异丙醇),聚焦光催化低碳小分子C—H键选择活化和C—C偶联制C₂₊化学品的研究,梳理了国内外近年该领域的重要研究进展;总结、探讨了影响光催化反应活性和选择性的关键因素,以及与C—H键选择活化和C—C键可控偶联相关的关键科学问题,并对光催化低碳小分子选择转化的未来发展方向提出展望.     

负载型金催化剂的制备及其对CO催化氧化性能的研究

通过沉积沉淀法制备了负载型金催化剂,测定了其对CO的催化氧化性能.结果表明,催化剂的活性与催化剂的载体种类、焙烧温度和放置时间等因素有关;Au/TiO2和Au/CeO2催化剂的催化活性较高,而Au/ZnO催化剂的催化活性较低;焙烧温度影响催化剂的性能,焙烧温度为400℃时,催化剂活性最高;较长的放置时间会降低催化剂性能,这可能与活性组分粒径长大有关.     

过渡金属催化的(杂)芳烃C—H/C—H交叉氧化偶联反应进展

过渡金属催化的(杂)芳烃与(杂)芳烃之间的氧化C-H/C-H交叉偶联反应已成为构筑联(杂)芳基骨架的重要策略。近年来,许多令人瞩目的研究成果不断涌现,其反应类型主要可以分为未活化芳烃间的交叉脱氢偶联反应、未活化芳烃与杂芳烃的交叉脱氢偶联反应以及杂芳烃与杂芳烃之间的交叉脱氢偶联反应三种类型。本文主要综述了这三类反应的最新研究进展,介绍了各类反应的特点、优势及在合成中的应用。     

纳米孔洞金属-有机骨架材料对o,p-苯二酚的选择性催化氧化

以不同孔洞尺寸及不同中心离子的纳米孔洞金属-有机骨架材料M_3(BTC)_2(H_2O)x(M=Cu~Ⅱ,Zn~Ⅱ,Co~Ⅱ,Ni ~Ⅱ,BTC=benzene tricarboxylic acid苯三甲酸)为催化剂,采用动力学方法,讨论其对p-苯二酚和o-苯二酚的选择性催化氧化性能.重点考察了催化剂孔洞尺寸,骨架中心离子,催化反应介质,反应温度对催化选择性的影响,以期对MOFs材料的选择性催化动力学方面有比较全面的认识.     

Theoretical advances of the structures and catalytic activities of small-sized gold nanoclusters

Gold nanoclusters exhibit extraordinary catalytic activities,but the dominating factor is still unclear due to the complexity of the structures.In this review,we briefly summarized the recent theoretical progress on their structures and catalytic activities.Combining the experimental and theoretical efforts,the structures of small-sized gold clusters have been explored systematically.Based on the determined structures,factors that influence the catalytic capabilities of small-sized gold clusters(Au_(16)-Au_(35))are studied using CO oxidation asa probe.The preadsorption energies of CO and O_2are found strongly correlated with catalytic activities,which could be affected by the clusters'geometries,sizes,and charge distributions.In addition,the presence of water could significantly lower the activation energy barrier of O_2 dissociation to enhance the clusters'catalytic activities.     

金属纳米团簇在电化学领域的应用研究进展

尺寸小于2nm的金属纳米团簇是由几个到几百个原子组成的纳米结构材料.对于金属纳米团簇,由于其大部分甚至所有金属原子可能暴露于表面而具有高的表面原子比例,该独特的原子堆积结构使其具有高的表面活性,因此其在催化反应中具有重要应用价值.同时,其明确的原子排列和堆积结构使其可作为模型催化剂,用于研究纳米结构-性能之间的关系.笔者简要总结了近年来金属纳米团簇的研究进展和现状,重点总结了其在电化学领域的应用,包括电催化和电化学传感,最后对其未来在电催化和电分析领域的应用前景进行了展望.     

Chiral ligand-protected gold nanoclusters: Considering the optical activity from a viewpoint of ligand dissymmetric field

Chirality is a geometric property of a physical, chemical, or biological object, which is not superimposable on its mirror image. Its significant presence has led to a strong demand in the development of chiral drugs, sensors, catalysts, and photofunctional materials. In recent years, chirality of nanoscale organic/inorganic hybrids has received tremendous attention owing to potential applications in chiral nanotechnology. In particular, with the recent progress in the syntheses and characterizations of atomically precise gold nanoclusters protected by achiral thiolates, atomic level origins of their chirality have been unveiled. On the other hand, chirality or optical activity in metal nanoclusters can also be introduced via the surface chiral ligands, which should be universal for the nanosystems. This tutorial review presents some optically-active metal (gold) nanoclusters protected by chiral thiolates or phosphines, and their chiroptical (or circular dichroism; CD) properties are discussed mostly from a viewpoint of the ligand dissymmetric field scheme. The examples are the gold nanoclusters protected by (R)-/(S)-2-phenylpropane-1-thiol, (R)-/(S)-mercaptosuccinic acid, phenylboronate-D/L-fructose complexes, phosphine sulfonate-ephedrinium ion pairs, or glutathione. Some methodologies for versatile asymmetric transformation and chiroptical controls of the nanocluster compounds are also described. In the dissymmetric field model as the origin of optical activity, the chiroptical responses of the gold nanoclusters are strongly associated with coupled oscillator and/or CD stealing mechanisms based on the concept of induced CD (ICD) derived from a perturbation theory, so on this basis, some characteristic features of the observed CD responses of chiral ligand-protected gold nanoclusters are presented in detail. We believe that various kinds of origins of chirality found in ligand-protected gold nanoclusters may provide models for understanding those of many related nanomaterials.     

Influence of composition and size on the thermodynamic stability and structural evolution of CuAlNi nanoclusters

The heating process for CuAlNi nanoclusters with cuboctahedral structure was studied by molecular dynamics simulation with the embedded atom method. A diffusionless martensitic transformation from the cuboctahedral (CO) to the icosahedral (ICO) structure before the melting point was found in some CuAlNi nanoclusters. The effects of element composition and cluster size on the thermodynamic stability and structural transformation of trimetallic nanoclusters were investigated. The results show that the CO–ICO transformation temperature was size-dependent and occurred only for small clusters. It was also observed that the CO–ICO transformation temperature firstly dropped and then raised as Al concentration increased, which may be strongly related to the release of excess energy. Furthermore, the surface segregation phenomenon was also observed that the lower surface energy components, such as Al and Cu atoms, segregated to the surface of CuAlNi nanoclusters. The changes in the melting points of CuAlNi nanoclusters with different alloy compositions and cluster sizes were also studied. And furthermore, the physical basis of structural transition of CuAlNi nanoclusters was discussed.     

贫金矿氰化浸出的初试研究报告

以某地贫金矿(2.8 g/t)为试验对象,在矿粉粒度为-200目≥80%,矿浆浓度为33.3%,NaCN用量为2 kg/t的情况下,SPW助剂用量为0.75 kg/t,pH=10±1,浸出时间≥10 h,金的浸出率可达到≥90%,而且浸出液循环使用,可使NaCN用量下降1/2左右.     

Co改性Pd/C催化的葡萄糖催化氧化反应

以活性炭为栽体,制备了Pd／C,Pd-Co／C催化剂．活性评价结果表明,Pd-Co／C催化剂显示出良好的催化性能,反应4h后,葡萄糖的转化率达98．8％,较Pd／C催化剂的活性有显著的提高．BET,XRD表征结果也表明．Co的添加及焙烧过程,使载体由无定形结构转变为晶型结构,且比表面积和微孔容积均有所增加,既提高了Pd的表面分散度,又增大了Pd在催化剂表面的裸露程度,从而使Pd-Co／C催化剂表现出良好的催化性能．     

MnO2催化剂的制备及其催化氧化挥发性有机污染物的研究进展

挥发性有机污染物(VOCs)由于其危害大、来源广,因此受到人们的普遍关注.热催化氧化技术在催化降解挥发性有机污染物方面具有独特的优势,而催化剂二氧化锰(MnO_2)由于其在室温下相对于其他催化剂具有较高的处理效果以及易制备等优点而被广泛研究和使用.本文作者着重讲述了催化剂MnO_2的特点、制备工艺、降解挥发性有机污染物效率的影响因素及其负载方式等在国内外的研究现状.     

秦岭二台子金矿床地质地球化学再研究

为了指导找矿，通过近年来找矿预测获得的新突破和积累的较新测试资料，对二台子金矿床作出进一步的认识和总结，在探讨矿床成矿大地构造背景的基础上，提出矿床所在盆地的容矿岩系发育模式，在矿床成矿作用演化研究中，进一步阐述了矿床形成经历的同生与后生两次成矿作用，分别与秦岭造山带南北陆块俯冲碰撞造山导致被动大陆一侧局部出现伸展断陷式盆地和转入陆内逆冲推覆造山的构造－岩浆活动密切耦合。     

热流固耦合动态边界理论研究

基于Biot理论,推导了考虑热渗流作用的热流固耦合问题的基本方程,建立了本问题的热渗流模型,给出了所考虑问题的热流体动力弥散分布概率及各项系数的表达式,进一步建立了微压热液体位移场,讨论了热流体动力弥散因素对多孔介质边界的影响,建立了描述多孔介质的动态边界方程,针对不同的外部因素,分别建立了4种边界模型,并进行了动态模拟.     

Fabrication of gold nanoelectrodes based on nanolithography electrochemically through a conductive AFM tip

Gold nanoelectrodes were fabricated by approach of combining surface self-assembly with nanolithography electrochemically through a conductive AFM tip. The controllahle structure with width and distance in nanometer as a template was constructed by nanolithography patterning process, which was accomplished by a conductive AFM tip on certain highly ordered long-tail organosilane monolayers. Then through adsorption of Cd^2＋ and exposure of the Cd^2＋-loaded surface to gaseous H2S, CdS nanowires were generated in a template-controlled self-assembly process. Finally, metallic gold nanowires were conversed from CdS nanowires by treatment with the aqueous solution of HAuCl4 via a redox chemical process, which had good conductivity proved by C-AFM.