醛与胺均相催化合成三级酰胺研究进展

酰胺类化合物是材料科学、化学生物学及药物化学中重要的有机化合物。醛容易得到且毒性较小,出于原子经济性考虑是合成酰胺的合适原料。近年来,随着绿色化学的兴起,利用醛作为酰化试剂,通过C—H键活化方式合成酰胺键的方法得到广泛关注。研究方法中,有机小分子、过渡金属、稀土盐或配合物的催化起到重要作用,纳米催化剂的催化在酰胺键形成方法的研究也有突破。纳米粒子应用于醛与胺合成三级酰胺的反应有金属胶体纳米催化剂(准均相型)和磁性非均相型。非均相催化剂的优势在于其较高的回收使用率,易与产物分离,便于回收再利用。磁性纳米材料与以往的均相催化剂相比,分离和回收更加简单方便,重复利用率更高,但催化剂表征受到限制。探索制备方法简单、操作步骤方便和催化效果显著的普通多相纳米催化剂是未来应用于催化醛合成酰胺的新领域。综述近年来利用醛作为酰化试剂,通过C—H键活化的方式,与铵盐、二级胺、三级胺和酰胺反应合成三级酰胺化合物的方法,并总结相关反应机理。     

Last Decade of Research on Activated Carbons as Catalytic Support in Chemical Processes

This review is devoted to the application and knowledge developed in the past 10 years in the area of chemical processes catalyzed by activated carbon supported catalysts. Activated carbons are well known for their catalytic properties and for being used as support in heterogeneous catalysis. The supported catalysts have been successfully used in the chemical industries for long time. In the last decade, carbon supported catalysts have opened the door for new chemical catalytic processes based on their intrinsic features. However, fundamental understanding of molecular structure-reactivity relationship of these carbon materials remains unexplored. Futures advances in all areas may be possible through combined experimental and theoretical approaches.     

碳纳米管改性对Au/CeO2催化剂乙醇部分氧化制氢的影响

采用沉积沉淀法制备了一系列碳纳米管改性的Au/CeO₂催化剂,以乙醇部分氧化制氢为探针反应,研究了碳纳米管对Au/CeO₂催化剂乙醇部分氧化性能的影响,并运用XRD、TPR、BET等方法对催化剂进行了表征。结果表明,碳纳米管的添加提高了Au/CeO₂催化剂的比表面积、孔容和吸氧量,催化剂的氢气选择性先随碳纳米管添加量的增加而大幅增加,碳纳米管的添加量达6%～10%时,氢气选择性达到43%。进一步提高碳纳米管的含量,氢气选择性增加幅度不大。碳纳米管的添加可以有效抑制副产物CO的产生。     

Use of microwave irradiation in the grafting modification of the polysaccharides - A review

Polysaccharides are a natural and renewable feed stock for synthesizing high performance macromolecular materials. A popular, versatile and convenient route to develop polysaccharide based materials is the grafting of synthetic polymers onto natural polysaccharides. In spite of the attractive chemical and physical properties of polysaccharide based copolymeric materials, undesired homopolymer formation in the concurrent competing reaction lowers the copolymer yield, posing problems in the commercialization of the grafting procedures. Moreover, the requirement for an inert atmosphere is an added disadvantage for many conventional grafting procedures. The use of microwave irradiation has been exploited in the past two decades to alleviate these limitations in the synthesis of a range of graft modified polysaccharide materials. Indeed, increasing interest in clean and green environment friendly chemistry has motivated the use of microwaves in the polysaccharide grafting modification for various applications. Microwave irradiation significantly reduces the use of toxic solvents, as well as the reaction time for almost all the grafting reactions of interest here, ensuring high yields, product selectivity and clean product formations. Moreover, in many instances, microwave synthesized polysaccharide copolymers exhibit better properties for commercial exploitation than their conventionally synthesized counterparts. This review highlights recent applications of microwave heating in the grafting modifications of polysaccharides and discusses the underlying mechanisms and issues.     

Olefin-Copper(I) Complexes and their Properties

The synthesis, structure and the novel chemical and physical properties of olefin-copper(I) complexes are the focus of this review. Particular emphasis is placed on the molecular assembly of these compounds and their potential applications as homogeneous catalysts in solution and as solids possessing unusual physical functional properties.Xi-Sen Wang:Equally ContributedHong Zhao:Equally Contributed     

An aerosol reactor for the controlled synthesis of heterogeneous catalyst particles

Commercialized catalysts are often needed in multiton quantities for industrial deployment. Although scalable, manufacturing methods to produce catalysts at quantity often produce materials with an ensemble of physical and chemical characteristics. This work explores an aerosol reactor to synthesize homogeneous, uniform catalyst materials in order to develop correlations between key chemical and physical characteristics and their resulting catalytic performance. With these insights, we optimize reactor processing conditions to engineer particles with the desired physical and chemical characteristics to produce enhanced performance catalysts. Control over several process parameters, including reactor residence time, temperature, precursor type, and precursor composition, allows for the rational determination of key physical and chemical characteristics on the resulting catalyst materials and enables process optimization to engineer catalysts with enhanced performance. To demonstrate the methodology, the aerosol reactor was used to synthesize and optimize WO _x catalyst materials for the isomerization and metathesis of a 2-butene feed into propylene.     

纳米多相催化材料在常温反应中的应用

近年来,纳米材料在化学反应过程中扮演着越来越重要的角色。纳米材料作为多相催化剂,具有高活性、高选择性、高稳定性而且易于回收利用等优点。将精心设计的纳米材料用于催化一系列反应,使其在常温下进行,可以促进资源的高效利用和节能减排,在化工领域有着广阔的应用前景。本文详细介绍了以下几种类型的纳米材料,即金属纳米粒子材料、固载型金属离子复合物纳米材料、金属氧化物纳米材料和固体酸纳米材料。并阐述了上述纳米材料的结构特点及在催化方面的优势,同时结合实例,着重探讨了上述纳米材料作为多相催化剂在氧化反应、还原反应、偶联反应等多种节能高效反应中的应用。纳米材料因其多方面的优点以及广阔的应用范围,是一种极具发展潜力的多相催化材料。     

Synthesis of Cycloparaphenylenes and Related Carbon Nanorings: A Step toward the Controlled Synthesis of Carbon Nanotubes

Since their discovery in 1991, carbon nanotubes (CNTs) have attracted significant attention because of their remarkable mechanical, electronic, and optical properties. Structural uniformity of the CNT is critically important because the sidewall structures (armchair, zigzag, and chiral) determine many of the significant properties of CNTs. Ideally researchers would synthesize CNTs with a defined target sidewall structure and diameter, but the current synthetic methods, such as arc discharge and chemical vapor deposition, only provide CNTs as the mixtures of various structures. Purification of these mixtures does not allow researchers to isolate a structurally uniform CNT, which is the bottleneck for fundamental studies and advanced applications of these materials. Therefore, the selective and predictable synthesis of structurally uniform CNTs would represent a critical advance in both nanocarbon science and synthetic chemistry. This Account highlights our efforts toward the bottom-up synthesis of structurally uniform carbon nanotubes (CNTs). We envisioned a bottom-up synthesis of structurally uniform CNTs through a controlled growth process from a short carbon nanoring (template) that corresponds to the target structure of CNTs. Our simple retrosynthetic analysis led to the identification of cycloparaphenylenes (CPPs), acene-inserted CPPs, and cyclacenes as the shortest sidewall segments of armchair, chiral, and zigzag CNTs, respectively. With this overall picture in mind, we initiated our synthetic studies of aromatic rings/belts as an initial step toward structurally uniform CNTs in 2005. This research has led to (i) a general strategy for the synthesis of CPPs and related carbon nanorings using cyclohexane derivatives as a benzene-convertible L-shaped unit, (ii) a modular, size-selective, and scalable synthesis of [n]CPPs (a shortest segment of armchair CNTs), (iii) the X-ray crystal structure analysis of CPPs, (iv) the design and synthesis of acene-inserted CPPs as the shortest segment of chiral CNTs, and (v) the first synthesis of cyclo-1,4-naphthylene, a π-extended CPP. We believe this work will serve as important initial steps toward a controlled synthesis of CNTs.     

Transformation of Biomass Products into Fine Chemicals Catalyzed by Solid Lewis- and Brønsted-acids

β-Pinene is a biomass product that can be obtained from turpentine oil and transformed into its epoxide by a standard reaction of synthetic organic chemistry. This epoxide can be used as cheap and easily available entry for other natural products with an added value employing different solids as catalysts. Hence, the Lewis acidic mesoporous molecular sieve Sn-MCM-41 provides predominantly myrtanal as product whereas commercial nitrogen containing resins treated with an acid convert β-pinene oxide into perillyl alcohol as main product.     

不对称催化合成手性泛解酸内酯的研究进展

泛解酸内酯是合成D-泛酸钙和D-泛醇的重要中间体,国内主要采用生物拆分法,虽取得一定进展,但存在底物浓度偏低、反应条件苛刻、光学纯度不高和催化剂活性不强等问题。化学不对称合成法成为近年来制备手性泛内酯的研究热点。根据手性源的不同,介绍过渡金属配合物催化不对称还原酮基泛内酯,过渡金属配合物催化羟醛缩合反应,有机小分子及其衍生物不对称催化羟醛缩合反应并经还原内酯化合成泛内酯以及光学活性化合物作为反应底物或非手性底物中加入手性助剂的合成手性泛内酯工艺。其中,有机小分子催化乙醛酸酯与醛的反应表现出良好的催化效果,且催化剂易得,反应条件温和,操作简单。缩合产物的收率和对映选择性均不高,设计具有高活性和高选择性的有机小分子手性催化剂是今后研究的重点。     

Role and impact of surfactants in carbon nanotube dispersions and sorting

Carbon nanotubes (CNTs) are proving to be versatile nanomaterials that exhibit superior and attractive electrical, optical, chemical, physical, and mechanical properties. Different kinds of CNTs exist, and their associated properties have been actively explored and widely exploited from fundamental studies to practical applications. Obtaining high-quality CNTs in large volumes is desirable, especially for scalable electronic, photonic, chemical, and mechanical systems. At present, abundant but random CNTs are synthesized by various growth methods including arc discharge, chemical vapor deposition, and molecular beam epitaxy. An economical way to secure pristine CNTs is to disperse the raw soot of CNTs in solutions, from which purified CNTs are collected via sorting methods. Individual CNTs are generally hydrophobic, not readily soluble, requiring an agent, known as a surfactant to facilitate effective dispersions. Furthermore, the combination of surfactants, polymers, DNA, and other additives can enhance the purity of specific types of CNTs in confidence dispersions. With highly-pure CNTs, designated functional devices are built to demonstrate improved performance. This review surveys and highlights the essential roles and significant impacts of surfactants in dispersing and sorting CNTs.     

Carbon nanotubes/SiC whiskers composite prepared by CVD method

Selective growth of carbon nanotubes (CNTs) on silicon carbide (SiC) substrate will create some new applications in composites and electronic devices by combining their mechanical and physical properties. Multi-walled CNTs were successfully grown on SiC whiskers using a conventional xylene–ferrocene chemical vapor deposition process. A thin oxide layer was created on the surface of the SiC whiskers by high-temperature annealing in air before CNT growth. The effect of catalyst morphology and chemistry on the growth of CNTs was analyzed. Our technique may be further applied to the controlled growth of CNTs on any other SiC substrates.     

TiO2-Based Photocatalysis at the Interface with Biology and Biomedicine

The conversion of sunlight into chemical energy by using photosynthetic machinery is at the heart of nature and life. Scientists have also learned to use light energy to promote a great variety of chemical reactions, most of which are based on redox processes involving electron-transfer steps. Indeed, the area of photoredox catalysis has recently emerged as one of the hottest fields in synthetic chemistry. Many of the photoredox reactions discovered so far take place in homogeneous phases, and rely on the use of soluble photoresponsive catalysts. However, in recent years, there have been many advances in the area of heterogeneous photocatalysis, most of which are based on the use of semiconductor materials, such as TiO₂, as a key photocatalytic system. These technologies have found different applications, especially in the field of sustainable chemistry and therapy. Herein, some of these applications, and the potential of TiO₂-based photocatalysts in biology and biomedicine, are reviewed.     

Vertical connection of carbon nanotubes to silicon at room temperature using a chemical route

The vertical connection of carbon nanotubes (CNTs) to silicon based on a chemical route at room temperature has been realized, using polyethylenimine (PEI) as a binding material between them. Chemical hydrogen bonding and electrostatic interaction between PEI, CNTs, and silicon effectively connect the CNTs to silicon. In this process, CNTs always keep their pristine structure and shape, so the unique physical properties of CNTs are maintained. Electric transport at this junction shows a tunneling behavior, which verifies PEI as a molecular link between CNT tips and the silicon. Control of both interaction and surface termination of the materials at the molecular level allows us to bind the CNTs to the silicon surface without modifying the properties of either.     

沸石择形催化在精细化工中的应用

本文评述沸石分子筛的择形催化作用及其在精细化学品和中间体合成过程中所涉及的一些重要有机反应,以及利用择形沸石催化剂所开发的一些精细化工过程。     

Towards Supramolecular Catalysis with Small Self-assembled Peptides

Self-assembly of small peptides offers unique opportunities for the bottom-up construction of supramolecular catalysts that aim to emulate the efficiency and selectivity of natural enzymes. Small, information-rich, simple molecules based on amino acids can self-organise autonomously into complex systems with emergent catalytic properties. The power of noncovalent interactions can be used to construct supramolecular peptidic tertiary structures. Moreover, specific functional groups present in amino acid side-chains may present either a catalytic activity by themselves or be able to bind cofactors such as metal ions. In this scenario, although relevant progress has been achieved in recent years, promising applications in biomaterials science are foreseen. In this review, we discuss the state-of-the-art of this approach at the interface between supramolecular chemistry and peptide science.     

CATALYST PRODUCT SEPARATION TECHNIQUES IN HECK REACTION

The Heck reaction finds several applications in industry because it is one of the effective tools for the formation of a new C─C bond. In addition to the catalytic activity and selectivity, catalyst-product separation strategies are very important for the industrial application. There are various methods of interest ranging from conventional heterogeneous catalysts to heterogenization of homogeneous catalysts. The heterogeneous catalysts are classified into supported metal catalysts, zeolite-encapsulated catalysts, colloids-nanoparticles, and intercalated metal compounds. The homogeneous metal complexes catalysts are heterogenized using modified silica catalysts, polymer-supported catalysts, biphasic catalysts, supported liquid-phase catalysts, nonionic liquids solvents, perfluorinated solvents, and reusable homogeneous complexes. In general, heterogeneous catalysts are effective and stable at higher temperatures, which may be important for the activation of less reactive but less expensive chloroaryls substrates. However, the heterogeneous catalysts have a major drawback of poor selectivity toward Heck coupling products. The heterogenized metal complexes catalysts operate under relatively mild conditions as compared with heterogeneous catalysts, and so they can be applied to the production of pharmaceuticals and fine chemicals. Catalysis using supercritical solvents with catalyst separation techniques is promising for the development of green chemistry processes. Although the concepts described in this article have been reviewed mainly for Heck reactions, they should be applicable to a wide range of other chemical transformations (hydrogenation, carbonylation, hydroformylation, and so on) that, currently, are homogeneously catalyzed reactions.     

Catalytic conversion of syngas into C2 oxygenates over Rh-based catalysts—Effect of carbon supports

Ethanol is considered as a potential alternative synthetic fuel to be used in automobiles or as a potential source of hydrogen for fuel cells. In this paper we first undertake a brief overview of the catalyst development for syngas conversion to C₂ oxygenates over Rh-based catalysts, mainly on the effects of various additives and supports on the activity and selectivity. Then we investigated the effects of carbon materials, which have been rarely studied as supports for Rh-based catalysts in this process. For example, rather well graphitized carbon black, very high surface area CMK-3 and activated carbon (AC) were compared to carbon nanotubes (CNTs), which exhibits a medium level surface area with well defined nanochannels. The CNT-supported catalyst shows a highest overall activity and yield of C₂ oxygenates compared to the other carbon-supported catalysts. The catalysts are characterized by N₂ adsorption–desorption, CO chemisorption, TEM, XRD and TPD. The graphitized structure combined with the tubular morphology of CNTs likely play an important role.     

纤维素辐照改性及其应用

辐照技术利用电离辐射诱发物理化学反应(例如交联、聚合、接枝、降解等)对材料进行加工或改性,与常规加工方法相比,具有节能、无环境污染等特点。将辐照技术应用于纤维素改性过程近年已成为非动力核技术应用领域研究的热点之一。本工作对目前纤维素的辐照技术及其基本反应机理进行了概述,其中包括纤维素膜材料、纤维素水凝胶、纤维素微晶/纳米材料,并对纤维素辐照改性过程的辐照环境,包括溶剂、敏化剂、温度、辐照剂量、环境氛围、结晶度等进行了总结。     

碳酸酯合成过程催化剂离子液体固载方式研究进展

有机碳酸酯是一类重要的化工原料,常被用在药物合成、绿色添加剂、锂电池电解液以及合成聚碳酸酯等领域,碳酸酯的合成是实现CO2碳资源化最有效的途径之一.固载化离子液体兼具均相催化剂的高活性和固相催化剂易于分离和回收等特点,在碳酸酯合成反应中具有广阔的工业应用前景.综述用于合成碳酸酯的固载化离子液体催化剂固载技术研究进展,总...