Recent Advances in Covalent Organic Frameworks for Catalysis

Covalent organic frameworks (COFs) as an emerging type of crystalline porous materials, have obtained considerable attention recently. They have exhibited diverse structure and attractive performance in various catalytic reactions. It is highly expected to have a systematic and comprehensive review summing up COFs‐derived catalysts in homogeneous and heterogeneous catalysis, which is favorable to the judicious design of an efficient catalyst for targeted reaction. Herein, we focus on summarizing recent and significant developments in COFs materials, with an emphasis on both the synthetic strategies and targeted functionalization, and categorize it in accordance with the different types of catalytic reactions. Their potential catalysis applications are reviewed thoroughly. Moreover, a personal view about the future development of COFs catalysts with respect to the large‐scale production is also discussed.     

Flexible and Hierarchical Metal–Organic Framework Composites for High‐Performance Catalysis

The development of porous composite materials is of great significance for their potentially improved performance over those of individual components and extensive applications in separation, energy storage, and heterogeneous catalysis. Now mesoporous metal–organic frameworks (MOFs) with macroporous melamine foam (MF) have been integrated using a one‐pot process, generating a series of MOF/MF composite materials with preserved crystallinity, hierarchical porosity, and increased stability over that of melamine foam. The MOF nanocrystals were threaded by the melamine foam networks, resembling a ball‐and‐stick model overall. The resulting MOF/MF composite materials were employed as an effective heterogeneous catalyst for the epoxidation of cholesteryl esters. Combining the advantages of interpenetrative mesoporous and macroporous structures, the MOF/melamine foam composite has higher dispersibility and more accessibility of catalytic sites, exhibiting excellent catalytic performance.     

Breakthrough and future: nanoscale controls of compositions,morphologies, and mesochannel orientations toward advanced mesoporous materials

Currently, ordered mesoporous materials prepared through the self‐assembly of surfactants have attracted growing interests owing to their special properties, including uniform mesopores and a high specific surface area. Here we focus on fine controls of compositions, morphologies, mesochannel orientations which are important factors for design of mesoporous materials with new functionalities. This Review describes our recent progress toward advanced mesoporous materials. Mesoporous materials now include a variety of inorganic‐based materials, for example, transition‐metal oxides, carbons, inorganic‐organic hybrid materials, polymers, and even metals. Mesoporous metals with metallic frameworks can be produced by using surfactant‐based synthesis with electrochemical methods. Owing to their metallic frameworks, mesoporous metals with high electroconductivity and high surface areas hold promise for a wide range of potential applications, such as electronic devices, magnetic recording media, and metal catalysts. Fabrication of mesoporous materials with controllable morphologies is also one of the main subjects in this rapidly developing research field. Mesoporous materials in the form of films, spheres, fibers, and tubes have been obtained by various synthetic processes such as evaporation‐mediated direct templating (EDIT), spray‐dried techniques, and collaboration with hard‐templates such as porous anodic alumina and polymer membranes. Furthermore, we have developed several approaches for orientation controls of 1D mesochannels. The macroscopic‐scale controls of mesochannels are important for innovative applications such as molecular‐scale devices and electrodes with enhanced diffusions of guest species. © 2010 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 9: 321–339; 2009: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.200900022     

Ordered mesoporous metal oxides: synthesis and applications

Great progress has been made in the preparation and application of ordered mesoporous metal oxides during the past decade. However, the applications of these novel and interesting materials have not been reviewed comprehensively in the literature. In the current review we first describe different methods for the preparation of ordered mesoporous metal oxides; we then review their applications in energy conversion and storage, catalysis, sensing, adsorption and separation. The correlations between the textural properties of ordered mesoporous metal oxides and their specific performance are highlighted in different examples, including the rate of Li intercalation, sensing, and the magnetic properties. These results demonstrate that the mesoporosity has a direct impact on the properties and potential applications of such materials. Although the scope of the current review is limited to ordered mesoporous metal oxides, we believe that the information may be useful for those working in a number of fields.     

Recent advances in synthesis and applications of transition metal containing mesoporous molecular sieves

Work in mesoporous silica-based materials began in the early 1990s with work by Mobil. These materials had pore sizes from 20-500 A and surface areas of up to 1500 m(2) g(-1) and were synthesized by a novel liquid crystal templating approach. Researchers subsequently extended this strategy to the synthesis of mesoporous transition metal oxides, a class of materials useful in catalysis, electronic, and magnetic applications because of variable oxidation states, and populated d-bands-features not found in silicates. These materials are already showing promise in electronic and optical applications hinging on the semiconducting properties of transition metal oxides and their potential to act as electron acceptors, an important feature in the design of cathodic materials. This is the first general review of non-silicate mesoporous materials and will focus on recent advances in this area, emphasizing materials possessing unique electronic, magnetic, or optical properties. Also covered are advances in the synthesis and applications of mesostructured sulfides as well as a new class of template-synthesized platinum-based materials that show promise in heterogeneous catalysis.     

Ionic‐Liquid‐Grafted Rigid Poly(p‐Phenylene) Microspheres: Efficient Heterogeneous Media for Metal Scavenging and Catalysis

Novel guanidinium ionic liquid‐grafted rigid poly(p‐phenylene) (PPPIL) microspheres have been developed for metal scavenging and catalysis. The noble‐metal nanoparticles supported on the microspheres surface can be used as efficient heterogeneous catalysts. The combination of nanoparticles and ionic liquid fragments on the microsphere surfaces enhance the activity and durability of the catalyst. The PPPIL ? Pd⁰ catalyst has been tested in the Suzuki cross‐coupling reaction, and exhibits much higher catalytic activity than Pd catalysts supported on porous polymer matrices. The PPPIL ? Pd⁰ catalyst can be recycled at least for nine runs without any significant loss of activity. The present approach may, therefore, have potential applications in transition‐metal‐nanocatalyzed reactions.     

Boron: A key functional component for designing high-performance heterogeneous catalysts

Heterogeneous catalysis is a vivid branch of traditional catalysis field, with the advantage of high efficiency and being easily separated from reactants and products after reaction, and have received widespread attentions in large-scale industrial production, especially in the field of energy utilization. Boron has been found to be a key functional component for designing high-performance heterogeneous catalysts. In this review, we cover and categorize the past and recent progress in boron-containing materials and their applications in heterogeneous catalysis particularly in energy‐related fields. The fundamental roles of boron components in the emerging heterogeneous catalysis of construction, regulation and stabilization of active phases/sites are highlighted, with the emphasis on how they regulating structural and electronic properties of host materials. We then categorize boron-containing catalysts into six kinds mainly including intermetallic boride catalysts, metal boride-derived catalysts, boron-doped catalysts, metal boride-decorated catalysts, boron-containing compounds as catalyst supports, and single-boron-site catalysts, as well as try to establish structure-catalytic activity relationship. The catalytic applications of these six boron-containing catalysts are discussed separately, focusing on the energy-related reactions such as hydrogen evolution reaction (HER), oxygen evolution reaction (OER), oxygen reduction reaction (ORR), carbon dioxide reduction reaction (CO₂RR) and nitrogen reduction reaction (NRR). Finally, the opportunities and challenges related to boron-containing compounds in the field of catalysis are prospected.     

Recent Progress of Single-Atom Alloys in Heterogeneous Catalytic Reactions

In decades, heterogeneous catalysis has played a more significant role in social progress. However, the exorbitant price and low reserves vastly limit the application of noble metal catalysts, which are extensively used in heterogeneous catalysis. The single-atom-alloy catalysts (SAAs) have been regarded as a crucial way to improve the dispersion ratio of noble metal while maintaining great heterogeneous catalytic performance by dispersing noble metal single atoms on the surface of another metal. Besides the benefit from the metal bonds between noble metals and support metals, SAAs is also a unique method to construct metallic metal single atoms and obtain its characteristic catalytic performance, which is not possessed by other single atoms catalysts with positive electricity metal atoms. Most recently, SAAs have been demonstrated to catalyze a lot of significant heterogeneous reactions. This review will introduce the synthesis methods of SAAs and then summarize their applications in heterogeneous catalysis.     

Functionalized Silicas for Metal‐Free and Metal‐Based Catalytic Applications: A Review in Perspective of Green Chemistry

Heterogeneous catalysis plays a key role in promoting green chemistry through many routes. The functionalizable reactive silanols highlight silica as a beguiling support for the preparation of heterogeneous catalysts. Metal active sites anchored on functionalized silica (FS) usually demonstrate the better dispersion and stability due to their firm chemical interaction with FSs. Having certain functional groups in structure, FSs can act as the useful catalysts for few organic reactions even without the need of metal active sites which are termed as the covetous reusable organocatalysts. Magnetic FSs have laid the platform where the effortless recovery of catalysts is realized just using an external magnet, resulting in the simplified reaction procedure. Using FSs of multiple functional groups, we can envisage the shortened reaction pathway and, reduced chemical uses and chemical wastes. Unstable bio‐molecules like enzymes have been stabilized when they get chemically anchored on FSs. The resultant solid bio‐catalysts exhibited very good reusability in many catalytic reactions. Getting provoked from the green chemistry aspects and benefits of FS‐based catalysts, we confer the recent literature and progress focusing on the significance of FSs in heterogeneous catalysis. This review covers the preparative methods, types and catalytic applications of FSs. A special emphasis is given to the metal‐free FS catalysts, multiple FS‐based catalysts and magnetic FSs. Through this review, we presume that the contribution of FSs to green chemistry can be well understood. The future perspective of FSs and the improvements still required for implementing FS‐based catalysts in practical applications have been narrated at the end of this review.     

Biochar-based functional materials as heterogeneous catalysts for organic reactions

The development of cheap, effective and heterogeneous catalysts remains a substantial challenge in organic synthesis. Of the extensive heterogeneous catalysis, biochar materials have attracted increasing attention to be considered as an important class of support materials in organic reactions due to their distinctive characteristics such as high porosity, large specific surface area, high adsorption ability, excellent cation exchange capacity and outstanding stability. This review highlights recent advances over the past 5 years, outlining the synthetic methods of biochar materials and their applications as catalysts or catalyst supports in a range of organic reactions including oxidation, reduction, esterification, coupling, alkylation and multi-component reactions.     

Synthesis, characterization, and applications of dendrimer-encapsulated nanoparticles

In this article we describe the synthesis, characterization, and applications of dendrimer-encapsulated nanoparticles (DENs). These materials are synthesized by a template approach in which metal ions are extracted into the interior of dendrimers and then subsequently chemically reduced to yield nearly size-monodisperse particles having dimensions of less than 3 nm. Monometallic, bimetallic (including core/shell), and semiconductor nanoparticles have been prepared by this route. The dendrimer component of these composites serves not only as a template for preparing the nanoparticle replica but also to stabilize the nanoparticle, makes it possible to tune solubility, and provides a means for immobilization of the nanoparticle on solid supports. These materials have a number of potential applications, but the focus here is on catalysis. Homogeneous catalytic reactions, including hydrogenations, Heck coupling, and Suzuki reactions, in water, organic solvents, biphasic fluorous/organic solvents, and liquid and supercritical CO2 are discussed. In many cases it is easy to recycle catalytic DENs. DENs can also be immobilized on supports, such as silica and titania, and used for heterogeneous catalysis. Bimetallic DENs are shown to have particularly interesting catalytic properties. In addition to a discussion of current progress in this field, a number of intriguing questions related to the properties and potential applications of these materials are examined.     

Highly Stable Mesoporous Zirconium Porphyrinic Frameworks with Distinct Flexibility

The construction of highly stable metal–porphyrinic frameworks (MPFs) is appealing as these materials offer great opportunities for applications in artificial light‐harvesting systems, gas storage, heterogeneous catalysis, etc. Herein, we report the synthesis of a novel mesoporous metal–porphyrinic framework (denoted as NUPF‐1) and its catalytic properties. NUPF‐1 is constructed from a new porphyrin linker and a Zr₆O₈ structural building unit, possessing an unprecedented doubly interpenetrating scu net. The structure exhibits not only remarkable chemical and thermal stabilities, but also a distinct structural flexibility, which is seldom seen in metal–organic framework (MOF) materials. By the merit of high chemical stability, NUPF‐1 could be easily post‐metallized with [Ru₃(CO)₁₂], and the resulting {NUPF‐1–RuCO} is catalytically active as a heterogeneous catalyst for intermolecular C(sp³)?H amination. Excellent yields and good recyclability for amination of small substrates with various organic azides have been achieved.     

介孔分子筛的酸性和水热稳定性

介孔分子筛材料在催化、吸附与分离以及化学组装制备先进材料和分子器件等方面具有潜在的应用价值.但是,由于介孔分子筛材料较低的水热稳定性和较弱的酸性,极大地影响了其在催化研究中的广泛应用.本文系统地综述了最近几年在提高介孔分子筛酸性和水热稳定性的研究工作.其中包括:(1)将超酸组份负载于介孔分子筛的孔道中以达到提高介孔分子筛材料的酸强度的目的;(2)通过在合成介孔分子筛的过程中加入无机盐和有机胺等助剂或采用合适的后处理方法以提高介孔分子筛的水热稳定性;(3)通过新型模板剂来合成具有较高水热稳定性的介孔分子筛材料;(4)利用具有沸石分子筛基本结构单元的沸石分子筛导向剂与表面活性剂自组装来合成具有强酸中心和高温水热稳定的介孔分子筛材料.     

Iron‐Catalyzed Cross‐Couplings in the Synthesis of Pharmaceuticals: In Pursuit of Sustainability

The scarcity of precious metals has led to the development of sustainable strategies for metal‐catalyzed cross‐coupling reactions. The establishment of new catalytic methods using iron is attractive owing to the low cost, abundance, ready availability, and very low toxicity of iron. In the last few years, sustainable methods for iron‐catalyzed cross‐couplings have entered the critical area of pharmaceutical research. Most notably, iron is one of the very few metals that have been successfully field‐tested as highly effective base‐metal catalysts in practical, kilogram‐scale industrial cross‐couplings. In this Minireview, we critically discuss the strategic benefits of using iron catalysts as green and sustainable alternatives to precious metals in cross‐coupling applications for the synthesis of pharmaceuticals. The Minireview provides an essential introduction to the fundamental aspects of practical iron catalysis, highlights areas for improvement, and identifies new fields to be explored.     

垂直取向介孔薄膜的制备

垂直取向介孔薄膜是指薄膜内部孔道垂直于基底定向排列的一类介孔薄膜,其在催化、吸附与分离、化学传感器、太阳能电池等领域具有广阔的应用前景。本文就近几年内垂直取向介孔薄膜的制备方法以及在若干领域的应用进行了回顾和综述。在此基础上,对这种特殊的薄膜材料未来的发展进行了展望。     

介孔沸石材料

介孔沸石材料是含有丰富介孔的结晶沸石,不仅保留了沸石材料优良的酸性和水热稳定性,而且由于介孔的引入改善了其对大分子的吸附和扩散性能,在催化领域特别是涉及大分子的催化反应中是极有应用前景的材料。本文综述了介孔沸石材料的制备方法并进行了比较分析,概述了近年来介孔沸石材料在不同催化反应中的应用,探讨了介孔沸石材料今后的研究方向。     

Materials with Nanoscale Porosity: Energy and Environmental Applications

In this personal account, several key inventions on designing novel microporous and mesoporous materials, and their applications in energy and environmental research are reviewed. Although, crystalline materials with sub‐nanometer pore size regime like zeolites, AlPOs, MOFs, ZIFs etc. are known over the years, silicious and non‐silicious mesoporous materials have revolutionized the research on the materials with nanoscale porosity in last two and half decades. A wide range of inorganic, organic‐inorganic hybrid as well as purely organic mesoporous materials with either periodic or disordered mesopores are known. Apart from conventional hydrothermal syntheses involving soft templating route, hard templating, evaporation induced self‐assembly (EISA), electrochemical or solvothermal (using hydrophilic solvents) synthetic routes are often employed in designing a large spectrum of mesoporous materials. Ease of synthesis using available cheap raw chemicals and versatility in the framework compositions together with the unique surface properties like exceptionally high surface area, pore volume and tunability in pore dimensions have made these materials very exciting to a wide range of researchers working on materials chemistry. Nanoscale porosity in the semiconductor nanomaterials is highly beneficial for the photocatalytic, optoelectronic and related light‐harvesting applications. Their high chemical stability has been explored intensively in designing novel heterogeneous catalysts for the synthesis of biofuels from biomass or CO₂ fixation to reactive organic molecules for the synthesis of fine chemicals and fuels, which has a large impact on energy and environmental research for the years to come. Diversity in mesoporous frameworks and their potential applications related to light harvesting, generation of renewable energy and synthesis of value added fine chemicals and fuels through environment friendly routes are mostly focused in this review.     

由沸石纳米粒子自组装制备具有高催化活性中心和水热稳定的新型介孔分子筛材料

 人们合成了一系列介孔分子筛材料，并发现它们在催化、吸附与分离以及化学组装制备先进材料和分子器件等方面具有很大的潜在应用价值．但是，介孔分子筛材料相对于微孔沸石分子筛存在着两个致命弱点：较低的水热稳定性和较不活泼的催化活性中心．这两个弱点大大地影响了介孔分子筛在催化反应中的广泛应用．本文系统地综述了最近几年利用沸石纳米粒子自组装制备具有高催化活性中心和水热稳定的介孔分子筛材料的研究进展．这包括利用硅铝沸石纳米粒子自组装制备具有强酸性和水热稳定的新型介孔硅铝分子筛材料，利用钛硅沸石纳米粒子自组装制备具有高催化氧化活性中心和水热稳定的新型钛硅介孔分子筛材料，以及利用含有不同杂原子的沸石纳米粒子自组装制备一系列水热稳定的新型介孔分子筛催化材料．     

Potential Utilization of Metal–Organic Frameworks in Heterogeneous Catalysis: A Case Study of Hydrogen‐Bond Donating and Single‐Site Catalysis

Crystalline solid materials are platforms for the development of effective catalysts and have shown vast benefits at the frontiers between homogeneous and heterogeneous catalysts. Typically, these crystalline solid catalysts outperformed their homogeneous analogs due to their high stability, selectivity, better catalytic activity, reusability and recyclability in catalysis applications. This point of view, comprising significant features of a new class of porous crystalline materials termed as metal‐organic frameworks (MOFs) engendered the attractive pathway to synthesize functionalized heterogeneous MOF catalysts. The present review includes the recent research progress in developing both hydrogen‐bond donating (HBD) MOF catalysts and MOF‐supported single‐site catalysts (MSSCs). The first part deals with the novel designs of urea‐, thiourea‐ and squaramide‐containing MOF catalysts and study of their crucial role in HBD catalysis. In the second part, we discuss the important classification of MSSCs with existing examples and their use in desired catalytic reactions. In addition, we describe the relative catalytic efficiency of these MSSCs with their homogeneous and similarly reported analogs. The precise knowledge of discussed heterogeneous MOF catalysts in this review may open the door for new research advances in the field of MOF catalysis.     

Mesoporous Silica Layer: Preparation and Opportunity

Periodic mesoporous silicas, which were prepared from silica‐surfactant mesostructured materials, have been investigated for a wide range of application due to their very large surface area, high porosity, pore size uniformity and variation, periodic pore arrangement and possible pore surface modification, after the pioneering papers on the formation of mesoporous silicas (MCM‐41 and FSM‐16). Morphosyntheses from such macroscopic morphologies as bulk monolith and film to nanoscopic ones, nanoparticles and their stable suspension, make mesoporous materials more attractive for applications and detailed characterization. Mesoporous silicas have been studied initially for such applications as adsorbent and catalyst, and more recently, optical, electronic, and bio‐related applications have been investigated. This review summarizes the studies on mesoporous silica film to highlight the present status and future of the preparation, characterization and application of the mesoporous silica film.