高效氧催化反应中的金属有机骨架材料（英文）

氧电催化反应包括氧气还原反应(ORR)和氧气析出反应(OER).作为核心电极反应,这两个反应对诸多能源存储与转换技术(比如燃料电池、金属空气电池以及全水分解制氢等)的能量效率起决定性作用.然而,ORR和OER涉及多个反应步骤、多个电子转移过程以及多相界面传质过程.这些复杂的过程较大程度上限制了ORR和OER的反应速率.从理论和实践两个方面来看,ORR和OER都需要高效电催化剂的参与来促进其反应速率,从而能够最终提高上述能源存储与转换技术的能量转换或利用效率.目前,以Pt,Pd,Ir,Ru为代表的贵金属基电催化剂具有十分突出的电催化性能.但是,过高的成本和过低的储量始终制约着贵金属基电催化剂在催化ORR和OER反应方面,乃至在能源存储与转换技术领域的规模化应用.因而,开发高效非贵金属基氧电催化剂成为近年来能源存储与转换领域的研究重点之一.在众多已经报道的非贵金属基氧电催化剂中,金属有机骨架材料(MOFs)备受瞩目.MOFs是一类由有机配体和金属节点通过配位键自组装而成的晶态多孔材料.它们具备超高比表面积、超高孔隙率以及规则性纳米孔道.相比较其他传统的多孔材料(比如活性炭、分子筛、介孔炭、介孔氧化硅等),MOFs最主要的优势在于它们的结构和功能可以依据需求通过选择合适的有机配体和金属节点进行便利地设计,或通过后处理进行必要的改性和调节.基于独特的多孔特性以及结构与功能的可设计、可调节性,MOFs在气体分离与存储、异相催化、化学传感、药物输送、环境保护以及能源存储与转化等领域都具有潜在的应用价值.因而,近年来,MOFs备受基础研究领域和工业界的青睐.针对MOFs开展的基础研究和应用开发逐渐成为诸多领域的研究焦点.也正由于MOFs具有的上述优异特性,尤其是结构与功能的可设计、可调节性,使得设计制备基于单纯MOFs以及MOFs衍生材料成为开发高效非贵金属基氧电催化剂的新途径.本综述首先论述了基于单纯MOFs的氧电催化剂(包括纯MOFs、活性物种修饰的MOFs以及与导电材料构成的复合MOFs)的合成以及它们在ORR或OER催化反应中应用的研究进展.在第二部分论述中,本综述主要针对MOFs衍生的各类氧电催化剂(包括无机微米-纳米结构/多孔碳复合材料、纯多孔碳材料、纯无机微米-纳米结构材料以及单原子型电催化材料)的研究进展进行了简要介绍和讨论.最后,本综述对MOFs基氧电催化剂目前存在的挑战进行了简要分析;同时,也对这类氧电催化剂的通用设计准则以及未来发展方向进行了展望.尽管存在诸多挑战,MOFs始终被认为是极好的"平台"材料.充分利用它们将有利于开发高效且实用的非贵金属基氧电催化剂.     

Development of Sulfonic-Acid-Functionalized Mesoporous Materials: Synthesis and Catalytic Applications

Sulfonic acid based mesostructures (SAMs) have been developed in recent years and have important catalytic applications. The primary applications of these materials are in various organic synthesis reactions, such as multicomponent reactions, carbon–carbon bond couplings, protection reactions, and Fries and Beckman rearrangements. This review aims to provide an overview of the recent developments in the field of SAMs with a particular emphasis on the reaction scope and advantages of heterogeneous solid acid catalysts.     

Functionalized Carbon Nanomaterials Derived from Carbohydrates

A tremendous growth in the field of carbon nanomaterials has led to the emergence of carbon nanotubes, fullerenes, mesoporous carbon and more recently graphene. Some of these materials have found applications in electronics, sensors, catalysis, drug delivery, composites, and so forth. The high temperatures and hydrocarbon precursors involved in their synthesis usually yield highly inert graphitic surfaces. As some of the applications require functionalization of their inert graphitic surface with groups like ? COOH, ? OH, and ? NH₂, treatment of these materials in oxidizing agents and concentrated acids become inevitable. More recent works have involved using precursors like carbohydrates to produce carbon nanostructures rich in functional groups in a single‐step under hydrothermal conditions. These carbon nanostructures have already found many applications in composites, drug delivery, materials synthesis, and Li ion batteries. The review aims to highlight some of the recent developments in the application of carbohydrate derived carbon nanostructures and also provide an outlook of their future prospects.     

Organic chemistry in water

Water has emerged as a versatile solvent for organic chemistry in recent years. Water as a solvent is not only inexpensive and environmentally benign, but also gives completely new reactivity. The types of organic reactions in water are broad including pericyclic reactions, reactions of carbanion equivalent, reactions of carbocation equivalent, reactions of radicals and carbenes, transition-metal catalysis, oxidations-reductions, which we discuss in this tutorial review. Aqueous organic reactions have broad applications such as synthesis of biological compounds from carbohydrates and chemical modification of biomolecules.     

2020 roadmap on pore materials for energy and environmental applications

Porous materials have attracted great attention in energy and environment applications. In this roadmap, several porous materials are discussed for energy storage and conversion. It will help the researchers to obtain them guidance from it in future.     

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.     

Metal Nanoparticles Supported on Biomass‐Derived Hierarchical Porous Heteroatom‐Doped Carbon from Bamboo Shoots: Design,Synthesis and Applications

Heteroatom‐doped porous carbon derived from biomass have recently received increasing attention due to their unique properties such as high electrical conductivity, large specific surface area, high porosity, and easy availability, which are appealing materials for versatile applications in catalysis, energy, separation and adsorption, and life sciences as well. On the basis of our previous work in this field, we summarized in this account our recent progress on design, synthesis of metal (e. g., Pd, Co) nanoparticles supported heteroatom‐doped hierarchical porous carbon material derived from bamboo shoots and their applications for important organic transformations, including chemoselective semihydrogenation of alkynes, hydrosilylation of alkynes, cascade synthesis of benzofurans from terminal alkynes and iodophenols, selective hydrogenation of functionalized nitroarenes to form anilines, imines, and formamides. Finally, the current state and future challenges in this field are discussed. We hope this account could shed light on the rational design of novel non‐noble metal based heterogeneous catalysts derived from biomass for efficient and sustainable organic transformations.     

2020 roadmap on pore materials for energy and environmental applications

Porous materials have attracted great attention in energy and environment applications, such as metal organic frameworks (MOFs), metal aerogels, carbon aerogels, porous metal oxides. These materials could be also hybridized with other materials into functional composites with superior properties. The high specific area of porous materials offer them the advantage as hosts to conduct catalytic and electrochemical reactions. On one hand, catalytic reactions include photocatalytic, photoelectrocatalytic and electrocatalytic reactions over some gases. On the other hand, they can be used as electrodes in various batteries, such as alkaline metal ion batteries and electrochemical capacitors. So far, both catalysis and batteries are extremely attractive topics. There are also many obstacles to overcome in the exploration of these porous materials. The research related to porous materials for energy and environment applications is at extremely active stage, and this has motivated us to contribute with a roadmap on ‘porous materials for energy and environment applications’.     

Hierarchically Porous Organic Materials Derived From Copolymers: Preparation and Electrochemical Applications

Abstract

Compared to conventional porous materials with a uniform pore size distribution, hierarchical ones containing interconnected macro-, meso-, and micropores have greatly enhanced material performance due to the increased specific surface area and mass transfer. Copolymer is a good candidate used for construction of such hierarchically porous structures, resulting from its tunable segment composition, unique phase separation, and self-assembly, etc. Hierarchically porous materials derived from copolymers can be served as a versatile support for many reactive molecules. Furthermore, hierarchically porous carbon materials (HPCMs) can also be prepared by carbonization of copolymers, one segment of which is converted to carbon while the other segment is responsible for the pore formation after its removal by pyrolysis. The obtained hierarchically porous copolymers or carbon materials have promising electrochemical applications especially in energy conversion and storage. In the present review, recent advances in preparation of hierarchically porous materials (HPMs) derived from copolymers are reviewed, and their electrochemical applications in supercapacitors, lithium-ion batteries, fuel cells, electrochemical biosensors, and electrocatalysis are also introduced. The rational design and control for the hierarchically porous microstructures are described deeply from the molecular level. Also, the relationship between the micro-structure and the electrochemical performance is revealed. This review can provide us a better understanding of both theory and experiment for the preparation of hierarchically porous organic materials and their electrochemical applications.     

衍生多孔碳材料在固相微萃取中的应用研究进展

固相微萃取是一种集采样、萃取、富集和进样于一体的样品前处理技术,其萃取效果与涂层材料密切相关。多孔碳材料具有比表面积大、多孔结构可控、活性位点多和化学稳定性好等优点,广泛应用于电池、超级电容器、催化、吸附和分离等领域,也是一种热门的用作固相微萃取探针的涂层材料。衍生多孔碳材料因种类丰富、可设计性强被广泛研究,研究主要集中在对衍生多孔碳材料的结构优化方面。但是衍生多孔碳材料在固相微萃取中的应用还存在如下问题:(1)共价有机框架衍生多孔碳材料的制备已取得较大进展,但将其应用于固相微萃取领域的研究仍较少;(2)有待进一步明确制备出的衍生多孔碳材料用作固相微萃取涂层表现出优异提取能力的机理;(3)有待进一步深入研究将衍生多孔碳材料用作固相微萃取涂层以实现对不同物理化学性质污染物的广谱高灵敏度分析。文章综述了近3年衍生多孔碳材料在固相微萃取中的应用研究,并展望了未来衍生多孔碳材料在固相微萃取中的研究前景。引用文献共56篇,主要来源于Elsevier。     

Recent Advances on Confining Noble Metal Nanoparticles Inside Metal-Organic Frameworks for Hydrogenation Reactions

Hydrogenation reaction is one of the pillars of the chemical industry for the synthesis of drugs and fine chemicals. To achieve high catalytic performance, it is still highly desirable for constructing novel supported metal catalysts. Different from conventional supports like metal oxides, zeolites and carbon materials, metal-organic frameworks(MOFs) as the emerging porous materials have Hexhibited great potential to host metal nanoparticles (NPs) for achieving hydrogenation reactions with high catalytic efficiency, due to their unique porous structures. Recently, many progresses have been made, and thus, it is necessary to summarize the recent progresses on confining metal NPs inside MOFs for hydrogenation reactions. In this review, we first introduced the general synthesis methods for confining noble metal NPs inside MOFs. Then, the applications of noble metal NPs/MOFs catalysts in hydrogenation reactions were summarized, and the synergistic catalytic performances among noble metal NPs, metal nodes, functional groups, and pore channels in MOFs were illustrated. Subsequently, the hydrogen spillover effect involved in the hydrogenation reactions was discussed. Finally, we provide an outlook on the future research directions and challenges of confining noble metal NPs inside MOFs for hydrogenation reactions.     

基于石墨烯基材料的非金属液相催化反应

非金属碳基催化剂因其具有合成简单、结构稳定、比表面积大、可调控性强等特点受到了研究者的关注,已成为最活跃的研究领域之一。以二维、单原子层、六方结构的碳为基础的石墨烯和其高度氧化形态——氧化石墨烯是一类新兴的碳基材料。这类材料在催化领域的应用在近五年内才刚刚兴起。此类材料可用于烃类转化、有机化学合成、能源转化等多种催化反应,本文主要综述了采用化学氧化还原法制备的石墨烯和氧化石墨材料为催化剂的各类催化反应的最新研究进展。     

Two-dimensional porphyrin- and phthalocyanine-based covalent organic frameworks

Covalent organic frameworks (COFs) represent an emerging class of porous crystalline materials and have recently shown interesting applications from catalysis to optoelectronic devices. In this review, by covering most of the reported work, we summarized the research progress of two-dimensional (2D) porphyrin- and phthalocyanine-based COFs, with highlighting the synthesis of these 2D COFs via various dynamic covalent reactions and emphasizing their potential applications in different areas.     

有序多孔过渡金属氧化物及其负载贵金属催化剂对挥发性有机物氧化的催化性能

大部分的挥发性有机物(VOCs)污染环境,危害人身健康.目前,我国虽然已开展了治理 VOCs污染的工作,但还缺乏有效的、拥有自主知识产权的 VOCs治理技术,因此研发新型高效 VOCs处理技术迫在眉睫.催化氧化法是公认的最有效消除 VOCs的途径之一,而高性能催化剂的研发是实现该过程的关键.近年来,人们围绕消除 VOCs的高效且价廉的催化剂的研发开展了卓有成效的工作,许多过渡金属氧化物、混合或复合金属氧化物及其负载贵金属催化剂均被认为是有效的催化氧化材料.与体相材料相比,多孔材料具有发达的孔道结构和高的比表面积,一方面有利于反应物的扩散、吸附和脱附,因而具有更高的催化活性和选择性;另一方面有利于活性组分(如贵金属等)在多孔材料表面的高分散,抑制活性组分的烧结,因而具有更好的催化稳定性.本文简述了近年来多孔金属氧化物在环境污染物消除领域的研究进展,阐述了以有序介孔或大孔过渡金属氧化物、钙钛矿型氧化物和负载贵金属催化剂的制备及其对典型 VOCs(如苯系物、醇类、醛类及酮类等)氧化的催化性能,重点介绍了四类催化材料,包括有序介孔过渡金属氧化物或复合氧化物(Co3O4, MnO2, Fe2O3, Cr2O3和 LaFeO3等)催化剂,有序介孔金属氧化物负载贵金属(Au/Co3O4, Au/MnO2和 Pd/Co3O4等)催化剂,三维有序大孔过渡金属氧化物或复合氧化物(Fe2O3, LaMnO3, La0.6Sr0.4MnO3和 La2CuO4等)催化剂,以及三维有序大孔金属氧化物负载贵金属(Au/Co3O4, Au/LaCoO3, Au/La0.6Sr0.4MnO3和 AuPd/Co3O4等)催化剂的制备及其物化性质与对苯、甲苯、二甲苯、乙醇、丙酮、甲醛、甲烷或氯甲烷等 VOCs氧化的催化性能之间的相关性.借助二氧化硅或聚甲基丙烯酸甲酯微球等硬模板,采用纳米浇铸法可制备出二维或三维的有序单一或多级孔道结构的金属氧化物.研究表明,多孔金属氧化物的催化性能远优于其体相甚至纳米催化剂的.有序多孔材料的优异催化性能与其拥有大的比表面积、高的吸附氧物种浓度、优良的低温还原性、独特的孔道结构、活性组分的高分散以及贵金属与氧化物载体之间的强相互作用等有关.探明影响催化剂活性的因素有利于从原子水平上认识催化过程,为新型高效催化剂的设计与制备奠定基础.本文还指出了此类研究中存在的一些问题,例如利用硬模板法制备多孔材料的缺点是目标催化剂的收率低,硬模板浪费严重,大规模制备多孔催化剂势必增加制备成本,这些问题有待于妥善解决.与此同时,还展望了 VOCs消除技术的未来发展趋势,采用多种技术联用的方法有望最大程度地提高 VOCs的消除效率.     

Selective chemical reactions in supercritical carbon dioxide,water, and ionic liquids

Abstract

Alternative solvents such as supercritical carbon dioxide, water, and ionic liquids are receiving an increase of interest as better replacements for conventional solvents in chemical reactions. They have been called sustainable green solvents because they are highly promising reaction mediums for organic synthesis. This review presents an overview of some selected chemical reactions that have been developed in these green solvents with a particular emphasis on metal-catalyzed reactions.     

Carbon-Based Material-Supported Palladium Nanocatalysts in Coupling Reactions: Discussion on their Stability and Heterogeneity

Scientific interest in carbon-based materials (CBMs) has grown dramatically over the past few decades. Due to a variety of atomic orbital hybrid forms (sp, sp² and sp³ hybridization), carbon can form a variety of materials with diverse structures and characteristics. CBMs used as efficient catalyst supports show extensive promise in organic reactions, which is attributed to their structural similarity with organics, large specific surface area, chemical stability, and photocatalytic properties. This review presents the synthesis of CBM-supported palladium nanocatalysts based on impregnation, template methods, etc. The CBMs include activated carbon (AC), graphene, carbon nanotubes (CNTs), and their functionalized products, as supports for improving the activity and recyclability of simple Pd nanocatalysts. After surveying the literature where these catalysts have been utilized for carbon–carbon coupling reactions, there is a particular emphasis on Suzuki, Heck, and Sonogashira reactions. The catalytic mechanism of these Pd nanocatalysts (surface heterogeneous catalysis or homogeneous catalysis caused by Pd leaching) is discussed in detail, especially the effect of Pd leaching on the stability of the catalyst.     

过渡金属催化氟代烯烃参与的交叉偶联反应进展

过渡金属催化（类）卤化物和不同金属试剂的交叉偶联反应是构建不同类型碳碳键和碳杂原子键的重要方法之一。该类反应一般使用活性较高的氯、溴、碘或类卤化物作为亲电试剂,尽管C—F键的键能较强,利用过渡金属直接活化较为惰性的芳基C—F键并参与实现的交叉偶联反应已有较多报道。此外,近期的研究表明,也可以通过直接活化烯基C—F键并催化实现该类底物参与不同类型的交叉偶联反应,从而进一步拓展了交叉偶联反应的底物适用范围,并应用于具有高附加值精细化学品的选择性合成。本文围绕钯或镍催化活化单氟或者多氟烯烃等底物参与的Negishi、Suzuki-Miyaura、Kumada、Hiyama和Sonogashira等5类交叉偶联反应,通过探讨已有方法的反应机理及其适用范围,综述了该领域的研究进展并进行了展望。     

A review on the green synthesis of hierarchically porous zeolite

Conventional bottom-up and top-down methods for synthesizing hierarchical zeolite have led to complicated economic and environmental issues due to the requirement of expensive and hazardous organic molecules, the large amount of acid/base solution, high energy, and expensive starting materials. Besides, the bottom-up method through the hydrothermal crystallization evokes safety issues due to the high autogenous pressure. Accordingly, considerable efforts have been made to develop green route synthesis of hierarchical zeolite by eliminating the use of a solvent (solvent-free), utilizing sustainable starting materials and green secondary template (mesoporogen), as well as eliminating the use of mesoporogen (mesoporogen-free). Other routes, including recycling of mother liquor, steam-assisted conversion, gel-like-solid phase method, and silanization, are also elaborated, as they are reported to promote a green and facile approach for the synthesis of hierarchical zeolites. In this review, we provide recent progress on the development of the green synthesis of hierarchically porous zeolite.     

Continuous flow synthesis of porous materials

Porous materials play an important role in chemical catalysis,separation and other industrial applications.High-efficiency preparation of porous materials has become an active research area.Conventional synthesis of porous materials has been dominated by one-pot solution processing conditions carried out by bulk mixing under conventional electric heating via hydrothermal,solvothermal or ionothermal reactions where high temperatures and pressures are the standard.Continuous flow synthesis has many key advantages in terms of efficient mass and heat transfer,precise control of residence times,improved opportunities for automation and feedback control of synthesis,scaling-up reactions and improved safety parameters compared to above mentioned conventional batch scale synthetic methods.In this review,continuous flow synthesis of various crystalline porous materials such as metal-organic frameworks(MOFs),covalent-organic frameworks(COFs),porous organic cages and zeolites is discussed.Combination of microfluidic methods with other techniques are also shown including various heating ways and various methods of substrate adding.     

用活性炭及部分热解碳材料进行的质子催化(英文)

The development of environmentally friendly solid acid catalysts is a priority task. Highly oxidized activated carbon and their ion-substituted (saline) forms are effective proton transfer catalysts in esterification, hydrolysis, and dehydration, and thus are promising candidates as solid acid cata-lysts. Computations by the ab initio method indicated the cause for the enchanced acidity of the carboxylic groups attached to the surface of highly oxidized carbon. The synthesis of phosphorilated carbon was considered, and the proton transfer reactions catalyzed by them in recent studies were analyzed. The development of an amorphous carbon acid catalyst comprising polycyclic carbonaceous (graphene) sheets with –SO3H, –COOH and phenolic type OH-groups was carried out. These new catalysts were synthesized by partial pyrolysis and subsequent sulfonation of carbohydrates, polymers, and other organic compounds. Their high catalytic activities in proton transfere reactions including the processing of bio-based raw materials was demonsrated.