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1.
Impact of Higher‐Order Structuralization on the Adsorptive Properties of Metal–Organic Frameworks
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The structural processing of metal–organic frameworks (MOFs) over multiple length scales is critical for their successful use as adsorbents in a variety of emerging applications. Although significant advances in molecular‐scale design have provided strategies to boost the adsorptive capacities of MOFs, relatively little attention has been directed toward understanding the influence of higher‐order structuralization on the material performance. Herein, we present the main strategies that are currently available for the structural processing of MOFs and discuss the influence these processes can impart on the adsorptive properties of the materials. In all, this intriguing area of research is expected to provide significant opportunities to enhance the properties of MOFs further, which will ultimately aid in their optimization in the context of specific real‐world applications. 相似文献
2.
Metal–Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production
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Prof. Dr. Amarajothi Dhakshinamoorthy Prof. Dr. Abdullah M. Asiri Prof. Dr. Hermenegildo García 《Angewandte Chemie (International ed. in English)》2016,55(18):5414-5445
Metal–organic frameworks (MOFs) are crystalline porous materials formed from bi‐ or multipodal organic linkers and transition‐metal nodes. Some MOFs have high structural stability, combined with large flexibility in design and post‐synthetic modification. MOFs can be photoresponsive through light absorption by the organic linker or the metal oxide nodes. Photoexcitation of the light absorbing units in MOFs often generates a ligand‐to‐metal charge‐separation state that can result in photocatalytic activity. In this Review we discuss the advantages and uniqueness that MOFs offer in photocatalysis. We present the best practices to determine photocatalytic activity in MOFs and for the deposition of co‐catalysts. In particular we give examples showing the photocatalytic activity of MOFs in H2 evolution, CO2 reduction, photooxygenation, and photoreduction. 相似文献
3.
Lei Sun Dr. Michael G. Campbell Prof. Mircea Dincă 《Angewandte Chemie (International ed. in English)》2016,55(11):3566-3579
Owing to their outstanding structural, chemical, and functional diversity, metal–organic frameworks (MOFs) have attracted considerable attention over the last two decades in a variety of energy‐related applications. Notably missing among these, until recently, were applications that required good charge transport coexisting with porosity and high surface area. Although most MOFs are electrical insulators, several materials in this class have recently demonstrated excellent electrical conductivity and high charge mobility. Herein we review the synthetic and electronic design strategies that have been employed thus far for producing frameworks with permanent porosity and long‐range charge transport properties. In addition, key experiments that have been employed to demonstrate electrical transport, as well as selected applications for this subclass of MOFs, will be discussed. 相似文献
4.
Metal–organic polyhedra (MOPs) are discrete, metal–organic molecular entities composed of edge‐sharing molecular polygons or connected molecular vertices. Unlike the infinite metal–organic coordination networks popularized by metal–organic frameworks (MOFs), spherical MOPs, also known as nanocages, nanospheres, nanocapsules, or nanoballs, are obtained through the self‐organization of metal–carboxylate or metal–pyridine/pyrimidine links to afford cage‐like nanoarchitectures. MOPs offer much promise as porous materials owing to their well‐defined structures and solution processability. However, these advantages become moot if their poor aqueous stability and/or guest‐removal‐induced aggregation handicaps remain unaddressed. The concise premise of this contribution limits our discussion to the design principles in action behind recent developments in stable carboxylate MOPs. To highlight the structure–property relationships between the structural and compositional features of these metal carboxylate polyhedra, related scientific challenges and state‐of‐the‐art research directions for further exploration are presented in brief. 相似文献
5.
Yifa Chen Siqing Li Xiaokun Pei Dr. Junwen Zhou Prof. Dr. Xiao Feng Shenghan Zhang Yuanyuan Cheng Haiwei Li Ruodan Han Prof. Dr. Bo Wang 《Angewandte Chemie (International ed. in English)》2016,55(10):3419-3423
Metal–organic frameworks (MOFs), with their well‐defined pores and rich structural diversity and functionality, have drawn a great deal of attention from across the scientific community. However, industrial applications are hampered by their intrinsic fragility and poor processability. Stable and resilient MOF devices with tunable flexibility are highly desirable. Herein, we present a solvent‐ and binder‐free approach for producing stable MOF coatings by a unique hot‐pressing (HoP) method, in which temperature and pressure are applied simultaneously to facilitate the rapid growth of MOF nanocrystals onto desired substrates. This strategy was proven to be applicable to carboxylate‐based, imidazolate‐based, and mixed‐metal MOFs. We further successfully obtained superhydrophobic and “Janus” MOF films through layer‐by‐layer pressing. This HoP method can be scaled up in the form of roll‐to‐roll production and may push MOFs into unexplored industrial applications. 相似文献
6.
David Farrusseng Dr. Sonia Aguado Dr. Catherine Pinel Dr. 《Angewandte Chemie (International ed. in English)》2009,48(41):7502-7513
The role of metal–organic frameworks (MOFs) in the field of catalysis is discussed, and special focus is placed on their assets and limits in light of current challenges in catalysis and green chemistry. Their structural and dynamic features are presented in terms of catalytic functions along with how MOFs can be designed to bridge the gap between zeolites and enzymes. The contributions of MOFs to the field of catalysis are comprehensively reviewed and a list of catalytic candidates is given. The subject is presented from a multidisciplinary point of view covering solid‐state chemistry, materials science, and catalysis. 相似文献
7.
Dr. Witold M. Bloch Prof. Neil R. Champness Prof. Christian J. Doonan 《Angewandte Chemie (International ed. in English)》2015,54(44):12860-12867
Open‐framework materials, such as metal–organic frameworks (MOFs) and coordination polymers have been widely investigated for their gas adsorption and separation properties. However, recent studies have demonstrated that their highly crystalline structures can be used to periodically organize guest molecules and non‐structural metal compounds either within their pore voids or by anchoring to their framework architecture. Accordingly, the open framework can act as a matrix for isolating and elucidating the structures of these moieties by X‐ray diffraction. This concept has broad scope for development as an analytical tool where obtaining single crystals of a target molecule presents a significant challenge and it additionally offers potential for obtaining insights into chemically reactive species that can be stabilized within the pore network. However, the technique does have limitations and as yet a general experimental method has not been realized. Herein we focus on recent examples in which framework materials have been utilized as a scaffold for ordering molecules for analysis by diffraction methods and canvass areas for future exploration. 相似文献
8.
Microporous metal–organic frameworks (MOFs) are comparatively new porous materials. Because the pores within such MOFs can be readily tuned through the interplay of both metal‐containing clusters and organic linkers to induce their size‐selective sieving effects, while the pore surfaces can be straightforwardly functionalized to enforce their different interactions with gas molecules, MOF materials are very promising for gas separation. Furthermore, the high porosities of such materials can enable microporous MOFs with optimized gas separation selectivity and capacity to be targeted. This Focus Review highlights recent significant advances in microporous MOFs for gas separation. 相似文献
9.
10.
A Stable Metal–Organic Framework Featuring a Local Buffer Environment for Carbon Dioxide Fixation
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Dr. Hongming He Dr. Qi Sun Dr. Wenyang Gao Dr. Jason A. Perman Dr. Fuxing Sun Prof. Guangshan Zhu Briana Aguila Katherine Forrest Prof. Brian Space Prof. Shengqian Ma 《Angewandte Chemie (International ed. in English)》2018,57(17):4657-4662
A majority of metal–organic frameworks (MOFs) fail to preserve their physical and chemical properties after exposure to acidic, neutral, or alkaline aqueous solutions, therefore limiting their practical applications in many areas. The strategy demonstrated herein is the design and synthesis of an organic ligand that behaves as a buffer to drastically boost the aqueous stability of a porous MOF (JUC‐1000), which maintains its structural integrity at low and high pH values. The local buffer environment resulting from the weak acid–base pairs of the custom‐designed organic ligand also greatly facilitates the performance of JUC‐1000 in the chemical fixation of carbon dioxide under ambient conditions, outperforming a series of benchmark catalysts. 相似文献
11.
Metal‐organic frameworks (MOFs) are highly promising Lewis acid catalysts; they either inherently possess Lewis acid sites (LASs) on it or the LASs can be generated through various post‐synthetic methods, the later can be performed in MOFs in a trivial fashion. MOFs are suitable platform for catalysis because of its highly crystalline and porous nature. Moreover, with recent advancements, thermal and chemical stability is not a problem with many MOFs. In this Minireview, an enormous versatility of MOFs, in terms of their microporosity/mesoporosity, size/shape selectivity, chirality, pore size, etc., has been highlighted. These are advantageous for designing and performing various targeted organic transformations. Although, many organic transformations catalyzed by MOFs with LASs have been reported in the recent past. In this Minireview, we have restricted ourselves to four important organic reactions: (i) cyanosilylation, (ii) Diels–Alder reaction, (iii) C?H activation, and (iv) CO2‐addition. The discussion focuses mostly on the recent reports (42 examples). 相似文献
12.
Saikat Das Dr. Shixian Xu Prof. Teng Ben Prof. Shilun Qiu 《Angewandte Chemie (International ed. in English)》2018,57(28):8629-8633
Endowed with chiral channels and pores, chiral metal–organic frameworks (MOFs) are highly useful; however, their synthesis remains a challenge given that most chiral building blocks are expensive. Although MOFs with induced chirality have been reported to avoid this shortcoming, no study providing evidence for the ee value of such MOFs has yet been reported. We herein describe the first study on the efficiency of chiral induction in MOFs using inexpensive achiral building blocks and fully recoverable chiral dopants to control the handedness of racemic MOFs. This method yielded chirality‐enriched MOFs with accessible pores. The ability of the materials to form host–guest complexes was probed with enantiomers of varying size and coordination and in solvents with varying polarity. Furthermore, mixed‐matrix membranes (MMMs) composed of chirality‐enriched MOF particles dispersed in a polymer matrix demonstrated a new route for chiral separation. 相似文献
13.
Dr. Ya‐Qian Lan Dr. Shun‐Li Li Dr. Hai‐Long Jiang Prof. Dr. Qiang Xu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(26):8076-8083
In this work, we have demonstrated a family of diamondoid metal–organic frameworks (MOFs) based on functionalized molecular building blocks and length‐adjustable organic linkers by using a stepwise synthesis strategy. We have successfully achieved not only “design” and “control” to synthesize MOFs, but also the functionalization of both secondary building units (SBUs) and organic linkers in the same MOF for the first time. Furthermore, the results of N2 and H2 adsorption show that their surface areas and hydrogen uptake capacities are determined by the most optimal combination of functional groups from SBUs and organic linkers, interpenetration, and free volume in this system. A member of this series, DMOF‐6 exhibits the highest surface area and H2 adsorption capacity among this family of MOFs. 相似文献
14.
Allendorf MD Schwartzberg A Stavila V Talin AA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(41):11372-11388
Metal-organic frameworks (MOFs) and related material classes are attracting considerable attention for applications such as gas storage, separations, and catalysis. In contrast, research focused on potential uses in electronic devices is in its infancy. Several sensing concepts in which the tailorable chemistry of MOFs is used to enhance sensitivity or provide chemical specificity have been demonstrated, but in only a few cases are MOFs an integral part of an actual device. The synthesis of a few electrically conducting MOFs and their known structural flexibility suggest that MOF-based electronic devices exploiting these properties could be constructed. It is clear, however, that new fabrication methods are required to take advantage of the unique properties of MOFs and extend their use to the realms of electronic circuitry. In this Concepts article, we describe the basic functional elements needed to fabricate electronic devices and summarize the current state of relevant MOF research, and then review recent work in which MOFs serve as active components in electronic devices. Finally, we propose a high-level roadmap for device-related MOF research, the objective of which is to stimulate thinking within the MOF community concerning the development these materials for applications including sensing, photonics, and microelectronics. 相似文献
15.
Martin Rieß Prof. Dr. Jürgen Senker Prof. Dr. Rainer Schobert Prof. Dr. Josef Breu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(9):2103-2111
The design of microporous hybrid materials, tailored for diverse applications, is a key to address our modern society's imperative of sustainable technologies. Prerequisites are flexible customization of host–guest interactions by incorporating various types of functionality and by adjusting the pore structure. On that score, metal–organic frameworks (MOFs) have been the reference in the past decades. More recently, a new class of microporous hybrid materials emerged, microporous organically pillared layered silicates (MOPS). MOPS are synthesized by simple ion exchange of organic or metal complex cations in synthetic layered silicates. MOFs and MOPSs share the features of “component modularity” and “functional porosity”. While both, MOFs and MOPS maintain the intrinsic characteristics of their building blocks, new distinctive properties arise from their assemblage. MOPS are unique since allowing for simultaneous and continuous tuning of micropores in the sub-Ångström range. Consequently, with MOPS the adsorbent recognition may be optimized without the need to explore different framework topologies. Similar to the third generation of MOFs (also termed soft porous crystals), MOPS are structurally ordered, permanently microporous solids that may also show a reversible structural flexibility above a distinct threshold pressure of certain adsorbents. This structural dynamism of MOPS can be utilized by meticulously adjusting the charge density of the silicate layers to the polarizability of the adsorbent leading to different gate opening mechanisms. The potential of MOPS is far from being fully explored. This Concept article highlights the main features of MOPS and illustrates promising directions for further research. 相似文献
16.
Materials that can recognize the changes in their local environment and respond by altering their inherent physical and/or chemical properties are strong candidates for future “smart” technology materials. Metal–organic frameworks (MOFs) have attracted a great deal of attention in recent years owing to their designable architecture, host–guest chemistry, and softness as porous materials. Despite this fact, studies on the tuning of the properties of MOFs by external stimuli are still rare. This review highlights the recent developments in the field of stimulus‐responsive MOFs or so‐called smart MOFs. In particular, the various stimuli used and the utility of stimulus‐responsive smart MOFs for various applications such as gas storage and separation, sensing, clean energy, catalysis, molecular motors, and biomedical applications are highlighted by using representative examples. Future directions in the developments of stimulus‐responsive smart MOFs and their applications are proposed from a personal perspective. 相似文献
17.
Dr. Meicheng Wen Dr. Kohsuke Mori Dr. Yasutaka Kuwahara Prof. Taicheng An Prof. Hiromi Yamashita 《化学:亚洲杂志》2018,13(14):1767-1779
Single‐site photocatalysts generally display excellent photocatalytic activity and considerably high stability compared with homogeneous catalytic systems. A rational structural design of single‐site photocatalysts with isolated, uniform, and spatially separated active sites in a given solid is of prime importance to achieve high photocatalytic activity. Intense attention has been focused on the design and fabrication of single‐site photocatalysts by using porous materials as a platform. Metal–organic frameworks (MOFs) have great potential in the design and fabrication of single‐site photocatalysts due to their remarkable porosity, ultrahigh surface area, extraordinary tailorability, and significant diversity. MOFs can provide an abundant number of binding sites to anchor active sites, which results in a significant enhancement in photocatalytic performance. In this focus review, the development of single‐site MOF photocatalysts that perform important and challenging chemical redox reactions, such as photocatalytic H2 production, photocatalytic CO2 conversion, and organic transformations, is summarized thoroughly. Successful strategies for the construction of single‐site MOF photocatalysts are summarized and major challenges in their practical applications are noted. 相似文献
18.
Exploring the Performance Improvement of the Oxygen Evolution Reaction in a Stable Bimetal–Organic Framework System
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Xiao‐Li Wang Long‐Zhang Dong Man Qiao Yu‐Jia Tang Dr. Jiang Liu Prof. Yafei Li Prof. Shun‐Li Li Jia‐Xin Su Prof. Ya‐Qian Lan 《Angewandte Chemie (International ed. in English)》2018,57(31):9660-9664
Despite wide applications of bimetallic electrocatalysis in oxygen evolution reaction (OER) owing to their superior performance, the origin of the improved performance remains elusive. The underlying mechanism was explored by designing and synthesizing a series of stable metal–organic frameworks (MOFs: NNU‐21–24 ) based on trinuclear metal carboxylate clusters and tridentate carboxylate ligands. Among the examined stable MOFs, NNU‐23 exhibits the best OER performance; particularly, compared with monometallic MOFs, all the bimetallic MOFs display improved OER activity. DFT calculations and experimental results demonstrate that introduction of the second metal atom can improve the activity of the original atom. The proposed model of bimetallic electrocatalysts affecting their OER performance can facilitate design of efficient bimetallic catalysts for energy storage and conversion, and investigation of the related catalytic mechanisms. 相似文献
19.
金属有机框架材料是由金属离子节点和有机配体通过配位键连接形成的具有序多孔骨架的材料, 因其具有比表面积大、 孔隙可调及表面性质可控等优点而备受关注. 通过对有机配体和金属离子进行选择及对金属有机框架材料进行后修饰处理, 可实现对金属有机框架材料表面性质的调控, 以提升其选择性吸附及特异性识别等性能, 进而拓展其在分离分析等领域的应用. 本文从金属有机框架材料的表面性质调控出发, 介绍了其表面性质与分离分析性能的关系, 总结了近年来该领域的代表性工作, 并展望了金属有机框架材料在分离分析领域的应用前景. 相似文献
20.
Dr. Manuel Souto Dr. Karol Strutyński Dr. Manuel Melle-Franco Prof. João Rocha 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(48):10912-10935
Electroactive organic molecules have received a lot of attention in the field of electronics because of their fascinating electronic properties, easy functionalization and potential low cost towards their implementation in electronic devices. In recent years, electroactive organic molecules have also emerged as promising building blocks for the design and construction of crystalline porous frameworks such as metal–organic frameworks (MOFs) and covalent-organic frameworks (COFs) for applications in electronics. Such porous materials present certain additional advantages such as, for example, an immense structural and functional versatility, combination of porosity with multiple electronic properties and the possibility of tuning their physical properties by post-synthetic modifications. In this Review, we summarize the main electroactive organic building blocks used in the past few years for the design and construction of functional porous materials (MOFs and COFs) for electronics with special emphasis on their electronic structure and function relationships. The different building blocks have been classified based on the electronic nature and main function of the resulting porous frameworks. The design and synthesis of novel electroactive organic molecules is encouraged towards the construction of functional porous frameworks exhibiting new functions and applications in electronics. 相似文献