Functional Macro‐Microporous Metal–Organic Frameworks for Improving the Catalytic Performance

Hu, Yu Lin; Xu, Xiujie; Zheng, Bing; Hou, Shanshan; Wang, Peng; Chen, Wanzheng; Gao, Cong; Gu, Zhida; Shen, Yu; Wu, Jiansheng; Fu, Yu; Zhang, Weina; Huo, Fengwei

doi:10.1002/smtd.201800547

Cited by 38 publications

(23 citation statements)

References 44 publications

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“…Furthermore, the pure MOFs structure‐activity relationship, namely, how MOFs structures affect electricity generation behavior is still a puzzle, warranting more attention and exploration. Since the physicochemical properties and functional features of MOFs are not only dependent on the coordination structure, [ 11–14 ] but also closely related to nano/micro structure including morphology [ 15–18 ] and assembly pattern, [ 19–22 ] establishing rational design principles for suitable MOFs is propitious to reveal clear structure‐activity relationship and lay the theoretical foundation for the water evaporation‐induced electricity generation.…”

Section: Introductionmentioning

confidence: 99%

Hierarchical Oriented Metal–Organic Frameworks Assemblies for Water‐Evaporation Induced Electricity Generation

Wang

et al. 2021

Adv Funct Materials

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Advances in metal–organic frameworks (MOFs) are stimulating interest in water‐evaporation induced electricity generation. Establishing design principles for desirable MOFs and revealing the structure‐activity relationship is essential to development of this field. Around this key issue, herein the concept of “hierarchical oriented MOFs” is proposed and the Cu(BDC‐OH) MOFs are organized into hierarchical oriented assemblies by successively using methods of hydrolysis, anion exchange reaction, and heteroepitaxy growth. It is discovered that this hierarchical oriented Cu(BDC‐OH) assemblies‐based generator containing long‐ranged ordered microporous channels exhibits a voltage of 0.6 V and electricity output of 1.56 nW cm–2 in the natural state of water evaporation. Finite element analysis and density functional calculation elucidate that hierarchical oriented structure of Cu(BDC‐OH) MOFs with certain surface charge density have an “aggregation effect,” dominating the final output voltages. This work not only offers valuable theoretical guidance for exploring self‐assembly of MOFs superstructures and water‐evaporation induced electricity generation, but also may open interesting perspectives for understanding some fundamental questions about structure‐activity relationship in MOFs materials science.

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Section: Introductionmentioning

confidence: 99%

Hierarchical Oriented Metal–Organic Frameworks Assemblies for Water‐Evaporation Induced Electricity Generation

Wang

et al. 2021

Adv Funct Materials

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“…Based on a similar strategy, through selectively etching the polystyrene NPs deposited in ZIF-8, the resulting macro-microporous Pt/ZIF-8 showed high catalytic activity in the Knoevenagel condensation-hydrogenation cascade reaction due to the hierarchical pores and exposed basic sites. [134] Furthermore, the hierarchically porous MNP@MOF catalysts can be obtained directly by using defects around MNPs. [135] Most recently, chemical environmental control of MOFs and MOF composites were found to be appealing in regulating catalytic performance.…”

Section: Post-treatmentmentioning

confidence: 99%

Programmable Logic in Metal–Organic Frameworks for Catalysis

et al. 2021

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the rational design of the basic building units, it is possible to incorporate MOF catalysts with high-density active sites and adjustable chemical/physical microenvironments, expanding MOFs' application prospects from the heterogeneous catalysis to more types of catalytic reactions, such as photocatalysis and electrocatalysis. [4] Over the past 20 years, over 88 000 structures have been recorded in Cambridge Structural Database (CSD), and the structural tunability allows us to tailormake MOF materials with different properties. [5] In the early stage, researchers mainly focused on pristine MOFs where active sites came from either the coordination unsaturated metal centers or organic ligands. [6] Additionally, considerable efforts have been made to regulate the porosity and pore shapes/sizes through optimizing the components and structures, which is conducive to not only the diffusion of molecules, but also the realization of size-selective catalysis. [7] Furthermore, some researchers added modifiers into the precursors which can control the sizes/morphologies and defects of MOF catalysts. Deliberately introducing defects into ordered frameworks is useful to expand the active sites species of MOF catalysts. [8] However, due to the limitation of the catalytic reaction types, the development of MOF catalysts has reached a bottleneck to some extent. Under this context, MOF composites emerged. The porous property of MOFs can be served as support to encapsulate different functional materials, such as metal nanoparticles (MNPs), organic molecules, biomolecules, and polymers into pores or cavities, which is an effective way to enrich active sites species and reaction types as well as to realize efficient catalysis. [4a,9] Further, the desire for energy related catalysis promoted the development of MOFbased catalysts. Specifically, the post-treatment methods for MOFs has rapidly advanced, which can modify the compositions, structures, and morphologies of as-synthesized MOFs. [10] This is best exemplified by the thermal treatment of MOFs to porous carbons, metal compounds, and single-atom catalysts (SACs), which show highly dispersed active centers, excellent stability, and adjustable components. [11] From a scientific point of view, MOF materials are interesting catalysts as their structural/component tunability allows us to tailor-make materials with various methods. However, it is quite complicated to construct specific MOF catalysts based on the numerous structures Metal-organic frameworks (MOFs) have emerged as one of the most widely investigated materials in catalysis mainly due to their excellent component tunability, high surface area, adjustable pore size, and uniform active sites. However, the overwhelming number of MOF materials and complex structures has brought difficulties for researchers to select and construct suitable MOF-based catalysts. Herein, a programmable design strategy is presented based on metal ions/clusters, organic ligands, modifiers, functional materials, and post-treatment modules, which c...

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“…To finalize this section and introduce the next one, we briefly comment on how to construct hierarchical pore architectures in MOFs with the help of functional nanoparticles. By dissolving MOF encapsulated polystyrene spheres (PSS) in methanol, a controlled macropore/micropore ratio in ZIF-8 can be achieved . After etching of the PSS, Pt nanoparticles can be introduced into the micro/mesoporous structure of cheeselike crystalline ZIF-8.…”

Section: Synthesis Of Hierarchical Mofs Assisted By Hard Templatingmentioning

confidence: 99%

Design of Hierarchical Architectures in Metal–Oganic Frameworks for Catalysis and Adsorption

2020

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A key factor to improve the performance of metal−organic frameworks (MOFs) is the design and synthesis of hierarchical interconnected porosity at different length scales. The presence of secondary mesopore systems, in addition to the intrinsic framework micropores, avoids inherent mass-transfer constraints that occur in multiple examples of liquid phase chemical processes. Different strategies to introduce ordered void spaces in the MOF materials are reviewed here, based on either bottom-up or top-down approaches. A thorough discussion of the different bottom-up synthesis protocols, based on the interactions of the molecular building blocks with soft or hard templates, is followed by presenting synthesis concepts relating to multidimensional MOF transformations, interfacial and modulated synthesis. The holy grail of defect engineering MOF crystals with controlled porosity is tackled through several topdown approaches in the nanoscale regime. The resultant hierarchical MOFs with interconnected porosity represent the next generation of advanced catalysts and adsorbents, as is presented here by using a vast number of examples where the hierarchical porous structure is key to the MOF performance. A combination of tailor-made pore shape, size, and functionality leads to a synergistic effect between the MOF structures and functions, which offers an improvement on catalysis and adsorption while preserving their porosity, reactivity, and stability. The hierarchical MOFs presented in the different sections of this Review are compared with the purely microporous parent MOFs, used as benchmark in challenging applications where the performance is boosted in the case of hierarchical MOFs.

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Functional Macro‐Microporous Metal–Organic Frameworks for Improving the Catalytic Performance

Cited by 38 publications

References 44 publications

Hierarchical Oriented Metal–Organic Frameworks Assemblies for Water‐Evaporation Induced Electricity Generation

Hierarchical Oriented Metal–Organic Frameworks Assemblies for Water‐Evaporation Induced Electricity Generation

Programmable Logic in Metal–Organic Frameworks for Catalysis

Design of Hierarchical Architectures in Metal–Oganic Frameworks for Catalysis and Adsorption

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