Heterogeneous Catalysis in Zeolites, Mesoporous Silica, and Metal-Organic Frameworks.
TL;DR: This review aims to highlight recent research advancements in zeolites, ordered mesoporous silica, and MOFs for heterogeneous catalysis, and inspire further studies in this rapidly developing field.
Abstract: Crystalline porous materials are important in the development of catalytic systems with high scientific and industrial impact. Zeolites, ordered mesoporous silica, and metal-organic frameworks (MOFs) are three types of porous materials that can be used as heterogeneous catalysts. This review focuses on a comparison of the catalytic activities of zeolites, mesoporous silica, and MOFs. In the first part of the review, the distinctive properties of these porous materials relevant to catalysis are discussed, and the corresponding catalytic reactions are highlighted. In the second part, the catalytic behaviors of zeolites, mesoporous silica, and MOFs in four types of general organic reactions (acid, base, oxidation, and hydrogenation) are compared. The advantages and disadvantages of each porous material for catalytic reactions are summarized. Conclusions and prospects for future development of these porous materials in this field are provided in the last section. This review aims to highlight recent research advancements in zeolites, ordered mesoporous silica, and MOFs for heterogeneous catalysis, and inspire further studies in this rapidly developing field.
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TL;DR: Some emerging applications of both groups of MOF-related materials as electrode materials for rechargeable batteries and electrochemical capacitors, efficient electrocatalysts, and even electrolytes for electrochemical devices are reviewed.
Abstract: In addition to their conventional uses, metal-organic frameworks (MOFs) have recently emerged as an interesting class of functional materials and precursors of inorganic materials for electrochemical energy storage and conversion technologies. This class of MOF-related materials can be broadly categorized into two groups: pristine MOF-based materials and MOF-derived functional materials. Although the diversity in composition and structure leads to diverse and tunable functionalities of MOF-based materials, it appears that much more effort in this emerging field is devoted to synthesizing MOF-derived materials for electrochemical applications. This is in view of two main drawbacks of MOF-based materials: the low conductivity nature and the stability issue. On the contrary, MOF-derived synthesis strategies have substantial advantages in controlling the composition and structure of MOF-derived materials. From this perspective, we review some emerging applications of both groups of MOF-related materials as electrode materials for rechargeable batteries and electrochemical capacitors, efficient electrocatalysts, and even electrolytes for electrochemical devices. By highlighting the advantages and challenges of each class of materials for different applications, we hope to shed some light on the future development of this highly exciting area.
786 citations
Cites background from "Heterogeneous Catalysis in Zeolites..."
...The remarkably high porosity and surface area ofMOFs are especially suitable for applications involving storage and interactionwith guest species (for example, gas storage/separation and catalysis) (4, 6)....
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TL;DR: In this paper, the authors systematically summarize the versatile synthetic strategies to fabricate MOF-derived porous materials and give an overview on their recent progress on organic heterogeneous catalysis, photocatalysis and electrocatalysis.
672 citations
TL;DR: Recent progress of MOFs and MOF composites for energy storage and conversion applications, including photochemical and electrochemical fuel production, water oxidation, supercapacitors, and Li-based batteries, is summarized.
Abstract: Metal-organic frameworks (MOFs), a new class of crystalline porous organic-inorganic hybrid materials, have recently attracted increasing interest in the field of energy storage and conversion. Herein, recent progress of MOFs and MOF composites for energy storage and conversion applications, including photochemical and electrochemical fuel production (hydrogen production and CO2 reduction), water oxidation, supercapacitors, and Li-based batteries (Li-ion, Li-S, and Li-O2 batteries), is summarized. Typical development strategies (e.g., incorporation of active components, design of smart morphologies, and judicious selection of organic linkers and metal nodes) of MOFs and MOF composites for particular energy storage and conversion applications are highlighted. A broad overview of recent progress is provided, which will hopefully promote the future development of MOFs and MOF composites for advanced energy storage and conversion applications.
546 citations
TL;DR: In this paper, the advantages and limitations of MOFs as catalysts are summarized and fundamental issues to be addressed about their potential applications, including shape-selective and bifunctional catalysis, and quantifying reaction/transport processes in MOFs, identifying catalytic sites, and determining intrinsic catalytic reaction rates.
Abstract: Metal organic frameworks (MOFs) have drawn wide attention as potential catalysts, offering high densities of catalytic sites in high-area porous solids, some with stabilities at high temperatures. The field is at an early stage, characterized by numerous discoveries and novel demonstrations of catalytic properties associated with the crystalline structures of MOFs, but applications of MOFs as catalysts are still lacking. In this perspective we summarize advantages and limitations of MOFs as catalysts and fundamental issues to be addressed about their potential applications. MOF framework compositions and pore structures can strongly influence catalytic performance, allowing, for example, shape-selective and bifunctional catalysis, but research is needed to quantify reaction/transport processes in MOFs, identify catalytic sites, and determine intrinsic catalytic reaction rates. Progress is hindered by the lack of understanding of the heterogeneity of MOFs, with catalytic sites sometimes being in structures...
529 citations
01 Jul 2019
TL;DR: In this article, a review of metal-organic frameworks (MOFs) derived nanomaterials for various electrochemical energy storage and conversion applications including Li-ion batteries, Li-S batteries, Na-ion battery, supercapacitors, water splitting, and oxygen reduction reaction is reviewed.
Abstract: As emerging crystalline porous organic-inorganic hybrid materials, metal-organic frameworks (MOFs) have been widely used as sacrificial precursors for the synthesis of carbon materials, metal/metal compounds, and their composites with tunable and controllable nanostructures and chemical compositions for electrochemical energy applications. Herein, recent progress of MOF-derived nanomaterials for various electrochemical energy storage and conversion applications including Li-ion batteries, Li-S batteries, Na-ion batteries, supercapacitors, water splitting, and oxygen reduction reaction is reviewed. Structural and compositional design of MOF-derived nanomaterials is systematically summarized, which may hopefully offer inspirations and guidances for future development of MOF-derived nanomaterials for more efficient and more durable electrochemical energy applications.
424 citations
References
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TL;DR: In this paper, the synthesis of mesoporous inorganic solids from calcination of aluminosilicate gels in the presence of surfactants is described, in which the silicate material forms inorganic walls between ordered surfactant micelles.
Abstract: MICROPOROUS and mesoporous inorganic solids (with pore diameters of ≤20 A and ∼20–500 A respectively)1 have found great utility as catalysts and sorption media because of their large internal surface area. Typical microporous materials are the crystalline framework solids, such as zeolites2, but the largest pore dimensions found so far are ∼10–12 A for some metallophosphates3–5 and ∼14 A for the mineral cacoxenite6. Examples of mesoporous solids include silicas7 and modified layered materials8–11, but these are invariably amorphous or paracrystalline, with pores that are irregularly spaced and broadly distributed in size8,12. Pore size can be controlled by intercalation of layered silicates with a surfactant species9,13, but the final product retains, in part, the layered nature of the precursor material. Here we report the synthesis of mesoporous solids from the calcination of aluminosilicate gels in the presence of surfactants. The material14,15 possesses regular arrays of uniform channels, the dimensions of which can be tailored (in the range 16 A to 100 A or more) through the choice of surfactant, auxiliary chemicals and reaction conditions. We propose that the formation of these materials takes place by means of a liquid-crystal 'templating' mechanism, in which the silicate material forms inorganic walls between ordered surfactant micelles.
15,125 citations
TL;DR: Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms.
Abstract: Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms. The SBA-15 materials are synthesized in acidic media to produce highly ordered, two-dimensional hexagonal (space group p6mm) silica-block copolymer mesophases. Calcination at 500°C gives porous structures with unusually large interlattice d spacings of 74.5 to 320 angstroms between the (100) planes, pore sizes from 46 to 300 angstroms, pore volume fractions up to 0.85, and silica wall thicknesses of 31 to 64 angstroms. SBA-15 can be readily prepared over a wide range of uniform pore sizes and pore wall thicknesses at low temperature (35° to 80°C), using a variety of poly(alkylene oxide) triblock copolymers and by the addition of cosolvent organic molecules. The block copolymer species can be recovered for reuse by solvent extraction with ethanol or removed by heating at 140°C for 3 hours, in both cases, yielding a product that is thermally stable in boiling water.
10,807 citations
TL;DR: In this paper, the synthesis, characterization, and proposed mechanism of formation of a new family of silicatelaluminosilicate mesoporous molecular sieves designated as M41S is described.
Abstract: The synthesis, characterization, and proposed mechanism of formation of a new family of silicatelaluminosilicate mesoporous molecular sieves designated as M41S is described. MCM-41, one member of this family, exhibits a hexagonal arrangement of uniform mesopores whose dimensions may be engineered in the range of - 15 A to greater than 100 A. Other members of this family, including a material exhibiting cubic symmetry, have ken synthesized. The larger pore M41S materials typically have surface areas above 700 m2/g and hydrocarbon sorption capacities of 0.7 cc/g and greater. A templating mechanism (liquid crystal templating-LCT) in which surfactant liquid crystal structures serve as organic templates is proposed for the formation of these materials. In support of this templating mechanism, it was demonstrated that the structure and pore dimensions of MCM-41 materials are intimately linked to the properties of the surfactant, including surfactant chain length and solution chemistry. The presence of variable pore size MCM-41, cubic material, and other phases indicates that M41S is an extensive family of materials.
10,349 citations
TL;DR: The aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers, and the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli.
Abstract: The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.
9,661 citations
TL;DR: This work has shown that highly porous frameworks held together by strong metal–oxygen–carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.
Abstract: The long-standing challenge of designing and constructing new crystalline solid-state materials from molecular building blocks is just beginning to be addressed with success. A conceptual approach that requires the use of secondary building units to direct the assembly of ordered frameworks epitomizes this process: we call this approach reticular synthesis. This chemistry has yielded materials designed to have predetermined structures, compositions and properties. In particular, highly porous frameworks held together by strong metal-oxygen-carbon bonds and with exceptionally large surface area and capacity for gas storage have been prepared and their pore metrics systematically varied and functionalized.
8,013 citations