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Modulating Adsorption and Stability Properties in Pillared Metal–Organic Frameworks: A Model System for Understanding Ligand Effects
Metal–organic frameworks (MOFs) are nanoporous materials with highly tunable properties that make them ideal for a wide array of adsorption applications. Through careful choice of metal and ligand precursors, one can target the specific functionality and pore characteristics desired for the applicat...
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Published in: | Accounts of chemical research 2015-11, Vol.48 (11), p.2850-2857 |
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description | Metal–organic frameworks (MOFs) are nanoporous materials with highly tunable properties that make them ideal for a wide array of adsorption applications. Through careful choice of metal and ligand precursors, one can target the specific functionality and pore characteristics desired for the application of interest. However, among the wide array of MOFs reported in the literature, there are varying trends in the effects that ligand identity has on the adsorption, chemical stability, and intrinsic framework dynamics of the material. This is largely due to ligand effects being strongly coupled with structural properties arising from the differing topologies among frameworks. Given the important role such properties play in dictating adsorbent performance, understanding these effects will be critical for the design of next generation functional materials. Pillared MOFs are ideal platforms for understanding how ligand properties can affect the adsorption, stability, and framework dynamics in MOFs. In this Account, we highlight our recent work demonstrating how experiment and simulation can be used to understand the important role ligand identity plays in governing the properties of isostructural MOFs containing interconnected layers pillared by bridging ligands. Changing the identity of the linear, ditopic ligand in either the 2-D layer or the pillaring third dimension allows targeted modulation of the chemical functionality, porosity, and interpenetration of the framework. We will discuss how these characteristics can have important consequences on the adsorption, chemical stability, and dynamic properties of pillared MOFs. The structures discussed in this Account comprise the greatest diversity of isostructural MOFs whose stability properties have been studied, allowing valuable insight into how ligand properties dictate the chemical stability of isostructural frameworks. We also discuss how functional groups can affect adsorbate energetics at their most favorable adsorption sites to elucidate how functional groups can affect the adsorptive performance of these materials in ways that are unexpected based on the isolated ligand’s properties. We then highlight a variety of simulation tools that not only can be used to understand the differing molecular-level behavior of the adsorbate and framework dynamics within these isostructural MOFs, but also can shed light on possible mechanisms that govern the differing chemical stability properties among these materials |
doi_str_mv | 10.1021/acs.accounts.5b00311 |
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Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)</creatorcontrib><description>Metal–organic frameworks (MOFs) are nanoporous materials with highly tunable properties that make them ideal for a wide array of adsorption applications. Through careful choice of metal and ligand precursors, one can target the specific functionality and pore characteristics desired for the application of interest. However, among the wide array of MOFs reported in the literature, there are varying trends in the effects that ligand identity has on the adsorption, chemical stability, and intrinsic framework dynamics of the material. This is largely due to ligand effects being strongly coupled with structural properties arising from the differing topologies among frameworks. Given the important role such properties play in dictating adsorbent performance, understanding these effects will be critical for the design of next generation functional materials. Pillared MOFs are ideal platforms for understanding how ligand properties can affect the adsorption, stability, and framework dynamics in MOFs. In this Account, we highlight our recent work demonstrating how experiment and simulation can be used to understand the important role ligand identity plays in governing the properties of isostructural MOFs containing interconnected layers pillared by bridging ligands. Changing the identity of the linear, ditopic ligand in either the 2-D layer or the pillaring third dimension allows targeted modulation of the chemical functionality, porosity, and interpenetration of the framework. We will discuss how these characteristics can have important consequences on the adsorption, chemical stability, and dynamic properties of pillared MOFs. The structures discussed in this Account comprise the greatest diversity of isostructural MOFs whose stability properties have been studied, allowing valuable insight into how ligand properties dictate the chemical stability of isostructural frameworks. We also discuss how functional groups can affect adsorbate energetics at their most favorable adsorption sites to elucidate how functional groups can affect the adsorptive performance of these materials in ways that are unexpected based on the isolated ligand’s properties. We then highlight a variety of simulation tools that not only can be used to understand the differing molecular-level behavior of the adsorbate and framework dynamics within these isostructural MOFs, but also can shed light on possible mechanisms that govern the differing chemical stability properties among these materials. 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Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)</creatorcontrib><title>Modulating Adsorption and Stability Properties in Pillared Metal–Organic Frameworks: A Model System for Understanding Ligand Effects</title><title>Accounts of chemical research</title><addtitle>Acc. Chem. Res</addtitle><description>Metal–organic frameworks (MOFs) are nanoporous materials with highly tunable properties that make them ideal for a wide array of adsorption applications. Through careful choice of metal and ligand precursors, one can target the specific functionality and pore characteristics desired for the application of interest. However, among the wide array of MOFs reported in the literature, there are varying trends in the effects that ligand identity has on the adsorption, chemical stability, and intrinsic framework dynamics of the material. This is largely due to ligand effects being strongly coupled with structural properties arising from the differing topologies among frameworks. Given the important role such properties play in dictating adsorbent performance, understanding these effects will be critical for the design of next generation functional materials. Pillared MOFs are ideal platforms for understanding how ligand properties can affect the adsorption, stability, and framework dynamics in MOFs. In this Account, we highlight our recent work demonstrating how experiment and simulation can be used to understand the important role ligand identity plays in governing the properties of isostructural MOFs containing interconnected layers pillared by bridging ligands. Changing the identity of the linear, ditopic ligand in either the 2-D layer or the pillaring third dimension allows targeted modulation of the chemical functionality, porosity, and interpenetration of the framework. We will discuss how these characteristics can have important consequences on the adsorption, chemical stability, and dynamic properties of pillared MOFs. The structures discussed in this Account comprise the greatest diversity of isostructural MOFs whose stability properties have been studied, allowing valuable insight into how ligand properties dictate the chemical stability of isostructural frameworks. We also discuss how functional groups can affect adsorbate energetics at their most favorable adsorption sites to elucidate how functional groups can affect the adsorptive performance of these materials in ways that are unexpected based on the isolated ligand’s properties. We then highlight a variety of simulation tools that not only can be used to understand the differing molecular-level behavior of the adsorbate and framework dynamics within these isostructural MOFs, but also can shed light on possible mechanisms that govern the differing chemical stability properties among these materials. Lastly, we provide perspective on the challenges and opportunities for utilizing the structure–property relationships arising from the ligand effects described in this Account for the design of further MOFs with enhanced chemical stability and adsorption properties.</description><subject>catalysis (heterogeneous), defects, membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)</subject><issn>0001-4842</issn><issn>1520-4898</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNp9kc1uEzEUhS0EoqHwBghZrNgkXM_Y88MuqlpAStVKpWvL9lwHlxk72B6h7FjxArwhT4KjpCxZ2Vf6zjnXPoS8ZrBiULH3yqSVMibMPqeV0AA1Y0_IgokKlrzru6dkAQCs3Hl1Rl6k9FDGijftc3JWNaLqoYEF-XUdhnlU2fktXQ8pxF12wVPlB3qXlXajy3t6G8MOY3aYqPP01o2jijjQa8xq_PPz903cKu8MvYpqwh8hfksf6JoWYxzp3T5lnKgNkd77AWPKxfoQtnHbQ8iltWhyekmeWTUmfHU6z8n91eWXi0_Lzc3HzxfrzVJxzvKy77oOWG95K6wC4LxvRCO0tqoZWsQyc9azCmoYEFEJoVnHbd-0Lde6RV2fk7dH35Cyk8m4jOarCd6XJSSrW-gqUaB3R2gXw_cZU5aTSwbLqz2GOUnW1qKuoat5QfkRNTGkFNHKXXSTinvJQB5qkqUm-ViTPNVUZG9OCbOecPgneuylAHAEDvKHMEdffuX_nn8BveGj7A</recordid><startdate>20151117</startdate><enddate>20151117</enddate><creator>Burtch, Nicholas C</creator><creator>Walton, Krista S</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>OTOTI</scope></search><sort><creationdate>20151117</creationdate><title>Modulating Adsorption and Stability Properties in Pillared Metal–Organic Frameworks: A Model System for Understanding Ligand Effects</title><author>Burtch, Nicholas C ; Walton, Krista S</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a441t-9888019f475fa004496565bbfa6d7ee44941912030deeea55b184f96774bb7eb3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>catalysis (heterogeneous), defects, membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Burtch, Nicholas C</creatorcontrib><creatorcontrib>Walton, Krista S</creatorcontrib><creatorcontrib>Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>OSTI.GOV</collection><jtitle>Accounts of chemical research</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Burtch, Nicholas C</au><au>Walton, Krista S</au><aucorp>Energy Frontier Research Centers (EFRC) (United States). Center for Understanding and Control of Acid Gas-induced Evolution of Materials for Energy (UNCAGE-ME)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Modulating Adsorption and Stability Properties in Pillared Metal–Organic Frameworks: A Model System for Understanding Ligand Effects</atitle><jtitle>Accounts of chemical research</jtitle><addtitle>Acc. Chem. Res</addtitle><date>2015-11-17</date><risdate>2015</risdate><volume>48</volume><issue>11</issue><spage>2850</spage><epage>2857</epage><pages>2850-2857</pages><issn>0001-4842</issn><eissn>1520-4898</eissn><abstract>Metal–organic frameworks (MOFs) are nanoporous materials with highly tunable properties that make them ideal for a wide array of adsorption applications. Through careful choice of metal and ligand precursors, one can target the specific functionality and pore characteristics desired for the application of interest. However, among the wide array of MOFs reported in the literature, there are varying trends in the effects that ligand identity has on the adsorption, chemical stability, and intrinsic framework dynamics of the material. This is largely due to ligand effects being strongly coupled with structural properties arising from the differing topologies among frameworks. Given the important role such properties play in dictating adsorbent performance, understanding these effects will be critical for the design of next generation functional materials. Pillared MOFs are ideal platforms for understanding how ligand properties can affect the adsorption, stability, and framework dynamics in MOFs. In this Account, we highlight our recent work demonstrating how experiment and simulation can be used to understand the important role ligand identity plays in governing the properties of isostructural MOFs containing interconnected layers pillared by bridging ligands. Changing the identity of the linear, ditopic ligand in either the 2-D layer or the pillaring third dimension allows targeted modulation of the chemical functionality, porosity, and interpenetration of the framework. We will discuss how these characteristics can have important consequences on the adsorption, chemical stability, and dynamic properties of pillared MOFs. The structures discussed in this Account comprise the greatest diversity of isostructural MOFs whose stability properties have been studied, allowing valuable insight into how ligand properties dictate the chemical stability of isostructural frameworks. We also discuss how functional groups can affect adsorbate energetics at their most favorable adsorption sites to elucidate how functional groups can affect the adsorptive performance of these materials in ways that are unexpected based on the isolated ligand’s properties. We then highlight a variety of simulation tools that not only can be used to understand the differing molecular-level behavior of the adsorbate and framework dynamics within these isostructural MOFs, but also can shed light on possible mechanisms that govern the differing chemical stability properties among these materials. Lastly, we provide perspective on the challenges and opportunities for utilizing the structure–property relationships arising from the ligand effects described in this Account for the design of further MOFs with enhanced chemical stability and adsorption properties.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>26529060</pmid><doi>10.1021/acs.accounts.5b00311</doi><tpages>8</tpages></addata></record> |
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subjects | catalysis (heterogeneous), defects, membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing) |
title | Modulating Adsorption and Stability Properties in Pillared Metal–Organic Frameworks: A Model System for Understanding Ligand Effects |
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