Post‐Synthetic Surface Modification of Metal–Organic Frameworks and Their Potential Applications

Figueroa-Quintero, Leidy; Villalgordo-Hernández, David; Delgado-Marín, José J.; Narciso, J.; Velisoju, Vijay Kumar; Castaño, Pedro; Gascón, Jorge; Ramos‐Fernández, Enrique V.

doi:10.1002/smtd.202201413

Cited by 43 publications

(22 citation statements)

References 191 publications

(285 reference statements)

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“…34,35 In contrast to direct synthesis methods, postsynthetic modification (PSM) holds distinct advantages in fine-tuning catalytic activity and is frequently employed to precisely tailor material properties and functions. 36 Cu−HAB (HAB = hexaiminobenzene) stands out as a conductive two-dimensional (2D) π-conjugated MOF boasting an impressive electrical conductivity of 13 S cm −1 . It is constructed through the tripodal bridging of HAB ligands and planar Cu−N 4 nodes.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Metal–organic frameworks (MOFs) constitute a class of crystalline porous materials characterized by well-defined structures and versatile design possibilities. , Given their innate ability to modulate the microenvironment and coordination configurations of metal ions, MOFs have garnered significant attention in the realm of eCO 2 RR. , While numerous MOFs have been explored for eCO 2 RR, only a limited few have exhibited noteworthy efficiency in catalyzing the conversion of CO 2 to EtOH. , In contrast to direct synthesis methods, postsynthetic modification (PSM) holds distinct advantages in fine-tuning catalytic activity and is frequently employed to precisely tailor material properties and functions …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

Zhao,

Huang,

Liao

et al. 2023

J. Am. Chem. Soc.

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Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

Zhao,

Huang,

Liao

et al. 2023

J. Am. Chem. Soc.

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“…The internal surface chemistry of a microporous particle is dictated by the composition and structure of the material, while the external surface can be modified through both covalent and noncovalent functionalization strategies. − This modularity creates myriad possibilities for microporous water with a wide range of properties and functionalities. In principle, the internal and external surfaces of microporous particles can be independently manipulated to design aqueous fluids with gas carrying capacities, gas selectivities, gas transport kinetics, colloidal stabilities, and biocompatibilities that are tailored to the requirements of a particular application.…”

Section: Introductionmentioning

confidence: 99%

Design Principles for Using Amphiphilic Polymers To Create Microporous Water

DelRe,

Hong,

Wenny

et al. 2023

J. Am. Chem. Soc.

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Aqueous dispersions of microporous nanocrystals with dry, gas-accessible pores�referred to as "microporous water"�enable high densities of gas molecules to be transported through water. For many applications of microporous water, generalizable strategies are required to functionalize the external surface of microporous particles to control their dispersibility, stability, and interactions with other solution-phase components� including catalysts, proteins, and cells�while retaining as much of their internal pore volume as possible. Here, we establish design principles for the noncovalent surface functionalization of hydrophobic metal−organic frameworks with amphiphilic polymers that render the particles dispersible in water and enhance their hydrolytic stability. Specifically, we show that block co-polymers with persistence lengths that exceed the micropore aperture size of zeolitic imidazolate frameworks (ZIFs) can dramatically enhance ZIF particle dispersibility and stability while preserving porosity and >80% of the theoretical O 2 carrying capacity. Moreover, enhancements in hydrolytic stability are greatest when the polymer can form strong bonds to exposed metal sites on the external particle surface. More broadly, our insights provide guidelines for controlling the interface between polymers and metal−organic framework particles in aqueous environments to augment the properties of microporous water.

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“…Several attempts have been made to upgrade the properties and improve the interfacial compatibility of UiO-66-based MOF materials by utilizing different strategies. ,− However, further exploration to develop PSM techniques to functionalize the outer crystal structure of MOFs is needed . A proper synthetic strategy and thorough study is missing in the literature to grow precise polymer chains on the outer nanosurface of UiO-66-based MOFs grafted covalently using the reversible addition–fragmentation chain-transfer (RAFT) polymerization process under aqueous medium.…”

Section: Introductionmentioning

confidence: 99%

“…23,26−29 However, further exploration to develop PSM techniques to functionalize the outer crystal structure of MOFs is needed. 22 A proper synthetic strategy and thorough study is missing in the literature to grow precise polymer chains on the outer nanosurface of UiO-66-based MOFs grafted covalently using the reversible addition−fragmentation chain-transfer (RAFT) polymerization process under aqueous medium. In the current work, surface-initiated RAFT (SI-RAFT) polymerization is used to grow functional polymer chains on the UiO-66-NH 2 MOF (referred to as UiO-66) surface through the graftingfrom approach in an aqueous medium.…”

Section: ■ Introductionmentioning

confidence: 99%

Grafting of Polymer Brushes on MOF Surface to Achieve Proton-Conducting Membranes

Mukherjee,

Das,

Mukhopadhyay

et al. 2023

ACS Appl. Polym. Mater.

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In recent years, postsynthetic modification (PSM) of a metal−organic framework (MOF) has gained immense interest for the synthesis of hybrid materials with improved functionality. However, further improvement in the PSM strategies to make them scalable and yield a synthetically tunable MOF surface can create polymer chain-grafted MOF hybrid materials in which polymer chains provide the stability, robustness, and desired functional performances and MOF offers interesting physical properties. Toward these goals, in this work we have developed a simple and effective method to functionalize the UiO-66-NH 2 MOF surface by grafting functional polymer brushes using surface-initiated reversible addition−fragmentation chain-transfer (RAFT) polymerization. At first, the MOF surface was transformed into a polymerizable surface by attaching a trithiocarbonate-based chain-transfer agent (CTA) and then, three different sets of polymer brushes consisting of (i) a neutral but basic nitrogen functionality (PGM-N), (ii) a trimethyl-substituted quaternary ammonium functionality (PGM-C), and (iii) a quaternary ammonium along with sulfonate functionality (PGM-Z) were grown on the activated MOF surface. The uniqueness of this work has additionally been enhanced by utilizing these synthesized PGMs as nanofillers into the oxypolybenzimidazole (OPBI) membrane matrix to obtain homogeneous mixed matrix membranes (OPBI@PGM) that show brilliant thermomechanical and tensile properties and exceptional thermal stability. Interestingly, these membranes exhibit superior proton conductivity when doped with H 3 PO 4 (PA) and minimal acid leaching. Grafting of functional polymer brushes on the MOF surface induces strong H-bonding and acid−base interactions with OPBI chains and H 3 PO 4 molecules, which are responsible for such high acid uptake and excellent acid retention, thereby displaying a proton conductivity as high as 0.241 S cm −1 at 160 °C (∼4fold increase when compared to OPBI), which is among the highest values reported till date for an MOF-based proton exchange membrane with excellent mechanical vigor.

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Post‐Synthetic Surface Modification of Metal–Organic Frameworks and Their Potential Applications

Cited by 43 publications

References 191 publications

Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

Design Principles for Using Amphiphilic Polymers To Create Microporous Water

Grafting of Polymer Brushes on MOF Surface to Achieve Proton-Conducting Membranes

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Post‐Synthetic Surface Modification of Metal–Organic Frameworks and Their Potential Applications

Cited by 43 publications

References 191 publications

Highly Efficient Electroreduction of CO2 to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

Highly Efficient Electroreduction of CO2 to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

Design Principles for Using Amphiphilic Polymers To Create Microporous Water

Grafting of Polymer Brushes on MOF Surface to Achieve Proton-Conducting Membranes

Contact Info

Product

Resources

About

Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites

Highly Efficient Electroreduction of CO₂ to Ethanol via Asymmetric C–C Coupling by a Metal–Organic Framework with Heterodimetal Dual Sites