Assembly of a Metal–Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular‐Level Control Over Heterogeneous CO<sub>2</sub> Reduction

Mukhopadhyay, Subhabrata; Shimoni, Ran; Liberman, Itamar; Ifraemov, Raya; Rozenberg, Illya; Hod, Idan

doi:10.1002/anie.202102320

Cited by 66 publications

(60 citation statements)

References 70 publications

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“…54 Furthermore, a combination of 1 H NMR spectroscopy and ICP-OES was used to accurately quantify the defect density in MOF-808 A−D. 62,63 From 1 H NMR data, the amount of H 3 BTC and formic acid in the structure could be estimated, while from ICP-OES, the amount of Zr in the MOFs could be determined (detailed analysis, calculation, and spectra are provided in Supporting Information, Section S3.4). The number of BTC linkers for MOF-808 A, MOF-808 B, MOF-808 C, and MOF-808 D as estimated from 1 H NMR was 1.84, 1.67, 1.33, and 1.60, respectively, which matches well with that obtained from TGA (Tables S2 and S4, Supporting Information).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Defect Engineering in a Metal–Organic Framework System to Achieve Super-Protonic Conductivity

et al. 2022

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Controlled incorporation of missing-linker defect sites could be achieved in four sister metal−organic frameworks (MOFs) of MOF-808, namely, MOF-808 A−D via modulated synthesis. An impressive enhancement in proton conductivity is observed in these sister MOFs (increase from 10 −3 to 10 −1 S cm −1 ) as compared to a highly crystalline, low-in-defect variant of MOF-808. MOF-808 C, having optimized defect density, shows a proton conductivity of 2.6 × 10 −1 S cm −1 at 80 °C and 98% relative humidity−the highest value reported to date for pure MOF-based proton conductors without extensive structural modifications. The introduction of defects induces super-protonic conductivity by modifying different properties, like porosity, water sorptivity, and acidity. Furthermore, an assembly of this super proton-conducting MOF with Pt�a versatile hydrogen evolution reaction (HER) catalyst, has been studied with the objective to influence the catalytic activity. This MOFcatalyst assembly was found to have lower overpotential requirements, owing to an increase in local acidity and efficient proton management around the catalyst.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Defect Engineering in a Metal–Organic Framework System to Achieve Super-Protonic Conductivity

et al. 2022

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“…The interface between Ag and Al-PMOF is verified to largely change the surface electronic structure of Ag through electron transfer from Al-PMOF to Ag, thus leading to suppression for HER but a promotion for CO 2 RR to CO. With the coating of MOF layer, the enhanced mass transfer and increased structural stability of Ag were also observed (Fig. 11(c)) [85]. Very recently, Ag@UiO-66 MOF was prepared to demonstrate the extra role of MOF as chemical modularity in electrocatalysis (Fig.…”

Section: Metal@mofsmentioning

confidence: 90%

Nanostructure@metal-organic frameworks (MOFs) for catalytic carbon dioxide (CO2) conversion in photocatalysis, electrocatalysis, and thermal catalysis

Wang

2021

Nano Res.

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The catalytic conversion of carbon dioxide (CO 2 ) into high value-added chemicals is of great significance to address the pressing carbon cycle issues. Reticular chemistry of metal-organic frameworks (MOFs)-based materials exhibits great potential and effectiveness to face CO 2 challenge from capture to conversion. To date, the integrated nanocomposites of nanostructure and MOF have emerged as a powerful heterogeneous catalysts featured with multifold advantages including synergistic effects between the two interfaces, confinement effect of meso-and micropores, tandem reaction triggered by multiple active sites, high stability and dispersion, and so on. Given burgeoning carbon cycle and nanostructure@MOFs, this review highlights some of important advancements to provide a full understanding on the synthesis and design of nanostructure@MOFs composites to facilitate carbon cycle through CO 2 photocatalytic, electrocatalytic, and thermal conversion. Afterward, the catalytic applications of some representative nanostructure@MOFs composites are categorized, in which the origin of activity or structure-activity relationship is summarized. Finally, the opportunities and challenges are proposed for inspiring the future development of nanostructure@MOFs composites for carbon cycle.

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“…[126] In recent years, MOFs have been known as the suitable starting materials for the construction of various electrocatalysts, such as heteroatomic doping and carbon-containing metal oxides. [127] These MOF-derived carbonaceous materials usually exhibit complete microporous properties, low graphitization, and unwanted aggregation of metallic nanoparticles. These results are generally detrimental to mass and electron transport in electrocatalytic processes.…”

Section: Electrocatalysismentioning

confidence: 99%

Metal–Organic Framework Membranes: Advances, Fabrication, and Applications

Jia

Wang

et al. 2022

Small Structures

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Metal-organic frameworks (MOFs) are porous crystal frameworks constructed by metal clusters and bridging organic ligands. [1] This class of materials not only has a highly tunable and regular pore structure, variable functionality, and internal connectivity, [2] but the superior designability enables them to accommodate the introduction of a variety of functional sites on frames, cavities, and channels. [3] These make them have important applications in many fields, including drug delivery, [4] adsorption, [5] antimicrobials, [6] electron conduction, [7] gas storage, [8] catalysis, [9] sensing, [10] and energy conversion. [11] MOFs were first developed by Hoskins and Robson via connecting discrete metal clusters and reappraising the Zn(CN) 2 and Cd(CN) 2 structure [12] and then termed MOFs in 1995. [13] Recent researches focus on the modulation of MOF chemistry to expending our understanding of the relationship between the MOFs structure, function, and applications. However, the poor adhesion and heterogeneous distribution of powdery MOFs hindered their detection in many applications. So, the development of the commercialization of MOFs was limited. [14] Membrane is a kind of material with small pore size and large specific surface area. [15] A series of structural features facilitate its rapid transfer of matters with the action of external driving forces in the field of biomedical, [16] energy storage, [17] and environmental protection. [18] The preparation of MOFs into membranes will play their role to the maximum extent [14,19] and endow more precisely pore size, pore structure, and molecular-/ion-specific groups with the membranes. [20] MOF membranes are mainly divided into two categories: pure MOF membranes and MOF/polymer hybrid membranes. Pure MOF membranes are the continuous thin layers of MOFs that are formed by growing (or depositing) on a porous support layer and/or inorganic substrate or a porous polymer substrate. These kinds of MOF membranes have the advantages of good thermal stability, high mechanical property, antifouling, antiswelling, and controllable pore structure. [21] As pure MOF membranes are composed of MOFs, the permeability and selectivity are completely determined by the pore sizes of MOFs, which endow pure MOF membranes with significant selectivity. [22] Pure MOF membranes should have the best performance in theory. However, their brittle texture, high cost, and difficulty in chemical modification still limit their practical applications. MOF/polymer hybrid membranes are composite materials that are composed of a dispersed phase (MOFs) and a continuous phase (polymer or another flexible matrix). There are two forms: MOFs embedded in the polymer matrix and MOFs on the surface of the flexible substrate. The thickness is much thicker than the diameter of the embedded porous MOFs; thus, the doped MOFs are surrounded by the polymer matrix. In this case, the selectivity and permeability of the MOF/polymer hybrid membranes are significantly dependent on the properties of the

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Assembly of a Metal–Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular‐Level Control Over Heterogeneous CO₂ Reduction

Cited by 66 publications

References 70 publications

Defect Engineering in a Metal–Organic Framework System to Achieve Super-Protonic Conductivity

Defect Engineering in a Metal–Organic Framework System to Achieve Super-Protonic Conductivity

Nanostructure@metal-organic frameworks (MOFs) for catalytic carbon dioxide (CO2) conversion in photocatalysis, electrocatalysis, and thermal catalysis

Metal–Organic Framework Membranes: Advances, Fabrication, and Applications

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Assembly of a Metal–Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular‐Level Control Over Heterogeneous CO2 Reduction

Cited by 66 publications

References 70 publications

Defect Engineering in a Metal–Organic Framework System to Achieve Super-Protonic Conductivity

Defect Engineering in a Metal–Organic Framework System to Achieve Super-Protonic Conductivity

Nanostructure@metal-organic frameworks (MOFs) for catalytic carbon dioxide (CO2) conversion in photocatalysis, electrocatalysis, and thermal catalysis

Metal–Organic Framework Membranes: Advances, Fabrication, and Applications

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Product

Resources

About

Assembly of a Metal–Organic Framework (MOF) Membrane on a Solid Electrocatalyst: Introducing Molecular‐Level Control Over Heterogeneous CO₂ Reduction