Postsynthetic Modification of Metal–Organic Frameworks by Vapor-Phase Grafting

Rong, Siyi; Chen, Shizheng; Su, Pengcheng; Tang, Haijie; Jia, Miaomiao; Xia, Yan; Li, Wanbin

doi:10.1021/acs.inorgchem.1c00284

Cited by 14 publications

(8 citation statements)

References 50 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Previous works have demonstrated that functionalized groups on the surface of metal‐organic frameworks produce a strong binding effect on the guest molecules [154] . DeCoste et al.…”

Section: Application Of Mofs In Industrial Waste Gas Treatmentmentioning

confidence: 99%

“…Previous works have demonstrated that functionalized groups on the surface of metal-organic frameworks produce a strong binding effect on the guest molecules. [154] DeCoste et al further propose that the strong removal of chlorine from NH 2 À UiO-66 is facilitated by the electrophilic substitution reaction during adsorption. However, the HCl byproducts from this chemisorption lead to the collapse of the MOF microstructure.…”

Section: Halogens and Its Compounds Removalmentioning

confidence: 99%

See 1 more Smart Citation

Surface, Interface and Structure Optimization of Metal‐Organic Frameworks: Towards Efficient Resourceful Conversion of Industrial Waste Gases

Zhao

Huo

et al. 2022

The Chemical Record

View full text Add to dashboard Cite

Industrial waste gas emissions from fossil fuel over‐exploitation have aroused great attention in modern society. Recently, metal‐organic frameworks (MOFs) have been developed in the capture and catalytic conversion of industrial exhaust gases such as SO2, H2S, NOx, CO2, CO, etc. Based on these resourceful conversion applications, in this review, we summarize the crucial role of the surface, interface, and structure optimization of MOFs for performance enhancement. The main points include (1) adsorption enhancement of target molecules by surface functional modification, (2) promotion of catalytic reaction kinetics through enhanced coupling in interfaces, and (3) adaptive matching of guest molecules by structural and pore size modulation. We expect that this review will provide valuable references and illumination for the design and development of MOF and related materials with excellent exhaust gas treatment performance.

show abstract

“…Previous works have demonstrated that functionalized groups on the surface of metal‐organic frameworks produce a strong binding effect on the guest molecules [154] . DeCoste et al.…”

Section: Application Of Mofs In Industrial Waste Gas Treatmentmentioning

confidence: 99%

Section: Halogens and Its Compounds Removalmentioning

confidence: 99%

Surface, Interface and Structure Optimization of Metal‐Organic Frameworks: Towards Efficient Resourceful Conversion of Industrial Waste Gases

Zhao

Huo

et al. 2022

The Chemical Record

View full text Add to dashboard Cite

show abstract

“…Through simple immersion in water, the MOF grafted with acyl chloride groups was transformed into a carboxylated material with high porosity and improved fluoride removal performance. 58 Vapor-phase metalation can be conducted in MOFs by ALD, which can deposit metals or metal oxides on the uncoordinated nodes of MOFs with high density (Figure 3e). 59 This approach breaks the limitation of metal-containing precursor solubility and shows potential in catalyst preparation.…”

Section: Functionalization Of Mofsmentioning

confidence: 99%

Section: Vapor-phase Postsynthetic Functionalization Of Mofsmentioning

confidence: 99%

“…Li and co-workers reported the vapor-phase grafting of NH 2 -UiO-66 by exposure to vaporized trimesoyl chloride based on the Schotten–Baumann reaction (Figure d). Through simple immersion in water, the MOF grafted with acyl chloride groups was transformed into a carboxylated material with high porosity and improved fluoride removal performance . Vapor-phase metalation can be conducted in MOFs by ALD, which can deposit metals or metal oxides on the uncoordinated nodes of MOFs with high density (Figure e) .…”

Section: Vapor-phase Postsynthetic Functionalization Of Mofsmentioning

confidence: 99%

See 1 more Smart Citation

Vapor-Phase Processing of Metal–Organic Frameworks

Ameloot

et al. 2021

Acc. Chem. Res.

Self Cite

View full text Add to dashboard Cite

Porous metal−organic frameworks (MOFs), formed from organic linkers and metal nodes, have attracted intense research attention. Because of their high specific surface areas, uniform and adjustable pore sizes, and versatile physicochemical properties, MOFs have shown disruptive potential in adsorption, catalysis, separation, etc. For many of these applications, MOFs are synthesized solvothermally as bulk powders and subsequently shaped as pellets or extrudates. Other applications, such as membrane separations and (opto)electronics, require the implementation of MOFs as (patterned) thin films. Most thin-film formation methods are adapted from liquid-phase synthesis protocols. Precursor transport and nucleation are difficult to control in these cases, often leading to particle formation in solution. Moreover, the use of solvents gives rise to environmental and safety challenges, incompatibility issues with some substrates, and corrosion issues in the case of dissolved metal salts. In contrast, vapor-phase processing methods have the merits of environmental friendliness, control over thickness and conformality, scalability in production, and high compatibility with other workflows. In this Account, we outline some of our efforts and related studies in the development and application of vapor-phase processing of crystalline MOF materials (MOF-VPP). We first highlight the advances and mechanisms in the vapor-phase deposition of MOFs (MOF-VPD), mainly focusing on the reactions between a linker vapor and a metal-containing precursor layer. The characteristics of the obtained MOFs (thickness, porosity, crystallographic phase, orientation, etc.) and the correlation of these properties with the deposition parameters (precursors, temperatures, humidity, post-treatments, etc.) are discussed. Some in situ characterization methods that contributed to a fundamental understanding of the involved mechanisms are included in the discussion. Second, four vapor-phase postsynthetic functionalization (PSF) methods are summarized: linker exchange, guest loading, linker grafting, and metalation. These approaches eliminate potential solubility issues and enable fast diffusion of reactants and guests as well as a high loading or degree of exchange. Vapor-phase PSF provides a platform to modify the MOF porosity or even introduce new functionalities (e.g., luminescence photoswitching and catalytic activity). Third, since vapor-phase processing methods enable the integration of MOF film deposition into a (micro)fabrication workflow, they facilitate a range of applications with improved performance (low-k dielectrics, sensors, membrane separations, etc.). Finally, we provide a discussion on the limitations, challenges, and further opportunities for MOF-VPP. Through the discussion and analysis of the vapor-phase processing strategies as well as the underlying mechanisms in this Account, we hope to contribute to the development of the controllable synthesis, functionalization, and application of MOFs and related materials.

show abstract