The unique opportunities of mechanosynthesis in green and scalable fabrication of metal–organic frameworks

Afshariazar, Farzaneh; Morsali, Ali

doi:10.1039/d2ta02699f

Cited by 13 publications

(10 citation statements)

References 243 publications

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“…Metal–organic frameworks (MOFs) are hybrid crystalline assemblies constructed from various metallic nodes and organic linkers via different synthesis strategies, providing an exceptional opportunity to obtain a variety of modular solid-state materials applicable in various technological fields. − The tailorability of the structure, tunable pore surfaces, and accessible channels are the remarkable features of these crystalline materials. In addition, the great possibility to incorporate active interaction sites via predesigned strategies or post-treatment processes has revealed profound influences on the characteristic properties of the final products advantageous for the development of their potential use. − The accessibility of the active interaction sites plays a major role in improving the performance for advanced practical purposes.…”

Section: Introductionmentioning

confidence: 99%

Investigation of the Influence of Functionalization Strategy on Urea 2D MOF Catalytic Performance

2023

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Urea-functionalized MOFs with unique properties have recently been used as efficient platforms to conduct organocatalytic reactions. To gain more insight into the key factors which govern an efficient organocatalytic reaction in urea-MOFs, two different urea-containing 2D MOFs TMU-58 ([Zn(L1)(oba)].CH3CN) and TMU-83 ([Zn(L2)(oba)].DMF), where L1 = (1E,5E)-1,5-bis(1-(pyridine-4-ylethylidene)carbonohydrazide, L2 = (1E,5E)-1,5-bis(1-(pyridine-4-ylmethylene)carbonohydrazide, and oba = 4,4′-oxybisbenzoic acid, with abundant accessible active sites, were selected and examined in the methanolysis of styrene oxide. TMU-58 with the ability to form a two-point H-bond with different substrates revealed a high organocatalytic efficiency in the regioselective ring opening of styrene oxide. The catalytic activation of epoxide oxygen by the urea N–H functional sites, followed by the nucleophilic attack of methanol at the benzylic carbon led to the formation of 2-methoxy-2-phenylethanol as the major product. DFT calculations were also performed to investigate the acidic strength of the urea hydrogens in both TMU-58 and TMU-83 structures as a major factor to conduct an efficient catalytic reaction. The results indicated the more acidic nature of the urea hydrogens in TMU-83; however, its catalytic efficiency was remarkably reduced due to the inappropriate orientation of the active interaction sites within the framework revealing the importance of proper orientation of the urea hydrogens in conducting an efficient organocatalytic reaction. The current study provides a comparative study on the function–property relationship in 2D MOF assemblies which has not been explored so far.

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Section: Introductionmentioning

confidence: 99%

Investigation of the Influence of Functionalization Strategy on Urea 2D MOF Catalytic Performance

2023

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“…Mechanochemistry induced by a mechanical force is an efficient, simple, green, and energy-saving method for physicochemical and chemical transformations on a large scale, [17][18][19] and has been widely applied in chemical production and numerous research fields such as organic synthesis, [20][21][22] inorganic synthesis, [23][24][25] advanced energy materials, [26,27] metalorganic frameworks, [28,29] and gas synthesis. [30][31][32] Pfennig et al reported a mechanochemical method to prepare Grignard reagents from organobromides and subsequently react with gaseous CO 2 or sodium methyl carbonate to obtain aryl and alkyl carboxylic acids reaching 82 % yield.…”

Section: Introductionmentioning

confidence: 99%

“…Mechanochemistry induced by a mechanical force is an efficient, simple, green, and energy‐saving method for physicochemical and chemical transformations on a large scale, [17–19] and has been widely applied in chemical production and numerous research fields such as organic synthesis, [20–22] inorganic synthesis, [23–25] advanced energy materials, [26,27] metal‐organic frameworks, [28,29] and gas synthesis [30–32] . Pfennig et al .…”

Section: Introductionmentioning

confidence: 99%

Mechanocatalysis: Simple and Rapid Mechanochemical Synthesis of Ammonia in Hydrogen, Nitrogen, and Water System

Hao

Wang

et al. 2023

ChemCatChem

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Mechanical force‐induced N2 fixation is an emerging strategy for single‐step ammonia synthesis under room temperature and atmospheric pressure. Here, we demonstrate a simple and rapid approach to synthesize NH3 in the N2+H2+H2O system and illustrate the reaction mechanism by theoretical calculations. The NH3 generation rate can reach 2.847 mg L−1 h−1 with an NH4+ selectivity of 99.45 wt.%. The presence of H2 can inhibit oxidation reactions to form NO3− by‐products and promote proton generation from H2O dissociation. The calculated formation energy of H‐adatom and OH‐adatom from H2O cleavage is −2.86 eV in N2+H2+H2O system, much lower than that in N2+H2O system, verifying much easier dissociation of H2O molecules and significantly facilitated proton generation to enlarge the NH4+ yield. This work provides a simple approach to improve mechanochemical N2 fixation performance and highlights a proton generation enhancement mechanism.

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“…Recent advances in mechanochemistry have made it possible to synthesize materials at room temperature without the need of large quantities of solvents and with excellent yields while also being ecologically benign. 24,25 Therefore, the objective of this work was to successfully synthesize ZIF-76 using a mechanochemical method and a green solvothermal synthesis that replaces DMF with gammavalerolactone (GVL). GVL, which can be easily generated from lignocellulosic biomass, is regarded as a green solvent due to its renewability, biodegradability, and nontoxicity.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Mechanochemistry is a strong contender as a replacement for traditional solution-based chemistry. Recent advances in mechanochemistry have made it possible to synthesize materials at room temperature without the need of large quantities of solvents and with excellent yields while also being ecologically benign. , …”

Section: Introductionmentioning

confidence: 99%

Green Synthesis Approaches toward Preparation of ZIF-76 and Its Thermal Behavior

Švegovec

Škrjanc

Krajnc

et al. 2023

Crystal Growth & Design

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With the current increase of interest in amorphous MOFs and ZIFs for various applications, there is a need for optimal and environmentally friendly synthesis of the parent materials. One of the ZIFs that has received the most research to date, along with ZIF-62, is ZIF-76. ZIF-62 has already been produced mechanochemically, while the majority of ZIF-76 is currently produced using solvothermal synthesis in an autoclave with DMF as the solvent. Herein, we present two new green synthesis methods for creating a ZIF-76 framework. The mechanochemical and precipitation approaches were developed to shorten reaction times and allow for room temperature synthesis. This work represents the first step toward green synthesis of ZIF-76 and its thermally treated variants.

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The unique opportunities of mechanosynthesis in green and scalable fabrication of metal–organic frameworks

Abstract: Due to the fascinating molecular structure of MOFs and their widespread practical use in various industrial applications, great attention has focused on the development of commercialization techniques for up-scaled production...

Cited by 13 publications

References 243 publications

Investigation of the Influence of Functionalization Strategy on Urea 2D MOF Catalytic Performance

Investigation of the Influence of Functionalization Strategy on Urea 2D MOF Catalytic Performance

Mechanocatalysis: Simple and Rapid Mechanochemical Synthesis of Ammonia in Hydrogen, Nitrogen, and Water System

Green Synthesis Approaches toward Preparation of ZIF-76 and Its Thermal Behavior

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