Gas adsorption in the topologically disordered Fe-BTC framework

Sapnik, Adam; Ashling, Christopher W.; Macreadie, Lauren K.; Lee, Seok J.; Johnson, Timothy J.; Telfer, Shane G.; Bennett, Thomas D.

doi:10.1039/d1ta08449f

Cited by 11 publications

(11 citation statements)

References 47 publications

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“…As an example, the BET surface area of Basolite F300, likely produced through an electrochemical method, 56 is reported as lying between 1300 and 1600 m 2 g –1 , but several reports found different values, ranging from 685 to 1055 m 2 g –1 . 51 , 54 , 55 , 57 − 60 Similarly, studies on Fe-BTC obtained by a sol–gel route report BET surface area values between 0 and 1618 m 2 g –1 , 33 , 55 , 58 − 62 while the amorphous phase obtained by ball-milling MIL-100(Fe), a m MIL-100, is non-porous. 63 All these reported phases share the same composition and local structure but have different properties in terms of porosity.…”

Section: Introductionmentioning

confidence: 99%

“…Fe-BTC has been abundantly studied as a catalyst for oxidation reactions, because its structure includes both Lewis sites (the terminal positions on iron(III) atoms in the trimer) and Brønsted acid sites that are ascribed to defective terminal carboxylic groups of protonated linkers that disrupt the network. ,, Fe-BTC has been reported to have a broad range of structural diversity, resulting in a family of materials showing different properties depending on the synthetic route adopted. As an example, the BET surface area of Basolite F300, likely produced through an electrochemical method, is reported as lying between 1300 and 1600 m 2 g –1 , but several reports found different values, ranging from 685 to 1055 m 2 g –1 . ,,,− Similarly, studies on Fe-BTC obtained by a sol–gel route report BET surface area values between 0 and 1618 m 2 g –1 , ,,− while the amorphous phase obtained by ball-milling MIL-100(Fe), a m MIL-100, is non-porous . All these reported phases share the same composition and local structure but have different properties in terms of porosity.…”

Section: Introductionmentioning

confidence: 99%

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Modeling the Effect of Defects and Disorder in Amorphous Metal–Organic Frameworks

et al. 2022

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Amorphous metal–organic frameworks (aMOFs) are a class of disordered framework materials with a defined local order given by the connectivity between inorganic nodes and organic linkers, but absent long-range order. The rational development of function for aMOFs is hindered by our limited understanding of the underlying structure–property relationships in these systems, a consequence of the absence of long-range order, which makes experimental characterization particularly challenging. Here, we use a versatile modeling approach to generate in silico structural models for an aMOF based on Fe trimers and 1,3,5-benzenetricarboxylate (BTC) linkers, Fe-BTC. We build a phase space for this material that includes nine amorphous phases with different degrees of defects and local order. These models are analyzed through a combination of structural analysis, pore analysis, and pair distribution functions. Therefore, we are able to systematically explore the effects of the variation of each of these features, both in isolation and combined, for a disordered MOF system, something that would not be possible through experiment alone. We find that the degree of local order has a greater impact on structure and properties than the degree of defects. The approach presented here is versatile and allows for the study of different structural features and MOF chemistries, enabling the derivation of design rules for the rational development of aMOFs.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Modeling the Effect of Defects and Disorder in Amorphous Metal–Organic Frameworks

et al. 2022

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show abstract

“…As an example, the BET surface area of Basolite® F300, likely produced through an electrochemical method, 56 is reported as lying between 1300-1600 m 2 g -1 , but several reports found different values, ranging from 685 to 1055 m 2 g -1 . 51,54,55,[57][58][59][60] Similarly, studies on Fe-BTC obtained by a sol-gel route report BET surface area values between 0 and 1618 m 2 g -1 , 33,55,[58][59][60][61][62] while the amorphous phase obtained by ball-milling MIL-100(Fe), a m MIL-100, is non-porous. 63 All these reported phases share the same composition and local structure but have different properties in terms of porosity.…”

Section: Introductionmentioning

confidence: 99%

Modelling the effect of defects and disorder in amorphous metal−organic frameworks

Bechis

Sapnik

Tarzia

et al. 2022

Preprint

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Amorphous metal−organic frameworks (aMOFs) are a class of disordered framework materials with a defined local order given by the connectivity between inorganic nodes and organic linkers, but absent longer-range order. The rational development of function for aMOFs is hindered by our limited understanding of the underlying structure-property relationships in these systems, a consequence of the absence of long-range order, which makes experimental characterization particularly challenging. Here, we use a versatile modelling approach to generate in-silico structural models for an aMOF based on Fe trimers and 1,3,5-benzenetricarboxylate (BTC) linkers, Fe-BTC. We build a phase space for this material that includes nine amorphous phases with different degrees of defects and local order. These models are analyzed through a combination of structural analysis, pore analysis and pair distribution functions. Therefore, we are able to systematically explore the effects of the variation of each of these features, both in isolation and combined, for a disordered MOF system, something that would not be possible through experiment alone. We find that the degree of local order has a greater impact on structure and properties than the degree of defects. The approach presented here is versatile and allows for the study of different structural features and MOF chemistries, enabling the development of design rules for the rational design of aMOFs.

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“…26,27 We recently demonstrated Fe-BTC's promise in the highly sought-after separation of propane and propene, which is currently an incredibly energy-intensive industrial process. 28 Despite its many applications, the structure of Fe-BTC is not fully understood due to its broad diffraction pattern [Fig. 2a].…”

Section: Introductionmentioning

confidence: 99%

Mapping nanocrystalline disorder within an amorphous metal–organic framework

Sapnik

Sun

Laulainen

et al. 2022

Preprint

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Intentionally disordered metal–organic frameworks (MOFs) display rich functional behaviour. However, the characterisation of their atomic structures remains incredibly challenging. X-ray pair distribution function techniques have been pivotal in determining their average local structure but are largely insensitive to spatial variations in the structure. Fe-BTC is a nanocomposite MOF, known for its catalytic properties, comprising crystalline nanoparticles and an amorphous matrix. Here, we use scanning electron diffraction to first map the crystalline and amorphous components to evaluate domain size and then to carry out electron pair distribution function analysis to probe the spatially separated atomic structure of the amorphous matrix. Further Bragg scattering analysis reveals systematic orientational disorder within Fe-BTC’s nanocrystallites, showing over 10° of continuous lattice rotation across single particles. Finally, we identify candidate unit cells for the crystalline component. These independent structural analyses quantify disorder in Fe-BTC at the critical length scale for engineering composite MOF materials.

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Gas adsorption in the topologically disordered Fe-BTC framework

Abstract: Fe-BTC, a disordered metal–organic framework, exhibits clear discrimination of propene and propane compared to its crystalline counterpart MIL-100.

Cited by 11 publications

References 47 publications

Modeling the Effect of Defects and Disorder in Amorphous Metal–Organic Frameworks

Modeling the Effect of Defects and Disorder in Amorphous Metal–Organic Frameworks

Modelling the effect of defects and disorder in amorphous metal−organic frameworks

Mapping nanocrystalline disorder within an amorphous metal–organic framework

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