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MOFs: Porosidade e Área Superficial Excepcionais

2004
  • Omar M. Yaghi
Pesquisador que analisa estruturas metal-orgânicas em um ambiente de laboratório, com foco em porosidade e área de superfície.

(Imagem gerada apenas para fins ilustrativos)

A defining characteristic of Metal-Organic Frameworks is their exceptionally high internal surface area and porosity. The ordered, crystalline structure creates well-defined pores and channels, leading to Brunauer–Emmett–Teller (BET) surface areas that can exceed 7,000 m²/g. This value far surpasses traditional porous materials like zeolites or activated carbons, making the vast internal surface readily accessible for molecular adsorção.

The high surface area in MOFs is a direct consequence of their low-density crystalline structure. Unlike amorphous materials like activated carbon, which have a wide distribution of irregular pores, MOFs possess uniform, precisely engineered cavities. The surface area is calculated from gas adsorption isotherms, typically using nitrogen or argon at cryogenic temperatures, and applying the BET theory. The formula for the BET surface area is [latex]S_{BET} = \frac{v_m N_A s}{V_M}[/latex], where [latex]v_m[/latex] is the monolayer volume of the adsorbate gas, [latex]N_A[/latex] is Avogadro’s number, [latex]s[/latex] is the adsorption cross-section of the gas molecule, and [latex]V_M[/latex] is the molar volume of the gas.

The ability to design MOFs with very long organic linkers and low-density metal nodes allows for the creation of frameworks with extremely large void fractions, sometimes exceeding 90% of the crystal volume. For example, MOF-5, one of the archetypal MOFs, has a BET surface area of around 3,000 m²/g. Later developments, such as MOF-177 and the NU series (e.g., NU-110), pushed these values to over 7,000 m²/g and even 10,000 m²/g, respectively. This immense internal ‘real estate’ is crucial for applications that rely on surface interactions, such as gas storage, where molecules are physisorbed onto the framework’s interior surfaces, and catalysis, where active sites can be distributed throughout the material’s volume.

UNESCO Nomenclature: 2211
Física do estado sólido

Tipo

Propriedade física

Interrupção

Substancial

Uso

Uso generalizado

Precursores

  • Brunauer–Emmett–Teller (BET) theory for surface area measurement
  • development of gas sorption analysis techniques
  • synthesis of early porous materials like zeolites and activated carbons
  • understanding of physisorption and chemisorption phenomena

Aplicações

  • high-density hydrogen and methane storage for vehicles
  • carbon capture and sequestration (CCS) from flue gas
  • purification of industrial gases
  • heterogeneous catalysis with high active site density
  • chromatographic separations

Patentes:

NA

Ideias de Inovação Potencial

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Related to: surface area, porosity, bet theory, gas adsorption, physisorption, MOF-5, mof-177, porous material, void fraction, crystal density.

Contexto histórico

MOFs: Porosidade e Área Superficial Excepcionais

1991
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2004
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2002
2015-09-14

(Caso a data seja desconhecida ou irrelevante, por exemplo, "mecânica dos fluidos", é fornecida uma estimativa aproximada de seu surgimento notável)

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