RESUMEN
Metal-organic frameworks (MOFs) as solid sorbents for carbon dioxide (CO2) capture face the challenge of merging efficient capture with economical regeneration in a durable, scalable material. Zinc-based Calgary Framework 20 (CALF-20) physisorbs CO2 with high capacity but is also selective over water. Competitive separations on structured CALF-20 show not just preferential CO2 physisorption below 40% relative humidity but also suppression of water sorption by CO2, which was corroborated by computational modeling. CALF-20 has a low enthalpic regeneration penalty and shows durability to steam (>450,000 cycles) and wet acid gases. It can be prepared in one step, formed as composite materials, and its synthesis can be scaled to multikilogram batches.
RESUMEN
Two complementary design strategies, isomorphous ligand replacement and heterocycle doping, have been applied to iteratively enhance the proton conductivity of a metal-organic framework, ß-PCMOF2. The resulting materials, PCMOF21/2(Pz) and PCMOF21/2(Tz) (Pz = 1H-pyrazole, Tz = 1H-1,2,4-triazole), have their proton conduction raised almost 2 orders of magnitude compared to ß-PCMOF2. The bulk conductivities of these materials are over 10-1 S cm-1 at 85 °C and 90% relative humidity (RH), while maintaining the parent MOF structure. A solid state synthetic route for doping 1-D channels is also presented.
RESUMEN
Using the concept of isomorphous replacement applied to entire ligands, a C(3)-symmetric trisulfonate ligand was substituted with a C(3)-symmetric tris(hydrogen phosphonate) ligand in a proton conducting metal-organic framework (MOF). The resulting material, PCMOF2½, has its proton conduction raised 1.5 orders of magnitude compared to the parent material, to 2.1 × 10(-2) S cm(-1) at 90% relative humidity and 85 °C, while maintaining the parent MOF structure.
Asunto(s)
Compuestos Organometálicos/química , Protones , Ligandos , Modelos MolecularesRESUMEN
Metal-organic framework (MOF) materials are a nontraditional route to ion conductors, but their crystallinity can give insight into molecular-level transport mechanisms. However, some MOFs can be structurally compromised in humid environments. A new 3D metal-organic framework, PCMOF-5, is reported which conducts protons above 10(-3) S/cm at 60 °C and 98% relative humidity. The MOF contains free phosphonic acid groups, shows high humidity stability, and resists swelling in the presence of hydration. Channels filled with crystallographically located water and acidic groups are also observed.
Asunto(s)
Compuestos Organometálicos/química , Protones , Agua/química , Humedad , Modelos Moleculares , SolubilidadRESUMEN
A metal organic framework with amine-lined pores gives high values for surface area and heat of adsorption with CO(2) gas.