A new and highly robust light-responsive Azo-UiO-66 for highly selective and low energy post-combustion CO2 capture and its application in a mixed matrix membrane for CO2/N2 separation

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Abstract

A new and robust generation-2 light-responsive MOF with UiO-66 topology applicable for post combustion CO ₂ capture has been successfully synthesized and is described in this article.

Abstract

A new and robust generation-2 light-responsive MOF with UiO-66 topology applicable for post combustion CO ₂ capture has been successfully synthesized and is described in this article. Azo-UiO-66 shows a satisfactory performance for CO ₂/N ₂ separation as observed through high CO ₂/N ₂ selectivity. Furthermore, due to the presence of azobenzene groups, Azo-UiO-66 also exhibits a very efficient CO ₂ photoswitching uptake, a characteristic that has never been observed in any generation-2 light-responsive MOF. Combined together with its robust character, this makes Azo-UiO-66 a promising candidate for highly selective and low energy CO ₂ capture applications. To further apply this material, Azo-UiO-66 was incorporated in Matrimid to form mixed matrix membranes (MMM). Composites with up to 20 wt% of Azo-UiO-66 were fabricated and tested. The resulting MMM showed increased performance in terms of CO ₂ permeability and CO ₂/N ₂ selectivity compared with the similar MOF-based MMM composites. This then shows another promising application of Azo-UiO-66 as a filler to enhance polymeric membrane performance for CO ₂ separation.

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Synthesis and Stability of Tagged UiO-66 Zr-MOFs

Karl Petter Lillerud, Mathivathani Kandiah, Sandro Usseglio … (2010)

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Modulated synthesis of Zr-based metal-organic frameworks: from nano to single crystals.

Andreas Schaate, Pascal Roy, Adelheid Godt … (2011)

We present an investigation on the influence of benzoic acid, acetic acid, and water on the syntheses of the Zr-based metal-organic frameworks Zr-bdc (UiO-66), Zr-bdc-NH(2) (UiO-66-NH(2)), Zr-bpdc (UiO-67), and Zr-tpdc-NH(2) (UiO-68-NH(2)) (H(2) bdc: terephthalic acid, H(2) bpdc: biphenyl-4,4'-dicarboxylic acid, H(2) tpdc: terphenyl-4,4''-dicarboxylic acid). By varying the amount of benzoic or acetic acid, the synthesis of Zr-bdc can be modulated. With increasing concentration of the modulator, the products change from intergrown to individual crystals, the size of which can be tuned. Addition of benzoic acid also affects the size and morphology of Zr-bpdc and, additionally, makes the synthesis of Zr-bpdc highly reproducible. The control of crystal and particle size is proven by powder XRD, SEM and dynamic light scattering (DLS) measurements. Thermogravimetric analysis (TGA) and Ar sorption experiments show that the materials from modulated syntheses can be activated and that they exhibit high specific surface areas. Water proved to be essential for the formation of well-ordered Zr-bdc-NH(2) . Zr-tpdc-NH(2), a material with a structure analogous to that of Zr-bdc and Zr-bpdc, but with the longer, functionalized linker 2'-amino-1,1':4',1''-terphenyl-4,4''-dicarboxylic acid, was obtained as single crystals. This allowed the first single-crystal structural analysis of a Zr-based metal-organic framework.