Metal-organic frameworks (MOFs) have recently emerged as a new type of nanoporous materials with tailorable structures and functions. Usually, MOFs have uniform pores smaller than 2 nm in size, limiting their practical applications in some cases. Although a few approaches have been adopted to prepare MOFs with larger pores, it is still challenging to synthesize hierarchical-pore MOFs (H-MOFs) with high structural controllability and good stability. Here we demonstrate a facile and versatile method, an in situ self-assembly template strategy for fabricating stable H-MOFs, in which multi-scale soluble and/or acid-sensitive metal-organic assembly (MOA) fragments form during the reactions between metal ions and organic ligands (to construct MOFs), and act as removable dynamic chemical templates. This general strategy was successfully used to prepare various H-MOFs that show rich porous properties and potential applications, such as in large molecule adsorption. Notably, the mesopore sizes of the H-MOFs can be tuned by varying the amount of templates.

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Preparation of defect‐free and optimized thin film nanocomposite (TFN) membranes is an effective way to enhance the process of organic solvent nanofiltration. However, it still remains a great challenge due to poor filler particle dispersibility in organic phase and compatible issue between fillers and polymers. Aiming at these difficulties, UiO‐66‐NH2 nanoparticles were surface modified with long alkyl chains and used in the preparation of TFN membranes. As a result, defect‐free TFN membranes with ultrathin MOF@polyamide layer were successfully prepared benefited from the improved particle dispersibility in n‐hexane. Significant enhancement was found in methanol permeance after nanoparticle incorporation, without comprising the tetracycline rejection evidently. Especially, the novel TFN membrane prepared with organic phase solution containing 0.15% (w/v) modified UiO‐66‐NH2 nanoparticles showed a superior methanol permeance of 20 L·m−2·h−1·bar−1 and a tetracycline rejection of about 99%, which is appealing to the application in pharmaceutical industry for example. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1303–1312, 2017

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