As one of the most appealing strategies for the synthesis of nanomaterials with various architectures, emulsion-directed methods have been rarely used to control the structure of metal-organic frameworks (MOFs). Herein, we report a versatile salt-assisted nanoemulsion-guided assembly to achieve continuous architecture transition of hierarchical Zr-based MOFs. The morphology of nanoemulsion can be facilely regulated by tuning the feed ratio of a dual-surfactant and the introduced amount of compatible hydrophobic compounds, which directs the assembly of MOFs with various architectures such as bowl-like mesoporous particle, dendritic nanospheres, walnut-shaped particles, crumpled nanosheets and nanodisks. The developed dendritic nanospheres with highly open and large mesochannels is successfully used as matrix for the co-immobilization of coenzymes and corresponding enzymes to realize the in situ heterogeneous regeneration of NAD+. This strategy is expected to pave a way for exploring sophisticated hierarchical MOFs which can be competent for practical applications with bulk molecules involved.

Metrics & MoreArticle Recommendations CONSPECTUS:The past few decades have been witnessing the rapid research boom of metal−organic frameworks (MOFs), which are assembled from metal nodes and multitopic organic linkers. In virtue of their modular assembly mode, they can be tailored according to desired functions to satisfy numerous potential applications. However, most initially reported MOFs were restricted to the microporous regime, limiting their practical applications with bulk molecules involved. Therefore, the research attention was immediately directed toward enlarging the intrinsic pore size of frameworks by extending the secondary building units or organic ligands. Unfortunately, the synthesis of more extended ligands is frequently tedious, and the most resultant MOFs are not sufficiently stable, restricting their popularization. The soft-template strategy is recognized as a promising avenue to produce hierarchically porous MOFs (HPMOFs), although early attempts generally failed due to the incompatibility between the surfactant self-assembly and guided crystallization process of MOF precursors in the organic phase. Therefore, developing a rational soft-template strategy to achieve the precise control of morphology and porosity of HPMOFs is of great significance.In this Account, we present our recent progress on the development and applications of HPMOFs prepared by soft-template strategies. We highlight the key issues upon using the soft-template strategy to synthesize HPMOFs. To enhance the interaction between the template and MOF precursor, a long-chain monocarboxylic acid strategy is introduced to synthesize HPMOFs with irregular mesopores in the organic phase. Then, to improve the order of mesopores, an aqueous-phase synthesis method using amphoteric surfactants as templates is developed to prepare ordered HPMOFs. To further enlarge the pore size and make the synthesis conditions of MOFs compatible with the self-assembly of surfactants, a salting-in species-induced self-assembly strategy is proposed and coupled with the structure-directing properties of copolymer templates to synthesize a series of HPMOFs with large mesopores and even macropores. This salting-in ion-mediated self-assembly (SIMS) strategy paves the way to modify the pore size, pore structure, morphology, and chemical composition of HPMOFs. The separated but intimately interconnected hierarchical pores in the resultant HPMOFs can not only realize rapid mass transport but also isolate different-size guest molecules so that they are competent for a broad range of applications including protein digestion, cascade catalysis, enzyme-assisted substrate sensing, and DNA cleavage. Finally, the limitations, challenges, and future developments of this rapidly evolving field are described. This Account with a highlight to the soft-template strategies not only provides interesting insights to understand the assembly process between templates and MOFs but also inspires an optimization of the properties of HPMOFs from diverse aspects for desired app...

A general strategy based on the Hoffmeister effect is proposed for the aqueous-phase and mild synthesis of stable metal–organic frameworks.

The creation of artificial microenvironments with specific functionalities to mimic multiple cascade biocatalytic processes in cells is highly desirable. Here, Zr-based large-pore mesoporous metal−organic frameworks (mesoMOFs) were successfully developed for the construction of such spatially organized cascade bioreactors. Thanks to the mediating effect of the Hofmeister ion and the flexibility of Zr-MOFs, large mesopores and functional microporous mesopore walls were integrated into a single nanoplatform, ensuring the efficient mass exchange between the interconnected pore units with different sizes. As a proof of concept, natural superoxide dismutase and catalase mimic were spatially positioned in these hierarchical mesoMOFs, which formed a cascade antioxidant defense system and presented an efficient intracellular reactive oxygen species scavenging ability. This model is expected to set a conceptual guideline for the design of compartmentalized bioreactors in nanoscale MOFs to mediate the complex intracellular catalytic networks.

Despite the fact that bimetallic metal−organic frameworks (MOFs) could afford multiple functionalities by a synergistic effect of individual metallic centers, their intrinsic microporous structure frequently restricts their wide applications with bulky molecules involved. An urgent need is consequently triggered to design bimetallic hierarchical mesoporous MOFs (mesoMOFs). Herein, Zr/Ce mesoMOFs with a uniform pore size of up to 8 nm was successfully synthesized by a copolymer template strategy with the aid of a Hoffmeister ion. The obtained Zr/Ce mesoMOFs feature high porosity, good chemical and thermal stabilities, and tunable element components, and up to 70% Zr could be incorporated into the mesoporous Ce-based framework without deteriorating its crystallinity. Thanks to the synergistic effect of inherent Ce and Zr as well as the large and open pore channels, a broad range of phosphopeptides with different molecule sizes could be effectively checked out, thanks to their simultaneous enrichment and dephosphorylation capabilities. Such an ability to efficiently concentrate phosphopeptides remained intact even in the presence of abundant non-phosphorylated species. The practical detection of phosphopeptides from human serum was also verified, prefiguring the great potentials of bimetallic largepore mesoMOFs for the proteome applications.