ABSTRACT
Vectorial catalysis-controlling multi-step reactions in a programmed sequence and by defined spatial localization in a microscale device-is an enticing goal in bio-inspired catalysis research. However, translating concepts from natural cascade biocatalysis into artificial hierarchical chemical systems remains a challenge. Herein, we demonstrate integration of two different surface-anchored nanometer-sized metal-organic frameworks (MOFs) in a microfluidic device for modelling vectorial catalysis. Catalyst immobilization at defined sections along the microchannel and a two-step cascade reaction was conducted with full conversion after 30â seconds and high turnover frequencies (TOF≈105 â h-1 ).
ABSTRACT
Metal-organic frameworks (MOFs) are an emerging class of porous materials composed of organic linkers and metal centers/clusters. The integration of MOFs onto the solid surface as thin films/coatings has spurred great interest, thanks to leveraging control over their morphology (such as size- and shape-regulated crystals) and orientation, flexible processability, and easy recyclability. These aspects, in synergy, promise a wide range of applications, including but not limited to gas/liquid separations, chemical sensing, and electronics. Dozens of innovative methods have been developed to manipulate MOFs on various solid substrates for academic studies and potential industrial applications. Among the developed deposition methods, the liquid-phase epitaxial layer-by-layer (LPE-LbL) method has demonstrated its merits over precise control of the thickness, roughness, homogeneity, and orientations, among others. Herein, we discuss the major developments of surface-mounted MOFs (SURMOFs) in LbL process optimization, summarizing the SURMOFs' performance in different applications, and put forward our perspective on the future of SURMOFs in terms of advances in the formulation, applications, and challenges. Finally, future prospects and challenges with respect to SURMOFs growth will be discussed, keeping the focus on their widening applications.
ABSTRACT
Flexible metal-organic frameworks (MOFs) are structurally flexible, porous, crystalline solids that show a structural transition in response to a stimulus. If MOF-based solid-state and microelectronic devices are to be capable of leveraging such structural flexibility, then the integration of MOF thin films into a device configuration is crucial. Here we report the targeted and precise anchoring of Cu-based alkylether-functionalised layered-pillared MOF crystallites onto substrates via stepwise liquid-phase epitaxy. The structural transformation during methanol sorption is monitored by in-situ grazing incidence X-ray diffraction. Interestingly, spatially-controlled anchoring of the flexible MOFs on the surface induces a distinct structural responsiveness which is different from the bulk powder and can be systematically controlled by varying the crystallite characteristics, for instance dimensions and orientation. This fundamental understanding of thin-film flexibility is of paramount importance for the rational design of MOF-based devices utilising the structural flexibility in specific applications such as selective sensors.
