RESUMO
Guiding metal organic framework (MOF) morphology, especially without the need for chemical additives, still remains a challenge. For the first time, we report a unique surface guiding approach in controlling the crystal morphology formation of zeolitic imidazole framework-8 (ZIF-8) and HKUST-1 MOFs on disrupted alkanethiol self-assembled monolayer (SAM)-covered Au substrates. Selective molecule removal is applied to generate diverse SAM matrices rich in artificial molecular defects in a monolayer to direct the dynamic crystal growth process. When a 11-mercaptoundecanol alkanethiol monolayer is ruptured, the hydroxyl tail groups of surface residue molecules act as nucleating sites by coordination with precursor metal ions. Meanwhile, the exposed alkane chain backbones stabilize a particular facet of MOF nuclei in the dynamic growth by slowing down their crystal growth rates along a specific direction. The competitive formation between the [110] and [100] planes of ZIF-8 ultimately regulates the crystal shapes from rhombic dodecahedron, truncated rhombic dodecahedron, and truncated cube to cube. Similarly, changeable morphologies of HKUST-1 crystals are also achieved from cube and tetrakaidekahedron to octahedron, originating from the competitive selection between the [100] and [111] planes. In addition to the artificial matrix preferred orientation of initial nucleation, parameters such as temperature also play a crucial role in the resulting crystal morphology. Standing on the additive-free MOF crystal morphology growth control, porous architectures prepared in this approach can act as templates for ligand-free metal (Au, Ag, and Cu) nanocluster synthesis. The nanocluster-embedded MOF structures represent distinct crystal morphology-dependent optical properties, and interestingly, their fluorescence emission can be highly enhanced by facet-induced nanocluster packing alignments. These findings not only provide a unique thought on MOF crystal morphology guidance but also pave a new route for the accompanied property investigation and further application.
RESUMO
Flexible and transparent electronics is a new generation of device enabling modern interactive designs, which facilitates the recent development of low-cost, lightweight, and flexible materials. Although conventional indium tin oxide material still dominates the major market, its brittleness and steadily increasing price drive scientists to search for other alternatives. To meet the high demand, numerous metallic or organic conductive materials have been developed, but their poor adhesion toward supporting substrates and the subsequent circuit patterning approach remains problematic. In this study, a robust metal-free flexible conductive film fabrication strategy is introduced. The flexible polyethylene terephthalate (PET) film is utilized as the base, where a poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) conductive layer is tightly linked onto this supporting substrate. An interface activation process, i.e., oxygen plasma treatment, generates PET surface active spots to react with the subsequently introduced poly(vinyl alcohol) (PVA) molecule functional groups. This spatially selective PVA molecular bridge therefore acts as a dual-function intermediate layer through covalent bonding toward PET and hydrogen bonding toward PEDOT:PSS to conjugate two distinct materials. This PEDOT:PSS/PVA/PET film delivers superior physical properties, such as a high conductivity of 38.2 Ω/sq and great optical transmittance of 84.1%, which are well tunable under conductive polymer thickness controls. The film is also durable and can maintain original electrical properties even under serious bending for hundreds of cycles. Relying on these outstanding performances, arbitrary conductive circuits are built on this flexible substrate and can function as normal electronics when integrated with multiple electronic parts, e.g., light-emitting diodes (LEDs). Superior electrical signal outputs are achieved when complicated stereo structures including folding, splicing, interlacing, and braiding are incorporated, enabling the use of these films for flexible three-dimensional electronics assembling. Space identifying smart key and lock pair, origami rabbit-carrot touch response, pressure-stimulated jumping frog, and moving dinosaur recognition designs realize these PEDOT:PSS/PVA/PET film-based human-machine interactive devices. This flexible, transparent, and conductive film generation approach by molecular bridge creation should facilitate future development of flexible or foldable devices with complex circuits.
RESUMO
Flexible pressure sensors have attracted increasing interest because of their potential applications on wearable sensing devices for human-machine interface connections, but challenges regarding material cost, fabrication robustness, signal transduction, sensitivity improvement, detection range, and operation convenience still need to be overcome. Herein, with a simple, low-cost, and scalable approach, a flexible and wearable pressure-sensing device fabricated by utilizing filter paper as the solid support, poly(3,4-ethylenedioxythiophene) to enhance conductivity, and silver nanoparticles to provide a rougher surface is introduced. Sandwiching and laminating composite material layers with two thermoplastic polypropylene films lead to robust integration of sensing devices, where assembling four layers of composite materials results in the best sensitivity toward applied pressure. This practical pressure-sensing device possessing properties such as high sensitivity of 0.119 kPa-1, high durability of 2000 operation cycles, and an ultralow energy consumption level of 10-5 W is a promising candidate for contriving point-of-care wearable electronic devices and applying it to human-machine interface connections.
