Self-assembly has proven to be a widely successful synthetic strategy for functional materials, especially for metal–organic materials (MOMs), an emerging class of porous materials consisting of metal–organic frameworks (MOFs) and metal–organic polyhedra (MOPs). However, there are areas in MOM synthesis in which such self-assembly has not been fully utilized, such as controlling the interior of MOM crystals. Here we demonstrate sequential self-assembly strategy for synthesizing various forms of MOM crystals, including double-shell hollow MOMs, based on single-crystal to single-crystal transformation from MOP to MOF. Moreover, this synthetic strategy also yields other forms, such as solid, core-shell, double and triple matryoshka, and single-shell hollow MOMs, thereby exhibiting form evolution in MOMs. We anticipate that this synthetic approach might open up a new direction for the development of diverse forms in MOMs, with highly advanced areas such as sequential drug delivery/release and heterogeneous cascade catalysis targeted in the foreseeable future.
Anti-icing aluminum (Al) surfaces with excellent durability and low icing adhesion strength were fabricated by forming hierarchical structures on Al surfaces and coating silanes with low surface energy. The Al plates were chemically etched and subsequently immersed in hot water to realize micro–nano hierarchical roughness on the surface. The rough Al plates were coated with a solution containing a mixture of 1H,1H,2H,2H-heptadecafluorodecyl (FD)-trimethoxysilane and poly(dimethylsiloxane) (PDMS)-triethoxysilane, and the wettability and anti-icing properties of the coated surface were compared according to the various ratios of FD and PDMS. The anti-icing surface with 2.9 wt % of the PDMS functional group exhibited a relatively low ice adhesion strength of 25.3 kPa despite a high relative humidity of 75% (at −20.5 °C). In addition, the ice adhesion strength achieved after 100 icing/melting cycles was 47.2 kPa, which indicated excellent durability of the anti-icing properties. This is attributed to the synergistic effect of PDMS and the low surface energy of FD groups, which exhibit chain flexibility, low glass-transition temperature, and repulsion against water molecules.
A novel n-octadecane/fumed silica phase change composite has been prepared as a building envelope with a high content of phase change material and improved energy efficiency. With a high porosity (88 vol%), the fumed silica provided sufficient space to impregnate a high quantity of n-octadecane (70 wt%). The composite exhibited high latent heat storage capacity (155.8 J/g), high crystallization fraction (96.5%), and a melting temperature of 26.76 °C close to that of pure n-octadecane. A 200 accelerated thermal cycle test confirmed good thermal reliability and chemical stability of the phase change composite. The thermal conductivity of n-octadecane was reduced by 34% after impregnation in fumed silica. A phase change composite panel was fabricated and compared to a commercial polystyrene foam panel. When used as the roof of a test room, the phase change composite panel more efficiently retarded heat transfer from a halogen lamp to the room and delayed the increase in the indoor temperature than that by the polystyrene panel. The indoor temperatures of the room with the phase change composite panel roof were 19.8 and 22.9 °C, while those with the polystyrene panel roof were 29.9 and 31.9 °C at 2200 and 9000 s after lamp illumination.
We present a facile approach to fabricate superamphiphobic surfaces by spray coating silica-fluoropolymer core-shell particles without substrate pretreatment with an additional binder resin. A series of SiO2@poly(1H,1H,2H,2H-heptadecafluorodecyl methacrylate) (SiO2@PFMA) core-shell particles with core particles of different sizes were prepared via thiol-lactam initiated radical polymerization (TLIRP). The surface of each SiO2 particle with an average particle size of 12, 80, 150, and 350 nm was modified with (3-mercaptopropyl) trimethoxysilane and used as a seed for TLIRP. The SiO2@PFMA particles with various SiO2 sizes and contents were coated on aluminum substrates by a spray gun and then thermally treated to form a stable, rough composite layer. During the spray coating, the core-shell particles were aggregated by rapid evaporation of the solvent and then irregularly adhered to the substrate resulting in hierarchical structures. In the case of SiO2@PFMAs with low SiO2 contents, the roughness created mainly by the polymer shell disappeared during heat treatment. However, the substrates coated with SiO2@PFMAs with high SiO2 contents maintained the roughness even after heat treatment. The core-shell particles prepared with 12 nm SiO2 formed a stable superamphiphobic surface. The water/hexadecane contact and sliding angles on an aluminum plate coated with SiO2@PFMA, prepared using 12 nm silica at 46 wt% silica content (12 nm-SiO2(46)@PFMA), were 178.5°/159.2° and 1°/7°, respectively. The cross-cut tape test showed that adhesion between the 12nm-SiO2(46)@PFMA and the aluminum substrate was classified as 5B. A glass surface spray-coated with the core-shell composite particles exhibited transparent superhydrophobicity and translucent superamphiphobicity by controlling the concentration of the coating solution.
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