Syntheses Of Metal-organic Frameworks Composites Via Pusled Laser Ablation

Metal-organic framework (MOFs), which has a three-dimensional grid structure made of metal ions or metal clusters with organic ligands, have adjustable pore size, high specific surface area and can also be introduced with different functional materials, etc. to the cavity. MOFs have great potential applications in gas storage and separation, sensing, proton conductor, drug transportation. Introducing functionalized nanoparticles to MOFs to improve original property, or developing new performance of MOFs, have become a new research hotspot. But there still lack of a common approach for the immobilization of MNPs in MOFs.In this paper, we develop a new method of pulsed laser ablation to rapid synthesis of MOFs such as MOF-5, MOF-177, HKUST-1, [Zn2(bdc)2dabco] and [Zn2(ndc)2dabco], etc; Nanocrystallization of graphitic carbon, Fe, Eu2O3, MgO, Fe3O4, CdS, CdSe, and PF of different materials while introducing these nano-materials to cavities of generated synchronously MOFs, to form NP@MOFs composites. Introducing nanoparticles to MOFs can not only reinforce the adsorption properties of MOFs, but also improve their proton conductivity, in addition fluorescence sensing capabilities can also be endowed. (1) Gas adsorption capability, the C2H2 and CO2 uptake in MgO@HK.UST-1 reaches the high value of 221 cm3/g and 161 cm3/g, respectively, at 296 K,1 atm. the C2H2 storage of 221 cm3/g is the highest C2H2 storage capacity ever reported at 296 K for porous materials. The CO2 storage capacity slightly less than the maximum ever reported at 296 K. Those value compared with pure HKUST-1 C2H2 and CO2 adsorption capacity increased by 10% and 60%, respectively. It is a very promising MOF composites material for the highly selective separation of C2H2/CH4 and C2H4/CH4 at room temperature with the highest C2H2/CH4 separation selectivity of 132.6 ever reported. (2) Proton conductivity, compared with pure HKUST-1 their conductivity increased by 1.5 times,1.8 times,2.0 times and 1l.5 times at 25℃ after CdSe, Eu2O3, MgO, CdS nanoparticles were immobilized with HKUST-1. (3) Fluorescence sensing, Eu2O3@[Zn2(bdc)2dabco](ZBDh) and Eu2O3@[Zn2(ndc)2dabco] can be used for the detection of small organic molecules. The pulsed laser ablation method we proposed have become a new way suitable for inorganic or polymer insoluble nanoparticles composite MOF, to promote the development of MOFs composite materials and functional materials.