(I) Synthesis and Properties of Mesoporous Aluminum Metal-Organic Framework (II) Carbonization and Applications of Metal-Organic Frameworks

• Main Authors: Kulandaivel Sivasankar, 施可達
• Other Authors: Chia-Her Lin
• Format: Others
• Language: en_US
• Published: 2019
• Online Access: http://ndltd.ncl.edu.tw/handle/pxc3xu

博士 === 中原大學 === 化學研究所 === 107 === The complete thesis primarily consists of:  Preparation of new aluminium mesoporous metal-organic framework (MOF) of [Al(OH)(PDA)] (CYCU-8 & CYCU-9).  Metal/Metal oxide embedded porous carbon preparation, based on the metal-organic framework mediated synthesis (MOFMS).  A highly defective sql topology of Al- porous coordination polymers (PCPs) was prepared by oxophilicity Al(III) ions and H2PDA ligand under conventional solvothermal reaction. Further, solvent-assisted lattice rearrangement was proceeded by solvent desorption and kgm topology of Al-PCPs was prepared. The detailed study was performed to overlooked the imperfect crystallinity to the highly crystalline product. Understand the host-guest interaction and defects in the porous-material lead the structural transformation. The unusual lattice rearrangement in PCPs was characterised via various physical techniques, such as powder X-ray diffraction (PXRD), N2 sorption analysis, solid-state nuclear magnetic resonance spectroscopy (SSNMR).  Metal-organic frameworks (MOFs) have been used as an attracting template for making graphitic porous materials. Herein, we have synthesized the hierarchical mesoporous graphite oxide (HMGO) material through simple single step carbonization method by using the well-known MOF, MIL-100(Al) as a template material under various carbonization temperatures (700, 800, and 900 °C) without using any additional source. The newly made HMGO materials showed uniform morphology, pore-size distribution centered around 10 nm with reasonably good BET surface areas (370-470 m2 g-1) and excellent electrochemical performance. Hence, we have constructed an amperometric sensor for the trace level detection of caffeic acid (CA) using HMGO as a modifier in glassy carbon electrode (GCE). The superior electro catalytic activity of HMGO film modified GCE can be explained from the low over potential and high redox peak current towards the detection of CA. Our demonstrated sensor works in a wide linear range (0.01-608 μM) with low limit of detection (0.004 μM) and high sensitivity (429 µA mM−1 cm−2). In addition, the selective determination of CA even in presence of other interfering molecules, reveals the good selectivity of HMGO/GCE. The commercial wine samples were further utilized to demonstrate the practical feasibility of HMGO modified GCE. The acceptable values of stability, repeatability, and reproducibility also support the practical applications of our fabricated electrode.  Copper nanoparticles with the diameter of 50±20 nm decorated nitrogen doped graphite oxide (NGO) have been prepared through simple single step carbonization method using copper metal-organic framework {Cu2(BDC)2(DABCO)} as a precursor. The surface morphology, porosity, surface area and elemental composition of CuNPs/NGO were characterized by various techniques. The as-synthesized CuNPs/NGO nanomaterials were coated on commercially available disposable screen-printed carbon electrode for the sensitive determination of glucose. The modified electrode can detect glucose between 1 μM and 1803 μM (linear range) with good sensitivity (2500 μA mM–1 cm–2). Our glucose sensor also possesses low limits of detection (0.44 μM) towards glucose determination. The highly selective nature of the fabricated electrode was clearly visible from the selectivity studies. The practicability of CuNPs/NGO modified electrode has been validated in the human serum samples. The storage stability along with better repeatability and reproducibility results additionally substantiate the superior electrocatalytic activity of our constructed sensor towards glucose.  Nitrogen-functionalized porous carbon (NPC) materials are successfully prepared by simple carbonization of Zn-containing metal-organic framework (Zn-MOF). The resulting NPC materials have been characterized using various physicochemical techniques which indicated that the NPC materials obtained at different carbonization temperature exhibited different properties. Pristine MOF morphology and pore size were retained after carbonization at particular temperatures (600 C and 800 C ). Zn-MOF carbonized at different temperature ZnO exhibit on to the NPC material pores, ZnO agglomeration affects the tuning pristine morphology were studied various physical techniques. The NPC material synthesized at 800 C shows a better surface area 1192 m2 g−1, total pore volume 0.92 cm3 g−1 and displays a higher CO2 capacity of 4.71 mmol g−1 at 273 k and 1 bar. The material contains nano cavities of combined pores and nitrogen anchored carbon material better accessibility towards CO2 capture. NPC (600) displays a good electrochemical sensing towards H2O2.