Synthesis, structure, and stability of metal-organic frameworks

Metal-organic frameworks (MOFs) obtained much attention because of their unusual structures and properties as well as their potential applications. This dissertation research was focused on (1) the effects of synthesis conditions on the structures of MOFs, (2) the thermal stability of MOFs, (3) pressure-induced amorphization, and (4) the effect of high-valent ions on the structure of a MOF. This research demonstrated that the crystal structure of MOF-5 could be controlled by drying solvents. If the vacuum solvent is dimethylformamide (DMF), the crystal structure of MOF-5 is tetragonal. In contrast, if the DMF is displaced by CH2Cl2 before the vacuum, the obtained MOF-5 occupies a cubic structure. Furthermore, it was found that the tetragonal MOF-5 exhibited a mediate surface area (300-1000 m2/g). The surface area of tetragonal MOF-5 is also dependent on Zn(NO3)2/H2BDC (H2BDC: terephthalic acid) molar ratios used for its synthesis. The optimum ratio is 1.38, at which synthesized tetragonal MOF-5 exhibits the highest crystallinity and surface area (1297 m2/g). The thermal stability and decomposition of MOF-5 were systematically investigated. The thermal decomposition of cubic and tetragonal MOF-5s resulted in the same products: CO2, benzene, amorphous carbon, and crystal ZnO. The thermal decomposition is due to breaking carboxylic bridges between benzene rings and Zn4O clusters. Identifying structural relationships between crystalline and noncrystalline states is of fundamental interest in materials research. Currently, amorphization of solid materials at ambient temperature requires an ultra-high pressure (several GPa). However, this research demonstrated that MOF-5 and IRMOF-8 can be irreversibly amorphized at ambient temperature by employing a low compressing pressure of 3.5 MPa, which is 100 times lower than that required for amorphization of other solids. Furthermore, the pressure-induced amorphization (PIA) of MOFs is strongly dependent on the changeability of bond angles. If the geometric structure of a MOF can allow bond angles to be changed without breaking bonds, it can easily be amorphized by compression. This can explain why MOF-5 and IRMOF-8 can easily be amorphized via compression than Cu-BTC. It is generally recognized that zeolitic imidazolate frameworks (ZIFs) occupy much higher stability than other types of MOFs. The representative of ZIFs is Zn(2-methylimidazole)2 (ZIF-8) exhibiting high-decomposition temperature and high chemical resistance to various solvents. However, so far, it is still unknown whether the high stability of ZIF-8 can be challenged by ions, which is important for its modification by doping ions. In this research, we performed aqueous salt solution treatment on ZIF-8, and the results showed that anions (Cl¯ and NO3¯) in a solution exhibited no effect on the crystal structure of ZIF-8. However, the effect of cations (in a solution) on structure of ZIF-8 strongly depends on the cation valences. The univalent metal cations showed no effect on the structure of ZIF-8, whereas the bivalent or higher-valent metal cations caused the collapse of ZIF-8 crystal structure. Therefore, structure stability of ZIF-8 is considered when it is subjected to the application, in which high-valent metal cations are involved.

The Electrical Resistance of Metals and Alloys in Their Hard and Soft States

It is known that the electrical resistance of annealed metals is usually smaller than that of metals in their cold worked state. The curve showing the relation between electrical resistance and annealing temperature reaches a minimum; continued annealing at higher temperature produces an increase in the electrical resistance. In the case of alloys it has been noted that a second decrease occurs at higher annealing temperature. The following work corroborates the observance of previous investigations. The electrical resistance of cold worked copper, gold, nickel, and iron decreased with annealing and then increased, the minimum being around 300° C. or 400° C. Monel metal showed a minimum resistance followed by an increase which in turn was followed by a second decrease.

Age Hardening of Silver-Platinum Alloys

The alloy system selected for study was the binary alloy of platinum and silver. An examination of the various silver alloy diagrams revealed that of several possible alloys, the silver platinum was the most suit­able with regard to solubility.

The Electroformation of Lithium-Lead Alloys from Molten Electrolytes

An attempt was made to make lead-lithium alloys by electrodeposition of lithium using a molten bath and a molten lead cathode.The variables taken into consideration were: composition of the melt, temperature of the melt, and current density. The purpose of changing these factors was to determine what effect each had on the current efficiency.

The Electrodeposition of Iron-Manganese Alloys

Various electrolytes were experimented with in an attempt to deposit an iron-manganese alloy. An Alloy was obtained from a solution containing ferrous ammonium sulfate, manganous sulfate, and ammonium sulfate. Further experimentation was done in an effort to determine the optimum conditions of deposition and the highest manganese alloy which could be produced.

The Electrodeposition of Iron-Manganese Alloys

An electrodeposition of an iron-manganese alloy was made from the same conditions determined by previous re­search. Various addition agents were experimented with in an attempt to produce better conditions for electro-deposition. It was found advantageous to add small a­mounts of sodium lauryl sulfate and ammonium sulfite to the electrolyte.

Age Hardening of Copper Antimony Alloys

A large number of alloys of varying percentages of copper and antimony were prepared. These alloys were treated in various ways which might be expected to produce age hardening. The effect of cold working was studied in the range where the alloys were malleable.

The Electrodeposition of Copper-Cobalt Alloys

An attempt was made to deposit a 50:50 copper-cobalt alloy from various sulfate electrolytes. No true 50:50 alloy was obtained but various mixtures of cobalt and copper rich crystals were deposited.

Corrosion Testing of Iron-Tin Alloys by the Salt Spray Method

The purpose of this study was to determine the rela­tive rate of corrosion of iron-tin alloys containing low percentages of tin. Since in the world today, a great deal of work is being done to develop large tin deposits and new methods devised to treat these ores, it is possible that the metal will become abundant and will obtain a more important position in the metal industry.

The Effect of Manganese and Magnesium on the Hardening of Copper-Aluminum Alloys

During recent years, duralumin and all aluminum alloys have been made the object of much discussion regarding their hardening mechanism. The commercial success of nearly all of the alloys of aluminum and mag­nesium is dependent on their ability to age or precipitation harden.

The Electrodeposition of Iron-Manganese Alloys

Although the alteration of properties resulting from the alloying of metals in their usual commercial forms has been extensively investigated, the field of electrodeposition of alloys is believed generally not to have received the atten­tion that it merits.