Studies of the reactions between rare earth salts and phosphoric acid in aqueous or ethanolic media have shown that in both cases stable gels can be formed. Upon drying, gels prepared in aqueous environments yield macrocrystalline REPO 4 products similar to those produced by conventional precipitation and drying. Gels prepared in ethanol, on the other hand, undergo dehydration to form dense microcrystalline products. This observation is based on optical and scanning electron microscopy, as well as on x-ray diffraction studies and infrared spectroscopy. These techniques, as well as differential thermal analysis, indicate that crystal growth of these products takes place around 600-700 ± C. The composition of the dehydrated gels produced in both the aqueous and ethanolic systems corresponds to an orthophosphate structure. Other characteristics of the microcrystalline REPO 4 products include high resistance to attack by water, absence of coloration upon exposure to gamma rays, and a high index of refraction.

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To mimic the activity regulated by a cysteinate axial ligand in cytochrome P450 enzymes, metal tetrakis(4-carboxyphenyl)porphyrins (M TCPP) were immobilized on ZnS. They were characterized by a variety of spectroscopic techniques and were used as a catalyst for cyclohexane oxidation. The small amount of metal (Co, Fe, or Mn) TCPP (1.1 μmol) in the immobilized catalyst could be reused three times for oxidation, providing more than 6.5 × 10 5 turnover number and 20% molar yield of cyclohexanone and cyclohexanol (KA oil) on average. The coordination of ZnS played a key role. These catalysts were applied to green catalytic oxidation of cyclohexane to produce KA oil products.

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