Synthesis, Structure, and Characterization of a Layered Mixed Metal Oxychloride, PbVO3Cl

Abstract

Experimental Section Synthesis. Pb(NO3)2 (Junsei, 99.5%), PbO (Kanto, 98.5%), PbCl2 (Hayashi, 99%), V2O5 (Junsei, 99.0%), and NaCl (Duksan, 99.0%) were used as received. Crystals of PbVO3Cl were prepared by a hydrothermal reaction method. 1.449 g (4.38 mmol) of Pb(NO3)2, 0.106 g (1.82 mmol) of NaCl, 0.113 g (0.63 mmol) of V2O5, and 5 mL of deionized water were placed in a 23-mL Teflon-lined stainless steel autoclave that was subsequently sealed. The autoclave was gradually heated to 230 o C, held for 3 days, and cooled slowly to room tem- perature at a rate of 1 o C min -1 . The products were recovered by filtration and washed with water. Powder X-ray diffraction patterns on the manually separated colorless needles, colorless blocks, and yellow rods were determined to be PbCl2, Pb(NO3)2, and PbVO3Cl, respectively. A yield of 48% based on lead was observed from the manually separated yellow rods of PbVO3Cl. Pure polycrystalline PbVO3Cl was synthesized through a stan- dard solid-state reaction technique. A stoichiometric mixture of PbO (0.653 g, 2.93 mmol), PbCl2 (0.814 g, 2.93 mmol), and V2O5 (0.532 g, 2.93 mmol) was thoroughly ground and pressed into a pellet. The pellet was introduced into a fused silica tube that was evacuated and sealed. The tube was gradually heated to 450 o C, held for 12 h, and cooled down to room temperature. The powder X-ray diffraction pattern on the resultant yellow powder indicated the material was single-phase and in a good agreement with the generated pattern from the single-crystal data. Crystallographic determination. The structure of PbVO3Cl was determined by standard crystallographic methods. A yellow plate crystal (0.02 × 0.05 × 0.22 mm 3 ) was used for single crystal X-ray diffraction. The data were collected using a Bruker SMART APEX CCD X-ray diffractometer at room