PubMed · 14391813
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V NAGEL. 1955. [Bismuth stomatitis].. https://pubmed.ncbi.nlm.nih.gov/14391813/
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CuBiP(2)Se(6), AgBiP(2)Se(6), and AgBiP(2)S(6) were prepared from the corresponding elements. CuBiP(2)Se(6) and AgBiP(2)Se(6) crystallize in the space group R with a = 6.5532(16) A and c = 39.762(13) A for CuBiP(2)Se(6) and a = 6.6524(13) A and c = 39.615(15) A for AgBiP(2)Se(6). AgBiP(2)S(6) crystallizes in the triclinic space group P with a = 6.3833(13) A, b = 7.1439(14) A, c = 9.5366(19) A, alpha = 91.89(3) degrees , beta = 91.45(3) degrees , gamma = 94.05(3) degrees . CuBiP(2)Se(6) was found to exhibit a temperature-dependent antiferroelectric ordering of the Cu(+) and Bi(3+) ions in the lattice. An intermediate and a fully ordered structure were refined at 173 and 97 K, respectively. Electronic band and total energy calculations at the DFT level clearly suggest that the antiferroelectric model is energetically favored over the paraelectric and hypothetical ferrielectric models. This phase transition can be classified as a second-order Jahn-Teller distortion. The antiferroelectric state of CuBiP(2)Se(6) is an indirect gap semiconductor. The compounds were characterized with differential thermal analysis and solid-state UV/vis diffuse reflectance spectroscopy. Generalized implications regarding the expected ferroelectric behavior of compounds in the CuMP(2)Se(6) system (M = trivalent metal) are discussed.
Cu(3)Bi(2)S(3)I(3) was crystallized during an attempt to synthesize Cu-Pb-Bi sulfosalts with iodine as the transport medium. The crystal structure was solved from a black needle-like crystal on a four-circle diffractometer with a CCD detector. The solution was obtained by direct methods and subsequent difference-Fourier syntheses. S and I atoms are arranged in a systematically distorted cubic eutaxy (close packing). Bi atoms have monocapped trigonal prismatic coordinations, while Cu atoms occupy coordination sites which vary from trigonal planar to distorted tetrahedral. A prominent feature is the distribution of Cu atoms over many closely spaced sites in the structure, the majority of them being only partly occupied, which strengthens the case for mobile Cu atoms during crystal growth at elevated temperatures. In this respect, Cu(3)Bi(2)S(3)I(3) represents an extreme example of a statistical distribution of Cu in the structure; a frequently observed property of this element in sulfosalts.
A new graphite-epoxy composite electrode (GECE) containing Bi(NO(3))(3) as a built-in bismuth precursor for simultaneous and individual anodic stripping analysis of heavy trace metals like lead and cadmium is reported. The developed Bi(NO(3))(3)-GECE is compatible with bismuth film electrodes reported previously including the composite electrodes (Bi-GECE) recently reported by our group. Bi(NO(3))(3)-GECE displays the ability for the detection of both individual and simultaneous determination of heavy trace metals and exhibits well defined, reproducible and sharp stripping signals. The sensitive response is combined with the minimal toxicity of Bi(NO(3))(3). This novel sensor would be an appropriate alternative tool to sensors using bismuth in solution during their utilization in environmental quality monitoring as well as other applications.