12019-11-3Relevant articles and documents
Preparation and crystal structure of the copper silicon polyphosphide Cu4SiP8
Kaiser, Peter,Jeitschko, Wolfgang
, p. 53 - 56 (1996)
The new compound Cu4SiP8 was prepared by solid state reaction of the elemental components. It crystallizes with a new structure type, which was determined from single-crystal X-ray diffractometer data: I41/a, a = 1218.6(2)pm, c = 573.2(2) pm, Z = 8, R = 0.023 for 970 structure factors and 31 variable parameters. Tetrahedral SiP4 groups are linked via additional phosphorus atoms to a three-dimensionally infinite silicon phosphorus network, accommodating Cu2 pairs with octahedral phosphorus coordination as is known for the closely related structure of CuP2. Using oxidation numbers the compound may be rationalized by the formula (Cu+1)4Si+4(P0)4(P -2)4 in agreement with the Zintl-Klemm concept. Johann Ambrosius Barth 1996.
Solution-liquid-solid growth of ternary Cu-In-Se semiconductor nanowires from multiple- and single-source precursors
Wooten, Alfred J.,Werder, Donald J.,Williams, Darrick J.,Casson, Joanna L.,Hollingsworth, Jennifer A.
, p. 16177 - 16188 (2009)
Ternary CuInSe2 nanowires were synthesized for the first time by the solution-liquid-solid (SLS) mechanism. Here, both metal-organic multiple- and single-source molecular precursors were thermally decomposed in the presence of molten metal nano
Phosphorus-Rich Metal Phosphides: Direct and Tin Flux-Assisted Synthesis and Evaluation as Hydrogen Evolution Electrocatalysts
Coleman, Nathaniel,Lovander, Matthew D.,Leddy, Johna,Gillan, Edward G.
, p. 5013 - 5024 (2019)
Metal phosphides from the 3d period exhibit a range of structures and compositions. Many metal-rich phosphides and monophosphides function as heterogeneous electrocatalysts in the hydrogen evolution reaction. This paper describes the direct and tin flux-assisted synthesis of phosphorus-rich metal phosphides with MP2 or MP3 compositions. The facile synthesis of FeP2, CoP3, NiP2, and CuP2 is thermochemically driven by PCl3 formation from reactions of anhydrous metal halides and P4 vapor at 500 °C. Well-crystallized micrometer-sized particles result from these solvent-free reactions. A tin flux leads to more complete reactions at lower temperature for FeP2 and enables synthesis of a monoclinic polymorph of NiP2 rather than the kinetic cubic product formed by direct reaction. These crystalline metal phosphides are investigated as electrocatalyts for hydrogen evolution in acidic and buffered aqueous solutions. All phosphorus-rich products show very good stability in strongly acidic media. The catalytic activity for hydrogen evolution ordered by higher current at a fixed electrode geometric area and low onset potential is CoP3 > NiP2 (cubic and monoclinic) > FeP2CuP2. At high applied potentials, CuP2 undergoes surface reactions and roughening that improve its electrocatalytic activity. Correlations of the observed electrocatalytic activity with electrochemically active surface area, particle size, metallic versus semiconducting properties, and local metal coordination environment are noted for these phosphorus-rich 3d metal phosphides.
Thorium copper phosphides: More diverse metal-phosphorus and phosphorus-phosphorus interactions than U analogues
Jin, Geng Bang,Malliakas, Christos D.,Lin, Jian
, p. 12041 - 12052 (2017)
To explore the chemical analogy between thorium and heavier actinides in soft anionic environments, three new thorium phosphides (ThCuP2, β-ThCu2P2, and ThCu5P3) have been prepared through solid-state reactions using CuI as a reaction promoter. The structure of ThCuP2 can be described as a filled UTe2-type with both dimeric P24- and monomeric P3- anions, in which Th is coordinated by eight P atoms in a bicapped trigonal prismatic arrangement and Cu is tetrahedrally coordinated by four P atoms. β-ThCu2P2 contains only P3- anions and is isostructural with BaCu2S2. In this structure, Th is coordinated by seven P atoms in monocapped trigonal prismatic geometry and Cu is tetrahedrally coordinated by four P atoms. ThCu5P3 adopts the YCo5P3-type structure consisting of P3- anions. This structure contains Th atoms coordinated by six P atoms in a trigonal prismatic arrangement and Cu atoms that are either tetrahedrally coordinated by four P atoms or square pyramidally coordinated by five P atoms. Electric resistivity measurements and electronic structure calculations on β-ThCu2P2 indicate a metal. These new compounds may be charge-balanced and formulated as Th4+Cu+(P24-)1/2P3-, Th4+(Cu+)2(P3-)2, and Th4+(Cu+)5(P3-)3, respectively. The structural, bonding, and property relationships between these Th compounds and related actinide and rare-earth phases are discussed. Titled compounds display more diverse ion-ion interactions and different electronic structures from those in UCuP2 and UCu2P2 that were synthesized under similar experimental conditions, suggesting divergence of thorium-phosphide chemistry from uranium-phosphide chemistry.
