Two new sodium zinc antimonides NaZn4Sb3 and HT-Na1-xZn4-ySb3 were synthesized by using reactive sodium hydride, NaH, as a precursor. The hydride route provides uniform mixing and comprehensive control over the composition, facilitating fast reactions and high-purity samples, whereas traditional synthesis using sodium metal results in inhomogeneous samples with a significant fraction of the more stable NaZnSb compound. NaZn4Sb3 crystalizes in the hexagonal P63/mmc space group (No. 194, Z = 2, a = 4.43579(4) Å, c = 23.41553(9) Å), and is stable upon heating in vacuum up to 736 K. The layered crystal structure of NaZn4Sb3 is related to the structure of the well-studied thermoelectric antimonides AeZn2Sb2 (Ae = Ca, Sr, Eu). Upon heating in vacuum NaZn4Sb3 transforms to HT-Na1-xZn4-ySb3 (x = 0.047(3), y = 0.135(1)) due to partial Na/Zn evaporation/elimination, as was determined from hightemperature in-situ synchrotron powder X-ray diffraction. HT-Na1-xZn4-ySb3 has a complex monoclinic structure with considerable degrees of structural disorder (P21/c (No. 14, Z = 32), a = 19.5366(7) Å, b = 14.7410(5) Å, c = 20.7808(7) Å, β = 90.317(2)°) and is stable exclusively in a narrow temperature range of 736 − 885 K. Further heating of HT-Na1-xZn4-ySb3 leads to a reversible transformation to NaZnSb above 883 K. Both compounds exhibit similarly low thermal conductivity at room temperature (0.9 W•m −1 K −1 ) and positive Seebeck coefficients (38-52 µV/K) indicative of holes as the main charge carriers. However, resistivities of the two phases differ by two orders of magnitude.Here, we have explored the ternary Na-Zn-Sb system and discovered two new compositionally similar, but structurally different ternary antimonides, both are featuring new structure types. Using the fast hydride route coupled with in-situ high-temperature powder X-ray diffraction experiments, compositional and temperature screening allowed for synthesis of two new ternary phases: NaZn4Sb3 phase and what at first appeared to be its polymorph, but in fact it is a different compound with slightly Na/Zn depleted composition HT-Na1-xZn4-ySb3, stable in narrow temperature range. The hydride route yields single phase samples of both antimonides, allowing for the experimental access to their transport properties. The crystal structures, synthesis, structural transformations, and transport properties of the NaZn4Sb3 and HT-Na1-xZn4-ySb3 are discussed herein.
Ternary metal oxides M2V2O7−δ (M = Zn and Cu) were synthesized by dissolving binary metal oxide precursors in an environmentally benign deep eutectic solvent (DES), which is a eutectic mixture of a hydrogen bond donor and acceptor, followed by annealing in an open crucible.
A layered Zintl antimonide NaZnSb (PbClF or Cu2Sb structure type; P4/nmm) was synthesized using the reactive sodium hydride NaH precursor. This method provides comprehensive compositional control and facilitates the fast preparation of high-purity samples in large quantities. NaZnSb is highly reactive to humidity/air and hydrolyzes to NaOH, ZnO, and Sb in aerobic conditions. On the other hand, NaZnSb is thermally stable up to 873 K in vacuum, as no structural changes were observed from high-temperature synchrotron powder X-ray diffraction data in the 300–873 K temperature range. The unit cell expansion upon heating is isotropic; however, interatomic distance elongation is not isotropic, consistent with the layered structure. Low- and high-temperature thermoelectric properties were measured on pellets densified by spark plasma sintering. The resistivity of NaZnSb ranges from 11 mΩ∙cm to 31 mΩ∙cm within the 2–676 K range, consistent with heavily doped semiconductor behavior, with a narrow band gap of 0.23 eV. NaZnSb has a large positive Seebeck coefficient (244 μV∙K−1 at 476 K), leading to the maximum of zT of 0.23 at 675 K. The measured thermoelectric properties are in good agreement with those predicted by theoretical calculations.
Metavanadates MV 2 O 6−δ (M = Zn and Cu) are synthesized by using a deep eutectic solvent (DES), a mixture of hydrogen bond donor and acceptor, as a reaction medium. Dissolution of stable binary metal oxides in a DES followed by a heat treatment yields phase-pure vanadates. According to in situ powder X-ray diffraction, ternary phases (α-Zn 2 V 2 O 7 and β-Cu 2−x V 2 O 7 , x ∼ 0.27) are intermediates in the reaction pathway taken. Identifying a polymorphic phase transformation temperature for CuV 2 O 6 as well as the narrow temperature range between formation and decomposition for both metavanadates allows for tackling the challenge of the synthesis of these materials. The oxygen vacancy introduced by the DES route is accompanied by the formation of reduced V 4+ and Cu + in the oxide matrix, based on X-ray photoelectron spectroscopy. These oxygen vacancies modify the vibrational modes in the corresponding Raman spectra and are also responsible for broad optical absorptions in the 1.8−1.1 eV range. The optical band gaps of the materials are found at 1.8 eV (CuV 2 O 6 ) and 2.2 eV (ZnV 2 O 6 ), approximately 0.1−0.3 eV below the values reported in the literature. The reduced band gaps and sub-band gap photon absorption are key features of the oxygendeficient metavanadates. Surface photovoltage spectroscopy reveals that all the synthesized vanadates are n-type materials with electrons as the majority charge carriers, and photoelectrochemical measurements confirm photoanodic currents for methanol oxidation. These results provide insight into the synthesis and structure−property relationship of the metavanadates for their potential use as photoanodes.
A precipitation method involving a deep eutectic solvent (DES)a mixture of hydrogen bond donor and acceptoris used to synthesize a ternary metal oxide. Without toxic reagents, precipitates consisting of Zn3(OH)2V2O7·nH2O and Zn5(OH)6(CO3)2 are obtained by simply introducing deionized H2O to the DES solution containing dissolved ZnO and V2O5. Manipulation of the synthetic conditions demonstrates high tunability in the size/morphology of the two-dimensional nanosheets precipitated during the dynamic equilibrium process. According to differential scanning calorimetry and high-temperature powder X-ray diffraction, Zn3V2O8 and ZnO obtained by the annealing of the precipitate are intermediates in the reaction pathway toward metastable Zn4V2O9. Intimate mixing of the metal precursors achieved by the precipitation method allows access to the metastable zinc-rich vanadate with unusually rapid heat treatment. The UV–vis and surface photovoltage spectra reveal the presence of sub-band gap states, stemming from the reduced vanadium (V4+) center. Photoelectrochemical measurements confirm weak photoanodic currents for water and methanol oxidation. For the first time, this work shows the synthesis of a metastable oxide with the DES-precipitation route and provides insight into the structure–property relationship of the zinc-rich vanadate.
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