Abstract
Hydrothermal syntheses of alkali-metal blue molybdenum bronze nanoribbons, which are expected to exhibit unique properties induced by a combined effect of extrinsic and intrinsic low-dimensionalities, from hydrated-alkali-metal molybdenum bronzes were investigated. Nanoribbons grown along the quasi-one-dimensional (1D) conductive direction of Cs0.3MoO3, which is difficult to prepare by the conventional methods, were first synthesized. The nanomorphology formation is achieved by a solid-state conversion (or crystallite splitting) and subsequent crystallite growth, and the structural changes of the starting material related to the conversion were first observed by powder X-ray diffraction and scanning transmission electron microscopy as a result of finely tuned reaction system and preparation conditions. The structural changes were analyzed by model simulations and were attributed to the structural modulations that were concerned with the intralayer packing disorder and with two-dimensional long-range ordered structure, formed in MoO3 sheets of the hydrated molybdenum bronze. Moreover, the modulations were related to displacement defects of the Mo-O framework units generated along the [100] direction in the hydrated molybdenum bronze. Then, it was suggested that the solid-state conversion into blue molybdenum bronze and the crystallite splitting to nanomorphology were initiated by the breaking of the Mo-O-Mo bonds at the defects.
Similar content being viewed by others
References
Borodin DV, Zaitsev-Zotov SV, Nad FY (1987) Coherence of a charge density wave and phase slip in small samples of a quasi-one-dimensional conductor TaS3. J Exp Theor Phys 66:793–802
Chin K, Eda K, Sotani N, Whittingham MS (2002) Hydrothermal synthesis of the blue potassium molybdenum bronze, K0.28MoO3. J Solid State Chem 164(1):81–87. https://doi.org/10.1006/jssc.2001.9450
Choain C, Marion F (1963) Dosage des oxydes de tungstene et de molybdene. Bull Soc Chim Fr 1963:212
Collins BT, Ramanujachary KV, Greenblatt M (1988) Preparation and transport properties of the substituted blue bronze (Rb1-xCs x )0.3MoO3. J Solid State Chem 77(2):348–355. https://doi.org/10.1016/0022-4596(88)90258-7
Dumas J, Schlenker C, Marcus J, Buder R (1983) Nonlinear conductivity and noise in the quasi one-dimensional blue bronze K0.30MoO3. Phys Rev Lett 50(10):757–760. https://doi.org/10.1103/PhysRevLett.50.757
Eda K, Miyazaki T, Hatayama F, Nakagawa M, Sotani N (1998) Cesium-sodium ion exchange on hydrated molybdenum bronze and formation of new cesium molybdenum bronze by a low-temperature synthesis route. J Solid State Chem 137(1):12–18. https://doi.org/10.1006/jssc.1997.7642
Eda K, Kunotani F, Uchiyama N (2005a) Low-temperature synthetic route based on the amorphous nature of giant species for preparation of lower valence oxides. J Solid State Chem 178(5):1471–1477. https://doi.org/10.1016/j.jssc.2005.02.020
Eda K, Chin K, Sotani N, Whittingham MS (2005b) Hydrothermal synthesis of potassium molybdenum oxide bronzes: structure-inheriting solid-state route to blue bronze and dissolution/deposition route to red bronze. J Solid State Chem 178(1):158–165. https://doi.org/10.1016/j.jssc.2004.10.043
Fleming RM, Schneemeyer LF (1983) Transient electrical response of K0.30MoO3. Phys Rev B 28(12):6996–6999. https://doi.org/10.1103/PhysRevB.28.6996
Graham J, Wadsley AD (1966) The crystal structure of the blue potassium molybdenum bronze, K0.28MoO3. Acta Crystallogr 20(1):93–100. https://doi.org/10.1107/S0365110X66000173
Grüner G (1994) Density waves in solids. Addison-Wesley, New York
Hosono E, Kudo T, Honma I, Matsuda H, Zhou H (2009) Synthesis of single crystalline spinel LiMn2O4 nanowires for a lithium ion battery with high power density. Nano Lett 9(3):1045–1051. https://doi.org/10.1021/nl803394v
Konno TJ, Uehara M, Hirosawa S, Sumiyama K, Suzuki K (1999) Electron diffraction study on the long-range-ordered metastable Fe-Nd-B phase. Philosophical Magazine A 79(10):2413–2436. https://doi.org/10.1080/01418619908214292
Lupan O, Cretu V, Deng M, Gedamu D, Paulowicz I, Kaps S, Mishra YK, Polonskyi O, Zamponi C, Kienle L, Trofim V, Tiginyanu I, Adelung R (2014) Versatile growth of freestanding orthorhombic α-molybdenum trioxide nano- and microstructures by rapid thermal processing for gas nanosensors. J Phys Chem C 118(27):15068–15078. https://doi.org/10.1021/jp5038415
Mumme WG, Watts JA (1970) The crystal structure of the molybdenum bronze Cs x MoO3 (x ≈ 0.25). J Solid State Chem 2(1):16–23. https://doi.org/10.1016/0022-4596(70)90026-5
Nam KT, Kim D-W, Yoo PJ, Chiang C-Y, Meethong N, Hammond PT, Chiang Y-M, Belcher AM (2006) Virus-enabled synthesis and assembly of nanowires for lithium ion battery electrodes. Science 312(5775):885–888. https://doi.org/10.1126/science.1122716
Nishida T, Eda K, Takahashi K, Sakurai T, Ohta H, Whittingham MS (2013) Preparation of nanoribbons of blue potassium molybdenum bronze. Chem Lett 42(12):1514–1516. https://doi.org/10.1246/cl.130792
Ogawa N, Shiraga A, Kondo R, Kagoshima S, Miyano K (2001) Photocontrol of dynamic phase transition in the charge-density wave material K0.3MoO3. Phys Rev Lett 87(25):256401. https://doi.org/10.1103/PhysRevLett.87.256401
Reid AF, Watts JA (1970) Single crystal syntheses by the electrolyses of molten titanates, molybdates and vanadates. J Solid State Chem 1(3-4):310–318. https://doi.org/10.1016/0022-4596(70)90110-6
Slot E, van der Zant HSJ, Thorne RE (2001) Electric-field distribution near current contacts of anisotropic materials. Phys Rev B 65(3):033403. https://doi.org/10.1103/PhysRevB.65.033403
Slot E, Holst MA, van der Zant HSJ, Zaitsev-Zotov SV (2004) One-dimensional conduction in charge-density-wave nanowires. Phys Rev Lett 93(17):176602. https://doi.org/10.1103/PhysRevLett.93.176602
Slot E (2005) Microscopic charge density wave transport. Ph.D. thesis, Leiden University
Sotani N, Suzuki T, Eda K, Yanagi-ishi M, Takagi S, Hatayama F (1997) Preparation of hydrated potassium molybdenum bronzes and their thermal decomposition. J Solid State Chem 132(2):330–336. https://doi.org/10.1006/jssc.1997.7469
Thomas DM, McCarron EM III (1986) The composition and proposed structure of the alkali metal layered molybdenum bronzes. Mater Res Bull 21(8):945–960. https://doi.org/10.1016/0025-5408(86)90132-7
van der Zant HSJ, Slot E, Zaitsev-Zotov SV, Artemenko SN (2001) Negative resistance and local charge-density-wave dynamics. Phys Rev Lett 87(12):126401. https://doi.org/10.1103/PhysRevLett.87.126401
Watanabe D, Ogawa S (1956) On the superstructure of the ordered alloy Cu3Pd I. electron diffraction study. J Phys Soc Jpn 11(3):226–239. https://doi.org/10.1143/JPSJ.11.226
Zaitsev-Zotov SV (2003) Transport properties of TaS3 and NbSe3 crystals of nanometer-scale transverse dimensions. Microelectron Eng 69(2-4):549–554. https://doi.org/10.1016/S0167-9317(03)00345-9
Funding
This work was supported by the Grant-in-Aid for Scientific Research (C) No. 23550226 and No. 26410073 of the Ministry of Education, Culture, Sports, Science and Technology of Japan.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Electronic supplementary material
ESM 1
(PDF 1323 kb)
Rights and permissions
About this article
Cite this article
Nishida, T., Eda, K. Hydrothermal preparation of blue molybdenum bronze nanoribbons: structural changes in mother crystals, related to solid-state conversion and crystallite splitting to nanomorphology. J Nanopart Res 20, 27 (2018). https://doi.org/10.1007/s11051-018-4134-5
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11051-018-4134-5