Hostname: page-component-cd9895bd7-gbm5v Total loading time: 0 Render date: 2024-12-29T02:35:30.209Z Has data issue: false hasContentIssue false
  • English
  • Français

Facile preparation and formation mechanism of three low valent transition metal oxides in supercritical methanol

Published online by Cambridge University Press:  18 April 2016

Shuangming Li ,
Zhe Zhang ,
Shengnan Jiang ,
Xin Ge ,
Jie Zhang ,
Wenxiu Li  and
Sansan Yu
Shuangming Li
Affiliation:
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China; and Key Laboratory of Chemical Separation Technology of Liaoning Province, Shenyang University of Chemical Technology, Shenyang 110142, China
Zhe Zhang
Affiliation:
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
Shengnan Jiang
Affiliation:
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
Xin Ge
Affiliation:
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
Jie Zhang
Affiliation:
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
Wenxiu Li
Affiliation:
Key Laboratory of Chemical Separation Technology of Liaoning Province, Shenyang University of Chemical Technology, Shenyang 110142, China
Sansan Yu*
Affiliation:
College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China; and Key Laboratory of Chemical Separation Technology of Liaoning Province, Shenyang University of Chemical Technology, Shenyang 110142, China
*
a)Address all correspondence to this author. e-mail: [email protected]
Get access

Abstract

Three important low valent transition metal oxides were synthesized in supercritical methanol by using inorganic metal salts as precursors. X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, and x-ray photoelectron spectroscopy were applied to analyze the composition, structure, and morphology of the products. Results showed that Cu2O, MoO2, and V2O3 were obtained successfully under a supercritical condition of 240 °C and 9.0 MPa. MoO2 and V2O3 displayed sphere-like morphology with average particle sizes of 20–40 and 20–50 nm, respectively. Cu2O particles displayed edge-truncated cubic morphology with a particle size of 2.5 μm. Formation mechanism proposed that high valent metal oxides (CuO, MoO3, and V2O5) were formed firstly in supercritical methanol by the decomposing of precursors and then reduced to target products by free hydroxyl anions. In addition, methanol performed important roles not only as a reaction medium but also as a reducing agent under supercritical fluid conditions.

Keywords

low valent transition metal oxidesinorganic precursorssupercritical alcoholspreparationformation mechanism
Type
Articles
Information
Journal of Materials Research , Volume 31 , Issue 10 , 28 May 2016 , pp. 1440 - 1447
Copyright
Copyright © Materials Research Society 2016 

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

Kuo, C.H. and Huang, M.H.: Morphologically controlled synthesis of Cu2O nanocrystals and their properties. Nano Today 5, 106–116 (2010).CrossRefGoogle Scholar
Hu, H., Xu, J., Deng, C., and Ge, X.: Easily controllable synthesis of alpha-MoO3 nanobelts and MoO2 microaxletrees through one-pot hydrothermal route. J. Nanosci. Nanotechnol. 14, 4462–4468 (2014).CrossRefGoogle ScholarPubMed
Santulli, A.C., Xu, W., Parise, J.B., Wu, L., Aronson, M.C., Zhang, F., Nam, C.Y., Black, C.T., Tiano, A.L., and Wong, S.S.: Synthesis and characterization of V2O3 nanorods. Phys. Chem. Chem. Phys. 11, 3718–3726 (2009).CrossRefGoogle ScholarPubMed
Zhao, Y., Wang, W., Li, Y., Zhang, Y., Yan, Z., and Huo, Z.: Hierarchical branched Cu2O nanowires with enhanced photocatalytic activity and stability for H2 production. Nanoscale 6, 195–198 (2014).CrossRefGoogle ScholarPubMed
Koo, B., Xiong, H., Slater, M.D., Prakapenka, V.B., Balasubramanian, M., Podsiadlo, P., Johnson, C.S., Rajh, T., and Shevchenko, E.V.: Hollow iron oxide nanoparticles for application in lithium ion batteries. Nano Lett. 12, 2429–2435 (2012).CrossRefGoogle ScholarPubMed
Guan, L., Pang, H., Wang, J., Lu, Q., Yin, J., and Gao, F.: Fabrication of novel comb-like Cu2O nanorod-based structures through an interface etching method and their application as ethanol sensors. Chem. Commun. 46, 7022–7024 (2010).CrossRefGoogle ScholarPubMed
Tsai, Y.H., Chanda, K., Chu, Y.T., Chiu, C.Y., and Huang, M.H.: Direct formation of small Cu2O nanocubes, octahedra, and octapods for efficient synthesis of triazoles. Nanoscale 6, 8704–8709 (2014).CrossRefGoogle ScholarPubMed
Wu, L., Jubert, P.O., Berman, D., Imaino, W., Nelson, A., Zhu, H., Zhang, S., and Sun, S.: Monolayer assembly of ferrimagnetic Co(x)Fe(3−x)O4 nanocubes for magnetic recording. Nano Lett. 14, 3395–3399 (2014).CrossRefGoogle Scholar
Xu, Y., Wang, H., Yu, Y., Tian, L., Zhao, W., and Zhang, B.: Cu2O Nanocrystals: Surfactant-free room-temperature morphology-modulated synthesis and shape-dependent heterogeneous organic catalytic activities. J. Phys. Chem. C 115, 15288–15296 (2011).CrossRefGoogle Scholar
Srivastava, R., Anu Prathap, M.U., and Kore, R.: Morphologically controlled synthesis of copper oxides and their catalytic applications in the synthesis of propargylamine and oxidative degradation of methylene blue. Colloids Surf., A 392, 271–282 (2011).CrossRefGoogle Scholar
Wu, H-Y., Hon, M-H., Kuan, C-Y., and Leu, I-C.: Preparation of TiO2 nanosheets by a hydrothermal process and their application as an anode for lithium-ion batteries. J. Electron. Mater. 43, 1048–1054 (2014).CrossRefGoogle Scholar
Wang, D.S., Xie, T., Peng, Q., Zhang, S.Y., Chen, J., and Li, Y.D.: Direct thermal decomposition of metal nitrates in octadecylamine to metal oxide nanocrystals. Chem.–Eur. J. 14, 2507–2513 (2008).CrossRefGoogle ScholarPubMed
Lenka Matějová, V.V., Fajgar, R., Matěj, Z., Holý, V., and Šolcová, O.: Reverse micelles directed synthesis of TiO2–CeO2 mixed oxides and investigation of their crystal structure and morphology. J. Solid State Chem. 198, 485–495 (2013).CrossRefGoogle Scholar
Susman, M.D., Feldman, Y., Vaskevich, A., and Rubinstein, I.: Chemical deposition of Cu2O nanocrystals with precise morphology control. ACS Nano 8, 162–174 (2014).CrossRefGoogle ScholarPubMed
Sikhwivhilu, L.M., Pillai, S.K., and Hillie, T.K.: Influence of citric acid on SnO2 nanoparticles synthesized by wet chemical processes. J. Nanosci. Nanotechnol. 11, 4988–4994 (2011).CrossRefGoogle ScholarPubMed
Wang, D. and Li, Y.: Controllable synthesis of Cu-based nanocrystals in ODA solvent. Chem. Commun. 47, 3604–3606 (2011).CrossRefGoogle ScholarPubMed
Cao, M., Hu, C., Wang, Y., Guo, Y., Guo, C., and Wang, E.: A controllable synthetic route to Cu, Cu2O, and CuO nanotubes and nanorods. Chem. Commun. 15, (2003) 1884–1885.CrossRefGoogle Scholar
Liang, X., Gao, L., Yang, S., and Sun, J.: Facile synthesis and shape evolution of single-crystal cuprous oxide. Adv. Mater. 21, 2068–2071 (2009).CrossRefGoogle Scholar
Giannousi, K., Sarafidis, G., Mourdikoudis, S., Pantazaki, A., and Dendrinou-Samara, C.: Selective synthesis of Cu2O and Cu/Cu2O NPs: Antifungal activity to yeast saccharomyces cerevisiae and DNA interaction. Inorg. Chem. 53, 9657–9666 (2014).CrossRefGoogle ScholarPubMed
Ramana, C.V., Utsunomiya, S., Ewing, R.C., and Becker, U.: Formation of V2O3 nanocrystals by thermal reduction of V2O5 thin films. Solid State Commun. 137, 645–649 (2006).CrossRefGoogle Scholar
Zheng, C., Zhang, X., He, S., Fu, Q., and Lei, D.: Preparation and characterization of spherical V2O3 nanopowder. J. Solid State Chem. 170, 221–226 (2003).CrossRefGoogle Scholar
Sediri, F. and Gharbi, N.: Hydrothermal synthesis and characterization of V2O3. Mater. Sci. Eng., B 123, 136–138 (2005).CrossRefGoogle Scholar
Zhang, K., Sun, X., Lou, G., Liu, X., Li, H., and Su, Z.: A new method for preparing V2O3 nanopowder. Mater. Lett. 59, 2729–2731 (2005).CrossRefGoogle Scholar
Shi, Y., Guo, B., Corr, S.A., Shi, Q., Hu, Y.S., Heier, K.R., Chen, L., Seshadri, R., and Stucky, G.D.: Ordered mesoporous metallic MoO2 materials with highly reversible lithium storage capacity. Nano Lett. 9, 4215–4220 (2009).CrossRefGoogle ScholarPubMed
Yang, L.C., Gao, Q.S., Tang, Y., Wu, Y.P., and Holze, R.: MoO2 synthesized by reduction of MoO3 with ethanol vapor as an anode material with good rate capability for the lithium ion battery. J. Power Sources 179, 357–360 (2008).CrossRefGoogle Scholar
Veriansyah, B., Kim, J-D., Min, B.K., and Kim, J.: Continuous synthesis of magnetite nanoparticles in supercritical methanol. Mater. Lett. 64, 2197–2200 (2010).CrossRefGoogle Scholar
Desmoulins-Krawiec, S., Aymonier, C., and Loppinet-Serani, A., Weill, F.o., Gorsse, S.p., Etourneau, J., and Cansell, F.o.: Synthesis of nanostructured materials in supercritical ammonia: Nitrides, metals and oxides. J. Mater. Chem. 14, 228 (2004).CrossRefGoogle Scholar
Shin, N.C., Lee, Y-H., Shin, Y.H., Kim, J., and Lee, Y-W.: Synthesis of cobalt nanoparticles in supercritical methanol. Mater. Chem. Phys. 124, 140–144 (2010).CrossRefGoogle Scholar
Cansell, F. and Aymonier, C.: Design of functional nanostructured materials using supercritical fluids. J. Supercrit. Fluids 47, 508–516 (2009).CrossRefGoogle Scholar
Chang, J-Y., Chang, J-J., Lo, B., Tzing, S-H., and Ling, Y-C.: Silver nanoparticles spontaneous organize into nanowires and nanobanners in supercritical water. Chem. Phys. Lett. 379, 261–267 (2003).CrossRefGoogle Scholar
Ziegler, K.J., Doty, R.C., Johnston, K.P., and Korgel, B.A.: Synthesis of organic monolayer-stabilized copper nanocrystals in supercritical water. J. Am. Chem. Soc. 123, 7797–7803 (2001).CrossRefGoogle ScholarPubMed
Sue, K., Suzuki, A., Suzuki, M., Arai, K., Hakuta, Y., Hayashi, H., and Hiaki, T.: One-Pot synthesis of nickel particles in supercritical water. Ind. Eng. Chem. Res. 45, 623–626 (2005).CrossRefGoogle Scholar
Marre, S., Cansell, F., and Aymonier, C.: Design at the nanometre scale of multifunctional materials using supercritical fluid chemical deposition. Nanotechnology 17, 4594–4599 (2006).CrossRefGoogle ScholarPubMed
Slostowski, C., Marre, S., Babot, O., Toupance, T., and Aymonier, C.: Near- and supercritical alcohols as solvents and surface modifiers for the continuous synthesis of cerium oxide nanoparticles. Langmuir 28, 16656–16663 (2012).CrossRefGoogle ScholarPubMed
Pascu, O., Marre, S., Aymonier, C., and Roig, A.: Ultrafast and continuous synthesis of crystalline ferrite nanoparticles in supercritical ethanol. Nanoscale 5, 2126–2132 (2013).CrossRefGoogle ScholarPubMed
Kim, J., Kim, D., Veriansyah, B., Won Kang, J., and Kim, J-D.: Metal nanoparticle synthesis using supercritical alcohol. Mater. Lett. 63, 1880–1882 (2009).CrossRefGoogle Scholar
Choi, H., Veriansyah, B., Kim, J., Kim, J-D., and Kang, J.W.: Continuous synthesis of metal nanoparticles in supercritical methanol. J. Supercrit. Fluids 52, 285–291 (2010).CrossRefGoogle Scholar
Veriansyah, B., Chun, M-S., and Kim, J.: Surface-modified cerium oxide nanoparticles synthesized continuously in supercritical methanol: Study of dispersion stability in ethylene glycol medium. Chem. Eng. J. 168, 1346–1351 (2011).CrossRefGoogle Scholar
Nugroho, A., Kim, S.J., Chang, W., Chung, K.Y., and Kim, J.: Facile synthesis of hierarchical mesoporous Li4Ti5O12 microspheres in supercritical methanol. J. Power Sources 244, 164–169 (2013).CrossRefGoogle Scholar
Liu, X., Zhang, Y., Yi, S., Huang, C., Liao, J., Li, H., Xiao, D., and Tao, H.: Preparation of V2O3 nanopowders by supercritical fluid reduction. J. Supercrit. Fluids 56, 194–200 (2011).CrossRefGoogle Scholar
Yu, S., Li, S., Ge, X., Niu, M., Zhang, H., Xu, C., and Li, W.: Influence of reducing atmosphere of subcritical/supercritical mild alcohols on the synthesis of copper powder. Ind. Eng. Chem. Res. 53, 2238–2243 (2014).CrossRefGoogle Scholar
Li, S., Ge, X., Jiang, S., Peng, X., Zhang, Z., Li, W., and Yu, S.: Synthesis of octahedral and cubic Cu2O microcrystals in sub- and super-critical methanol and their photocatalytic performance. J. Mater. Sci. 50, 4115–4121 (2015).CrossRefGoogle Scholar
Pessey, V., Garriga, R., Weill, F., Chevalier, B., Etourneau, J., and Cansell, F.: Control of particle growth by chemical transformation in supercritical CO2/ethanol mixtures. J. Mater. Chem. 12, 958–965 (2002).CrossRefGoogle Scholar
Selim, K.M.K., Lee, J-H., Kim, S-J., Xing, Z., Kang, I-K., Chang, Y., and Guo, H.: Surface modification of magnetites using maltotrionic acid and folic acid for molecular imaging. Macromol. Res. 14, 646–653 (2006).CrossRefGoogle Scholar
Selim, K.K., Xing, Z.C., Choi, M.J., Chang, Y., Guo, H., and Kang, I.K.: Reduced cytotoxicity of insulin-immobilized CdS quantum dots using PEG as a spacer. Nanoscale Res. Lett. 6, 528 (2011).CrossRefGoogle ScholarPubMed
Andanson, J-M., Bopp, P.A., and Soetens, J-C.: Relation between hydrogen bonding and intramolecular motions in liquid and supercritical methanol. J. Mol. Liq. 129, 101–107 (2006).CrossRefGoogle Scholar
Sawyer, D.T. and Roberts, J.L.: Hydroxide ion: An effective one-electron reducing agent? Acc. Chem. Res. 21, 469–476 (1988).CrossRefGoogle Scholar
Gardner, S.D., Singamsetty, C.S.K., Booth, G.L., He, G-R., and Pittman, C.U.: Surface characterization of carbon fibers using angle-resolved XPS and ISS. Carbon 33, 587–595 (1995).CrossRefGoogle Scholar
Chen, K. and Xue, D.: Crystallisation of cuprous oxide. Int. J. Nanotechnol. 10, 4–12 (2013).CrossRefGoogle Scholar
Wang, X., Jiao, S., Wu, D., Li, Q., Zhou, J., Jiang, K., and Xu, D.: A facile strategy for crystal engineering of Cu2O polyhedrons with high-index facets. CrystEngComm 15, 1849 (2013).CrossRefGoogle Scholar
Chan, G.H., Zhao, J., Hicks, E.M., Schatz, G.C., and Van Duyne, R.P.: Plasmonic properties of copper nanoparticles fabricated by nanosphere lithography. Nano Lett. 7, 1947–1952 (2007).CrossRefGoogle Scholar
Hu, B., Mai, L., Chen, W., and Yang, F.: From MoO3 nanobelts to MoO2 nanorods: Structure transformation and electrical transport. ACS Nano 3, 478–482 (2009).CrossRefGoogle ScholarPubMed
Weber, D., Stork, A., Nakhal, S., Wessel, C., Reimann, C., Hermes, W., Muller, A., Ressler, T., Pottgen, R., Bredow, T., Dronskowski, R., and Lerch, M.: Bixbyite-type V2O3—a metastable polymorph of vanadium sesquioxide. Inorg. Chem. 50, 6762–6766 (2011).CrossRefGoogle ScholarPubMed