Abstract
Li1 + xHf2–xInx(PO4)3 (x = 0, 0.05, 0.1) materials have been prepared by solid-state reactions and characterized by X-ray diffraction, low-temperature nitrogen adsorption measurements, and scanning electron microscopy. The materials consist of NASICON-type lithium hafnium double phosphates with a hexagonal structure. Milling in a planetary mill has been found to increase the specific surface area of the Li1 + xHf2–xInx(PO4)3 materials by almost one order of magnitude (from 1.5 to 13 m2/g in the case of LiHf2(PO4)3). The materials with a larger surface area exhibit catalytic activity for ethanol dehydration reactions and are less active for ethanol dehydrogenation. Ethanol conversion predominantly yields diethyl ether at low temperatures and ethylene at higher temperatures. The diethyl ether selectivity of the catalytic processes reaches 85% at 350°C, with 60% conversion, and the ethylene selectivity reaches 96% at 510°C, with 100% conversion. Indium doping raises the high-temperature acetaldehyde selectivity from 4 to 8% and leads to the formation of C4 hydrocarbons as reaction products. C4 selectivity reaches 15 and 17% in the case of the Li1.05Hf1.95In0.05(PO4)3 and Li1.1Hf1.9In0.1(PO4)3 materials, respectively (420°C, 97 and 92% conversion, respectively).
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Yaroslavtsev, A.B. and Stenina, I.A., Complex phosphates with the NASICON structure (MxA2(PO4)3), Russ. J. Inorg. Chem., 2006, vol. 51, pp. S97–S116.
Pet’kov, V.I., Mixed phosphates of metal cations in the oxidation states I and IV, Russ. Chem. Rev., 2012, vol. 81, no. 7, pp. 606–637.
Anantharamulu, N., Rao, K.K., Rambabu, G., Kumar, B.V., Radha, V., and Vithal, M., A wide-ranging review on Nasicon type materials, J. Mater. Sci., 2011, vol. 46, no. 9, pp. 2821–2837.
Jian, Z., Hu, Y.-S., Ji, X., and Chen, W., NASICONstructured materials for energy storage, Adv. Mater., 2017, vol. 29, no. 20, paper 1 601 925.
Goodenough, J.B., Hong, H.Y.-P., and Kafalas, J.A., Fast Na+-ion transport in skeleton structures, Mater. Res. Bull., 1976, vol. 11, pp. 203–220.
Noguchi, Y., Kobayashi, E., Plashnitsa, L.S., Okada, Sh., and Yamaki, J., Fabrication and performances of all solid-state symmetric sodium battery based on NASICON-related compounds, Electrochim. Acta, 2013, vol. 101, pp. 59–65.
Naqash, S., Ma, Q., Tietz, F., and Guillon, O., Na3Zr2(SiO4)2(PO4) prepared by a solution-assisted solid state reaction, Solid State Ionics, 2017, vol. 302, pp. 83–91.
Safronov, D.V., Stenina, I.A., Maksimychev, A.V., Shestakov, S.L., and Yaroslavtsev, A.B., Phase transitions and ion transport in NASICON materials of composition Li1 + xZr2–xInx(PO4)3 (x = 0–1), Russ. J. Inorg. Chem., 2009, vol. 54, no. 11, pp. 1697–1703.
Knauth, Ph., Inorganic solid Li ion conductors: an overview, Solid State Ionics, 2009, vol. 180, pp. 911–916.
Svitan’ko, A.I., Novikova, S.A., Safronov, D.V., and Yaroslavtsev, A.B., Cation mobility in Li1 + xTi2–x-Crx(PO4)3 NASICON-type phosphates, Inorg. Mater., 2011, vol. 47, no. 12, pp. 1391–1395.
Kotobuki, M. and Koishi, M., Sol–gel synthesis of Li1.5Al0.5Ge1.5(PO4)3 solid electrolyte, Ceram. Int., 2015, vol. 41, pp. 8562–8567.
Moshareva, M.A. and Novikova, S.A., Synthesis and conductivity study of solid electrolytes Li1+ xAlxGe2–x(PO4)3 (x = 0–0.65), Russ. J. Inorg. Chem., 2018, vol. 63, no. 3, pp. 319–323.
Voropaeva, D.Yu., Moshareva, M.A., Ilin, A.B., Novikova, S.A., and Yaroslavtsev, A.B., Phase transitions and proton conductivity in hafnium hydrogen phosphate with the NASICON structure, Mendeleev Commun., 2016, vol. 26, pp. 152–153.
Moshareva, M.A., Novikova, S.A., and Yaroslavtsev, A.B., Synthesis and ionic conductivity of (NH4)1–xHx-Hf2(PO4)3 (x = 0–1) NASICON-type materials, Inorg. Mater., 2016, vol. 52, no. 12, pp. 1283–1290.
Stenina, I.A. and Yaroslavtsev, A.B., Low-and intermediate-temperature proton-conducting electrolytes, Inorg. Mater., 2017, vol. 53, no. 3, pp. 253–262.
Chekannikov, A., Kapaev, R., Novikova, S., Tabachkova, N., Kulova, T., Skundin, A., and Yaroslavtsev, A., Na3V2(PO4)3/C/Ag nanocomposite materials for Naion batteries obtained by the modified Pechini method, J. Solid State Electrochem., 2017, vol. 21, no. 6, pp. 1615–1624.
Hirose, N. and Kuwano, J., Ion-exchange properties of NASICON-type phosphates with the frameworks [Ti2(PO4)3] and [Ti1.7Al0.3(PO4)3], J. Mater. Chem., 1994, vol. 4, pp. 9–12.
Agaskar, P., Grasselli, R., Buttrey, D., and White, B., Structural and catalytic aspects of some NASICONbased mixed metal phosphates, Stud. Surf. Sci. Catal., 1997, vol. 110, pp. 219–225.
Orlova, A.I., Pet’kov, V.L., Gul’yanova, S.T., Ermilova, M.M., Ienealem, S.L., Samuilova, O.K., Chekhlova, T.K., and Gryaznov, V.M., The catalytic properties of new complex zirconium and iron orthophosphates, Russ. J. Phys. Chem. A, 1999, vol. 73, no. 11, pp. 1767–1769.
Brik, Y., Kacimi, M., Bozon-Verduraz, F., and Ziyad, M., Characterization of active sites on AgHf2(PO4)3 in butan-2-ol conversion, Microporous Mesoporous Mater., 2001, vol. 43, pp. 103–112.
Il’in, A.B., Novikova, S.A., Sukhanov, M.V., Ermilova, M.M., Orekhova, N.V., and Yaroslavtsev, A.B., Catalytic activity of NASICON-type phosphates for ethanol dehydration and dehydrogenation, Inorg. Mater., 2012, vol. 48, no. 4, pp. 397–401.
Ermilova, M.M., Sukhanov, M.V., Borisov, R.S., Orekhova, N.V., Pet’kov, V.I., Novikova, S.A., Il’in, A.B., and Yaroslavtsev, A.B., Synthesis of the new framework phosphates and their catalytic activity in ethanol conversion into hydrocarbons, Catal. Today, 2012, vol. 193, pp. 37–41.
Pylinina, A.I. and Mikhalenko, I.I., Influence of compensator ions in the anionic part of Na3ZrM(PO4)3 phosphate with M = Zn, Co, Cu on the acidity and catalytic activity in reactions of butanol-2, Russ. J. Phys. Chem. A, 2013, vol. 87, no. 3, pp. 372–375.
Asabina, E.A., Pet’kov, V.I., Glukhova, I.O., Orekhova, N.V., Ermilova, M.M., Zhilyaeva, N.A., and Yaroslavtsev, A.B., Synthesis and catalytic properties of M0.5(1 + x)FexTi2–x(PO4)3 (M = Co, Ni, Cu; 0 ≤ x ≤ 2) for methanol conversion reactions, Inorg. Mater., 2015, vol. 51, no. 8, pp. 793–793.
Danilova, M.N., Pylinina, A.I., Kasatkin, E.M., Bratchikova, I.G., Mikhalenko, I.I., and Yagodovskii, V.D., Reactions of isobutanol over a NASICON-type Ni containing catalyst activated by plasma treatments, Kinet. Catal., 2015, vol. 56, no. 4, pp. 476–479.
Bondarenko, G.N., Ermilova, M.M., Efimov, M.N., Zemtsov, L.M., Karpacheva, G.P., Mironova, E.Yu., Orekhova, N.V., Rodionov, A.S., and Yaroslavtsev, A.B., In situ IR spectroscopy study of ethanol steam reforming in the presence of Pt–Ru/DND nanocatalysts, Nanotechnol. Russ., 2016, vol. 11, nos. 11–12, pp. 727–737.
Il’in, A.B., Ermilova, M.M., Orekhova, N.V., and Yaroslavtsev, A.B., Synthesis of framework lithium zirconium molybdate phosphates and their catalytic properties in ethanol conversion reactions, Inorg. Mater., 2015, vol. 51, no. 7, pp. 711–717.
Lytkina, A.A., Ilin, A.B., and Yaroslavtsev, A.B., Study of methanol steam reforming and ethanol conversion in conventional and membrane reactors, Petrol. Chem., 2016, vol. 56, no. 11, pp. 1048–1055.
Ilin, A.B., Orekhova, N.V., Ermilova, M.M., and Yaroslavtsev, A.B., Catalytic activity of LiZr2(PO4)3 Nasicon-type phosphates in ethanol conversion process in conventional and membrane reactors, Catal. Today, 2016, vol. 268, pp. 29–36.
Mitran, G., Mieritz, D.G., and Seo, D., Highly selective solid acid catalyst H1–xTi2(PO4)3–x(SO4)x for non-oxidative dehydrogenation of methanol and ethanol, Catalysts, 2017, vol. 7, pp. 95–98.
Serghini, A., Brochu, R., Ziyad, M., and Vedrine, J.C., Behaviour of copper–zirconium Nasicon-type phosphate, CuIZr 2(PO4)3, in the decomposition of isopropyl alcohol, J. Chem. Soc., Faraday Trans., 1991, vol. 87, no. 15, pp. 2487–2493.
Serghini, A., Brochu, R., Ziyad, M., and Vedrine, J.C., Synthesis, characterization and catalytic behaviour of Cu0.5M2(PO4)3 (M = Zr, Sn, Ti), J. Alloys Compd., 1992, vol. 188, pp. 60–64.
Brik, Y., Kacimi, M., Bozon-Verduraz, F., and Ziyad, M., Characterization of active sites on AgHf2(PO4)3 in butan-2-ol conversion, Microporous Mesoporous Mater., 2001, vol. 43, pp. 103–112.
Sukhanov, M.V., Ermilova, M.M., Orekhova, N.V., Pet’kov, V.I., and Tereshchenko, G.F., Catalytic properties of zirconium phosphate and double phosphates of zirconium and alkali metals with a NaZr2(PO4)3 structure, Russ. J. Appl. Chem., 2006, vol. 79, no. 4, pp. 614–618.
Pet’kov, V.I., Sukhanov, M.V., Ermilova, M.M., Orekhova, N.V., and Tereshchenko, G.F., Development and synthesis of bulk and membrane catalysts based on framework phosphates and molybdates, Russ. J. Appl. Chem., 2010, vol. 83, no. 10, pp. 1731–1741.
Moshareva, M.A., Il’in, A.B., Zhilyaeva, N.A., Novikova, S.A., and Yaroslavtsev, A.B., Catalytic activity of materials based on complex hafnium phosphates with the NASICON structure in ethanol conversion, Nanotechnol. Russ., 2017, vol. 12, nos. 9–10, pp. 514–519.
Zonetti, P.C., Celnik, J., Letichevsky, S., Gaspar, A.B., and Appel, L.G., Chemicals from ethanol—the dehydrogenative route of the ethyl acetate one-pot synthesis, J. Mol. Catal. A: Chem., 2011, vol. 334, pp. 29–34.
Sun, J. and Wang, Y., Recent advances in catalytic conversion of ethanol to chemicals, ACS Catal., 2014, vol. 4, pp. 1078–1090.
Matsumura, Y., Hashimoto, K., and Yoshida, S., Selective dehydrogenation of ethanol to acetaldehyde over silicalite-1, J. Catal., 1990, vol. 122, pp. 352–361.
Takei, T., Iguchi, N., and Haruta, M., Support effect in the gas phase oxidation of ethanol over nanoparticulate gold catalysts, New J. Chem., 2011, vol. 35, pp. 2227–2233.
Liu, P., Zhu, X., Yang, S., Li, T., and Hensen, E.J.M., On the metal–support synergy for selective gas-phase ethanol oxidation over MgCuCr2O4 supported metal nanoparticle catalysts, J. Catal., 2015, vol. 331, pp. 138–146.
Santacesaria, E., Carotenuto, G., Tesser, R., and Di Serio, M., Ethanol dehydrogenation to ethyl acetate by using copper and copper chromite catalysts, Eng. J., 2012, vol. 179, pp. 209–220.
Nikolaev, S.A., Chudakova, M.V., Chistyakov, A.V., Kriventsov, V.V., and Tsodikov, M.V., Reductive dehydration of ethanol to hydrocarbons on Ni-and Au-containing nanocomposites, Nanotechnol. Russ., 2012, vol. 7, nos. 7–8, pp. 327–338.
Mironova, E.Yu., Ermilova, M.M., Orekhova, N.V., Muraviev, D.N., and Yaroslavtsev, A.B., Production of high purity hydrogen by ethanol steam reforming in membrane reactor, Catal. Today, 2014, vol. 236, pp. 64–69.
Lytkina, A.A., Zhilyaeva, N.A., Ermilova, M.M., and Yaroslavtsev, A.B., Influence of the support structure and composition of Ni–Cu-based catalysts on hydrogen production by methanol steam reforming, Int. J. Hydrogen Energy, 2015, vol. 40, no. 31, pp. 9677–9684.
Shannon, R.D., Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr., Sect. A: Cryst. Phys., Diffr., Theor. Gen. Crystallogr., 1976, vol. 32, no. 5, pp. 751–767.
Boldyrev, V.V., Mechanochemistry and mechanical activation of solids, Russ. Chem. Rev., 2006, vol. 75, pp. 177–189.
Maier, J., Defect chemistry and ion transport in nanostructured materials: Part II. Aspects of nanoionics, Solid State Ionics, 2003, vol. 157, pp. 327–334.
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Original Russian Text © S.A. Novikova, A.B. Il’in, N.A. Zhilyaeva, A.B. Yaroslavtsev, 2018, published in Neorganicheskie Materialy, 2018, Vol. 54, No. 7, pp. 713–720.
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Novikova, S.A., Il’in, A.B., Zhilyaeva, N.A. et al. Catalytic Activity of Li1 + xHf2–xInx(PO4)3-Based NASICON-Type Materials for Ethanol Conversion Reactions. Inorg Mater 54, 676–682 (2018). https://doi.org/10.1134/S0020168518070117
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DOI: https://doi.org/10.1134/S0020168518070117