Identification of Barium Hydroxo-Hydroperoxostannate Precursor for Low-Temperature Formation of Perovskite Barium Stannate

Alexander G Medvedev; Alexey A Mikhaylov; Alexander I Shames; Andrey B Ilyukhin; Andrei V Churakov; Dmitry A Grishanov; Elena A Mel'nik; Tatiana A Tripol'skaya; Ovadia Lev; Petr V Prikhodchenko

doi:10.1021/acs.inorgchem.0c02993

Identification of Barium Hydroxo-Hydroperoxostannate Precursor for Low-Temperature Formation of Perovskite Barium Stannate

Inorg Chem. 2020 Dec 21;59(24):18358-18365. doi: 10.1021/acs.inorgchem.0c02993. Epub 2020 Dec 7.

Affiliations

¹ Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Prospekt 31, Moscow 119991, Russia.
² Department of Physics, Ben-Gurion University of the Negev, P.O. Box 653, Be'er-Sheva 8410501, Israel.
³ The Casali Center of Applied Chemistry, The Institute of Chemistry and The Harvey M. Krueger Family Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Edmond J. Safra Campus, Jerusalem 91904, Israel.
⁴ Singapore-HUJ Alliance for Research and Enterprise (SHARE), NEW-CREATE Phase II Campus for Research Excellence and Technological Enterprise (CREATE), Singapore 138602, Singapore.

PMID: 33285066
DOI: 10.1021/acs.inorgchem.0c02993

Abstract

A breakthrough "superoxide colloidal solution route" for low-temperature synthesis of barium and strontium stannate perovskites and their doped analogues was recently introduced. The synthesis starts from hydrogen peroxide-rich stannate solutions and yields a so-called "crystalline superoxide molecular cluster" that is converted by low temperature (<300 °C) to the respective perovskites. In this paper, the so-called "crystalline superoxide molecular cluster" is identified as a superoxide-free, barium trihydroxo(hydroperoxo)peroxostannate, BaSn(OH)₃(OOH)(OO) phase (BHHPS). EPR and Raman spectroscopy studies reveal the absence of superoxide in this crystalline phase. FTIR of the deuterated sample, ¹¹⁹Sn NMR, and elemental analysis uncovered the empirical formula, H₄O₇SnBa with two peroxides per each tin element. Rietveld refinement of the XRD confirms the BHHPS cubic phase with replacement of the perovskite oxygen atoms by the OH- and OOH-ligands and peroxobridging groups.