Discovery of a ternary pseudobrookite phase in the earth-abundant Ti–Zn–O system

Perry, Nicola H.; Stevanovic, Vladan; Lim, Linda Y.; Mason, Thomas O.

doi:10.1039/c5dt04145g

Title: Discovery of a ternary pseudobrookite phase in the earth-abundant Ti–Zn–O system

Journal Article · Mon Dec 14 00:00:00 EST 2015 · Dalton Transactions

DOI:https://doi.org/10.1039/c5dt04145g· OSTI ID:1238274

Perry, Nicola H. ^[1]; Stevanovic, Vladan ^[2]; Lim, Linda Y. ^[3]; Mason, Thomas O. ^[4]

Kyushu Univ., Fukuoka (Japan); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Colorado School of Mines, Golden, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Stanford Univ., CA (United States)
Northwestern Univ., Evanston, IL (United States)

In this work, we combine theory with experiment in searching for “missing”, stable materials within the Zn–Ti–O chemical system, leading to the discovery of a new pseudobrookite phase, ZnxTi_3–xO_5–δ. This ternary system was chosen for (1) technological relevance, (2) earth abundance, and (3) the fact that many compounds in this system are predicted from enthalpies of formation to be borderline stable, suggesting an important role of entropic contributions in their stabilization and making this chemical system a perfect test bed for exploring the limits of theoretical predictions. The initial set of exploratory experimental syntheses, via sintering in evacuated ampoules and quenching, resulted in a single phase ZnxTi_3–xO_5–δ composition with x ≈ 0.6 and an almost stoichiometric oxygen content, as evaluated by X-ray fluorescence, energy dispersive spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The theoretically calculated lowest energy crystal structure for the closest stoichiometric ZnTi₅O₁₀composition matched that measured experimentally by synchrotron X-ray diffraction (allowing for differences attributable to cation disorder). The measured broad optical absorption, n-type electrical conductivity, and stability in acidic media are comparable to those of other ternary pseudobrookites and Ti–O Magnéli phases, suggesting comparable applicability as a robust electrode or catalyst support in electrochemical devices or water remediation. However, the new phase decomposes upon heating in air as it oxidizes. The success of the present approach to identify a “missing material” in an earth-abundant and applications-rich system suggests that future efforts to experimentally realize and theoretically confirm missing materials in this and similar systems are warranted, both scientifically and technologically.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Ministry of Education, Culture, Sports, Science and Technology (MEXT); National Science Foundation (NSF)

Grant/Contract Number:: AC36-08GO28308; AC02-06CH11357; DMR-1121262

OSTI ID:: 1238274

Journal Information:: Dalton Transactions, Vol. 45, Issue 4; ISSN 1477-9226

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 6 works

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