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Record W4390265404 · doi:10.1021/acs.inorgchem.3c03305

Selective Synthesis of Defect-Rich LaMnO<sub>3</sub> by Low-Temperature Anion Cometathesis

2023· article· en· W4390265404 on OpenAlex
Gia Thinh Tran, Allison Wustrow, Daniel O’Nolan, Songsheng Tao, Christopher J. Bartel, Tanjin He, Matthew J. McDermott, Brennan C. McBride, Karena W. Chapman, Simon J. L. Billinge, Kristin A. Persson, Gerbrand Ceder, James R. Neilson

Why this work is in the frame

A frame that forgets how it found something cannot be audited. These are the routes that admitted this work.

affAt least one author lists a Canadian institution in the pinned OpenAlex snapshot.

Bibliographic record

VenueInorganic Chemistry · 2023
Typearticle
Languageen
FieldMaterials Science
TopicElectronic and Structural Properties of Oxides
Canadian institutionsUniversité de Sherbrooke
FundersBasic Energy Sciences
KeywordsChemistryHalideMetathesisSalt metathesis reactionStoichiometryManganeseInorganic chemistryAlkali metalOxidation stateLanthanumCatalysisPhysical chemistryOrganic chemistry

Abstract

fetched live from OpenAlex

The synthesis of complex oxides at low temperatures brings forward aspects of chemistry not typically considered. This study focuses on perovskite LaMnO 3, which is of interest for its correlated electronic behavior tied to the oxidation state and thus the spin configuration of manganese. Traditional equilibrium synthesis of these materials typically requires synthesis reaction temperatures in excess of 1000 °C, followed by subsequent annealing steps at lower temperatures and different p (O 2 ) conditions to manipulate the oxygen content postsynthesis (e.g., LaMnO 3+ x ). Double-ion exchange (metathesis) reactions have recently been shown to react at much lower temperatures (500–800 °C), highlighting a fundamental knowledge gap for how solids react at lower temperatures. Here, we revisit the metathesis reaction, LiMnO 2 + LaOX, where X is a halide or mixture of halides, using in situ synchrotron X-ray diffraction. These experiments reveal low reaction onset temperatures (ca. 450–480 °C). The lowest reaction temperatures are achieved by a mixture of lanthanum oxyhalide precursors: 2 LiMnO 2 + LaOCl + LaOBr. In all cases, the resulting products are the expected alkali halide salt and defective La 1–ϵ Mn 1–ϵ O 3, where ϵ = x /(3 + x ). We observe a systematic variation in defect concentration, consistent with a rapid stoichiometric local equilibration of the precursors and the subsequent global thermodynamic equilibration with O 2 (g), as revealed by computational thermodynamics. Together, these results reveal how the inclusion of additional elements (e.g., Li and a halide) leads to the local equilibrium, particularly at low reaction temperatures for solid-state chemistry.

Fetched live from OpenAlex and de-inverted. Abstracts are not stored in this database: the inverted indexes are 8.6 GB of the frame’s 9.3 GB of text, and the host has 13 GB free.

Full frame distilled prediction

Teacher imitation

Not calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.

metaresearch head score (Codex)0.000
metaresearch head score (Gemma)0.000
Version: codex-gemma-dda1882f352aValidation status: machine_predicted_unvalidated
Candidate categoriesnone
Consensus categoriesnone
DomainCandidate signal: none · Consensus signal: none
Study designCandidate signal: Bench or experimental · Consensus signal: Bench or experimental
GenreCandidate signal: Empirical · Consensus signal: Empirical
Teacher disagreement score0.003
Threshold uncertainty score0.865

Codex and Gemma teacher scores by category

CategoryCodexGemma
Metaresearch0.0000.000
Meta-epidemiology (narrow)0.0000.000
Meta-epidemiology (broad)0.0000.000
Bibliometrics0.0000.001
Science and technology studies0.0000.000
Scholarly communication0.0000.000
Open science0.0000.000
Research integrity0.0000.000
Insufficient payload (model declined to judge)0.0000.000

Machine scores (provisional)

The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.

Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.

Opus teacher head0.004
GPT teacher head0.190
Teacher spread0.185 · how far apart the two teachers sit on this one work
Validation statusscore_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from it