Defect-induced anisotropic surface reactivity and ion transfer processes of anatase nanoparticles

Lee, M.-S.; Han, K. S.; Lee, J.; Shin, Y.; Kaspar, T. C.; Chen, Y.; Engelhard, M. H.; Mueller, K. T.; Murugesan, V.

doi:10.1016/j.mtchem.2020.100290

Title: Defect-induced anisotropic surface reactivity and ion transfer processes of anatase nanoparticles

Journal Article · 01 September 2020 · Materials Today Chemistry

DOI: https://doi.org/10.1016/j.mtchem.2020.100290 · OSTI ID:1631805

^[1]; Han, K. S. ^[2]; Lee, J. ^[1]; Shin, Y. ^[1]; Kaspar, T. C. ^[1]; Chen, Y. ^[2];

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Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Joint Center for Energy Storage Research, Lemont, IL (United States)

In this study, surface reactivity and ion transfer processes of anatase TiO₂ nanocrystals were studied using Lithium bis(trifluoromethylsulfone)imide (LITFSI) as a probing molecule. The HRTEM analysis of synthesized anatase TiO₂ reveals aggregated nanoparticles (average size ~8nm) with significant defects (holes and cracks). With the introduction of LiTFSI salt, the Li propensity towards defective surface along the anatase (100) plane is evident in XRD and HRTEM analysis. Ab initio molecular dynamics (AIMD) analysis corroborates the site-preferential interaction of Li⁺ cations with oxygen vacancies and the thermodynamically favourable transport through the (100) step edge plane. Using ⁷Li NMR chemical shift and relaxometry measurements, the Li⁺ cation near the TiO₂ interface and the bulk LiTFSI phase were speciated, and subsequent diffusion properties were analyzed. The lower activation energy derived from NMR analysis reveals enhanced mobility of Li⁺ cations along the surface, in good agreement with AIMD calculations. On the other hand, the TFSI anion interaction with defect sites leads to CF₃ bond dissociation and subsequent generation of carbonyl fluoride-type species. The multimodal spectroscopic analysis including NMR, EPR and XPS analysis confirms the decomposition of TFSI anions near the anatase surface. The reaction mechanism and electronic structure of interfacial constituents were simulated using AIMD calculations. Ultimately, this work demonstrates the role of defects at the anatase nanoparticle surface on charge transfer and interfacial reaction processes.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1631805

Alternate ID(s):: OSTI ID: 1631198; OSTI ID: 1639158

Report Number(s):: PNNL-SA-150217

Journal Information:: Materials Today Chemistry, Vol. 17; ISSN 2468-5194

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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