Elucidating the genesis of Bi2MoO6 catalyst by combination of synchrotron radiation experiments and Raman scattering

Kongmark, Chanapa; Martis, Vladimir; Rubbens, Annick; Pirovano, Caroline; Löfberg, Axel; Sankar, Gopinathan; Bordes‐Richard, Elisabeth; Vannier, R-N.; Beek, Wouter van

doi:10.1039/b907935a

Cited by 49 publications

(48 citation statements)

References 20 publications

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“…The weakening of the characteristic peaks of the Mo 3 O 13 clusters after 50 cycles indicates the decreasing quantity of the Mo 3 O 13 clusters. It was believed that trapping of the Mo ions on the interstitial tetrahedral sites leads to the generation of characteristic peaks at 897 and 841 cm −1 for the MoO 4 tetrahedra . The absence of these peaks in any of the above samples indicates that the octahedral Mo ions do not migrate to the tetrahedral sites.…”

Section: Resultsmentioning

confidence: 99%

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides

Han

Jiao

Liu

et al. 2020

Advanced Energy Materials

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Lithium‐rich layered oxides are promising candidate cathode materials for the Li‐ion batteries with energy densities above 300 Wh kg−1. However, issues such as the voltage hysteresis and decay hinder their commercial applications. Due to the entanglement of the transition metal (TM) migration and the anionic redox upon lithium extraction at high potentials, it is difficult to recognize the origin of these issues in conventional Li‐rich layered oxides. Herein, Li2MoO3 is chosen since prototype material to uncover the reason for the voltage hysteresis as the TM migration and anionic redox can be eliminated below 3.6 V versus Li+/Li in this material. On the basis of comprehensive investigations by neutron powder diffraction, scanning transmission electron microscopy, synchrotron X‐ray absorption spectroscopy, and density functional theory calculations, it is clarified that the ordering–disordering transformation of the Mo3O13 clusters induced by the intralayer Mo migration is responsible for the voltage hysteresis in the first cycle; the hysteresis can take place even without the anionic redox or the interlayer Mo migration. A similar suggestion is drawn for its iso‐structured Li2RuO3 (C2/c). These findings are useful for understanding of the voltage hysteresis in other complicated Li‐rich layered oxides.

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Section: Resultsmentioning

confidence: 99%

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides

Han

Jiao

Liu

et al. 2020

Advanced Energy Materials

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“…[253] The presence of isolated MoO 4 2À ions in the initial stages of the reaction was confirmed through XANES (X-ray absorption near edge structure) and Raman investigations and the following reaction pathway was proposed on the basis of refined HRPD data (Figure 14 a): Firstly, a Bi 2 O 3 -related intermediate with a distorted fluorite structure is formed. These particles are converted into the layered Aurivillius-type structure of Bi 2 MoO 6 upon prolonged reaction times.…”

Section: Reviews 844mentioning

confidence: 97%

“…a) Crystallization mechanism proposed for the growth of gBi 2 MoO 6 under hydrothermal conditions. [253] Reproduced with permission from The Royal Society of Chemistry. b) Experimental setup for SAXS and WAXS in situ studies.…”

Section: Reviews 844mentioning

confidence: 99%

Oxide Nanomaterials: Synthetic Developments, Mechanistic Studies, and Technological Innovations

et al. 2010

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Oxide nanomaterials are indispensable for nanotechnological innovations, because they combine an infinite variety of structural motifs and properties with manifold morphological features. Given that new oxide materials are almost reported on a daily basis, considerable synthetic and technological work remains to be done to fully exploit this ever increasing family of compounds for innovative nano-applications. This calls for reliable and scalable preparative approaches to oxide nanomaterials and their development remains a challenge for many complex nanostructured oxides. Oxide nanomaterials with special physicochemical features and unusual morphologies are still difficult to access by classic synthetic pathways. The limitless options for creating nano-oxide building blocks open up new technological perspectives with the potential to revolutionize areas ranging from data processing to biocatalysis. Oxide nanotechnology of the 21st century thus needs a strong interplay of preparative creativity, analytical skills, and new ideas for synergistic implementations.

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“…Raman studies of Bi 2 MoO 6 have been presented in a few papers but no detailed assignment has been proposed 4, 6, 12, 13. IR spectra have not been yet published for this material.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and phonon properties of nanosized Aurivillius phase of Bi₂MoO₆

Mączka

Macalik

Hermanowicz

et al. 2010

J Raman Spectroscopy

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MoO 6 of a platelet shape were synthesized by a mild hydrothermal crystallization process. The effect of particle size on the structure and properties of Bi 2 MoO 6 was studied by X-ray diffraction, transmission electron microscopy, as well as Raman and infrared (IR) spectroscopies. Moreover, temperature-dependent Raman spectra were collected for bulk and nanocrystalline Bi 2 MoO 6 . These studies showed that the thickness of the smallest crystallites is about 8-11 nm. Raman and IR studies have revealed that the damping and the intensity of Raman and IR bands are significantly modified with decreasing particle size and temperature. Moreover, some bands experience significant shifts both towards lower and higher wavenumbers. The obtained results indicate that, similar to the isostructural Bi 2 WO 6 , the orthorhombic distortion decreases with decreasing particle size. However, the structure of nanocrystalline Bi 2 MoO 6 remains orthorhombic and noncentrosymmetric, and the structural changes are not the same as those observed in Bi 2 WO 6 .

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Elucidating the genesis of Bi2MoO6 catalyst by combination of synchrotron radiation experiments and Raman scattering

Abstract: Combination of in situ Raman scattering with high-resolution XRD and XAS techniques has proven to be a powerful tool to elucidate the crystal growth of gamma-Bi2MoO6 under hydrothermal conditions.

Cited by 49 publications

References 20 publications

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides

Oxide Nanomaterials: Synthetic Developments, Mechanistic Studies, and Technological Innovations

Synthesis and phonon properties of nanosized Aurivillius phase of Bi₂MoO₆

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Elucidating the genesis of Bi2MoO6 catalyst by combination of synchrotron radiation experiments and Raman scattering

Abstract: Combination of in situ Raman scattering with high-resolution XRD and XAS techniques has proven to be a powerful tool to elucidate the crystal growth of gamma-Bi2MoO6 under hydrothermal conditions.

Cited by 49 publications

References 20 publications

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides

Oxide Nanomaterials: Synthetic Developments, Mechanistic Studies, and Technological Innovations

Synthesis and phonon properties of nanosized Aurivillius phase of Bi2MoO6

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Synthesis and phonon properties of nanosized Aurivillius phase of Bi₂MoO₆