Creating self-assembled arrays of mono-oxo (MoO3)1 species on TiO2(101) via deposition and decomposition of (MoO3)n oligomers

Nassar Doudin; Greg Collinge; Pradeep Kumar Gurunathan; Mal Soon Lee; Vassiliki Alexandra Glezakou; Roger Rousseau; Zdenek Dohnálek

doi:10.1073/pnas.2017703118

Creating self-assembled arrays of mono-oxo (MoO₃)₁ species on TiO₂(101) via deposition and decomposition of (MoO₃)_n oligomers

Nassar Doudin, Greg Collinge, Pradeep Kumar Gurunathan, Mal Soon Lee, Vassiliki Alexandra Glezakou, Roger Rousseau, Zdenek Dohnálek

Research output: Contribution to journal › Article › peer-review

11 Scopus citations

Abstract

Hierarchically ordered oxides are of critical importance in material science and catalysis. Unfortunately, the design and synthesis of such systems remains a key challenge to realizing their potential. In this study, we demonstrate how the deposition of small oligomeric (MoO₃)₁–₆ clusters—formed by the facile sublimation of MoO₃ powders—leads to the self-assembly of locally ordered arrays of immobilized mono-oxo (MoO₃)₁ species on anatase TiO₂(101). Using both high-resolution imaging and theoretical calculations, we reveal the dynamic behavior of the oligomers as they spontaneously decompose at room temperature, with the TiO₂ surface acting as a template for the growth of this hierarchically structured oxide. Transient mobility of the oligomers on both bare and (MoO₃)₁-covered TiO₂(101) areas is identified as key to the formation of a complete (MoO₃)₁ overlayer with a saturation coverage of one (MoO₃)₁ per two undercoordinated surface Ti sites. Simulations reveal a dynamic coupling of the reaction steps to the TiO₂ lattice fluctuations, the absence of which kinetically prevents decomposition. Further experimental and theoretical characterizations demonstrate that (MoO₃)₁ within this material are thermally stable up to 500 K and remain chemically identical with a single empty gap state produced within the TiO₂ band structure. Finally, we see that the constituent (MoO₃)₁ of this material show no proclivity for step and defect sites, suggesting they can reliably be grown on the (101) facet of TiO₂ nanoparticles without compromising their chemistry.

Original language	English
Article number	e2017703118
Journal	Proceedings of the National Academy of Sciences of the United States of America
Volume	118
Issue number	4
DOIs	https://doi.org/10.1073/pnas.2017703118
State	Published - Jan 26 2021
Externally published	Yes

Funding

This work was supported by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. Experiments were performed in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830. Computational Resources were provided by a user proposal at the National Energy Research Scientific Computing Center located at Lawrence Berkley National Laboratory. ACKNOWLEDGMENTS. This work was supported by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. Experiments were performed in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle under Contract DE-AC05-76RL01830. Computational Resources were provided by a user proposal at the National Energy Research Scientific Computing Center located at Lawrence Berkley National Laboratory.

Funders	Funder number
U.S. Department of Energy
Battelle	DE-AC05-76RL01830
Office of Science
Basic Energy Sciences
Biological and Environmental Research
Lawrence Berkeley National Laboratory
Pacific Northwest National Laboratory
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

Hierarchical oxides
Molybdenum trioxide
Oxide clusters
Self-assembly
TiO(101)

Access to Document

10.1073/pnas.2017703118

Cite this

Doudin, N., Collinge, G., Gurunathan, P. K., Lee, M. S., Glezakou, V. A., Rousseau, R., & Dohnálek, Z. (2021). Creating self-assembled arrays of mono-oxo (MoO₃)₁ species on TiO₂(101) via deposition and decomposition of (MoO₃)_n oligomers. Proceedings of the National Academy of Sciences of the United States of America, 118(4), Article e2017703118. https://doi.org/10.1073/pnas.2017703118

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title = "Creating self-assembled arrays of mono-oxo (MoO3)1 species on TiO2(101) via deposition and decomposition of (MoO3)n oligomers",

abstract = "Hierarchically ordered oxides are of critical importance in material science and catalysis. Unfortunately, the design and synthesis of such systems remains a key challenge to realizing their potential. In this study, we demonstrate how the deposition of small oligomeric (MoO3)1–6 clusters—formed by the facile sublimation of MoO3 powders—leads to the self-assembly of locally ordered arrays of immobilized mono-oxo (MoO3)1 species on anatase TiO2(101). Using both high-resolution imaging and theoretical calculations, we reveal the dynamic behavior of the oligomers as they spontaneously decompose at room temperature, with the TiO2 surface acting as a template for the growth of this hierarchically structured oxide. Transient mobility of the oligomers on both bare and (MoO3)1-covered TiO2(101) areas is identified as key to the formation of a complete (MoO3)1 overlayer with a saturation coverage of one (MoO3)1 per two undercoordinated surface Ti sites. Simulations reveal a dynamic coupling of the reaction steps to the TiO2 lattice fluctuations, the absence of which kinetically prevents decomposition. Further experimental and theoretical characterizations demonstrate that (MoO3)1 within this material are thermally stable up to 500 K and remain chemically identical with a single empty gap state produced within the TiO2 band structure. Finally, we see that the constituent (MoO3)1 of this material show no proclivity for step and defect sites, suggesting they can reliably be grown on the (101) facet of TiO2 nanoparticles without compromising their chemistry.",

keywords = "Hierarchical oxides, Molybdenum trioxide, Oxide clusters, Self-assembly, TiO(101)",

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Doudin, N, Collinge, G, Gurunathan, PK, Lee, MS, Glezakou, VA , Rousseau, R & Dohnálek, Z 2021, 'Creating self-assembled arrays of mono-oxo (MoO₃)₁ species on TiO₂(101) via deposition and decomposition of (MoO₃)_n oligomers', Proceedings of the National Academy of Sciences of the United States of America, vol. 118, no. 4, e2017703118. https://doi.org/10.1073/pnas.2017703118

Creating self-assembled arrays of mono-oxo (MoO₃)₁ species on TiO₂(101) via deposition and decomposition of (MoO₃)_n oligomers. / Doudin, Nassar; Collinge, Greg; Gurunathan, Pradeep Kumar et al.
In: Proceedings of the National Academy of Sciences of the United States of America, Vol. 118, No. 4, e2017703118, 26.01.2021.

Research output: Contribution to journal › Article › peer-review

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