Mass-selected cluster deposition and scanning tunneling microscopy (STM) were used to investigate the surface structure and thermal stability of Ti3Oy (y = 5, 6) clusters on a Cu(111) surface. STM imaging shows that the substoichiometric Ti3O5 clusters aggregate into large dendritic assemblies at step edges, while the stoichiometric Ti3O6 clusters are highly dispersed as single or small groupings of clusters. Cluster deposition also results in extensive reconstruction of the Cu(111) surface. The Ti3O5/Cu(111) surface exhibits one Cu-layer deep pits that are ringed by cluster assemblies that nucleate and grow at the perimeter step edges. By comparison, the Ti3O6/Cu(111) surface consists of irregular step edges and small one Cu-layer islands that are decorated with clusters. The restructuring of the Cu(111) surface is attributed to strong Cu-cluster interactions that release Cu adatoms from the step edges. This mechanism is supported by density functional theory (DFT) calculations, which predict that the Cu adatom attachment to the clusters is energetically favorable. Annealing the surfaces at elevated temperatures (400-700 K) results in higher densities of irregular steps, pits and isolated Cu islands as well as increased cluster aggregation. In conclusion, this work highlights adatom-cluster interactions as another manifestation of strong cluster-support interactions that can significantly alter the nature of the oxide-metal interface.
Wang, Jason, et al. "Composition-Dependent Reconstructions of Titanium Oxide Clusters and Cu(111) Support via Cluster-Adatom Interactions." Journal of Physical Chemistry. C, vol. 128, no. 40, Sep. 2024. https://doi.org/10.1021/acs.jpcc.4c04803
Wang, Jason, Shi, Luolin, Tong, Xiao, & White, Michael G. (2024). Composition-Dependent Reconstructions of Titanium Oxide Clusters and Cu(111) Support via Cluster-Adatom Interactions. Journal of Physical Chemistry. C, 128(40). https://doi.org/10.1021/acs.jpcc.4c04803
Wang, Jason, Shi, Luolin, Tong, Xiao, et al., "Composition-Dependent Reconstructions of Titanium Oxide Clusters and Cu(111) Support via Cluster-Adatom Interactions," Journal of Physical Chemistry. C 128, no. 40 (2024), https://doi.org/10.1021/acs.jpcc.4c04803
@article{osti_2475955,
author = {Wang, Jason and Shi, Luolin and Tong, Xiao and White, Michael G.},
title = {Composition-Dependent Reconstructions of Titanium Oxide Clusters and Cu(111) Support via Cluster-Adatom Interactions},
annote = {Mass-selected cluster deposition and scanning tunneling microscopy (STM) were used to investigate the surface structure and thermal stability of Ti3Oy (y = 5, 6) clusters on a Cu(111) surface. STM imaging shows that the substoichiometric Ti3O5 clusters aggregate into large dendritic assemblies at step edges, while the stoichiometric Ti3O6 clusters are highly dispersed as single or small groupings of clusters. Cluster deposition also results in extensive reconstruction of the Cu(111) surface. The Ti3O5/Cu(111) surface exhibits one Cu-layer deep pits that are ringed by cluster assemblies that nucleate and grow at the perimeter step edges. By comparison, the Ti3O6/Cu(111) surface consists of irregular step edges and small one Cu-layer islands that are decorated with clusters. The restructuring of the Cu(111) surface is attributed to strong Cu-cluster interactions that release Cu adatoms from the step edges. This mechanism is supported by density functional theory (DFT) calculations, which predict that the Cu adatom attachment to the clusters is energetically favorable. Annealing the surfaces at elevated temperatures (400-700 K) results in higher densities of irregular steps, pits and isolated Cu islands as well as increased cluster aggregation. In conclusion, this work highlights adatom-cluster interactions as another manifestation of strong cluster-support interactions that can significantly alter the nature of the oxide-metal interface.},
doi = {10.1021/acs.jpcc.4c04803},
url = {https://www.osti.gov/biblio/2475955},
journal = {Journal of Physical Chemistry. C},
issn = {ISSN 1932-7447},
number = {40},
volume = {128},
place = {United States},
publisher = {American Chemical Society},
year = {2024},
month = {09}}
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)
Grant/Contract Number:
SC0012704
OSTI ID:
2475955
Report Number(s):
BNL--226306-2024-JAAM
Journal Information:
Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 40 Vol. 128; ISSN 1932-7447