Dopant-Dependent SFG Response of Rhenium CO2 Reduction Catalysts Chemisorbed on SrTiO3 (100) Single Crystals

Aimin Ge, Pablo E. Videla, Benjamin Rudshteyn, Qiliang Liu, Victor S. Batista, Tianquan Lian

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

Abstract

Monolayers of fac-Re(4,4′-dicarboxyl-2,2′-bipyridine)(CO)3Cl (ReC0A) complexes, covalently bound to TiO2-terminated SrTiO3 (100) (STO) single crystals, were studied by both vibrational Sum Frequency Generation (SFG) spectroscopy and Density Functional Theory (DFT). Homodyne-detected SFG results show that the SFG spectral shape of ReC0A on Nb-doped STO surfaces is almost opposite to that of ReC0A on undoped or Fe-doped STO surfaces, which we assign to a phase change of the SFG response of STO induced by the Nb rather than a change in orientation of the molecule. DFT calculations show that the doping with Nb populates the conduction band of the system, giving a metallic nature to the otherwise insulator STO substrate. This change in electronic structures of the substrate leads to a big nonresonant SFG response and thus interference with the spectra. The orientation of the ReC0A on all three substrates was found to be tilted by 45-50°, with a bidentate binding geometry and the Cl atom facing the surface. The reported results indicate that a molecular probe can be used to obtain information about the underlying material.

Original languageEnglish
Pages (from-to)13944-13952
Number of pages9
JournalJournal of Physical Chemistry C
Volume122
Issue number25
DOIs
Publication statusPublished - 2018 Jun 28
Externally publishedYes

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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