Interferometric 2D Sum Frequency Generation Spectroscopy Reveals Structural Heterogeneity of Catalytic Monolayers on Transparent Materials.
Molecular monolayers exhibit structural and dynamical properties that are different from their bulk counterparts due to their interaction with the substrate. Extracting these distinct properties is crucial for a better understanding of processes such as heterogeneous catalysis and interfacial charge transfer. Ultrafast nonlinear spectroscopic techniques such as 2D infrared (2D IR) spectroscopy are powerful tools for understanding molecular dynamics in complex bulk systems. Here, we build on technical advancements in 2D IR and heterodyne-detected sum frequency generation (SFG) spectroscopy to study a CO2reduction catalyst on nanostructured TiO2with interferometric 2D SFG spectroscopy. Our method combines phase-stable heterodyne detection employing an external local oscillator with a broad-band pump pulse pair to provide the first high spectral and temporal resolution 2D SFG spectra of a transparent material. We determine the overall molecular orientation of the catalyst and find that there is a static structural heterogeneity reflective of different local environments at the surface.
Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14853, United States.
Heather
http://orcid.org/0000-0002-7868-3900
H
Vanselous
Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14853, United States.
Ashley M
AM
Stingel
Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14853, United States.
Poul B
http://orcid.org/0000-0002-9821-700X
PB
Petersen