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Cetyltrimethylammonium bromide (CTAB) has been used to enhance the selectivity of CO2 electrochemical reduction. Traditionally, this selectivity was attributed to repulsion of water molecules due to a CTAB self-assembled monolayer, which forms under negative potential and disassembles at positive voltage due to electrostatic repulsions. In this report, using in operando interface sensitivity sum frequency generation spectroscopy, we investigated the self-assembly behavior of CTAB across a broad electrochemical potential range. We observed that CTAB molecules form a stable monolayer at the Stern layer over the entire potential scan, even when the electrodes are positively charged. Rather than disassembling, the CTAB molecules reorient themselves to balance the electrostatic interactions and the non-covalent hydrophobic effects, the latter being the primary driving force maintaining the monolayer at a positive potential. This finding contrasts the traditional view that CTAB monolayers are absent when the electrodes are positively charged, indicating a stable and ordered monolayer with respect to the electrostatic repulsions at liquid/electrode interfaces. The balance between non-covalent and electrostatic interactions offers a facile and reversible electrochemical method to control the local environment and dominating interactions at the Stern layer of the electrode surface, thus providing a means for engineering a micro-electrochemical environment. 

Abstract In this work, we investigate trion dynamics occurring at the heterojunction between organometallic molecules and a monolayer transition metal dichalcogenide (TMD) with transient electronic sum frequency generation (tr‐ESFG) spectroscopy. By pumping at 2.4 eV with laser pulses, we have observed an ultrafast hole transfer, succeeded by the emergence of charge‐transfer trions. This observation is facilitated by the cancellation of ground state bleach and stimulated emission signals due to their opposite phases, making tr‐ESFG especially sensitive to the trion formation dynamics. The presence of charge‐transfer trion at molecular functionalized TMD monolayers suggests the potential for engineering the local electronic structures and dynamics of specific locations on TMDs and offers a potential for transferring unique electronic attributes of TMD to the molecular layers. 

We introduce a new data analysis method, which can be applied to transient vibrational sum-frequency generation spectroscopy to reveal hidden molecular dynamics of charge transfer at molecular heterojunction interfaces. After validating the method, we used it to extract molecular dynamics at organic semiconductor/metal interfaces, which was otherwise dominated by electronic dynamics. Such an ability can advance the understanding of the roles of molecules in interfacial charge transfer dynamics. 

Understanding hydrogen-bond interactions in self-assembled lattice materials is crucial for preparing such materials, but the role of hydrogen bonds (H bonds) remains unclear. To gain insight into H-bond interactions at the materials’ intrinsic spatial scale, we investigated ultrafast H-bond dynamics between water and biomimetic self-assembled lattice materials (composed of sodium dodecyl sulfate and β-cyclodextrin) in a spatially resolved manner. To accomplish this, we developed an infrared pump, vibrational sum-frequency generation (VSFG) probe hyperspectral microscope. With this hyperspectral imaging method, we were able to observe that the primary and secondary OH groups of β-cyclodextrin exhibit markedly different dynamics, suggesting distinct H-bond environments, despite being separated by only a few angstroms. We also observed another ultrafast dynamic reflecting a weakening and restoring of H bonds between bound water and the secondary OH of β-cyclodextrin, which exhibited spatial uniformity within self-assembled domains, but heterogeneity between domains. The restoration dynamics further suggest heterogeneous hydration among the self-assembly domains. The ultrafast nature and meso- and microscopic ordering of H-bond dynamics could contribute to the flexibility and crystallinity of the material––two critically important factors for crystalline lattice self-assemblies––shedding light on engineering intermolecular interactions for self-assembled lattice materials.