We report the potential-dependent interactions of trimesic acid with Cu surfaces in EtOH. CV experiments and electrochemical surface-enhanced Raman spectroscopy show the presence of an adsorbed trimesic acid layer on Cu at potentials lower than 0 V vs Cu. The BTC coverage increases as the potential increases, reaching a maximum at 0 V. Based on molecular dynamics simulations, we report adsorption geometries and possible structures of the organic adlayer. We find that, depending on the crystal facet, trimesic acid adsorbs either flat or with one or two of the carboxyl groups facing the metal surface. At higher coverages, a multi-layer forms that is composed mostly of flat-lying trimesic acid molecules. Increasing the potential beyond 0 V activates the Cu-adsorbate interface in such a way that under oxidation of Cu to Cu2 +, a 3-D metal-organic framework forms directly on the electrode surface.

AbstractElectrochemical surface activity arises from the interaction and geometric arrangement of molecules at electrified interfaces. We present a novel electrochemical tip-enhanced Raman spectroscope that can access the vibrational fingerprint of less than 100 small, non-resonant molecules adsorbed at atomically flat Au electrodes to study their adsorption geometry and chemical reactivity as a function of the applied potential. Combining experimental and simulation data for adenine/Au(111), we conclude that protonated physisorbed adenine adopts a tilted orientation at low potentials, whereas it is vertically adsorbed around the potential of zero charge. Further potential increase induces adenine deprotonation and reorientation to a planar configuration. The extension of EC-TERS to the study of adsorbate reorientation significantly broadens the applicability of this advanced spectroelectrochemical tool for the nanoscale characterization of a full range of electrochemical interfaces.

In this work, we evaluate the dependence of tip-enhanced Raman (TER) spectra of a monolayer of thiophenol at a Au(111) electrode on the scanning tunneling microscope’s tunneling current set-point and bias voltage parameters. We find an increase of the TER intensity upon set-point increase or bias decrease as expected from a gap-distance reduction. The relations obtained follow a theoretical model considering a simple gap-distance change when tuning the mentioned parameters. We find that the value of the bias voltage affects the TER intensity to a larger extent than the current set-point. Therefore it is advisable to work in a low-bias regime when aiming for ultrasensitive TER measurements.

AbstractElectrochemical surface activity arises from the interaction and geometric arrangement of molecules at electrified interfaces. We present a novel electrochemical tip-enhanced Raman spectroscope that can access the vibrational fingerprint of less than 100 small, non-resonant molecules adsorbed at atomically flat Au electrodes to study their adsorption geometry and chemical reactivity as a function of the applied potential. Combining experimental and simulation data for adenine/Au(111), we conclude that protonated physisorbed adenine adopts a tilted orientation at low potentials, whereas it is vertically adsorbed around the potential of zero charge. Further potential increase induces adenine deprotonation and reorientation to a planar configuration. The extension of EC-TERS to the study of adsorbate reorientation significantly broadens the applicability of this advanced spectroelectrochemical tool for the nanoscale characterization of a full range of electrochemical interfaces.

Lead chalcogenide quantum dots (QDs) are promising candidates for the use as sunlight absorbers in sensitized solar cells. While conversion efficiencies of QD solar cells have reached potentially commercially interesting values in the order of 10%, the devices are prone to fast oxidative degradation whose mechanism is not understood in detail yet. Furthermore, O2 and/or H2O present during fabrication has been observed to strongly influence device performance. Analytical tools to monitor the chemical state of QDs in situ and on-line, e.g. during fabrication and operation, are sought for. In this work, we demonstrate that surface-enhanced Raman spectroscopy (SERS) provides the chemical selectivity and high sensitivity required to investigate the oxidation behavior of QDs. We investigate the SER signature of PbS QDs that is commonly employed as sensitizer material in solar cells because of their tunable absorption range and simple and cheap fabrication. We observe SERS fingerprints for a set of three model PbS QD samples with different oxidation degrees. Intact PbS QDs exhibit a strong phonon mode around 196 cm−1. With increasing PbS oxidation, a relative band intensity increase can be observed in the 250–380 cm−1 region. At strong oxidation levels, additional Pb-(sulf)oxide marker bands appear at 614 and 980 cm−1. Based on our results, we suggest to employ PbS-oxidation SER spectral markers as monitoring tools during photovoltaic device fabrication.

To employ the full potential of electrochemical (ec) synthesis to grow metal–organic frameworks (MOFs) in more complex organizations at the mesoscale, it is vital to understand the underlying crystallization reaction pathway. For the MOF most typically grown electrochemically, CuBTC, we systematically investigated the role of oxygen species in the synthesis.

In situ characterization of surfaces with tip-enhanced Raman spectroscopy (TERS) provides chemical and topographic information with high spatial resolution and submonolayer chemical sensitivity. To further the versatility of the TERS approach toward more complex systems such as biological membranes or energy conversion devices, adaptation of the technique to solid/liquid working conditions is essential. Here, we present a home-built side-illumination TERS setup design based on a commercial scanning tunneling microscope (STM) as a versatile, cost-efficient solution for TERS at solid/liquid interfaces. Interestingly, the results obtained from showcase resonant dye and nonresonant thiophenol monolayers adsorbed on Au single crystals suggest that excitation beam aberrations due to the presence of the aqueous phase are small enough not to limit TER signal detection. The STM parameters are found to play a crucial role for solid/liquid TERS sensitivity. Raman enhancement factors of 105 at μW laser power demonstrate the great potential the presented experimental configuration holds for solid/liquid interfacial spectroscopic studies.

To employ the full potential of electrochemical (ec) synthesis to grow metal–organic frameworks (MOFs) in more complex organizations at the mesoscale, it is vital to understand the underlying crystallization reaction pathway. For the MOF most typically grown electrochemically, CuBTC, we systematically investigated the role of oxygen species in the synthesis.