Most of the electrochemistry processes occur within the thin layer of electrolyte at the electrolyte/electrode interfaces, commonly denoted as the electrical double layer (EDL). Although some classic continuum theories about EDL have been established and widely accepted over the past century, very little experimental information is available regarding the molecular-level details at such solid/liquid interfaces. We have developed in-situ liquid cells to study such solid/liquid interfaces by means of soft x-ray absorption spectroscopy [1]. Because the fluorescence x-ray photon has much larger mean free path in condensed matters than the secondary electrons, by comparing the total fluorescence yield (TFY) and total electron yield (TEY) spectra, we can extract useful information about the compositional, structural or chemical difference between the bulk and the interfacial electrolyte. Under different bias, by modulating the incident x-ray, the TEY signal current becomes alternating and can be separated from the dominant faradaic current so that we can obtain surface-sensitive TEY signal under electrochemical conditions.

With this in-situ and operando XAS technique, we investigated the gold/water interface [1] and platinum/sulfuric acid solution interface. It was found that at gold/water interface, the interfacial water layer has significantly different hydrogen-bonding network structure compared to the bulk water. Under different bias, the polar water molecules respond to the external electrical field and reorient at the gold electrode surface, which significantly changes the amount of distorted or broken hydrogen bonds. First-principle simulations were able to corroborate the experimental results and qualitatively reproduce the change in the x-ray absorption spectra at different bias. In the platinum/sulfuric acid system, the charged solute species, such as SO₄­^2- ions, hydronium ions, introduce extra complexity at the surface under different bias. Using the same in-situ technique, we were also able to identify some intermediate surface species in the potential window of OER reaction.

[1]. J.J. Velasco-Velez, C.H. Wu, T.A. Pascal, L.F. Wan, J.-H. Guo, D. Prendergast, and M. B. Salmeron, Science, 346, 831-834 (2014).

Tip Enhanced Raman Spectroscopy (TERS) is currently one of the most powerful probe techniques available and could be used to study reactions on surfaces at the single molecule level. TERS combines two very well developed techniques scanning probe microscopy (SPM), used to image single molecules on surfaces, and surface enhanced Raman spectroscopy (SERS), used to characterize vibrational spectra also of single molecules on surfaces. TERS could therefore provide unique and heretofore unprecedented insight on adsorbate reactions at the single-molecule level, e.g., image a molecule while it evolves from reactant to product at well defined surface sites as well as monitor vibrational spectra to provide bond specific information about the reaction. However, in order to clarify the vibrational structure in TERS, the details of the enhancement mechanism and the issues regarding the plasmonic background that is almost always observed in TER spectra as well the “blinking” that occurs in the SERS part of TERS must be resolved. Towards this end here we will report studies of Graphene and Graphene Nanoribbons (GNR’s) on Au surfaces as a model systems because their electronic and vibrational structure are clearly defined. Specifically, Near and Far-field Raman spectra will be reported for these systems and the above issues will be addressed experimentally and a simple theoretical model will be presented for the TERS observations.

As the energy and fuel demands of our growing world continue to increase, non-fossil fuel carbon sources are increasingly attractive – especially if these carbon sources can be easily converted to transportable fuels and higher-value chemicals. Much attention has been focused on carbon dioxide, as capture and storage technology has emerged to mitigate emissions and CO₂ can be used to produce methanol.

Recently, we reported a catalyst for the low-pressure conversion of CO₂ to methanol¹. Manganese oxide nanoparticles supported in mesoporous Co₃O₄ produced methanol in high yields and at significantly lower pressure conditions than typical Cu/ZnO catalysts used industrially. The advantage of this catalyst is in its lower pressure requirement, its high yield of methanol, and its evidence of carbon-carbon bond formation (10% ethylene production).

Catalytic testing of the material has shown the catalyst to be more than the sum of its parts; when each component is tested separately (MnO_x nanoparticles supported in SiO₂; mesoporous Co₃O₄ alone) CH₄ and CO are the major products. Preparation and testing of an inverse catalyst – CoO_x nanoparticles on a mesoporous MnO₂ support – proves the importance of the hybrid architecture in determining the selectivity of the catalyst, as the inverse catalyst is dominated by the selectivity of the support (>80% selective to CO).

Towards understanding this catalyst, in-situ X-ray Absorption Spectroscopy (XAS) utilizing both soft and hard x-ray energies has allowed for a detailed characterization of the catalyst under oxidation, reduction, and reaction conditions. In addition to CO₂, in-situ characterization under CO hydrogenation conditions was used to understand the Fischer-Tropsch activity of the catalyst for making longer chain hydrocarbons. The results of these in-situ studies are correlated with catalytic reaction data to help understand the nature of the active site/interface and guide future catalyst design.

References

(1) C. S. Li, G. Melaet, W. T. Ralston, et al. High-performance hybrid oxide catalyst of manganese and cobalt for low-pressure methanol synthesis. Nature Communications, 6:6538, 2015.

Operando methodology combines in situ spectroscopy during reaction with simultaneous performance measurement in a cell that behaves like a catalytic reactor. Operando methodology connects changes in the performance and in the structure in a simultaneous manner; this is fundamental to assess the structure-performance relationships at a molecular level.

Molecularly dispersed vanadia on oxide carriers is a key component in many catalytic formulations in environmental and selective oxidation and ammoxidation catalysis. The actual state of vanadia catalysts in specific environments depends on its surface density, the nature of the support and the presence of additives. We will summarize our experience on the state of supported vanadia paying particular attention to how the environment and reaction conditions finally shape the structure of vanadia catalysts. Operando Raman spectroscopy is an invaluable approach to fully understand the actual state of the catalyst, its transformations during reaction and how these correlate with changes in catalytic performance.

A single technique, may no deliver the complete vista, thus collaboration with complementary talents and techniques is critical. We show the outcome of collaborations with theoretical chemistry approaches to bring the rationale behind structure-activity relationships inferred through operando Raman methodology. We also show the interaction with engineering approaches.

It is a challenge to study 2D materials, such as Graphene, MoS₂, WeSe₂, etc. at temperatures down to 10^oK when one considers the wide variety of physical phenomena that have to be applied to get a full picture of the functionality of these materials. This involves questions of structure, nanometric photoconductivity, electrical properties, thermal properties, near-field optical in the apertured and scattering modes, Kelvin probe, and of course Raman. All of these phenomena are common not only to 2D materials but also to carbon nanotubes and related nanomaterials. This presentation will describe both the instrumental development of such a multiprobe cryogenic system that allows for state of the art on-line optical measurements and will also include a review of the probe developments that permit such multifunctional multiprobe operation with on-line full optical access. The system that will be described has a completely free optical axis from above and below that is not obscured by electrical or other probes that have been developed for this system for multiprobe operation. This permits on-line Raman and Tip Enhanced NanoRaman Scattering. With such a system we have investigated graphene and HfO2 using multiprobe electrical, Kelvin probe, NSOM and on-line Raman. The results have yielded new insights into the chemical changes that are correlated to the electrical conductivity.