Interfaces play an important role in nearly all aspects of life, and are essential for electrochemistry. Electrochemical systems ranging from high temperature solid oxide fuel cells (SOFC) to batteries to capacitors have a wide range of important interfaces between solids, liquids, and gases which play a pivotal role in how energy is stored, transferred, and/or converted. This talk will focus on our use of ambient pressure XPS (APXPS) to directly probe the solid/liquid electrochemical interface. In particular, I will discuss how we were able to probe the potential drop within the electrochemical double layer (EDL) as well as the potential of zero charge under polarization conditions. This unique approach was accomplished by measuring spectral changes observed in both the electrolyte (water) and a neutral spectator probing molecule (pyrazine). By combining these experiments with numerical simulations provided the ability to discern the shape of the electrochemical double layer profile as a function of both electrolyte concentration and applied potentials. Extending beyond the EDL, I will highlight some of our recent investigations into both the oxygen evolution reaction on a platinum electrode as well as a magnesium electrode in a non-aqueous electrolyte. Information gained from these studies will aid in the guided design and control of future electrochemical interfaces.

Riboflavin is of vital significance in living processes as a precursor of the two important coenzymes flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD).[1] The isoalloxazine ring in riboflavin plays an important role in energy supplementation and cellular respiration, since it has the capability to accept electrons in some redox reactions.[2] Understanding riboflavin reduction could potentially bring insight into the electron transfer process between cell surfaces and conductive materials. Thus, the electrochemical reduction process of riboflavin has drawn increasing attention. In this study, the riboflavin reduction mechanism in an aqueous solution has been investigated using time-of-flight secondary ion mass spectrometry (ToF-SIMS) with the electrochemical cell.[3, 4] Positive and negative ion mode mass spectra were used to depict the molecular information of species dissolved in the electrolyte. The distribution of key reduction intermediates were mapped at the electrode-electrolyte interface using dynamic depth profiling. To examine product formation as a function of applied potentials, measurements were made by holding the potential at 0, -0.3, 0.3, and 0.6 V respectively, once interesting electrochemistry was determined using the cyclic voltammogram. Furthermore, gold and graphite electrodes were both used in our experiment to investigate if the electrode surface plays a role in in the electrochemical reaction mechanism. Preliminary spectral principal component analysis (PCA) results have shown key chemical distinctions in the electrolyte at 0, -0.3, 0.3, and 0.6 V. Selected peak spectral PCA is required to gain a better understanding of this observation, which will allow for a more comprehensive chemical profile of the electron transfer process in riboflavin redox reactions.

Key words: in situ liquid SIMS, SALVI, riboflavin reduction, electrochemistry, electron transfer

References

1. Y Wang, G Zhu, E Wang, Electrochemical behavior of FAD at a gold electrode studied by electrochemical quartz crystal microbalance. Anal. Chem. Acta. (1997), 338, 97-101.

2. W Chen, J-J Chen, R Lu, C Qian, W-W Li, H-Q Yu, Redox reaction characteristics of riboflavin: A fluorescence spectroelectrochemical analysis and density functional theory calculation. Bioelectrochemistry (2014), 98, 103-8.

3. B Liu, et al., In situ chemical probing of the electrode–electrolyte interface by ToF-SIMS. Lab Chip (2014), 14, 855-9.

4. J Yu et al., Capturing the transient species at the electrode-electrolyte interface by in situ dynamic molecular imaging. Chem. Comm. (2016), 73, 10929-11206.

*This work is partially supported by TUBITAK through Grant No. 215Z534

Chemical reactions take place on the surfaces and interfaces of heterogeneous catalyst systems. Depending on the phase of the reactant, the reactive interfaces include those between solid-gas, solid-liquid, and triple-phase interfaces of solid-gas-liquid. At these interfaces, the catalyst provides active sites where the reactants are adsorbed, activated, and converted to new chemical species that are eventually released from the catalyst surface. The ability of catalysts in promoting these reactions is determined by the surface binding energy, which can be modified by tuning the interfacial atomic arrangements or by forming new interfaces, e.g., forming core-shell structures. Understanding the formation of these interfaces during synthesis and their structural and chemical evolution during operation are important to the rational design of future high-performance catalysts. Probing these dynamically evolving interfaces at a sufficient spatial resolution, however, presents many challenging. Recent work on elucidating the formation and the operation mechanisms of interfaces in precious metal-based heterogeneous catalysts using in situ atomic-scale scanning transmission electron microscopy (STEM) techniques will be discussed. Several emerging STEM-based methods, such as vibration spectroscopy and atomic-scale differential phase contrast imaging that are currently under development within the microscopy community will be introduced, and their prospective influence on future studies to design functional interfaces in heterogeneous catalysts will be discussed.

Acknowledgements: Research supported by the Center for Nanophase Materials Sciences, which is a U.S. Department of Energy (DOE) Office of Science User Facility.