AVS2018 Session PC+AS+BI+EM+PB+SS-WeM: Novel Approaches and Challenges of Interfaces

Wednesday, October 24, 2018 8:00 AM in Room 202A
Wednesday Morning

Session Abstract Book
(274KB, May 6, 2020)
Time Period WeM Sessions | Abstract Timeline | Topic PC Sessions | Time Periods | Topics | AVS2018 Schedule

Start Invited? Item
8:00 AM Invited PC+AS+BI+EM+PB+SS-WeM-1 Probing Chemical Species and Potential Profiles of Electrified Interfaces
Ethan J. Crumlin (Advanced Light Source, Lawrence Berkeley National Laboratory)

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.

8:40 AM PC+AS+BI+EM+PB+SS-WeM-3 Observation of Electron Transfer in Riboflavin Reduction by In Situ Liquid SIMS
Rachel Komorek, Xiaofei Yu, Zihua Zhu, Xiao-Ying Yu (Pacific Northwest National Laboratory)

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.

9:00 AM PC+AS+BI+EM+PB+SS-WeM-4 Electrowetting of Liquid Drops Revisited by XPS
Sefik Suzer, PinarAydogan Gokturk, Burak Ulgut (Bilkent University, Turkey)
Electrowetting behavior of liquid drops has been followed in-situ and in-vacuum using XPS in a chemically resolved fashion, under both dc and ac excitations. Various Liquid drops, compatible with the UHV conditions, consisted of an Ionic Liquid (DEME-TFSI), Poly-ethylene-glycol (M.W. ~600 amu) and their mixtures. For the dielectric substrate, a ~300 nm thick silicon oxide (SiO2/Si) without and with a thin hydrophobic coating (CYTOP) has been employed. XPS data have been recorded both in the conventional scan- and also in the fast (<1s) snap-shot modes. Intensity and position of the peaks, representing the liquid drops (F1s in the case of the IL, or C1s/O1s of the PEG) as well as those of the substrates (Si2p for the oxide only and F1s for the hydrophobic coated one) have been recorded under various electrical excitations. Under ac excitation at a fixed frequency, intensity modulations in the XPS peaks reveal geometrical changes of the drops, while the peak position modulations reveal electrical potentials developed. Monitoring position modulations as a function of the changes in the ac frequency (10-2 – 105 Hz) allows us to tap into ionic, dipolar and electrical contributions of the dielectric susceptibility of both the liquid drops and the substrates. Experimental details and various application will be presented and discussed.

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

9:20 AM Invited PC+AS+BI+EM+PB+SS-WeM-5 Probing Interfaces in Heterogeneous Catalysts at Atomic Scale: Current and Emerging STEM Techniques
Miaofang Chi (Oak Ridge National Laboratory)

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.

10:00 AM BREAK - Complimentary Coffee in Exhibit Hall
11:00 AM PC+AS+BI+EM+PB+SS-WeM-10 From 2D to Advanced 3D Surface Functionalization using Self-limiting Reactions in the Fluidized Bed Reactor Technology
Didier Arl, Tairan Da Cunha, Noureddine Adjeroud, Kevin Menguelti, Mathieu Gerard, Damien Lenoble (Luxembourg Institute of Science and Technology (LIST), Luxembourg)
The integration of novel functional nanomaterials like high specific surface powders in polymeric or inorganic matrices requires a fine control of their properties. The design of these nanoscopic agents is linked to the development of nanotechnology processes which can be transferred from planar substrates to complex 3D surfaces. In this framework we showed how self-limiting reactions inspired by Atomic Layer Deposition can be applied to functionalize powder by using a specifically designed Fluidized Bed Reactor. A specific interest has been given to work in non-saturated regime with nickel or Cobalt acetylacetonate to obtain well controlled metal nanocatalysts of 5-10nm diameter. Depending on the process window, some interesting properties have been demonstrated such as ferromagnetic behavior or the systematic recover of the Metal-Carbide phase that increase the throughput of Carbon Nanotubes growth. These activated nanostructures can expressly improve the electrical, the thermal or the mechanical properties of some related composites depending on how some processing parameters such as exposure time, pressure or local temperature can be tailored.
Session Abstract Book
(274KB, May 6, 2020)
Time Period WeM Sessions | Abstract Timeline | Topic PC Sessions | Time Periods | Topics | AVS2018 Schedule