(631a) Electro-Dynamic Formic Acid Oxidation across Different Metal Descriptors

As developments into more efficient ways to extract energy and transform chemical materials continue to evolve, catalytic research has iterated towards the application of external stimuli in order to create dynamic systems. This fairly novel research area was first demonstrated through theoretical calculations to increase catalyst performance by orders of magnitude through oscillating the binding energy of adsorbed species on the catalyst surface¹. We demonstrated this dynamic concept experimentally using electric potential as a means of resonating the selectivity between the pathways that facilitate formic acid oxidation over Pt²; the rates of formic acid oxidation under potentiodynamic conditions were more than an order of magnitude larger than potentiostatic operation. It was found that the key player in this process was adsorbed CO, which is an intermediate in one of the available pathways; Adsorbed CO formed via the dehydration of formic acid was found to be key to the potentiodynamic promotion, whereby oscillating the rate of it’s formation and subsequent oxidation, the overall rate of formic acid oxidation could be increase beyond potentiostatic limitations.

The goal of this study is to provide a quantitative comparison of different metals for formic acid oxidation under both potentio-static and potentio-dynamic conditions. Previous investigations have primarily focused on the kinetics under potentiostatic conditions, focusing more on currents evolved at relatively short times on stream. With adsorbed CO playing an important role under dynamic conditions, particularly for group VIII metals, we investigate how formic acid oxidation rates respond to potentiodynamic modulation over different metals with varying CO binding energy (BE_CO).

References

1. Ardagh, M. A., O. A. Abdelrahman and P. J. Dauenhauer. "Principles of Dynamic Heterogeneous Catalysis: Surface Resonsance and Turnover Frequency Response." ACS Catalysis (2019): 6929-6937.

2. Gopeesingh, J., et al. "Resonance-Promoted Formic Acid Oxidation via Dynamic Electrocatalytic Modulation." ChemRxiv (2020).