(666b) Elucidating the Mechanism of Electrocatalytic Alkane Fragmentation and Oxidation Using Time-Dependent Potential Profiles

Electrochemistry provides an attractive avenue to a Net-Zero chemical industry by replacing fossil fuel derived heat with renewable electricity as the driving force for chemical synthesis. However, most studies remain focused on the transformation of inorganic species such as CO₂, N₂, and H₂O or biomass conversion. Achieving a Net-Zero chemical industry requires electrification efforts to be expanded to high-volume petrochemical transformations involving the manipulation of C(sp³)−H and C(sp³)−C(sp³) bonds and requires a fundamental understanding of the interfacial processes occurring in transformation organic species at electrode surfaces.

Here we investigate room temperature alkane transformations on platinum as a model system using electrochemical mass spectrometry (EC-MS). We show that the potential provides control over the conversion of catalytic alkane intermediates while they are bound to an electrocatalyst surface. The ability to manipulate the chemical identity of intermediates after their adsorption by changing the applied potential represents a significant advancement in controlling catalytic reactions. Exploiting the phenomenon using time dependent potential profiles provides an avenue to both control the product distribution of alkane fragmentation reactions as well as conduct mechanistic investigations into reaction pathways. Using this technique, we investigated the reaction network connecting butane electrooxidation and fragmentation to provide insight to guide alcohol and alkane fuel cell catalyst design. The manipulation of adsorbed species through the applied potential is a widely applicable for reaction control and investigation and thus holds the promise of enabling a broad swath of electrocatalytic transformations.