Thermoplasmonic In Situ Fabrication of Nanohybrid Electrocatalysts over Gas Diffusion Electrodes for Enhanced H 2 O 2 Electrosynthesis.

Large-scale development of electrochemical cells is currently hindered by the lack of Earth-abundant electrocatalysts with high catalytic activity, product selectivity, and interfacial mass transfer. Herein, we developed an electrocatalyst fabrication approach which responds to these requirements by irradiating plasmonic titanium nitride (TiN) nanocubes self-assembled on a carbon gas diffusion layer in the presence of polymeric binders. The localized heating produced upon illumination creates unique conditions for the formation of TiN/F-doped carbon hybrids that show up to nearly 20 times the activity of the pristine electrodes. In alkaline conditions, they exhibit enhanced stability, a maximum H 2 O 2 selectivity of 90%, and achieve a H 2 O 2 productivity of 207 mmol g TiN -1 h -1 at 0.2 V vs RHE. A detailed electrochemical investigation with different electrode arrangements demonstrated the key role of nanocomposite formation to achieve high currents. In particular, an increased TiO x N y surface content promoted a higher H 2 O 2 selectivity, and fluorinated nanocarbons imparted good stability to the electrodes due to their superhydrophobic properties.