Prof. L. Robert Baker
Department of Chemistry and Biochemistry, The Ohio State University, USA
Directly observing active surface intermediates and interfacial solvation structure represents a major challenge for bridging surface science to electrocatalysis. Toward this goal, we utilize plasmon-enhanced vibrational sum frequency generation spectroscopy to measure reaction intermediates and interfacial solvation structure at the electrode/electrolyte interface during electrochemical carbon dioxide reduction (CO2R). Using CO as a Stark reporter, we quantify the total electric field present during site-specific catalytic turnover and deconvolute this field into contributions from 1) the electrochemical double layer and 2) the Onsager, or solvation-induced, reaction field. Contrary to theoretical reports, CO2R kinetics are not correlated with the double layer field but instead are controlled by the strength of the Onsager reaction field, showing that interfacial solvation structure must be explicitly considered for accurate understanding of reaction kinetics. I will also describe the recent development of ultrafast XUV spectroscopy to study charge and spin dynamics at catalytic surfaces and highlight capabilities will soon become available at the NSF National eXtreme Ultrafast Science Facility (NeXUS) currently under development at Ohio State University.