Coherent Acoustic Interferometry during the Photodriven Oxygen Evolution Reaction Associates Strain Fields with the...

The oxygen evolution reaction (OER) from water requires the formation of metastable, reactive oxygen intermediates to enable oxygen-oxygen bond formation. Conversely, such reactive intermediates could also structurally modify the catalyst. A descriptor for the overall catalytic activity, the first electron and proton transfer OER intermediate from water, (M-OH*), has been associated with significant distortions of the metal-oxygen bonds upon charge-trapping. Time-resolved spectroscopy of in situ, photodriven OER on transition metal oxide surfaces has characterized M-OH* for the charge trapping and the symmetry of the lattice distortions by optical and vibrational transitions, respectively, but had yet to detect an interfacial strain field arising from a surface coverage M-OH*. Here, we utilize picosecond, coherent acoustic interferometry to detect the uniaxial strain normal to the SrTiO₃/aqueous interface directly caused by Ti-OH*. The spectral analysis applies a fairly general methodology for detecting a combination of the spatial extent, magnitude, and generation time of the interfacial strain through the coherent oscillations' phase. For lightly n-doped SrTiO₃, we identify the strain generation time (1.31 ps), which occurs simultaneously with Ti-OH* formation, and a tensile strain of 0.06% (upper limit 0.6%). In addition to fully characterizing this intermediate across visible, mid-infrared, and now GHz-THz probes on SrTiO₃, we show that strain fields occur with the creation of some M-OH*, which modifies design strategies for tuning catalytic activity and provides insight into photo-induced degradation so prevalent for OER. To that end, the work put forth here provides a unique methodology to characterize intermediate-induced interfacial strain across OER catalysts.