In Situ Surface X-Ray Diffraction Studies of the Electrochemical Double Layer on Pt(111)

The molecular structure of the electrochemical double layer is an important fundamental topic in interfacial electrochemistry. It has received renewed interest in the last years, because of its influence on many electrochemical reactions and the emergence of ab initio molecular dynamics simulations that allow a detailed description of the interface structure and dynamics [1,2]. In the measurements presented here, we investigated the properties of the electrochemical double layer on Pt(111) via in situ surface X-ray diffraction (SXRD), a technique that is well-established for single crystal studies [3-7]. Platinum electrodes are widely used as electrocatalysts, for example as cathodes in proton exchange membrane fuel cells due to their high ORR reactivity. The single-crystalline Pt(111) surface, which is a well studied model system, is especially interesting for studies of the electrochemical double layer. Recent electrochemical measurements revisited this system and found evidence for a double layer structure that strongly deviated from the traditional Gouy-Chapman-Stern model and indicated a complex structural influence of water [8,9]. The water structure within the electrochemical double layer is also of major interest in computational studies. For non-adsorbing, aqueous electrolyte the electrode surface charge can be partly compensated by a layer of oriented water molecules due to their dipole moment. For potentials around the potential of zero charge (PZC), a potential-dependent orientation of water molecules with respect to the electrode surface was suggested [1,2,10]. To investigate the arrangement and orientation of the water molecules near the Pt(111) surface we used in situ SXRD methods, focussing on X-ray reflectivity (XRR) and crystal truncation rod (CTR) analysis. These methods allow to acquire detailed information about the electrode surface structure as well as the electrochemical double layer. By measuring multiple CTR sets at different surface potentials, information on the potential-dependence of the interface processes can be obtained. The experiments were performed at beamline ID31 of the European Synchrotron Radiation Facility using high photon energies of 75 keV, which provide very large data sets. This allows significantly improved structural modeling as compared to conventional SXRD. The studies employed an electrochemical hanging-meniscus X-ray diffraction cell that allows for SXRD measurements of fast dynamic systems in a well-defined electrochemical environment. We will report results on the water structure in the double layer obtained in perchloric acid at potentials around the PZC. We gratefully acknowledge financial support by the Deutsche Forschungsgemeinschaft via project no. 418603497 and the BMBF via 05K19FK3 and 05K22FK1. References [1] A. Groß, S. Sakong, Chem. Rev. 122 (2022) 10746. [2] R. Sundararaman et al., Chem. Rev 122, (2022) 10651. [3] J. Drnec et al, Electrochim. Acta, 224 (2017) 22. [4] M. Ruge et al., J. Electrochem. Soc., 164 (2017) H608. [5] J. Drnec et al., Current Opinion Electrochem., 4 (2017) 69. [6] J. Drnec et al., Electrochem. Comm., 84 (2017) 8577, ibid 100, 4699. [7] Y. Liu, et al., J. Phys. Chem. Lett. 9, (2018) 1265. [8] K. Ojha et al., PNAS 119 (2022) e2116016119. [9] K. Ojha et al., Angew. 59 (2020) 711. [10] A. Bouzid et al., J. Phys. Chem. Lett. 9, (2018) 1880.

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