Shedding Synchrotron Light on Catalyst Strain Dynamics in Electrochemical Environment
Authors: Drnec Jakub , Chattot Raphael , Martens Isaac , Ronovsky Michal 
Published: July 2022

In the case of heterogeneous catalysis (where the reactions occur onto the catalyst surface), the most promising approach in material design follows the Sabatier principle: the ability of the surface to bind adsorbates and the strength of the bonds define the reaction thermodynamics and kinetics. In this respect, the catalyst surface chemistry and structure (crystallographic orientation of the facets and/or strain) are used as levers to optimize its performance. However, it is largely accepted that the structure of PEMWE anode and PEMFC cathode catalysts does not remain unaltered over the long term operation due to harsh (electro)chemical conditions and it is of a high interest to understand the structural changes during the electrocatalysis. In this contribution we use X-ray diffraction techniques to qualitatively and quantitatively describe those changes and shed light on the strain evolution in nanostructured catalysts during operation in the electrochemical environment.

Using the newly upgraded 4th generation EBS source at European Synchrotron Radiation Facility, we study Pt and Pd catalysts in liquid half cells at various potentials. In the Pd case we focus on the phase and structural dynamics during H insertion, allowing to unveil the electrochemically-driven Pd hydrides phase transition, which was until now mostly investigated in the gas phase. The fine XRD patterns measured operando provided the first detection of theoretically predicted supersaturated and undersaturated metastable states, involved in a core-shell mechanism of the phase transition (Figure 1) [1].

In the case of Pt nanocatalyst, monitoring the structural features of the catalyst during cyclic voltammetry permits studying adsorption and oxidation processes. Deconvoluting both effects (adsorption and oxidation) is possible by following different parameters of the analyzed XRD patterns with high temporal resolution. Such experiments reveal important dynamic trends linked to the surface oxidation and degradation, directly impacting the output of accelerated stress tests (AST) [2]. Carefully determining the charge passed through the circuit during the CV also allows to establish a near-linear correlation between the expansion of the bulk lattice parameter of Pt nanoparticles and their oxide surface coverage. Since the latter is known to be a descriptor of catalysts activity toward numerous reactions (oxygen reduction and fuel oxidation), the measurement of the lattice parameter according to this simple diffraction approach allows experimental access to this descriptor during operando measurements in device-relevant sample environments [2]. This constitutes a main advantage compared to spectroscopic techniques and is foreseen to find a wide range of applications, as demonstrated by measuring the structural behavior of the state-of-the-art PtNiIr octahedra catalyst in operating PEMFC. In this case, the results allow correlating the degradation of the catalysts cycled to different lower potentials with the oxidation and strain dynamics. Based on this data, the operating conditions for this catalyst can be determined, further defining the application of this material.

[1] Chattot, R. et al.,
J. Am. Chem. Soc.
143(41), 17068–17078 (2021).

[2] Martens, I. et al.,
ACS Appl. Energy Mater.
2 (11), 7772-7780 (2019).

Figure 1