• Energy Research

Comprehensive understanding of the catalyst corrosion dynamics is a prerequisite for the development of an efficient cathode catalyst in proton-exchange membrane fuel cells. To reach this aim, the behavior of fuel cell catalysts must be investigated directly under reaction conditions. Herein, we applied a strategic combination of in situ/online techniques: in situ electrochemical atomic force microscopy, in situ grazing incidence small angle X-ray scattering, and electrochemical scanning flow cell with online detection by inductively coupled plasma mass spectrometry. This combination of techniques allows in-depth investigation of the potential-dependent surface restructuring of a PtNi model thin film catalyst during potentiodynamic cycling in an aqueous acidic electrolyte. The study reveals a clear correlation between the upper potential limit and structural behavior of the PtNi catalyst, namely, its dealloying and coarsening. The results show that at 0.6 and 1.0 VRHE upper potentials, the PtNi catalyst essentially preserves its structure during the entire cycling procedure. The crucial changes in the morphology of PtNi layers are found to occur at 1.3 and 1.5 VRHE cycling potentials. Strong dealloying at the early stage of cycling is substituted with strong coarsening of catalyst particles at the later stage. The coarsening at the later stage of cycling is assigned to the electrochemical Ostwald ripening process.

Nowadays, electrochemistry has a considerable technological impact, involving fuel cells, super capacitors and batteries. These devices are based on complex architectures, which complicates monitoring their evolution in situ under operating conditions to reveal the reasons for reduced lifetime and performances. Here, we present a design of a multipurpose electrochemical cell for grazing incidence small and wide angle X-ray scattering (GISAXS and GIWAXS) where the environment for operating conditions can be recreated. We focus on proton exchange membrane fuel cells (PEMFCs) which operational conditions are simulated by means of potentiodynamic-based accelerated stress tests, applied to a thin film of Pt nanoparticles representing a model system of a benchmark catalyst. Two different upper potentials are used to mimic fuel cell operating conditions: at 1.0 V RHE the catalyst film preserves its initial morphology, while at 1.5 V RHE (simulating fuel cell start-up/shut-down cycles) significant coarsening has been observed. The initial dimension of the Pt particles of 4.0 nm increases to 8.7 nm due to the predominant process of coalescence and final Ostwald ripening. In parallel, the distance between the particles increases, the catalyst film (9 nm thick) becomes thinner at first and exhibit a higher roughness at the end.

Abstract The elevated price of Pt limits the large-scale implementation of commercial proton exchange membrane fuel cells, which effectively convert chemical energy into electricity. In order to increase the cost-efficiency in proton-exchange membrane fuel cells, we have designed a family of novel anode catalysts consisting of thin films of ceria with low Pt loadings sputtered on a nanostructured carbon support. Remarkably, only such small amounts of Pt are necessary for achieving power density values comparable to the reference commercial catalysts, which results in excellent specific activities of our samples. By combining photoelectron spectroscopy and catalytic performance analysis, we have shown that the surface Pt 2+ species in cerium oxide exhibit high electrocatalytic activity. Density functional theory calculations show that the great stability of Pt 2+ species on ceria makes these resistant to reduction by hydrogenation and suggests that the formation of such stable surface complexes prevents degradation of the nanostructured composite.

Platinum-based bimetallic alloys have been largely investigated during the last few years as a valid alternative to bare Pt cathode catalysts for proton-exchange membrane fuel cells (PEMFCs) to improve their cost-efficiency. Nonetheless, Pt bimetallic alloys are characterized by a reduced stability, which is poorly understood at a fundamental level. It is thus essential to describe the entire chain of interconnected degradation mechanisms to formulate a comprehensive model of catalyst degradation that will help interpret bimetallic alloy behavior in real complex fuel cell systems. By combining in situ inductively coupled plasma mass spectroscopy, in situ grazing-incidence small-angle X-ray scattering, and ex situ scanning electron microscopy, we have studied the morphological evolution of PtXNi100–X model catalysts with different Ni contents (ranging from 0 to 75%) undergoing potentiodynamic cycling to two different upper potentials mimicking the different operational conditions of a PEMFC: 1.0 and 1.3 VRHE. Data analysis allowed us to develop a methodology to distinguish the influence of Ni dissolution, particle coalescence, and Ostwald ripening on particle size distribution and interparticle distance and to realize time-dependent interplay maps to highlight the timeframe in which the aforementioned phenomena are prevailing or coexisting. Results show that Ni dissolution is the only phenomenon inducing morphological evolution when the lower upper potential is chosen. On the contrary, at 1.3 VRHE, Ni dissolution is rapidly overcome by particle coalescence at first and by Ostwald ripening in the later stages of the investigated time range. The onset of every phenomenon was found to occur earlier in time for larger values of Ni concentrations.