The foreseeable worldwide energy and environmental challenges demand renewable alternative sources, energy conversion, and storage technologies. Therefore, electrochemical energy conversion devices like fuel cells, electrolyzes, and supercapacitors along with photoelectrochemical devices and batteries have high potential to become increasingly important in the near future. Catalytic performance in electrochemical energy conversion results from the tailored properties of complex nanometer-sized metal and metal oxide particles, as well as support nanostructures. Exposed facets, surface defects, and other structural and compositional features of the catalyst nanoparticles affect the electrocatalytic performance to varying degrees. The characterization of the nanometer-size and atomic regime of electrocatalysts and its evolution over time are therefore paramount for an improved understanding and significant optimization of such important technologies like electrolyzers or fuel cells. Transmission electron microscopy (TEM) and scanning transmission electron microscope (STEM) are to a great extent nondestructive characterization tools that provide structural, morphological, and compositional information with nanoscale or even atomic resolution. Due to recent marked advancement in electron microscopy equipment such as aberration corrections and monochromators, such insightful information is now accessible in many institutions around the world and provides huge benefit to everyone using electron microscopy characterization in general. Classical ex situ TEM characterization of random catalyst locations however suffers from two limitations regarding catalysis. First, the necessary low operation pressures in the range of 10^–6 to 10^–9 mbar for TEM are not in line with typical reaction conditions, especially considering electrocatalytic solid–liquid interfaces, so that the active state cannot be assessed. Second, and somewhat related, is the lack of time resolution for the evaluation of alterations of the usually highly heterogeneous nanomaterials. Two methods offer a solution to these shortcomings, namely, identical location TEM (IL-TEM) and electrochemical in situ liquid TEM. The former is already well established and has delivered novel insights particularly into degradation processes; however, characterization is still performed in vacuum. The latter circumvents this issue by using dedicated in situ TEM holders but introduces extremely demanding technical challenges. Although the introduction of revolutionizing thin SiN window cells, which elegantly confine the specimen from vacuum, has allowed demonstration of the potential of the in situ approach, the reproducibility and data interpretation is still limited predominately due to the strong interaction of the electron beam with the supporting electrolyte and electrode material. Because of the importance of understanding the nanoelectrochemical structure–function relationship, this Account aims to convey a timely perspective on the opportunities and particularly the challenges in electrochemical identical location TEM and in situ liquid cell TEM with a focus on electrochemical energy conversion.

One of the most important practical issues in low‐temperature fuel‐cell catalyst degradation is platinum dissolution. According to the literature, it initiates at 0.6–0.9 V_RHE, whereas previous time‐ and potential‐resolved inductively coupled plasma mass spectrometry (ICP–MS) experiments, however, revealed dissolution onset at only 1.05 V_RHE. In this manuscript, the apparent discrepancy is addressed by investigating bulk and nanoparticulated catalysts. It is shown that, given enough time for accumulation, traces of platinum can be detected at potentials as low as 0.85 V_RHE. At these low potentials, anodic dissolution is the dominant process, whereas, at more positive potentials, more platinum dissolves during the oxide reduction after accumulation. Interestingly, the potential and time dissolution dependence is similar for both types of electrode. Dissolution processes are discussed with relevance to fuel‐cell operation and plausible dissolution mechanisms are considered.

Water electrolysis powered by renewables is regarded as the feasible route for the production of hydrogen, obtained at the cathode side through electrochemical hydrogen evolution reaction (HER). Herein, we present a rational strategy to improve the overall HER catalytic performance of Pt, which is known as the best monometallic catalyst for this reaction, by supporting it on a conductive titanium oxynitride (TiON _x ) dispersed over reduced graphene oxide nanoribbons. Characterization of the Pt/TiON _x composite revealed the presence of small Pt particles with diameters between 2 and 3 nm, which are well dispersed over the TiON _x support. The Pt/TiON _x nanocomposite exhibited improved HER activity and stability with respect to the Pt/C benchmark in an acid electrolyte, which was ascribed to the strong metal-support interaction (SMSI) triggered between the TiON _x support and grafted Pt nanoparticles. SMSI between TiON _x and Pt was evidenced by X-ray photoelectron spectroscopy (XPS) through a shift of the binding energies of the characteristic Pt 4f photoelectron lines with respect to Pt/C. Density functional theory (DFT) calculations confirmed the strong interaction between Pt nanoparticles and the TiON _x support. This strong interaction improves the stability of Pt nanoparticles and weakens the binding of chemisorbed H atoms thereon. Both of these effects may result in enhanced HER activity.