Operando Electron Microscopy of Catalysts: The Missing Cornerstone in Heterogeneous Catalysis Research?

Abstract

Heterogeneous catalysis in thermal gas-phase and electrochemical liquid-phase chemical conversion plays an important role in our modern energy landscape. However, many of the structural features that drive efficient chemical energy conversion are still unknown. These features are, in general, highly distinct on the local scale and lack translational symmetry, and thus, they are difficult to capture without the required spatial and temporal resolution. Correlating these structures to their function will, conversely, allow us to disentangle irrelevant and relevant features, explore the entanglement of different local structures, and provide us with the necessary understanding to tailor novel catalyst systems with improved productivity. This critical review provides a summary of the still immature field of operando electron microscopy for thermal gas-phase and electrochemical liquid-phase reactions. It focuses on the complexity of investigating catalytic reactions and catalysts, progress in the field, and analysis. The forthcoming advances are discussed in view of correlative techniques, artificial intelligence in analysis, and novel reactor designs.

Impact of quantum size effects to the band gap of catalytic materials: a computational perspective*

“…Nowadays, the power of synthetic chemistry and advanced spectroscopy have reached a point where active single atomic species can be achieved. To cite a relevant example, it is enough to mention that extended x-ray absorption fine structure spectroscopy can trace local metal-metal interaction in a solid matrix [10,11], and scanning tunneling electron microscopy can detect isolated metal atoms [12,13]. At the same time, there are several advanced synthetic strategies allowing to selectively stabilize metal atoms with atomic dispersion on a solid matrix [14][15][16][17][18][19].…”

Recent development and applications of differential electrochemical mass spectrometry in emerging energy conversion and storage solutions

“…The small amount of analytes generated by electrochemistry in comparison with those from conventional solution chemistry poses another challenge for accurate quantification. Thanks to the recent technological progress, various in situ spectroscopic (e.g., Raman, infrared and X-ray absorption) [23][24][25] and microscopic techniques (e.g., transmission electron microscopy) 26,27 have become available and easily accessible today. They enable rapid monitoring and real-time tracking of dynamic electrochemical processes, providing valuable insights for addressing various fundamental research questions such as investigating the structure/reactivity correlation of catalysts, deducing the catalysis mechanism and revealing the reconstruction of electrodes.…”

“…, Raman, infrared and X-ray absorption) 23–25 and microscopic techniques ( e.g. , transmission electron microscopy) 26,27 have become available and easily accessible today. They enable rapid monitoring and real-time tracking of dynamic electrochemical processes, providing valuable insights for addressing various fundamental research questions such as investigating the structure/reactivity correlation of catalysts, deducing the catalysis mechanism and revealing the reconstruction of electrodes.…”

Electrochemical liquid phase TEM in aqueous electrolytes for energy applications: the role of liquid flow configuration

“…Li-based batteries have been benefitting a lot of this innovative characterization approach and the first commercial technological solutions have been optimized to match the experimental need in this scientific frame [6], [7], [8]. In more recent years, electrocatalysis has been raising a lot of interest and the experimental set-up has been adapted to match the experimental needs as well [9]. Among the various possible electrochemical applications, catalytic reactions for energy transition (hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), oxygen reduction reaction (ORR), oxygen evolution reaction (OER)) have been extensively studied in recent years, due to the growing importance of the global energy issue.…”