Operando Neutron Imaging.

In the past, neutron imaging has been the little brother of advanced neutron spectroscopy techniques due to its apparent simplicity. However, this simplicity allows the studying of complex chemical and electrochemical processes and related devices even under harsh reaction conditions such as high pressure, high temperature, corrosive and/or air sensitive environments. We review a number of highly relevant case studies as archetypal examples of modern energy technology; that is heat storage, power-to-X, batteries, fuel cells, and catalysis. The promising results trigger the further development of neutron imaging towards a chemical imaging method.

Hydrogen Transport and Evolution in Ni-MH Batteries by Neutron Imaging.

Efficiency losses due to side reactions are one of the main challenges in battery development. Despite providing valuable insights, the results of standard analysis on the individual components cannot be simply extrapolated to the full operating system. Therefore, non-destructive, and high resolution approaches that allow the investigation of the full system are desired. Herein, we combined neutron radiography and tomography with electrical monitoring of the state of charge of commercial Ni-mischmetal hydride batteries, to track the exchange and transport of hydrogen under operating conditions. This non-destructive approach allowed both the quantification of the hydrogen distribution in the electrodes in 4D, and the distinction between the electrochemically exchanged hydrogen and the hydrogen gas pressure generated by side reactions, as a function of the applied potential and current. One of the most counter-intuitive observation is that the generation of hydrogen gas during discharge depends on the charging state of the battery. The results presented provide critical new insights in the mechanisms governing the electrochemical processes during Nimischmetal hydride battery operation, and also pave the way for the extrapolation of this approach to the investigation of state-of-the-art Li-ions batteries.

Combinatorial neutron imaging methods for hydrogenation catalysts.

Heterogeneous catalysts are materials with a complex structure at the atomic to mesoscopic scale, which depends on a variety of empirical parameters applied during preparation and processing. Although model systems clarified the general physical and chemical phenomena relevant to catalysis, such as hydrogen spillover, a rational design of heterogeneous catalysts is impeded by the sheer number of parameters. Combinatorial methods and high-throughput techniques have the potential of accelerating the development of optimal catalysts. We describe here a combinatorial approach based on hydrogen adsorption/absorption and hydrogen-deuterium exchange quantified by neutron imaging. The method coined CONI is capable of measuring more than 50 samples simultaneously. As a proof of concept, we study Pt catalyzed WO3 as an archetypal spillover system, and a Ni-catalyst supported on Al2O3 and SiO2. CONI is ideally suited to distinguish between irreversible surface adsorption and reversible bulk absorption, providing quantitative information. Concretely, CONI yields the number of reversibly adsorbed/absorbed hydrogen atoms in and on a great number of various catalysts in a single experiment.

Imaging the Chemistry of Materials Kinetics.

The kinetics of most of chemical energy storage and conversion processes is rate-limited by the mass transport through matter. There is an uncertainty on the corresponding kinetic models, especially if based solely on kinetic theory. Henceforth analytical strategies coupled to setups, in order to capture data for overcoming this limitation are essential. Operando chemical imaging of the kinetics process supports the identification of rate-limiting barriers and definition of actionable kinetic insights. After an overview of the chemical and physical processes in various energy storage/conversion systems, and examples of chemical imaging applied on them, analytical challenges are discussed with particular focus on novel methods and fundamental limitations. Despite convincing success technologies, various scientific challenges of operando chemical kinetics await solution. Apart from technical improvements of the analysis instrumentation, promising developments are seen in advanced digital science.

Catalytic Impedance Spectroscopy: Concept and Application on CO2 Methanation.

Complex modeling of periodic excitation combined with time-resolved product detection is used to describe the complex response function of a catalytic system. We describe this concept of catalytic impedance spectroscopy (CIS) and the underlying general experimental approach and a concrete setup. The feasibility of CIS is experimentally demonstrated along the catalytic CO2 methanation reaction. The measurements confirm the theoretically anticipated rate-determining step of HCO* → CH* on Ni catalysts. Limitations and prospects of CIS to unravel reaction mechanisms are discussed.

Neutron Insights into Sorption Enhanced Methanol Catalysis.

Sorption enhanced methanol production makes use of the equilibrium shift of the CO 2 hydrogenation reaction towards the desired products. However, the increased complexity of the catalyst system leads to additional reactions and thus side products such as dimethyl ether, and complicates the analysis of the reaction mechanism. On the other hand, the unusually high concentration of intermediates and products in the sorbent facilitates the use of inelastic neutron scattering (INS) spectroscopy. Despite being a post-mortem method, the INS data revealed the change of the reaction path during sorption catalysis. Concretely, the experiments indicate that the varying water partial pressure due to the adsorption saturation of the zeolite sorbent influences the progress of the reaction steps in which water is involved. Experiments with model catalysts support the INS findings.