Electrocatalysis under the atomic force microscope

The newly developed method was used to scan the surface of a bimetallic catalyst material in an aqueous medium. The figure shows an overlay of the current signal on a three-dimensional representation of the height image. This clearly shows island-like regions.

The newly developed method was used to scan the surface of a bimetallic catalyst material in an aqueous medium. The figure shows an overlay of the current signal on a three-dimensional representation of the height image. This clearly shows island-like regions. © M. Munz/HZB

The principle of correlative atomic force microscopy in contact mode: a fine tip at the end of a cantilever scans the surface. This allows force interactions between the tip and the sample surface to be measured, including frictional forces. If a voltage is also applied, the electric current flowing through the contact can also be measured.

The principle of correlative atomic force microscopy in contact mode: a fine tip at the end of a cantilever scans the surface. This allows force interactions between the tip and the sample surface to be measured, including frictional forces. If a voltage is also applied, the electric current flowing through the contact can also be measured.

A further development in atomic force microscopy now makes it possible to simultaneously image the height profile of nanometre-fine structures as well as the electric current and the frictional force at solid-liquid interfaces. A team from the Helmholtz-Zentrum Berlin (HZB) and the Fritz Haber Institute (FHI) of the Max Planck Society has succeeded in analysing electrocatalytically active materials and gaining insights that will help optimise catalysts. The method is also potentially suitable for studying processes on battery electrodes, in photocatalysis or on active biomaterials.

To manage the energy transition, it will also be important to rapidly develop cheap and efficient materials that can be used to split water or CO2 by electrocatalysis. In this process, part of the electrical energy is stored in the chemical reaction products. The efficiency of such electrocatalysts depends largely on the nature of the electrode-electrolyte interfaces, i.e. the interfaces between the solid electrodes and the typically aqueous electrolyte. However, spatially resolved physical studies of such solid-liquid interfaces are still relatively scarce.

More insights with AFM

Dr Christopher S. Kley and his team have now developed a new approach to correlative atomic force microscopy (AFM). An extremely sharp tip is scanned across the surface and its height profile is recorded. By attaching the tip to the end of a miniaturised cantilever, the force interactions between the tip and the sample surface, including frictional forces, can be measured with high sensitivity. In addition, the electrical current flowing through the mechanical contact can be measured, provided a voltage is applied. "This allowed us to simultaneously determine the electrical conductivity, the mechanical-chemical friction and the morphological properties in situ (i.e. under the relevant liquid-phase conditions rather than in vacuum or in air)," emphasises Kley.

Copper-gold electrocatalyst

Using this method, the scientists now studied a nanostructured and bimetallic copper-gold electrocatalyst, in collaboration with Prof. Beatriz Roldán Cuenya from the Fritz-Haber-Institute (FHI). Among others, such materials are used in the electrocatalytic conversion of CO2 into energy carriers. "We were able to clearly identify islands of copper oxide with higher electrical resistance, but also grain boundaries and low-conductivity regions in the hydration layer where the catalyst surface comes into contact with the aqueous electrolyte," says Dr Martin Munz, first author of the study.

Such results on catalyst-electrolyte interfaces help to optimise them in a targeted manner. "We can now observe how local electrochemical environments influence charge transfer at the interface," says Kley.

Focus on solid-liquid interfaces

"However, our results are also of general interest to energy research, especially for the study of electrochemical conversion processes, which also play a role in battery systems." Insights into solid-liquid interfaces can also be useful in completely different areas of research, such as understanding corrosion processes, nanosensor systems, and possibly addressing scientific queries in fluidics and environmental sciences, such as dissolution or deposition processes on metal surfaces exposed to water.

Note: This work was carried out within the framework of the CatLab project, where researchers from the HZB and the FHI of the MPG are working together, to develop thin-film catalysts for the energy transition.

arö

You might also be interested in

  • Green hydrogen: How photoelectrochemical water splitting may become competitive
    Science Highlight
    20.03.2023
    Green hydrogen: How photoelectrochemical water splitting may become competitive
    Sunlight can be used to produce green hydrogen directly from water in photoelectrochemical (PEC) cells. So far, systems based on this "direct approach" have not been energetically competitive. However, the balance changes as soon as some of the hydrogen in such PEC cells is used in-situ for a catalytic hydrogenation reaction, resulting in the co-production of chemicals used in the chemical and pharmaceutical industries. The energy payback time of photoelectrochemical "green" hydrogen production can be reduced dramatically, the study shows.
  • Perovskite solar cells from the slot die coater - a step towards industrial production
    Science Highlight
    16.03.2023
    Perovskite solar cells from the slot die coater - a step towards industrial production
    Solar cells made from metal halide perovskites achieve high efficiencies and their production from liquid inks requires only a small amount of energy. A team led by Prof. Dr. Eva Unger at Helmholtz-Zentrum Berlin is investigating the production process. At the X-ray source BESSY II, the group has analyzed the optimal composition of precursor inks for the production of high-quality FAPbI3 perovskite thin films by slot-die coating. The solar cells produced with these inks were tested under real life conditions in the field for a year and scaled up to mini-module size.
  • Superstore MXene: New proton hydration structure determined
    Science Highlight
    13.03.2023
    Superstore MXene: New proton hydration structure determined
    MXenes are able to store large amounts of electrical energy like batteries and to charge and discharge rather quickly like a supercapacitor. They combine both talents and thus are a very interesting class of materials for energy storage. The material is structured like a kind of puff pastry, with the MXene layers separated by thin water films. A team at HZB has now investigated how protons migrate in the water films confined between the layers of the material and enable charge transport. Their results have been published in the renowned journal Nature Communications and may accelerate the optimisation of these kinds of energy storage materials.