BESSY II: Localisation of d-electrons determined
At BESSY II, Auger photoelectron coincidence spectroscopy (APECS) can be used to precisely determine the localisation of d electrons in cobalt compared to nickel and copper. © adobestock
Transition metals have many applications in engineering, electrochemistry and catalysis. To understand their properties, the interplay between atomic localisation and delocalisation of the outer electrons in the d orbitals is crucial. This insight is now provided by a special end station at BESSY II with highest precision, as demonstrated by a study of copper, nickel and cobalt with interesting quantitative results. The Royal Society of Chemistry has selected the paper as a HOT Article 2022.
Transition metals and non-ferrous metals such as copper, nickel and cobalt are not only suitable as materials in engineering and technology, but also for a wide range of applications in electrochemistry and catalysis. Their chemical and physical properties are related to the occupation of the outer d-orbital shells around the atomic nuclei. The energetic levels of the electrons as well as their localisation or delocalisation can be studied at the X-ray source BESSY II, which offers powerful synchrotron radiation.
Copper, Nickel, Cobalt
The team of the Uppsala-Berlin Joint Lab (UBjL) around Prof. Alexander Föhlisch and Prof. Nils Mårtensson has now published new results on copper, nickel and cobalt samples. They confirmed known findings for copper, whose d-electrons are atomically localised, and for nickel, in which localised electrons coexist with delocalised electrons. In the case of the element cobalt, which is used for batteries and as an alloy in fuel cells, however, previous findings were contradictory because the measurement accuracy was not sufficient to make clear statements.
Spectroscopy combined with highly sensitive detectors
At BESSY II the Uppsala-Berlin joint Lab has set up an instrument which enables measurements with the necessary precision. To determine electronic localisation or delocalisation, Auger photo-electron coincidence spectroscopy (APECS) is used. APECS requires the newly developed "Angle resolved Time of Flight" (ArTOF) electron spectrometers, whose detection efficiency exceeds that of standard hemispherical analysers by orders of magnitude. Equipped with two ArTOF electron spectrometers, the CoESCA@UE52-PGM end station supervised by UBjL scientist Dr. Danilo Kühn is unique worldwide.
Analysing (catalytical) materials
In the case of the element cobalt, the measurements now revealed that the d-electrons of cobalt can be regarded as highly delocalised. "This is an important step for a quantitative determination of electronic localisation on a variety of materials, catalysts and (electro)chemical processes," Föhlisch points out.
Guest users are welcome
The Royal Society of Chemistry has therefore selected the paper as a HOT Article 2022, also because this measurement method might arouse broad interest in the broader research community. The end station is also available to international users at BESSY II, who can apply for beamtime twice a year.
- Porous Radical Organic framework improves lithium-sulphur batteriesA team led by Prof. Yan Lu, HZB, and Prof. Arne Thomas, Technical University of Berlin, has developed a material that enhances the capacity and stability of lithium-sulphur batteries. The material is based on polymers that form a framework with open pores (known as radical-cationic covalent organic frameworks or COFs). Catalytically accelerated reactions take place in these pores, firmly trapping polysulphides, which would shorten the battery life. Some of the experimental analyses were conducted at the BAMline at BESSY II.
- Metallic nanocatalysts: what really happens during catalysisUsing a combination of spectromicroscopy at BESSY II and microscopic analyses at DESY's NanoLab, a team has gained new insights into the chemical behaviour of nanocatalysts during catalysis. The nanoparticles consisted of a platinum core with a rhodium shell. This configuration allows a better understanding of structural changes in, for example, rhodium-platinum catalysts for emission control. The results show that under typical catalytic conditions, some of the rhodium in the shell can diffuse into the interior of the nanoparticles. However, most of it remains on the surface and oxidises. This process is strongly dependent on the surface orientation of the nanoparticle facets.
- Shedding light on insulators: how light pulses unfreeze electronsMetal oxides are abundant in nature and central to technologies such as photocatalysis and photovoltaics. Yet, many suffer from poor electrical conduction, caused by strong repulsion between electrons in neighboring metal atoms. Researchers at HZB and partner institutions have shown that light pulses can temporarily weaken these repulsive forces, lowering the energy required for electrons mobility, inducing a metal-like behavior. This discovery offers a new way to manipulate material properties with light, with high potential to more efficient light-based devices.