Dynamic measurements in liquids now possible in the laboratory

A team of researchers in Berlin has developed a laboratory spectrometer for analysing chemical processes in solution – with a time resolution of 500 ps. This is of interest not only for the study of molecular processes in biology, but also for the development of new catalyst materials. Until now, however, this usually required synchrotron radiation, which is only available at large, modern X-ray sources such as BESSY II. The process now works on a laboratory scale using a plasma light source.

“Our laboratory setup now makes this measurement method available to a wider community,” says HZB physicist Dr. Ioanna Mantouvalou, who drove the development together with partners from the Technische Universität Berlin, the Max Born Institute, the Physikalisch-Technische Bundesanstalt and the company Nano Optics Berlin. “In a first step, the laboratory measurements can also more precisely define where further analyses at synchrotron sources are useful and promising. This allows us to make better use of scarce resources,” says Mantouvalou.

Time-resolved soft X-ray spectroscopy provides access to the properties of organic materials and is therefore ideal for studying dynamic changes in the electronic structure of individual elements in disordered systems. However, measurements of liquid solutions in which these molecules or complexes are dissolved are particularly challenging. They require a high photon flux and extremely low noise. Therefore, these experiments require usually large-scale facilities such as modern synchrotron light sources.

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Image: The dashed black lines mark the first thin liquid ‘sheet’ in which the molecules are dissolved. There are two nozzles in the upper part and a collecting vessel in the lower part (left image). Transmission image of the flat jet (centre image). X-ray spectrum of the solution on the CCD detector (right image).

Credit: © HZB

Electrocatalysis – Iron and Cobalt Oxyhydroxides examined

A team led by Dr. Prashanth W. Menezes (HZB/TU-Berlin) has now gained insights into the chemistry of one of the most active anode catalysts for green hydrogen production. They examined a series of Cobalt-Iron Oxyhydroxides at BESSY II and were able to determine the oxidation states of the active elements in different configurations as well as to unveil the geometrical structure of the active sites. Their results might contribute to the knowledge based design of new highly efficient and low cost catalytical active materials.

Very soon, we need to become fossil free, not only in the energy sector, but as well in industry. Hydrocarbons or other raw chemicals can be produced in principle using renewable energy and abundant molecules such as water and carbon dioxide with the help of electrocatalytically active materials. But at the moment, those catalyst materials either consist of expensive and rare materials or lack efficiency.

Key reaction in water splitting

A team led by Dr. Prashanth W. Menezes (HZB/TU-Berlin) has now gained insights into the chemistry of one of the most active catalysts for the anodic oxygen evolution reaction (OER), which is a key reaction to supply electrons for the hydrogen evolution reaction (HER) in water splitting. The hydrogen can then be processed into further chemical compounds, e.g., hydrocarbons. Additionally, in the direct electrocatalytic carbon dioxide reduction to alcohols or hydrocarbons, the OER also plays a central role.

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Image: LiFex-1Cox Borophosphates have been used as inexpensive anodes for the production of green hydrogen. Their dynamic restructuring during OER as well as their catalytically active structure, have been elucidated via  X-ray absorption spectroscopy.

Credit: © P. Menezes / HZB /TU Berlin

Direct observation of the ad- and desorption of guest atoms into a mesoporous host

Battery electrodes, storage devices for gases, and some catalyst materials have tiny functional pores that can accommodate atoms, ions, and molecules. How these guest atoms are absorbed into or released from the pores is crucial to understanding the porous materials’ functionality. However, usually these processes can only be observed indirectly. A team from the Helmholtz Zentrum Berlin (HZB) has employed two experimental approaches using the ASAXS instrument at the PTB X-ray beamline of the HZB BESSY II synchrotron to directly observe the adsorption process of atoms in a mesoporous model system. The work lays the foundations for new insights into these kinds of energy materials.

Most battery materials, novel catalysts, and storage materials for hydrogen have one thing in common: they have a structure comprised of tiny pores in the nanometer range. These pores provide space which can be occupied by guest atoms, ions, and molecules. As a consequence, the properties of the guest and the host can change dramatically. Understanding the processes inside the pores is crucial to develop innovative energy technologies.

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Image: From the measurement data, the team was able to determine that the xenon atoms first accumulate on the inner walls of the pores (state 1), before they fill them up (state 2). The X-ray beam penetrates the sample from below.

Credit: © M. Künsting/HZB