Conversion of substances
DFG approves second funding period of the CRC 1316
Plasmas for the Systems for material conversion are an important component in the utilization and storage of decentrally generated renewable energies. The Collaborative Research Center 1316 (CRC 1316) "Transient Atmospheric Pressure Plasmas - from Plasma to Liquids to Solids" is dedicated to combining atmospheric pressure plasmas with catalysis to develop the most flexible solutions possible for this material conversion. "They should be scalable, controllable and robust against external influences, such as impurities in the starting materials," explains Prof. Dr. Achim von Keudell, spokesman of the CRC.
The first funding period of the CRC 1316 was dedicated to the elucidation of transient phenomena in atmospheric pressure plasmas as well as interfacial processes at the surface of catalysts. Here, the focus was on three systems: the plasma-catalytic conversion of gases, the combination of plasmas with electrolysis at the interface between liquid and solid, and plasma-assisted biocatalysis, in which enzymes very selectively produce new molecules. The researchers were able to make great progress in these areas: For example, they achieved precise control of the formation of reactive particles in these plasmas. They were also able to gain a deeper understanding of the atomic and molecular surface processes in these systems.
In the second funding period, these findings will be brought together to make the best possible use of the interplay between a plasma with its reactive particles and a catalytically active surface. There are many further questions in this regard, since in traditional catalysis, for example, stable molecules are essentially reaction partners, whereas in plasma catalysis, reactive particles or highly excited species can accelerate or suppress a specific reaction path. On this basis, the first prototype plants for plasma catalysis, plasma electrolysis and plasma biocatalysis are to be developed.
In addition to the RUB as the host university, researchers from the University of Ulm, the Jülich Research Center and the Fritz Haber Institute in Berlin are involved in the CRC.
Conference
Japan Workshop
A workshop between CRC1316 and Japanese universities/research institutions will take part between November 29th and December 3rd, 2021. The organizers are Prof. Czarnetzki, Satoshi Hamaguchi, Jan Kuhfeld and two PhD students from Nagoya University. Further information can be found here.
Please note that the deadline is already October 27. Active participation is by invitation only, but passive participation is completely open. Participants must register in any case.
Insights into the SFB 1316
Virtual public 360° tour of the SFB 1316
Insights into the projects and laboratories, the opportunity to take a look at the various experiments and diagnostics and ask live questions about them - this opportunity is available to everyone on 27.10.2021 at 4 pm during a virtual 360° tour. The tour is aimed at the general public and thus offers not only researchers and students but also interested persons outside of university the opportunity to experience research interactively and get to know the projects better.
- To participate in the virtual tour, registration is requested at
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PUBLIC RELATIONS
Plasmas for all
A great many everyday technologies would not exist without plasmas. The teams of the Collaborative Research Centres want to share knowledge about their relevance with the public.
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Driving the plasma van to school
For many years, the plasma researchers at RUB have been committed to introducing plasmas to school students in different year groups. “Physics teachers sometimes conduct experiments that involve plasmas, but the word plasma doesn’t even appear in the curriculum,” explains Science Manager Dr. Marina Prenzel. In order to familiarise secondary school students with the concept of a plasma, the SFB team, in cooperation with Professor Heiko Krabbe and other physics didactics experts, has constructed various plasma experiments that can be stowed away in boxes and handily transported in a minibus. The researchers use them for interesting 90-minute workshops in sixth-form classes, where students can do their own experiments and learn about different applications of plasmas. “This is how we want to create awareness that plasmas are extremely important for many of our current technologies,” says Prenzel.
Students evaluate research projects
Students should not only be given the chance to learn what a plasma actually is and where it is used. Rather, the SFB team is also currently setting up a project in collaboration with the physics didactics department that aims at promoting the evaluation skills of adolescents and young adults. Here, students are to gain insights into various plasma research projects and evaluate which of these projects they would support. Another goal is to convey the significance of plasmas for the challenges of global warming.
More than 20 years of plasma summer school
For more than 20 years, plasma researchers at RUB have been organising an annual international summer school for Master’s students and doctoral candidates. It originally emerged from a European Erasmus project, acquired under the auspices of the Eindhoven University of Technology. When the funding ran out in 2000, the RUB team dedicated itself to continuing it. “The school is practically always overbooked,” says co-organiser Dr. Marc Böke. The 80 to 90 participants each year and the lecturers come from all over the world. The aim of the seven-day school is to give them insights into all the major technically relevant plasmas and, at the same time, to enable them to network with each other and with established researchers in the field. “Some of the former participants are now themselves running plasma labs,” says Böke. The RUB team hopes to resume the successful format soon, despite the coronavirus situation.
adapted from Julia Weiler, RUB
DIAGNOSTICS
Plasmas as chemistry labs![](/images/czarnetzki_plasmen_als_chemielabor_2021_gor4987.jpg)
The smaller a plasma, the larger the experimental setup needed to study it. It is worth the effort, because the reaction conditions found in cubic-millimetre-sized plasmas are very much unique. Even though plasmas at atmospheric pressure are often only a few cubic millimetres in size, they pack quite a punch. This is because special non-equilibrium states can be set up in them, which facilitate physical and chemical processes that are not possible in any other environment. The plasma thus becomes a special kind of laboratory, where atoms and molecules can be excited without their surroundings heating up. “Such excitations could theoretically also be generated in a gas, but to do so we would have to heat it to several thousand degrees Kelvin. As a result, the molecules would decompose,” explains Professor Uwe Czarnetzki, Head of the Chair of Plasma and Atomic Physics at the Faculty of Physics and Astronomy. For many years, he and his team have been developing methods to explore the processes inside plasmas and to characterise the plasmas. Plasmas boast a unique feature: electric fields can be used to supply energy to the electrons in the plasma; the electrons in turn interact with molecules such as nitrogen or carbon dioxide while transferring the energy to them. The molecules are excited, and this happens without the environment heating up in the process, as would be the case in a gas. The molecules that are excited to vibrate have a much higher reactivity than those in the ground state. Plasma can therefore change chemistry or even enable certain chemical processes in the first place. Consequently, plasma provides basic researchers with a unique opportunity to study the excitation of molecules and the associated chemistry beyond thermodynamic equilibrium. Uwe Czarnetzki is therefore primarily interested in the vibrational states of molecules in plasmas.
MGK Colloquium
Virtual MGK Colloquium
The scientific exchange among the CRC members and the group of Early Career Researcher occurred continuously during the three yearly project meetings and in the workshops organized by the CRC 1316 since it starting in 01/2018. However, it is very important that the ECR have also a platform to interact in a conference setting without the impact of their adviser to stimulate the discussions among the ECR. Instead, the CRC 1316 decided to organize an MGK Colloquium on its own by inviting the ECR from the CRC 1316 and from the SFB-TR 87. This meeting was organized by the ECRs J. Kuhfeld and P. Preissing in a virtual format on 21/04/2021. Prominent invited speakers at this event were Prof. A. Bogaerts (university Antwerp), Dr. S. Iseni (GREMI, Orléans) and Dr. T.L. Chng (LPP Paris). Beside presentations within a zoom meeting, virtual poster sessions were performed, enhancing the interaction between the ECR.
Honour of research of project A5
Project A5 on the Inside Front Cover of Plasma Processes and Polymers
The current issue (April 2021) of Plasma Processes and Polymers features work from project A5 of the CRC 1316 on the topic of "positive and negative streamer propagation in volume dielectric barrier discharges with planar and porous electrodes" on its inside front cover.
The scientists have found that the discharge characteristics of negative surface streamers differ significantly from those of positive surface streamers. While negative streamers develop along the dielectric surface, allowing them to propagate into much smaller dielectric pores, positive streamers floatingly develop above the dielectric.
- The article on the research findings and the Inside Front Cover are freely accessible online.
Project A7 - Catalysis
Catalytic carbon monoxide oxidation over potassium-doped manganese dioxide nanoparticles synthesized by spray drying
One of the major objectives of the CRC 1316 is the investigation and understanding of the complex interactions between a non-thermal plasma and heterogeneous catalysts. The first results of project A7 describing the thermocatalytic oxidation of CO over MnO2 catalysts were recently published in Emission Control Science and Technology. Particularly, the effect of the incorporated alkali ions on K+ and Na+ on the structural properties and the catalytic performance was emphasized to derive structure-activity correlations.
The MnO2 catalysts were synthesized by a semi-continuous spray drying procedure based on the comproportionation reaction of Mn(NO3)2 and KMnO4. Solutions of both compounds were continuously mixed in a micromixer and the emerging suspension was rapidly quenched by spray drying to inhibit further particle growth. In order to exchange the K+ ions by Na+ ions, NaMnO4 was used instead of KMnO4 during the synthesis. After washing and drying of the catalysts a fine brown powder was obtained, which was used as prepared or calcined at 450°C or 500°C for 4 h in synthetic air.
As shown by the XPS results and TPO profiles Mn (IV) is the predominant oxidation state of all samples prior to calcination proving that all catalysts consist of MnO2. However, the XRD patterns of the uncalcined catalysts reveal an X-ray amorphous structure preventing a more in-depth phase identification. After calcination the phase structure strongly depends on the type and amount of the incorporated alkali ion. The presence of K+ promotes the formation of crystalline alpha-MnO2 and stabilizes its tunnel structure up to temperatures of 500°C. Lower amounts of K+ or the exchange with Na+ lead to less crystalline phases after calcination at 450°C and to the formation of crystalline alpha-Mn2O3 after calcination at 500°C.
The catalytic CO oxidation was performed in a microreactor set up equipped with a non-dispersive IR detector. All uncalcined catalysts revealed a similar catalytic performance regardless of the type or amount of the incorporated alkali ion. Even though the specific surface area of the catalyst decreased from 77 m2/g to 37 m2/g during calcination the pure alpha-MnO2 phase exhibited a superior catalytic activity. Over alpha-MnO2 the temperature at which full conversion was achieved was shifted towards lower temperatures by more than 100°C. In contrast the catalyst containing alpha-Mn2O3 show a catalytic activity similar to the uncalcined catalysts indicating that not only the higher degree of crystallinity but also the structural properties of alpha-MnO2 cause its high catalytic activity. The incorporation of K+ ions is required to stabilize the tunnel structure of alpha-MnO2
PLASMA RESEARCH, project B7
Lightning bolt underwater
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A plasma tears through the water within a few nanoseconds. It may possibly regenerate catalytic surfaces at the push of a button.
Electrochemical cells help recycle CO2. However, the catalytic surfaces get worn down in the process. Researchers at the Collaborative Research Centre 1316 “Transient atmospheric plasmas: from plasmas to liquids to solids” at Ruhr-Universität Bochum (RUB) are exploring how they might be regenerated at the push of a button using extreme plasmas in water. In a first, they deployed optical spectroscopy and modelling to analyse such underwater plasmas in detail, which exist only for a few nanoseconds, and to theoretically describe the conditions during plasma ignition. They published their report in the journal Plasma Sources Science and Technology on 4 June 2019.
A plasma tears through the water within a few nanoseconds. Following plasma ignition, there is a high negative pressure difference at the tip of the electrode, which results in ruptures forming in the liquid. Plasma then spreads across those ruptures.
Video: Experimentalphysik II
Plasmas are ionised gases: they are formed when a gas is energised that then contains free electrons. In nature, plasmas occur inside stars or take the shape of polar lights on Earth. In engineering, plasmas are utilised for example to generate light in fluorescent lamps, or to manufacture new materials in the field of microelectronics. “Typically, plasmas are generated in the gas phase, for example in the air or in noble gases,” explains Katharina Grosse from the Institute for Experimental Physics II at RUB.
Ruptures in the water
In the current study, the researchers have generated plasmas directly in a liquid. To this end, they applied a high voltage to a submerged hairline electrode for the range of several billionth seconds. Following plasma ignition, there is a high negative pressure difference at the tip of the electrode, which results in ruptures forming in the liquid. Plasma then spreads across those ruptures. “Plasma can be compared with a lightning bolt – only in this case it happens underwater,” says Katharina Grosse.
Hotter than the sun
Using fast optical spectroscopy in combination with a fluid dynamics model, the research team identified the variations of power, pressure, and temperature in these plasmas. “In the process, we observed that the consumption inside these plasmas briefly amounts to up to 100 kilowatt. This corresponds with the connected load of several single-family homes,” points out Professor Achim von Keudell from the Institute for Experimental Physics II. In addition, pressures exceeding several thousand bars are generated – corresponding with or even exceeding the pressure at the deepest part of the Pacific Ocean. Finally, there are short bursts of temperatures of several thousand degrees, which roughly equal and even surpass the surface temperature of the sun.
Water is broken down into its components
Such extreme conditions last only for a very short time. “Studies to date had primarily focused on underwater plasmas in the microsecond range,” explains Katharina Grosse. “In that space of time, water molecules have the chance to compensate for the pressure of the plasma.” The extreme plasmas that have been the subject of the current study feature much faster processes. The water can’t compensate for the pressure and the molecules are broken down into their components. “The oxygen that is thus released plays a vital role for catalytic surfaces in electrochemical cells,” explains Katharina Grosse. “By re-oxidating such surfaces, it helps them regenerate and take up their full catalytic activity again. Moreover, reagents dissolved in water can also be activated, thus facilitating catalysis processes.”
By Meike Drießen, Translated by Donata Zuber