One research topic focusses on functional materials based on cellulose/paper. By an appropriate surface functionalization of the cellulose containing carrier material with polymers, small organic or biomolecules these materials can be tuned to become applicable in energy storage, as sensoric or optical devices. The Gutmann’s group is developing and applying analytical techniques to identify the surface functionalizations and to characterize the structure and dynamics in these disordered materials. As important tool they use a combination of solid-state NMR and Dynamic Nuclear Polarization techniques.

Since September 2023, the group is involved in the European Innovation Council (EIC) pathfinder project VanillaFlow (Artificial Intelligence Guided Development of Vanillin-based Flow Batteries) (www.vanillaflow.eu). Here, the group works on advanced solid-state NMR analytics for novel paper-based membranes, which can beused in modern redox flow battery technology.

[1] Limprasart, W., Höfler, M. V., Kunzmann, N., Rösler, L., Herr, K., Breitzke, H., Gutmann, T.* Peptides as Model Systems for Biofunctionalizations of Cellulose – Synthesis and Structural Characterization by Advanced Solid-State NMR Techniques. J. Phys. Chem. C, (2023), accepted Manuscript ID: jp-2023-050685.R1

[2] Höfler, M. V., Limprasart, W., Rösler, L., Fleckenstein, M., Brodrecht, M., Herr, K., Schäfer, J.-L., Biesalski, M., Breitzke, H., Gutmann, T.*, Fluorine Labeled N-Boc-L-Proline as Marker for Solid-State NMR Characterization of Biofunctionalizations on Paper Substrates. J. Phys. Chem C 117, (2023), 3570–3578. DOI: 10.1021/acs.jpcc.2c08370

[3] Höfler, M. V., Hoinka, N., Schäfer, T., Horn, M., Aussenac, F., Fuhrmann-Lieker, T.*, Gutmann, T.*, Light Amplification Materials based on Biopolymers doped with Dye Molecules – Structural Insights from 15N and 13C Solid state Dynamic Nuclear Polarization. J. Phys. Chem C 125, (2021), 21550–21558. DOI: 10.1021/acs.jpcc.1c06737 [Add to Citavi project by DOI]

[4] Gutmann, T.*, Kumari, B., Zhao, L., Breitzke, H.; Schöttner, S., Rüttiger, C., Gallei, M.*, DNP Signal Amplification as Sensitive Probe for Specific Functionalization of Complex Paper Substrates, J. Phys. Chem. C 121, (2017), 3896-3903. DOI: 10.1021/acs.jpcc.6b11751 [Add to Citavi project by DOI]

[5] Zhao, L., Smolarkiewicz, I., Limbach, H.-H., Breitzke, H., Pogorzelec-Glaser, K., Pankiewicz, R., Tritt-Goc, J.*, Gutmann, T.*, Buntkowsky, G.*, Imidazole Doped Cellulose as Membrane for Fuel Cells – Structural and Dynamic Insights from Solid-State NMR, J. Phys. Chem. C 120, (2016), 19574-19585. DOI: 10.1021/acs.jpcc.6b07049

In 2021 the group started the investigation of sodium /sodium Ion battery components employing ex-situ and in-situ solid-state NMR in the frame of the EU project SIMBA (www.simba-h2020.eu). Questions such as the structural intercalation of sodium in electrode materials in solid-phase battery systems are addressed. Furthermore, structural changes of the materials are investigated under working conditions to understand processes during cycling that may affect the efficiency and lifetime of the energy storage systems.

[1] Šić, E., Schutjajew, K., Haagen, U., Breitzke, H., Oschatz, M., Buntkowsky, G.*, Gutmann, T.* Electrochemical Sodium Storage in Hard Carbon Powder Electrodes Implemented in an Improved Cell Assembly: Insights from In-Situ and Ex-Situ Solid-State NMR. ChemSusChem, (2023), e202301300. DOI: 10.1002/cssc.202301300

[2] Šić, E., Rohrer, J.*, Ricohermoso, E., Albe, K., Ionescu, E., Riedel, R., Breitzke, H., Gutmann, T.*, Buntkowsky, G.* SiCO Ceramics as Storage Materials for Alkali Metals/Ions – Insights on Structure Moieties from Solid-State NMR and DFT Calculations. ChemSusChem, (2023), e202202241. DOI: 10.1002/cssc.202202241

[3] Šić, E., Melzi d'Eril, M., Schutjajew, K., Graczyk-Zajac, M., Breitzke, H., Riedel, R., Oschatz, M., Gutmann, T*, Buntkowsky, G.*, SiCN Ceramics as Electrode Materials for Sodium/Sodium Ion Cells – Insights from 23Na In-situ Solid-State NMR. Batter. Supercaps 5, (2022), e202200066. DOI: 10.1002/batt.202200066

The group is further interested in covalent organic frameworks as they can by employed in energy storage systems or in catalysis. Here, we wish to broaden the applicability of solid-state NMR techniques including dynamic nuclear polarization to characterize such materials. In future we will further extent the approach to study these materials under conditions they are used in energy storage systems or in catalysis.

[1] Krusenbaum, A., Kraus, F. J. L., Hutsch, S., Grätz, S., Höfler, M. V., Gutmann, T., Borchardt, L.*, The Rapid Mechanochemical Synthesis of Microporous Covalent Triazine Networks: Elucidating the Role of Chlorinated Linkers by a Solvent‑free Approach. Adv. Sustain. Syst., (2023), 2200477. DOI: 10.1002/adsu.202200477

[2] Krusenbaum, A., Geisler, J., Kraus, F. J. L., Grätz, S., Höfler, M. V., Gutmann, T., Borchardt, L.* The Mechanochemical Friedel Crafts Polymerization as a Solvent-free Cross-linking Approach towards Microporous Polymers. J. Polym. Sci. 60, (2022), 62-71. DOI: 10.1002/pol.20210606

[3] Grätz, S., de Oliveira Jr., M., Gutmann, T.*, Borchardt, L.*, A comprehensive approach for the Characterization of Porous Polymers by 13C and 15N Dynamic Nuclear Polarization NMR Spectroscopy. Phys. Chem. Chem. Phys. 22, (2020), 23307-23314. DOI: 10.1039/D0CP04010J

For many years, the group focusses on heterogenized catalysts. As examples metallic nanoparticles as well as supported catalysts, which are of high interest in technical reactions such as in hydrogenation, CO oxidation, hydroformylation, water gas shift reaction etc. are investigated. Our interest is to identify catalytic sites as well as to get insights into the surface chemistry of these catalyst systems, which is the basic step to optimize them for technical applications. Here, we are using a combination of solid-state NMR and gas phase NMR. Since 2022 the group is involved in the CRC 1487 “Iron Upgraded” (www.chemie.tu-darmstadt.de/iron-upgraded) where we look on H/D exchange reactions.

[1] Schumacher, L., Pfeiffer, J., Shen, J., Gutmann, T., Breitzke, H., Buntkowsky, G., Hofmann, K., Hess, C.* Collaborative Mechanistic Effects between Vanadia and Titania during the Oxidative Dehydrogenation of Propane Investigated by Operando and Transient Spectroscopy. ACS Catalysis 13, (2023), 8139–8160. DOI: 10.1021/acscatal.3c01404

[2] Rothermel, N., Limbach, H.-H., del Rosal, I., Poteau, R.*, Mencia, G., Chaudret, B., Buntkowsky, G.*, Gutmann, T.* Surface reactions of ammonia on ruthenium nanoparticles revealed by 15N and 13C solid-state NMR. Catal. Sci. Technol. 11, (2021), 4509 – 4520. DOI: 10.1039/D0CY02476G

[3] de Oliveira Jr, M., Seeburg, D., Weiss, J., Wohlrab, S., Buntkowsky, G.*, Bentrup, U.*, Gutmann, T.* Structural characterization of vanadium environments in MCM-41 molecular sieve catalysts by solid state 51V NMR. Catal. Sci. Technol. 9, (2019), 6180–6190. DOI: 10.1039/C9CY01410A

[4] Klimavicius, V., Neumann, S., Kunz, S., Gutmann, T.*, Buntkowsky, G.* Room temperature CO oxidation catalysed by supported Pt nanoparticles revealed by solid-state NMR and DNP spectroscopy. Catal. Sci. Technol. 9, (2019), 3743–3752. DOI: 10.1039/c9cy00684b