Dr. Saskia Heumann - Carbon Synthesis and Applications

Dr. Saskia Heumann
Head of Group Carbon Synthesis and Application
Department Heterogeneous Reactions

Vita

Diploma
Christian-Albrechts-Universität zu Kiel, Dipl. Chem. (2003-2008)
Diploma thesisIFM-GEOMAR, Leibnitz Institute, Maritime Chemistry (2009)
Dr. rer. nat.Christian-Albrechts-Universität zu Kiel, Inorganic Chemistry (Prof. Dr. W. Bensch) (2012)
Group leaderMPI CEC (since 2012)

Publications

Full publications list | ORCID | ResearcherID

Selected MPI CEC publications

  • Ding, Y., Zhang, P., Xiong, H., Sun, X., Klyushin, A., Zhang, B., Liu, Z., Zhang, J., Zhu, H., Xiao, Z.-A., Heumann, S., Dai, S. (2020). Tuning Regioselective Oxidation toward Phenol via Atomically Dispersed Iron Sites on Carbon Green Chemistry 22(18), 6025-6032. https://doi.org/10.1039/D0GC01717E
  • Ding, Y., Greiner, M., Schlögl, R., Heumann, S. (2020). A Metal Free Electrode: From Biomass Derived Carbon to Hydrogen ChemSusChem 13(16), 4064-4048. https://doi.org/10.1002/cssc.202000714
  • Park, H., Uluca-Yazgi, B., Heumann, S., Schlögl, R., Granwehr, J., Heise, H., Schleker, P.P.M. (2020). Heteronuclear cross-relaxation effect modulated by the dynamics of N-functional groups in the solid state under 15N DP-MAS DNP Journal of Magnetic Resonance 312, 106688. https://doi.org/10.1016/j.jmr.2020.106688
  • Ding, Y., Gu, Q., Klyushin, A., Huang, X., Choudhury, S.H., Spanos, I., Song, F., Mom, R., Düngen, P., Mechler, A.K., Schlögl, R., Heumann, S. (2020). Dynamic carbon surface chemistry: revealing the role of carbon in electrolytic water oxidation Journal of Energy Chemistry 47, 155-159. https://doi.org/10.1016/j.jechem.2019.12.006
  • Kraus, P., Massué, C., Heumann, S., Schlögl, R. (2019). Reliable long-term performance assessment of commercial photovoltaic modules tested under field conditions over 5 years Journal of Renewable and Sustainable Energy 11, 063501. https://doi.org/10.1063/1.5128171
  • Lin, Y., Liu, Z., Niu, Y., Zhang, B., Lu, Q., Wu, S., Centi, G., Perathoner, S., Heumann, S., Lu, Y., Su, D.S. (2019). Highly Efficient Metal-Free Nitrogen-Doped Nanocarbons with Unexpected Active Sites for Aerobic Catalytic Reactions ACS Nano https://doi.org/10.1021/acsnano.9b05856
  • Park, H., Schleker, P.P.M., Liu, Z., Kowalew, N., Stamm, T., Schlögl, R., Eichel, R.-A., Heumann, S., Granwehr, J. (2019). Insights on Water Interaction at the Interface of Nitrogen Functionalized Hydrothermal Carbons The Journal of Physical Chemistry C 123(41), 25146-25156. https://doi.org/10.1021/acs.jpcc.9b05323
  • Ding, Y., Schlögl, R., Heumann, S. (2019). The role of supported atomically distributed metal species in electrochemistry and how to create them ChemElectroChem 6(15), 3860-3877. https://doi.org/10.1002/celc.201900598
  • Lin, Y., Lu, Q., Song, F., Yu, L., Mechler, A.K., Schlögl, R., Heumann, S. (2019). Oxygen Evolution Reaction at Carbon Edge Sites: Activity Evolution and Structure‐Function Relationships Clarified by Polycyclic Aromatic Hydrocarbons Angewandte Chemie International Edition 58(26), 8917-8921. https://doi.org/10.1002/anie.201902884
  • Gu, Q., Ding, Y., Liu, Z., Lin, Y., Schlögl, R., Heumann, S., Su, D. (2019). Probing the intrinsic catalytic activity of carbon nanotubes for the metal-free oxidation of aromatic thiophene compounds in ionic liquids Journal of Energy Chemistry 32, 131-137. https://doi.org/10.1016/j.jechem.2018.07.004
  • Rodenas, T., Beeg, S., Spanos, I., Neugebauer, S., Girgsdies, F., Algara-Siller, G., Schleker, P.P.M., Jakes, P., Pfänder, N., Willinger, M., Greiner, M., Prieto, G., Schlögl, R., Heumann, S. (2018). 2D Metal Organic Framework-Graphitic Carbon Nanocomposites as Precursors for High-Performance O2-Evolution Electrocatalysts Advanced Energy Materials 8(35), 1802404. https://doi.org/10.1002/aenm.201802404
  • Lin, Y., Wu, K.-H., Lu, Q., Gu, Q., Zhang, L., Zhang, B., Sheng Su, D., Plodinec, M., Schlögl, R., Heumann, S. (2018). Electrocatalytic Water Oxidation at Quinone-on-Carbon: A Model System Study Journal of the American Chemical Society 140(44), 14717-14724. https://doi.org/10.1021/jacs.8b07627
  • Düngen, P., Greiner, M., Böhm, K.H., Spanos, I., Huang, X., Auer, A.A., Schlögl, R., Heumann, S. (2018). Atomically dispersed vanadium oxides on multiwalled carbon nanotubes via atomic layer deposition: A multiparameter optimization Journal of Vacuum Science & Technology A 36(1), 01A126. https://doi.org/10.1116/1.5006783
  • Ding, Y., Klyushin, A., Huang, X., Jones, T., Teschner, D., Girgsdies, F., Rodenas, T., Schlögl, R., Heumann, S. (2018). Cobalt Bridged with Ionic Liquid Polymer on Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity Angewandte Chemie International Edition 57(13), 3514-3518. https://doi.org/10.1002/anie.201711688
  • Düngen, P., Schlögl, R., Heumann, S. (2018). Non-linear thermogravimetric mass spectrometry of carbon materials providing direct speciation separation of oxygen functional groups Carbon 130, 614-622. https://doi.org/10.1016/j.carbon.2018.01.047
  • Straten, J.W., Schlecker., P., Krasowska, M., Veroutis, E., Granwehr, J., Auer, A.A., Hateba, W., Becker, S., Schlögl, R., Heumann, S. (2018). N-Funtionalized Hydrothermal Carbon Materials using Urotropine as N-Precursor Chemistry - A European Journal 24(47), 12298-12317. https://doi.org/10.1002/chem.201800341
  • Gu, Q.Q., Lin, Y.M., Heumann, S., Su, D.S. (2017). Nanocarbons for Catalytic Desulfurization Chemistry - An Asian Journal 12(22), 2876-2883. https://doi.org/10.1002/asia.201700995
  • Yi, Y.M., Weinberg, G., Prenzel, M., Greiner, M., Heumann, S., Becker, S., Schlögl, R. (2017). Electrochemical corrosion of a glassy carbon electrode Catalysis Today 295, 32-40. https://doi.org/10.1016/j.cattod.2017.07.013
  • Lin, Y.M., Wu, K.H., Yu, L.H., Heumann, S., Su, D.S. (2017). Efficient and Highly Selective Solvent-Free Oxidation of Primary Alcohols to Aldehydes Using Bucky Nanodiamond ChemSusChem 10(17), 3497-3505. https://doi.org/10.1002/cssc.201700968
  • Düngen, P., Prenzel, M., Van Stappen, C., Pfänder, N., Heumann, S., Schlögl, R. (2017). Investigation of Different Pre-Treated Multi-Walled Carbon Nanotubes by Raman Spectroscopy Materials Sciences and Applications 8, 628-641 https://doi.org/10.4236/msa.2017.88044
  • Hävecker, M., Düngen, P., Buller, S., Knop-Gericke, A., Trunschke, A., Schlögl, R. (2017). Restructuring of silica supported vanadia during propane oxidative dehydrogenation studied by combined synchrotron radiation based in situ soft X-ray absorption and photoemission Catalysis Structure and Reactivity 3, 104-111. https://doi.org/10.1080/2055074X.2017.1287535
  • Buller, S., Strunk, J. (2016). Nanostructure in energy conversion Journal of Energy Chemistry 25(2), 171-190. https://doi.org/10.1016/j.jechem.2016.01.025
  • Buller, S., Heise-Podleska, M., Pfänder, N., Willinger, M., Schlögl, R. (2016). Carbon nanotubes as conducting support for potential Mn-oxide electrocatalysts: Influences of pre-treatment procedures Journal of Energy Chemistry 25(2), 265-271. https://doi.org/10.1016/j.jechem.2016.01.022



Group Members

Scientific staff

  • Dr. Yang-Ming Lin
  • Dr. Lin-Hui Yu

Postdocs

  • Dr. Guillermo Álvarez Ferrero
  • Dr. Johannes Franz Peter Colell
  • Dr. Yuxiao Ding
  • Dr. Peter Philipp Maria Schleker

PhD students

  • Heeyong Park

Lab staff

  • Marius Heise-Podleska
  • Natalia Kowalew
  • Dieter Oppenberg
  • Teresa Stamm
  • Tobias Stamm

Carbon Synthesis and Application

The aim of our research is the knowledge-based development of advanced electrode materials consisting of a structured carbon backbone. The work is focused on electrode materials for the oxygen evolution reaction (OER) in water electrolysis. The general idea is to use glucose as model precursor for biomass (a), which can be used as cheap and abundant carbon source. The initial liquid solutions convert into modified liquid and solid carbonaceous materials during the autoclave process (b) under high pressure and temperature. The liquid products can be further converted in biorefinery facilities to produce fuels or other value-added chemicals. The solid products can be pressed into mechanically stable pellets by an annealing step under inert gas atmosphere. The high number of functional groups within the hydrothermal carbon (HTC) lead to intrinsic binding properties during the pellet formation (c). No additional binder, like for instance Nafion, is needed and the specific material properties can be investigated.

The carbon based electrode materials are applied in electrochemical cells (d) to investigate their electrochemical activity as well as stability. The gaseous products of hydrogen and oxygen are produced during the water splitting process. In this way, the electrical energy from renewable sources like solar or wind energy is converted into the chemical energy carrier hydrogen, which can be further converted to methanol or ammonia by using exhaust gases from industry (e).

Interests & Challenges:

  • increasing long-term stability while maintaining high activity
  • investigation of active sites
  • increasing the surface areas
  • understanding of the condensation process in the autoclaves
  • investigation of the carbonaceous structures
  • influence of hetero-atoms in the autoclave process
  • incorporation of nitrogen / metal (oxides)
  • understanding of structure-property correlations

Hydrothermal Carbon Synthesis[1],[2]

The carbon synthesis strategy of the group is based on the use of molecular precursors and controllable condensation reactions in liquid phase. Glucose is used for this bottom-up approach to obtain solid hydrothermal carbons. The incorporation of oxygen or nitrogen functional groups can be adjusted by varying the initial synthesis pH and by the addition of nitrogen containing precursor like for example urotropine. The distribution of the oxygen functional groups, as well as the morphology of the carbonaceous product, is controlled by process parameters, in particular the pH. For lower initial synthesis pH, i. e. pH 0, extended carbonaceous structures were confirmed by Raman spectroscopy, whereas for pH > 3 furanic structural entities from the 5-hydroxymethyl furfural intermediate remained the dominant structural motive of the carbon. The high number of functional groups leads to intrinsic binding properties that allow the preparation of functional disc electrodes by pressing and thermal annealing to 900°C. In the absence of Nafion, material-only properties can be studied for further fundamental understanding of electrochemical processes. The macroscopic dimension of the bulk electrode allows quantitative analytical investigations after electrochemical testing.

Post-functionalization techniques such as plasma treatment, electrochemical oxidation and (hydro)thermal treatments in active gases/solvents complete the methodical variety for the introduction of desired surface termination for the stabilization of catalysts.

Characterization[3],[4],[5]

In order to distinguish differently functionalized carbon materials established characterization methods were modified to obtain deeper knowledge about the synthesized carbon materials and their modification under electrochemical conditions. For Raman spectroscopy, a single-phonon resonance (SPR) fitting procedure was developed for graphitic materials based on multi-walled carbon nanotubes (MWCNT). The theory derived fit resulted in accurate ratios of the ideal graphitic lattice vibrations (G-Band) and lattice vibrations induces by defects/functional groups (D- and D'-Band). Furthermore, the direct speciation separation of functional groups could be achieved with a non-linear heating procedure by the thermogravimetric mass spectrometry setup. Supported by further characterization techniques such as microscopy and XPS the type and quantity of functionalization of graphitic carbon materials can be derived.

Metal deposition[6],[7]

We further studied options of anchoring metals on structured carbon materials. A strong interaction between catalytic active species and electric conductive carbon support is essential for high activity and stability of the catalyst materials. Techniques like atomic layer deposition (ALD), wet impregnation, adsorption of colloids or the usage of polymerized ionic liquids were applied to achieve intense synergy effects. We applied different pre-treated multi-walled carbon nanotubes as support materials and were able to generate atomically dispersed metal oxides on their surface. The materials showed remarkably high activities as well as stabilities.


References

1. S. Reiche, N. Kowalew, R. Schlögl, Influence of Synthesis pH and Oxidative Strength of the Catalyzing Acid on the Morphology and Chemical Structure of Hydrothermal Carbon, ChemPhysChem. https://doi.org/10.1002/cphc.201402834

2. J. W. Straten, P. Schlecker, M. Krasowska, E. Veroutis, J. Granwehr, A.A. Auer, W. Hateba, S. Becker, R. Schlögl, S. Heumann, N-Funtionalized Hydrothermal Carbon Materials using Urotropine as N-Precursor, Chemistry - A European Journal, https://doi.org/10.1002/chem.201800341

3. P. Düngen, M. Prenzel, Casey Van Stappen, Norbert Pfänder, Saskia Heumann, and Robert Schlögl, Investigation of different pre-treated multi-walled carbon nanotubes by Raman spectroscopy, Materials Sciences and Applications https://doi.org/10.4236/msa.2017.88044

4.  P. Düngen, R. Schlögl, S. Heumann, Non-linear thermogravimetric mass spectrometry of carbon materials providing direct speciation separation of oxygen functional groups, Carbon https://doi.org/10.1016/j.carbon.2018.01.047


5.  Y. Yi, G. Weinberg, M. Prenzel, M. Greiner, S. Heumann, S. Becker, R. Schlögl, Electrochemical corrosion of a glassy carbon electrode, Catalysis Today https://doi.org/10.1016/j.cattod.2017.07.013

6.  P. Düngen, M. Greiner, K.-H. Boehm, I. Spanos, X. Huang, A.A. Auer, R. Schloegl, S. Heumann, Atomically dispersed vanadium oxides on multiwalled carbon nanotubes via atomic layer deposition: A multiparameter optimization, Journal of Vacuum Science & Technology A https://doi.org/10.1116/1.5006783

7.  Y. Ding, A. Klyushin, X. Huang, T. Jones, D. Teschner, F. Girgsdies, T. Rodenas, R. Schlögl, S. Heumann, Cobalt Bridged with Ionic Liquid Polymer on Carbon Nanotube for Enhanced Oxygen Evolution Reaction Activity, Angewandte Chemie Int. Ed, doi.org/10.1002/anie.201711688, https://doi.org/10.1002/ange.201711688

Alumni

Dr. Sylvia Becker   Dr. Jan Willem Straten
Dr. Pascal DüngenFabian Wachholz
Dr. Qingqing Gu   Dr. Shuchang Wu
Dr. Marina Prenzel   Dr. Youngmi Yi
Dr. Tania Rodenas