Emeriti

Prof. Dr. Robert Schlögl

Direktor 2011-2022

Vita

Diplom	Maximilians Universität München (1979)
Dr. rer. nat.	Maximilians Universität München (1982)
Postdoc	Heterogeneous Catalysis, Cambridge University (Sir J. Meurig Thomas); Physics, Switzerland (Prof. H.J. Güntherodt) (1982 - 1983)
Gruppenleiter	Hoffmann La Roche AG, Basel, Schweiz
Habilitation	Structure of industrial ammonia-synthesis catalysts (Prof. Gerhard Ertl), FHI Berlin
Professor	Inorganic Chemistry, Universität Frankfurt (1989 - 1994)
Direktor	Fritz-Haber-Institut der MPG (seit 1994)
Honorarprofessor	Technische Universität Berlin (seit 1994)
Honorarprofessor	Humboldt-Universität Berlin (seit 1998)
Gründungs-Direktor	MPI CEC (since 2011)
Honorarprofessor	Universität Duisburg-Essen (seit 2013)

Publications

Full publications list

Selected MPI CEC publications

Tesch, M. F., Neugebauer, S., Narangoda, P. V., Schlögl, R., Mechler, A. K. (2023). The rotating disc electrode: measurement protocols and reproducibility in the evaluation of catalysts for the oxygen evolution reaction. ENERGY ADVANCES, 2(11), 1823-1830. doi:10.1039/d3ya00340j.
Blume, R., Calvet, W., Ghafari, A., Mayer, T., Knop-Gericke, A., Schögl, R. (2023). Structural and Chemical Properties of NiOx Thin Films: Oxygen Vacancy Formation in O-2 Atmosphere. ChemPhysChem, e202300231, pp. 1-11. doi:10.1002/cphc.202300231.
Rohner, C., Pratsch, C., Schlögl, R., Lunkenbein, T. (2023). Structural Identification and Observation of Dose Rate-Dependent Beam-Induced Structural Changes of Micro- and Nanoplastic Particles by Pair Distribution Function Analysis in the Transmission Electron Microscope (ePDF). Microscopy and Microanalysis, (29), 1566-1578. doi:10.1093/micmic/ozad087.
Mom, R. V., Sandoval-Diaz, L.-E., Gao, D., Chuang, C.-H., Carbonio, E. A., Jones, T. E., Arrigo, R., Ivanov, D., Hävecker, M., Roldan Cuenya, B., Schlögl, R., Lunkenbein, T., Knop-Gericke, A.,Velasco Vélez, J. (2023). Assessment of the Degradation Mechanisms of Cu Electrodes during the CO2 Reduction Reaction. ACS Applied Materials and Interfaces, (15), 30052-30059. doi:10.1021/acsami.2c23007.
Carbonio, E. A., Sulzmann, F., Klyushin, A. Y., Hävecker, M., Piccinin, S., Knop-Gericke, A., Schlögl, R., Jones, T. E. (2023). Adjusting the Chemical Reactivity of Oxygen for Propylene Epoxidation on Silver by Rational Design: The Use of an Oxyanion and Cl. ACS Catalysis, 13(9), 5906-5913. doi:10.1021/acscatal.3c00297.
Velasco-Velez, J. J., Poon, J., Gao, D., Chuang, C.-H., Bergmann, A., Jones, T. E., Haw, S.-C., Chen, J.-M., Carbonio, E., Mom, R. V., Ivanov, D., Arrigo, R., Cuenya, B. R., Knop-Gericke, A., Schlögl, R. (2023). Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO2 Revealed by In Situ X-Ray Spectroscopy. Advanced Sustainable Systems, 2200453, pp. 1-7. doi:10.1002/adsu.202200453.
Esquius, J. R., Morgan, D. J., Siller, G. A., Gianolio, D., Aramini, M., Lahn, L., Kasian, O., Kondrat, S. A., Schlögl, R., Hutchings, G. J., Arrigo, R., Freakley, S. J. (2023). Lithium-Directed Transformation of Amorphous Iridium (Oxy)hydroxides To Produce Active Water Oxidation Catalysts. The Journal of Physical Chemistry A, (145), 6398-6409. doi:10.1021/jacs.2c13567.
Foppa, L., Rüther, F., Geske, M., Koch, G., Girgsdies, F., Kube, P., Carey, S. J., Hävecker, M., Timpe, O., V. Tarasov, A., Scheffler, M., Rosowski, F., Schlögl, R., Trunschke, A. (2023). Data-Centric Heterogeneous Catalysis: Identifying Rules and Materials Genes of Alkane Selective Oxidation. Journal of the American Chemical Society, (145), 3427-3442. doi:10.1021/jacs.2c11117.
Song, F., Straten, J. W., Lin, Y.-M., Ding, Y., Schlögl, R., Heumann, S., Mechler, A. K. (2023). Binder-Free N-Functionalized Carbon Electrodes for Oxygen Evolution Reaction. ChemElectroChem,(10) e202201075, pp. 1-10. doi:10.1002/celc.202201075.
Kube, P., Dong, J., Sanchez Bastardo, N., Ruland, H., Schlögl, R., Margraf, J. T., Reuter, K., Trunschke, A. (2023). Green synthesis of propylene oxide directly from propane. Nature Communications, 13(1): 7504, pp. 1-8. doi:10.1038/s41467-022-34967-2.
Klingenhof, M., Hauke, P., Kroschel, M., Wang, X., Merzdorf, T., Binninger, C., Thanh, T. N., Paul, B., Teschner, D., Schlögl, R., Strasser, P. (2022). Anion-Tuned Layered Double Hydroxide Anodes for Anion Exchange Membrane Water Electrolyzers: From Catalyst Screening to Performance. ACS Energy Letters, (7), 3415-3422. doi:10.1021/acsenergylett.2c01820.
Righi, G., Plescher, J., Schmidt, F.-P., Campen, R. K., Fabris, S., Knop-Gericke, A., Schlögl, R., Jones, T. E., Teschner, D., Piccinin, S. (2022). On the origin of multihole oxygen evolution in haematite photoanodes. Nature Catalysis, (5), 888-899. doi:10.1038/s41929-022-00845-9.
Kang, S., Im, C., Spanos, I., Schlögl, R., Ham, K., Lim, A., Jacobs, Timo , Lee, Jaeyoung (2022). Durable Nickel-Iron (Oxy)hydroxide Oxygen Evolution Electrocatalysts through Surface Functionalization with Tetraphenylporphyrin. (61): e202214541, pp. 1-10. doi:10.1002/anie.202214541.
Žeradjanin, A. R., Narangoda, P., Masa, J., Schlögl, R. (2022). What Controls Activity Trends of Electrocatalytic Hydrogen Evolution Reaction?-Activation Energy Versus Frequency Factor. ACS CATALYSIS, (19), 11597-11605. doi:10.1021/acscatal.2c02964.
Ghampson, I. T., Lundin, S.-T.-B., Vargheese, V., Kobayashi, Y., Huff, G. S., Schlögl, R., Trunschke, A., Oyama, S. T. (2022). Methane selective oxidation on metal oxide catalysts at low temperatures with O2 using an NO/NO2 oxygen atom shuttle. Journal of Catalysis, (408), 401-412. doi:10.1016/j.jcat.2021.07.014.
Streibel, V., Velasco-Velez, J. J., Teschner, D., Carbonio, E. A., Knop-Gericke, A., Schlögl, R., Jones, T. E. (2022). Merging operando and computational X-ray spectroscopies to study the oxygen evolution reaction. Current Opinion in Electrochemistry, (35) 101039, doi:10.1016/j.coelec.2022.101039.
Choudhury, S. H., Ding, Y., Yi, Y., Rohner, C., Frandsen, W., Lunkenbein, T., Greiner, M., Schlögl, R., Heumann, S. (2022). Oxidation Behavior of Glassy Carbon in Acidic Electrolyte. ChemElectroChem, (9): e202200637, pp. 1-7. doi:10.1002/celc.202200637.
Deerberg, G., Oles, M., Schlögl, R. (2022). Carbon2Chem (R) - A Key Building Block for Climate Protection. SI, 94(10), 1387-1387. doi:10.1002/cite.202271002.
Türk, H., Götsch, T., Schmidt, F.-P., Hammud, A., Ivanov, D., de Haart, L. G. J., Vinke, I. C., Eichel, R.-A., Schlögl, R., Reuter, K., Knop-Gericke, A., Lunkenbein, T., Scheurer, C. (2022). Sr Surface Enrichment in Solid Oxide Cells - Approaching the Limits of EDX Analysis by Multivariate Statistical Analysis and Simulations. ChemCatChem, (14): e202200300, pp. 1-13. doi:10.1002/cctc.202200300.
Hegen, O., Salazar Gomez, J. I., Gruenwald, C., Rettke, A., Sojka, M., Klucken, C., Pickenbrock, J., Filipp, J., Schlögl, R., Ruland, H. (2022). Bridging the Analytical Gap Between Gas Treatment and Reactor Plants in Carbon2Chem (R). CHEMIE INGENIEUR TECHNIK, (94), 1405-1412. doi:10.1002/cite.202200015.
Ristig, S., Poschmann, M., Folke, J., Gomez-Capiro, O., Chen, Z., Sanchez-Bastardo, N., Schlögl, R., Heumann, S., Ruland, H. (2022). Ammonia Decomposition in the Process Chain for a Renewable Hydrogen Supply. Chemie-Ingenieur-Technik, (94), 1413-1425. doi:10.1002/cite.202200003.
Lin, Y., Yu, L., Tang, L., Song, F., Schlögl, R., Heumann, S. (2022). In Situ Identification and Time-Resolved Observation of the Interfacial State and Reactive Intermediates on a Cobalt Oxide Nanocatalyst for the Oxygen Evolution Reaction. ACS Catalysis, 12(9), 5345-5355. doi:10.1021/acscatal.1c05598.
Haase, F. T., Rabe, A., Schmidt, F.-P., Herzog, A., Jeon, H. S., Frandsen, W., Narangoda, P. V., Spanos, I., Ortega, K. F., Timoshenko, J., Lunkenbein, T., Behrens, M., Bergmann, A., Schlögl, R., Cuenya, B. R. (2022). Role of Nanoscale Inhomogeneities in Co2FeO4 Catalysts during the Oxygen Evolution Reaction. Journal of the American Chemical Society, 144(27), 12007-12019. doi:10.1021/jacs.2c00850.
Papakonstantinou, G., Spanos, I., Dam, A. P., Schlögl, R., Sundmacher, K. (2022). Electrochemical evaluation of the de-/re-activation of oxygen evolving Ir oxide. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 24(23), 14579-14591. doi:10.1039/d2cp00828a.
Sandoval-Diaz, L. E., Schlögl, R., Lunkenbein, T. (2022). Quo Vadis Dry Reforming of Methane?-A Review on Its Chemical, Environmental, and Industrial Prospects. Catalysts, 12(5): 465. doi:10.3390/catal12050465.
Schlögl, R. (2022). Interfacial catalytic materials; challenge for inorganic synthetic chemistry. ZEITSCHRIFT FUR NATURFORSCHUNG SECTION B-A JOURNAL OF CHEMICAL SCIENCES, (xx), xx-xx. doi:10.1515/znb-2022-0070.
Velasco Vélez, J., Bernsmeier, D., Jones, T. E., Zeller, P., Carbonio, E., Chuang, C.-H., Falling, L. J., Streibel, V., Mom V, R., Hammud, A., Hävecker, M., Arrigo, R., Stotz, E., Lunkenbein, T., Knop-Gericke, A., Krähnert, R., Schlögl, R. (2022). The rise of electrochemical NAPXPS operated in the soft X-ray regime exemplified by the oxygen evolution reaction on IrOx electrocatalysts. Faraday Discussions, (236), 103-125. doi:10.1039/d1fd00114k.
Kenmoe, S., Douma, D. H., Raji, A. T., M'Passi-Mabiala, B., Goetsch, T., Girgsdies, F., Knop-Gericke, A., Schlögl, R., Spohr, E. (2022). X-ray Absorption Near-Edge Structure (XANES) at the O K-Edge of Bulk Co3O4: Experimental and Theoretical Studies. Nanomaterials, 12(6): 921, pp. 1-10. doi:10.3390/nano12060921.
Codeco, C. F. S., Klyushin, A. Y., Carbonio, E. A., Knop-Gericke, A., Schlögl, R., Jones, T., Rocha, T. C. R. (2022). Insights into the electronic structure of hydroxyl on Ag(110) under near ambient conditions. Physical Chemistry Chemical Physics, 24(15), 8832-8838. doi:10.1039/d1cp02929k.
Schlögl, R. (2022). Chemical Batteries with CO2. Angewandte Chemie, International Edition in English, (61): e202007397, pp. 1-23. doi:10.1002/anie.202007397.
Arrigo, R., Blume, R., Streibel,V., Genovese, C., Roldan, A., Schuster, M. E., Ampelli, C., Perathoner, S., Velasco Vélez, J., Hävecker, M., Knop-Gericke, A., Schlögl, R., Centi, G. (2022). Dynamics at Polarized Carbon Dioxide-Iron Oxyhydroxide Interfaces Unveil the Origin of Multicarbon Product Formation. ACS Catalysis, (12), 411-430. doi:10.1021/acscatal.1c04296.
Hegen, O., Salazar Gomez, J. I., Schlögl, R., Ruland, H. (2022). The potential of NO+ and O-2(+center dot) in switchable reagent ion proton transfer reaction time-of-flight mass spectrometry. Mass Spectrometry Reviews, e21770. doi:10.1002/mas.21770.
Folke, J., Dembele, K., Girgsdies, F., Song, H., Eckert, R., Reitmeier, S., Reitzmann, A., Schlögl, R., Lunkenbein, T., Ruland, H. (2022). Promoter effect on the reduction behavior of wuestite-based catalysts for ammonia synthesis. Catalysis Today, (387) 12-22. doi:10.1016/j.cattod.2021.03.013.
Wang, Y., Rosowski, F., Schlögl, R., Trunschke, A. (2022). Oxygen Exchange on Vanadium Pentoxide. The Journal of Physical Chemistry C, 126(7), 3443-3456. doi:10.1021/acs.jpcc.2c00174.
Lange, T., Reichenberger, S., Ristig, S., Rohe, M., Strunk, J., Barcikowski, S., Schlögl, R. (2022). Zinc sulfide for photocatalysis: White angel or black sheep? Progress in Materials Science, 124: 100865. doi:10.1016/j.pmatsci.2021.100865.
Sanchez-Bastardo, N., Schlögl, R., Ruland, H. (2021). Response to Comment on "Methane Pyrolysis for Zero-Emission Hydrogen Production: A Potential Bridge Technology from Fossil Fuels to a Renewable and Sustainable Hydrogen Economy". Industrial and Engineering Chemistry Research, 60(48), 17795-17796. doi:10.1021/acs.iecr.1c04435.
Schlögl, R. (2021). Chemical Batteries with CO2. Angewandte Chemie, International Edition in English, (60), 2-25. doi:10.1002/anie.202007397.
Dreyer, M., Cruz, D., Hagemann, U., Zeller, P., Heidelmann, M., Salamon, S., Landers,J., Rabe,A., Ortega,K.F. , Najafishirtari,S., Wende,H., Hartmann,N., Knop-Gericke,A., Schlögl,R., Behrens,M. (2021) The Effect of Water on the 2-Propanol Oxidation Activity of Co-Substituted LaFe1-CoxO3 Perovskites. SI, (27) 17127 - 17144 doi:10.1002/chem.202102791.
Narangoda, P., Spanos, I., Masa, J., Schlögl, R., Zeradjanin, A. R. (2021) Electrocatalysis Beyond 2020: How to Tune the Preexponential Frequency Factor. ChemElectroChem, (8), 1-9. doi:10.1002/celc.202101278.
Schlögl, R. (2021) Material Science for catalysis: Quo vadis? Zeitschrift für anorganische und allgemeine Chemie, (647) 1998-2000. doi:10.1002/zaac.202100277.
Ronge, E., Ohms, J., Roddatis, V., Jones, T., Sulzmann, F., Knop-Gericke, A., Schlögl. R., Kurz, P.,Jooss, C., Skorupska, K. (2021) Operation of calcium-birnessite water-oxidation anodes: interactions of the catalyst with phosphate buffer anions. Sustainable Energy & Fuels, (5) 5535-5547. doi:10.1039/d1se01076j.
Koch, G., Hävecker, M., Kube, P., Tarasov, A., Schlögl, R., Trunschke, A. (2021). The Influence of the Chemical Potential on Defects and Function of Perovskites in Catalysis. Frontiers in Chemistry, 9, 746229-746229. doi:10.3389/fchem.2021.746229.
Zeradjanin, A. R., Narangoda, P., Spanos, I., Masa, J., Schlögl, R. (2021). How to minimise destabilising effect of gas bubbles on water splitting electrocatalysts? CURRENT OPINION IN ELECTROCHEMISTRY, 30: 100797. doi:10.1016/j.coelec.2021.100797.
Salazar Gomez, J. I., Sojka, M., Klucken, C., Schlögl, R., Ruland, H. (2021). Determination of trace compounds and artifacts in nitrogen background measurements by proton transfer reaction time-of-flight mass spectrometry under dry and humid conditions. Journal of Mass Spectrometry, 56(8): e4777, pp. 1-22. doi:10.1002/jms.4777.
Sanchez-Bastardo, N., Schlögl, R., Ruland, H. (2021). Methane Pyrolysis for Zero-Emission Hydrogen Production: A Potential Bridge Technology from Fossil Fuels to a Renewable and Sustainable Hydrogen Economy. INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 60(32), 11855-11881. doi:10.1021/acs.iecr.1c01679.
Türk, H., Schmidt, F. P., Götsch, T., Girgsdies, F., Hammud, A., Ivanov, D., Vinke, I.,de Haart, L.G.J.,Eichel, R.A., Reuter, K., Schlögl, R., Knop-Gericke, A., Scheurer, C., Lunkenbein, T. (2021). Complexions at the Electrolyte/Electrode Interface in Solid Oxide Cells. Advanced Materials Interfaces, 8 (18): 2100967, pp. 1-9. doi:10.1002/admi.202100967.
Ronge, E., Ohms, J., Roddatis, V., Jones, T., Sulzmann, F., Knop-Gericke, A., Schlögl, R., Kurz, P., Jooss, C., Skorupska, K. (2021). Operation of calcium-birnessite water-oxidation anodes: interactions of the catalyst with phosphate buffer anions. Sustainable Energy & Fuels (5) 5535-5547. doi:10.1039/d1se01076j.
Foppa, L., Ghiringhelli, L. M., Girgsdies, F., Hashagen, M., Kube, P., Hävecker, M., Carey, S., Tarasov, A., Kraus, P., Rosowski, F., Schlögl, R., Trunschke, A., Scheffler, M. (2021) Materials genes of heterogeneous catalysis from clean experiments and artificial intelligence. MRS Bulletin (46) 1016-1026. doi:10.1557/s43577-021-00165-6.
Velasco Vélez, J., Carbonio, E. A., Chuang, C.-H., Hsu, C.-J., Lee, J.-F., Arrigo, R., Hävecker, M., Wang, R., Plodinec, M., Wamg, F.R., Centeno, A., Zurutuza, A., Falling, L.J., Mom, V., Hofmann, S., Schlögl, R., Knop-Gericke, A., Jones, T.,(2021). Surface Electron-Hole Rich Species Active in the Electrocatalytic Water Oxidation. Journal of the American Chemical Society, 143(32) 12524-12534 . doi:10.1021/jacs.1c01655.
Zeradjanin, A. R., Narangoda, P., Spanos, I., Masa, J., Schlögl, R. (2021). Expanding the frontiers of hydrogen evolution electrocatalysis & ndash;searching for the origins of electrocatalytic activity in the anomalies of the conventional model. ELECTROCHIMICA ACTA, 388: 138583. doi:10.1016/j.electacta.2021.138583.
Schlögl, R. (2021). Quo vadis carbocatalysis? Journal of Energy Chemistry, 61, 219-227. doi:10.1016/j.jechem.2021.02.024.
Hausmann, J. N., Schlögl, R., Menezes, P. W., Driess, M. (2021). Is direct seawater splitting economically meaningful? Energy & Environmental Science, (14), 3679-3685. doi:10.1039/d0ee03659e.
Hartwig, C., Schweinar, K., Jones, T. E., Beeg, S., Schmidt, F.-P., Schlögl, R., Greiner, M . (2021). Isolated Pd atoms in a silver matrix: Spectroscopic and chemical properties. The Journal of Chemical Physics, 154(18): 184703, pp. 1-10. doi:10.1063/5.0045936.
Fan, H., Folke, J., Liu, Z., Girgsdies, F., Ruland, H., Imlau, R., Ruland,H., Heumann, S., Granwehr, J., Eichel,R.- A., Schlögl, R., Frei, E.,Xing, H. (2021) Ultrathin 2D Fe-Nanosheets Stabilized by 2D Mesoporous Silica: Synthesis and Application in Ammonia Synthesis. ACS Appl. Mater. Inerfaces, 13(25), 30187-30197. doi:10.1021/acsami.1c06771
Huang, X., Jones, T., Federov, A., Farra, R., Coperet, C., Schlögl, R., Willinger,M.-G. (2021). Phase Coexistence and Structural Dynamics of Redox Metal Catalysts Revealed by Operando TEM. Advanced Materials,(33) 2101772, pp. 1-11. doi:10.1002/adma.202101772.
Ding, Y., Zhang, L., Gu, Q., Spanos, I., Pfänder, N., Wu, K. H., Schlögl, R., Heumann, S. (2021). Tuning of Reciprocal Carbon-Electrode Properties for an Optimized Hydrogen Evolution. ChemSusChem, 14(12), 2547-2553. doi:10.1002/cssc.202100654.
Pielsticker, L., Nicholls, R., Beeg, S., Hartwig, C., Klihm, G., Schlögl, R., Tougaard, S., Greiner, M.(2021). Inelastic electron scattering by the gas phase in near ambient pressure XPS measurements. Surface and Interface Analysis, (53) 605-617. doi:10.1002/sia.6947.
Chee, S. W., Lunkenbein, T., Schlögl, R., Cuenya, B. R. (2021). In situ and operando electron microscopy in heterogeneous catalysis-insights into multi-scale chemical dynamics. Journal of Physics: Condensed Matter, 33(15): 153001, pp. 1-28. doi:10.1088/1361-648X/abddfd.
Lange, T., Reichenberger, S., Rohe, M., Bartsch, M., Kampermann, L., Klein, J., Schlögl, R., Barcikowski, S. (2021). Alumina-Protected, Durable and Photostable Zinc Sulfide Particles from Scalable Atomic Layer Deposition. Advanced Functional Materials, 31(14): 2009323, pp. 1-15. doi:10.1002/adfm.202009323.
Schlögl, R. (2021). Chemical energy storage enables the transformation of fossil energy systems to sustainability. Green Chemistry, 23(4), 1584-1593. doi:10.1039/d0gc03171b.
Zeradjanin, A. R., Masa, J., Spanos, I., Schlögl, R. (2021). Activity and Stability of Oxides During Oxygen Evolution Reaction---From Mechanistic Controversies Toward Relevant Electrocatalytic Descriptors. Frontiers in Energy Research, 8, 613092. https://doi:10.3389/fenrg.2020.613092.
Nong, H. N., Falling, L. J., Bergmann, A., Klingenhof, M., Tran, H. P., Spori, C., Mom, R., Timoshenko, J., Zichittella, G., Knop-Gericke, A., Piccinin, S., Perez-Ramirez, J., Cuenya, B. R., Schlögl, R., Strasser, P., Teschner, D., Jones, T. E. (2021). Key role of chemistry versus bias in electrocatalytic oxygen evolution (vol 587, pg 408, 2020). Nature, E8. https://www.nature.com/articles/s41586-020-03141-3.pdf
Spanos, I., Masa, J., Zeradjanin, A., Schlögl, R. (2021). The Effect of Iron Impurities on Transition Metal Catalysts for the Oxygen Evolution Reaction in Alkaline Environment: Activity Mediators or Active Sites? Catalysis Letters 151, 1843-1856 https://doi.org/10.1007/s10562-020-03478-4
Klingenhof, M., Hauke, P., Brückner, S., Dresp, S., Wolf, E., Nong, H.N., Spöri, Merzdorf, T., Bernsmeier, D., Teschner, D., Schlögl, R., Strasser, P. (2021). Modular Design of Highly Active Unitized Reversible Fuel Cell Electrocatalysts ACS Energy Letters 6(1), 177-183. https://doi.org/10.1021/acsenergylett.0c02203
Ruiz Esquius, J., Algara-Siller, G., Spanos, I., Freakley, S.J., Schlögl, R., Hutchings, G.J. (2020). Preparation of Solid Solution and Layered IrO_x–Ni(OH)₂ Oxygen Evolution Catalysts: Toward Optimizing Iridium Efficiency for OER ACS Catalysis 10(24), 14640-146448. https://doi.org/10.1021/acscatal.0c03866
Boniface, M., Plodinec, M., Schlögl, R., Lunkenbein, T. (2020). Quo Vadis Micro-Electro-Mechanical Systems for the Study of Heterogeneous Catalysts Inside the Electron Microscope? Topics in Catalysis 63(15-18), 1623-1643. https://doi.org/10.1007/s11244-020-01398-6
Nong, H.N., Falling, L.J., Bergmann, A., Klingenhof, M., Tran, H.P., Spöri, C., Mom, R., Timoshenko, J., Zichittella, G., Knop-Gericke, A., Piccinin, S., Pérez-Ramírez, J., Roldan Cuenya, B., Schlögl, R., Strasser, P., Teschner, D., Jones, T.E. (2020). Key role of chemistry versus bias in electrocatalytic oxygen evolution Nature 587, 408-413. https://doi.org/10.1038/s41586-020-2908-2
Barrios Jiménez, A.M., Burkhardt, U., Cardoso-Gil, R., Höfer, K., Altendorf, S.G., Schlögl, R., Grin, Y., Antonyshyn, I. (2020). Hf₂B₂Ir₅: A Self-Optimizing Catalyst for the Oxygen Evolution Reaction ACS Applied Energy Materials 3(11), 11042-11052. https://doi.org/10.1021/acsaem.0c02022
Schlögl, R. (2020). Mobilität CO₂ neutral? Bunsen-Magazin 4, 74-78. https://bunsen.de/fileadmin/user_upload/media/Aspekte-Artikel/Aspekte_Schloegl.pdf
Masliuk, L., Schmidt, F.-P., Hetaba, W., Plodinec, M., Auffermann, G., Hermann, K., Teschner, D., Girgsdies, F., Trunschke, A., Schlögl, R., Lunkenbein, T. (2020). Compositional Decoupling of Bulk and Surface in Open-Structured Complex Mixed Oxides The Journal of Physical Chemistry C 124(42), 23069-23077. https://doi.org/10.1021/acs.jpcc.0c04777
Trunschke, A., Bellini, G., Boniface, M., Carey, S.J., Dong, J., Erdem, E., Foppa, L., Frandsen, W., Geske, M., Ghiringhello, L.M., Girgsdies, F., Hanna, R., Hashagen, M., Hävecker, M., Huff, G., Knop-Gericke, A., Koch, G., Kraus, P., Kröhnert, J., Kube, P., Lohr, S., Lunkenbein, T., Masliuk, L., d’Alnoncourt, R.N., Omojola, T., Pratsch, C., Richter, S., Rohner, C., Rosowski, F., Rüther, F., Scheffler, M., Schlögl, R., Tarasov, A., Teschner, D., Timpe, O., Trunschke, P., Wang, Y., Wrabetz, S. (2020). Towards Experimental Handbooks in Catalysis Topics in Catalysis 63(19-20), 1683-1699. https://doi.org/10.1007/s11244-020-01380-2
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Pfeifer, V., Jones, T.E., Velasco-Vélez J.J., Massué, C., Arrigo, R., Teschner, D., Girgsdies, F., Scherzer, M., Greiner, M.T., Allan, J., Hashagen, M., Weinberg, G., Piccinin, S., Hävecker, M., Knop-Gericke, A., Schlögl, R. (2016). The electronic structure of iridium and its oxides Surface and Interface Analysis 48(5), 261-273. https://doi.org/10.1002/sia.5895
Schumann, J., Tarasov, A., Thomas, N., Schlögl, R., Behrens, M. (2016). Cu,Zn-based catalysts for methanol synthesis: On the effect of calcination conditions and the part of residual carbonates Applied Catalysis A - General 516, 117-126. https://doi.org/10.1016/j.apcata.2016.01.037
Pfeifer, V., Jones, T.E., Velasco-Vélez, J.J., Massué, C., Greiner, M.T., Arrigo, R., Teschner, D., Girgsdies, F., Scherzer, M., Allan, J., Hashagen, M., Weinberg, G., Piccinin, S., Hävecker, M., Knop-Gericke, A., Schlögl, R. (2016). The electronic structure of iridium oxide electrodes active in water splitting Physical Chemistry Chemical Physics 18(4), 2292-2296. https://doi.org/10.1039/c5cp06997a
Pfeifer, V., Jones, T.E., Wrabetz, S., Massué, C., Velasco-Vélez, J.J., Arrigo, R., Scherzer, M., Piccinin, S., Hävecker, M., Knop-Gericke, A., Schlögl, R. (2016). Reactive oxygen species in iridium-based OER catalysts Chemical Science 7(11), 6791-6795. https://doi.org/10.1039/c6sc01860b

Forschung - Heterogeneous Reactions

Scheme of electrochemical watersplitting — Process of energy conversion from renewable sources via water splitting to chemical energy carriers like methanol or ammonia.

Heterogeneous Reactions

The energy challenge can be seen as the major challenge for today’s society and future generations. Chemistry plays a central role in the energy challenge, since most energy conversion systems work on (bio)chemical energy carriers and require for their use suitable process and material solutions. The enormous scale of their application demands optimization beyond the incremental improvement of empirical discoveries. For this reason we work on the development of knowledge-based systematic approaches in order to arrive at scalable and sustainable solutions.

Analysis of the processes that are essential to convert the current energy systems into sustainable systems indicates that the conversion of electricity into chemical energy is a critical process in the network of chemical energy conversion reactions. Both electrolysis and heterogeneous photochemical reactions are of relevance here. The difficult elementary steps are in the oxygen evolution reaction.

In a concerted effort the department develops a concept of carbon-based functional materials that operate in oxygen evolution either alone or doped with functional transition metal oxides. In parallel we study with advanced in-situ spectroscopic tools the reaction on performing systems with noble metals to learn about design requirements for systems operating with materials as used in the biological analogue. The resulting material solutions and synthesis tools will be transferred to catalytic processes binding primary hydrogen onto carrier molecules such as CO₂ and N₂ to arrive at practically useful solar fuels.

The work of the department is strictly knowledge-oriented to generate generic insight and solutions for synthesis and analysis of chemical energy conversion systems. Theory and molecular model studies with the other departments critically deepen our insight. The department engages into method development for operating advanced spectroscopic methods on heterogeneous and on homogeneous systems. Projects are performed in close collaboration with the Fritz-Haber-Institute of the Max Planck Society in Berlin.

Prof. Dr. Wolfgang Lubitz

Direktor 2000-2017

Vita

Chemie Studium	Freie Universität Berlin (1969 - 1974)
Dr. rer. nat	Freie Universität Berlin (1977)
Habilitation	Freie Universität Berlin (1982)
Research Fellow	University of California, San Diego, USA (1983 - 1984)
Assoc. Professor	Organic Chemistry FU Berlin (1986 - 1989)
Assoc. Professor	Experimental Physics, Universität Stuttgart (1989 - 1991)
Professor	Physical Chemistry, Max-Volmer-Institut, TU Berlin (1991 - 1999)
Honorarprofessor	Heinrich-Heine-Universität Düsseldorf (seit 2000)
wiss. Mitglied	Max-Planck-Gesellschaft (seit 2000)
Direktor	MPI für Bioanorganische Chemie; heute: MPI CEC (2000-2017)

Publikationen

Full List of Publications

Selected Publications

F. Lendzian, M. Huber, R.A. Isaacson, B. Endeward, M. Plato, B. Bönigk, K. Möbius, W. Lubitz and G. Feher The Electronic Structure of the Primary Donor Cation Radical in Rhodobacter sphaeroides R-26: ENDOR and TRIPLE Resonance Studies in Single Crystals of Reaction Centers Biochim. Biophys. Acta 1183, 139-160 (1993)
W. Lubitz and G. Feher The Primary and Secondary Acceptors in Bacterial Photosynthesis III. Characterization of the Quinone Radicals Q^-·_A and Q^-·_B and by EPR and ENDOR Appl. Magn. Res. 17, 1-48 (1999)
W. Lubitz, F. Lendzian, R. Bittl Radicals, Radical Pairs and Triplet States in Photosynthesis Acc. Chem. Res. 35, 313-320 (2002)
M. Brecht, M. van Gastel, T. Buhrke, B. Friedrich, W. Lubitz Direct Detection of a Hydrogen Ligand in the [NiFe] Center of the Regulatory H₂-Sensing Hydrogenase from Ralstonia eutropha in its Reduced State by HYSCORE and ENDOR Spectroscopy J. Am. Chem. Soc. 125, 13075-13083 (2003)
A. Savitsky, A. A. Dubinskii, M. Flores, W. Lubitz, K. Möbius Orientation-resolving Pulsed Electron Dipolar High-field EPR Spectroscopy on Disordered Solids: I. Structure of Spin-correlated Radical Pairs in Bacterial Photosynthetic Reaction Centers J. Phys. Chem. B 111, 6245-6262 (2007)
L. V. Kulik, B. Epel, W. Lubitz, J. Messinger Electronic Structure of the Mn₄O_xCa Cluster in the S₀ and S₂ States of the Oxygen-evolving Complex of Photosystem II Based on Pulse ⁵⁵Mn-ENDOR and EPR Spectroscopy J. Am. Chem. Soc. 129, 13421 -13435 (2007)
A. Silakov, E. J. Reijerse, S. P. J. Albracht, E. C. Hatchikian, W. Lubitz The Electronic Structure of the H-cluster in the [FeFe]-hydrogenase from Desulfovibrio desulfuricans: A Q-band ⁵⁷Fe-ENDOR and HYSCORE Study J. Am. Chem. Soc. 129, 11447-11458 (2007)
A. Silakov, B. Wenk, E.J. Reijerse, W. Lubitz ¹⁴N HYSCORE Investigation of the H-cluster of [FeFe] Hydrogenase: Evidence for a Nitrogen in the Dithiol Bridge Phys. Chem. Chem. Phys. 11, 6592 – 6599 (2009)
N. Cox, H. Ogata, P. Stolle, E.J. Reijerse, G. Auling, W. Lubitz A Tyrosyl-Dimanganese Coupled Spin System is the Native Metalloradical Cofactor of the R2F Subunit of the Ribonucleotide Reductase of Corynebacterium ammoniagenes J. Am Chem. Soc. 132, 11197–11213 (2010)
M.E. Pandelia, W. Nitschke, P. Infossi, M.-T. Giudici-Orticoni, E. Bill, W. Lubitz Characterization of a Unique [FeS] Cluster in the Electron Transfer Chain of the Oxygen Tolerant [NiFe] Hydrogenase from Aquifex aeolicus P. Natl. Acad. Sci. USA, 108, 6097-6102 (2011)
D.A. Pantazis, W. Ames, N. Cox, W. Lubitz, F. Neese Two Interconvertible Structures Explain the Spectroscopy of the Oxygen Evolving Complex in the S₂ State Angew. Chem. Int. Ed. 51, 9935 –9940 (2012) Angew.Chem. 124, 10074 –10079 (2012)
L. Rapatskiy, N. Cox, A. Savitsky, W. Ames, J. Sander, M. Nowacyzk, M. Rögner, A. Boussac, F. Neese, J. Messinger, W. Lubitz Detection of the Water Binding Sites of the Oxygen-evolving Complex of Photosystem II Using W-band ¹⁷O Electron-Electron Double Resonance Detected NMR Spectroscopy J. Am. Chem. Soc. 134, 16619-16634 (2012)
G. Berggren, A. Adamska, C. Lambertz, T. Simmons, J. Esselborn, M. Atta, S. Gambarelli, J.M. Mouesca, E.J. Reijerse, W. Lubitz, T. Happe, V. Artero, M. Fontecave Biomimetic Assembly and Activation of [FeFe]-Hydrogenases Nature 499, 66–69 (2013)
J. Esselborn, C. Lambertz, A. Adamska-Venkatesh, T. Simmons, G. Berggren, J. Noth, J. Siebel, A. Hemschemeier, V. Artero, E.J. Reijerse, M. Fontecave, W. Lubitz, T. Happe Spontaneous Activation of [FeFe]-hydrogenases by an inorganic [2Fe] Active Site Mimic Nat. Chem. Biol. 9, 607-609 (2013)
W. Lubitz, H. Ogata, O. Rüdiger, E.J. Reijerse Hydrogenases Chem. Rev. 114, 4081-4148 (2014)
N. Plumeré, O. Rüdiger, A. A. Oughli, R. Williams, J. Vivekananthan, S. Pöller, W. Schuhmann, W. Lubitz A Redox Hydrogel Protects Hydrogenase from High Potential Deactivation and Oxygen Damage Nat. Chem. 6, 822–827 (2014)
N. Cox, M. Retegan, F. Neese, D.A. Pantazis, A. Boussac, W. Lubitz Electronic Structure of the Oxygen-evolving Complex in Photosystem II Prior to O-O Bond Formation Science 345, 804-808 (2014)
H. Ogata, K. Nishikawa, W. Lubitz Hydrogens Detected by Subatomic Resolution Protein Crystallography in a [NiFe] Hydrogenase Nature 520, 571-574 (2015)
V. Krewald, M. Retegan, N. Cox, J. Messinger, W. Lubitz, S. DeBeer, F. Neese, D.A. Pantazis Metal Oxidation States in Biological Water Splitting Chem. Sci. 6, 1676-1695 (2015)
F. Wang, R. Büchel, A. Savitsky, M. Zalibera, D. Widmann, S. E. Pratsinis, W. Lubitz, F. Schüth In situ EPR Study of the Redox Properties of CuO-CeO₂ Catalysts for the Preferential CO Oxidation (PROX) ACS Catal. 6, 3520-3530 (2016)
C. Sommer, A. Adamska-Venkatesh, K. Pawlak, J. Birrell, E. Reijerse, W. Lubitz Proton Coupled Electron Transfer whithin the H-Cluster as an Essential Step in the Catalytic Cycle of [FeFe] Hydrogenases J. Am. Chem. Soc. 139, 1440-1443 (2017)
E. Reijerse, C. Pham, V. Pelmenschikov, R. Gilbert-Wilson, A. Adamska-Venkatesh, J. Siebel, L. Gee, Y. Yoda, K. Tamasaku, W. Lubitz, T. Rauchfuss, S. Cramer Direct Observation of an Iron-bound Terminal Hydride in [FeFe]-hydrogenase by Nuclear Resonance Vibrational Spectroscopy J. Am. Chem. Soc. 139, 4306-4309 (2017)
S. Rumpel, E. Ravera, C. Sommer, E. Reijerse, C. Farés, C. Luchinat, W. Lubitz 1H NMR Spectroscopy of [FeFe] Hydrogenase: Insight into the Electronic Structure of the Active Site J. Am. Chem. Soc. 140, 131-134 (2018)
S. Rumpel, C. Sommer, E. Reijerse, C. Farès, W. Lubitz Direct Detection of the Terminal Hydride Intermediate in [FeFe] Hydrogenase by NMR Spectroscopy J. Am. Chem. Soc. 140, 3863-3866 (2018)
K. Möbius, W. Lubitz, N. Cox, A. Savitsky Biomolecular EPR Meets NMR at High Magnetic Fields Magnetochemistry, 4, 50, doi: 10.3390/magnetochemistry4040050 (2018)

Full Publicationslist

Funktionen & Aufgaben

Vorstandsrat Gesellschaft Deutscher Naturforscher und Ärzte e.V. (GDNÄ), Fachvertreter Fachgruppe Chemie (since 2017)
Member of the Editorial Board of Energy & Environmental Sciences (since 7/2016)
Vice President of the Council of the Lindau Nobel Laureate Meetings (since 2015)
Chair, Gordon Research Conferences on "Renewable Energy: Solar Fuels", 13.-18.05.2012, Lucca (Barga), Italy
Vice Chair, Gordon Research Conferences on "Renewable Energy: Solar Fuels", 16.-21.01.2011, Ventura, CA (USA)
Managing Director of the MPI for Bioinorganic Chemistry (2004-2011)
Member of the International Advisory Board of the University of East Anglia Energy Materials Laboratory (since 2008)
Chairman of the Advisory Board of the Farkas Minerva Advisory Board; Jerusalem (2007-2013)
President of the International EPR/ESR Society (2005-2008)
Member of the Council of the Nobel Laureate Meetings in Lindau (since 2004)
Member of the Advisory Board Physical Chemistry Chemical Physics (since 2011)
Member of the Advisory Board Biopolymers: Biospectroscopy (since 1995)
Member of the Editorial Advisory Board Journal of Biological Inorganic Chemistry (since 1999)
Member of the Advisory Board of Applied Magnetic Resonance (since 2001)
Member of the Advisory Board Energy & Environmental Science (since 2007)
Member of the International Advisory Board for the International Conference on Clean Energy (2011)
Member of the Editorial Advisory Board of the Book Series "Sustainable Energy Developments" (CRC Press)

Preise & Auszeichnungen

Ehrenmitgliedschaft der GDCh-Fachgruppe Magnetische Resonanz (2022)
Fellow of the International EPR Society 2017
Robert Bunsen Vorlesung, Deutsche Bunsen-Gesellschaft für physikalische Chemie e.V. (2017)
Doctorat honoris causa, Université d'Aix-Marseille, France (2014) - Prof. Dr. Dr. h. c. Dr. h.c. Wolfgang Lubitz
Foreign Member of the Academy of Sciences of the Republic of Tatarstan (2012)
Fellow of ISMAR (International Society of Magnetic Resonance) Fellow (2010)
Honorary doctorate Dr. h. c., Uppsala University, Sweden (2008) - Prof. Dr. Dr. h. c. Wolfgang Lubitz
Gold Medal of the International EPR Society (2005)
Fellow of the Royal Society of Chemistry. U.K. (2004)
Bruker Prize, Royal Society of Chemistry, ESR group, U.K. (2003)
International Zavoisky Award, Russian and Tatarstan Academy of Sciences, Kazan, Russia (2002)
Max-Kade-Fellowship, New York (1983)
Otto-Klung-Preis für Chemie, FU Berlin (1978)

Forschung - Biophysikalische Chemie

Fig. 1: Artistic sketch of natural and artificial photosynthesis (cover: special issue *Phys. Chem. Chem. Phys.*, 16 (24) 2014; editors J. Messinger, W. Lubitz, J.-R. Shen)

Fig. 2: Rapid Freeze-Quench set-up based on a BioLogic QFM 400 showing the mixing chamber and the laser for sample flashing as well as the brass cups in a liquid nitrogen bath for sample freezing (left) and a single cup with a frozen sample (right). W-band EPR tubes are fixed at the bottom of the cup to which the frozen snow is then transferred mechanically.

Figure 3 (A) — Fig. 3 (A): Reaction cycle for standard [NiFe] hydrogenases including the activation from the oxidized state(s), Ni-A/Ni-B; and the enzymatic cycle including 4 states. H₂ oxidation to 2 H⁺ and 2 e^- is presented; a reverse reaction is also possible. Ni (redox active) is taking up H₂, whereas Fe remains low spin Fe(II). The hydride is found in the Ni-Fe bridge that is occupied by OH^- in the oxidized state. The proton is accepted by a Cys sulfur acting as a base.

Figure 3 (B) — Fig. 3 (B): Electron density plot of the Ni-Fe active site in the Ni-R1 form of the enzyme showing the hydride in the bridge between Ni and Fe and the extra hydrogen at a cysteine sulfur, for details see [23].

Fig. 4: **(A)** The H-cluster of the active site of [FeFe] hydrogenases in its protein surrounding, showing the two subclusters [4Fe-4S]_H (left) and [2Fe]_H (right); **(B)**: picture showing a selection of non-native active site mimics of the [2Fe]_H -subcluster that could be introduced into the apo-protein (carrying only the [4Fe-4S]_H -subcluster) via artificial maturation of the hydrogenase from *Chlamydomonas reinhardtii*; for details see [30].

Fig. 5: ⁵⁷Fe ENDOR, HYSCORE and Mössbauer spectra of the CO-inhibited H-cluster in the [FeFe] hydrogenase of *Chlamydomonas reinhardtii*. A: EPR (inset) and ⁵⁷Fe ENDOR spectra of the H-cluster in which either the [4Fe-4S]H or the [2Fe]_H subcluster was labeled (large couplings of the 4Fe-cluster) B: ⁵⁷Fe HYSCORE spectrum of labeled [2Fe]_H-subcluster (small couplings of the 2Fe-cluster, assignment) C: ⁵⁷Fe Mössbauer spectra of the H-cluster in which only the [4Fe-4S]_H-subcluster was ⁵⁷Fe-labeled D: ⁵⁷Fe Mössbauer spectra of the H-cluster in which only the [2Fe]_H-subcluster was ⁵⁷Fe-labeled The Mössbauer simulations with different iron species are shown in shaded colors; for details see [31].

Fig. 6: NRVS (nuclear resonance vibrational spectroscopy) directly detecting the iron-hydride bending vibrational modes (range 400-800 cm^-1) for an [FeFe] hydrogenase from C. reinhardtii, artificially matured with a [257Fe]H cofactor carrying an oxo-dithiolate bridge (odt). Solid lines: sample in H₂O/H₂ (blue), sample in D₂O/D₂ (red) Dotted line: DFT calculated spectra Top right: model of the [2⁵⁷Fe]_H subcluster of the active site carrying a hydride/ deuteride at the distal Fe_d position. Note that the O in the bridgehead of the odt is less basic than the native N in this position (adt) and is thus a poor proton relay. This stabilizes the (transient) hydride-carrying state.

Fig.7: Cyclic voltammetry measurements of a Pt disc electrode (black trace), a D. *vulgaris* MF [NiFe] hydrogenase modified electrode (blue trace), and a [Ni(P₂^Cy N₂^Gly)₂]²⁺ complex (red trace) modified electrode, comparing the onset potentials for each catalyst under exactly the same experimental conditions (pH 5.0, 25ºC, 1 bar H₂). The vertical dashed line represents the equilibrium potential for the 2H⁺/H₂ couple. The structures of the hydrogenase (left) and the catalyst (right) immobilized on the pyrolytic graphite electrode (PGE) are shown; for details see [17].

Fig. 8: The water splitting clockwork of PS II in oxygenic photosynthesis showing the flash-induced S-state cycle (S₀ – S₄) with the release of electrons and protons, the water binding events and the time constants for each step. Furthermore the oxidation states of the 4 Mn ions are given. The outer circle shows the Mn₄O_xCa cluster passing through the S-state cycle; atoms are color labeled. Note that the “active” oxygen atoms are in green, the others are in red. In the S₂-state two isomeric forms are possible (A and B) indicating a switch from a low spin state to a high spin state of the cluster (indicated by the light blue and the dark blue shaded background) [19].

The Department of Biophysical Chemistry*

*please note that this text was last updated in 2016

The department of Biophysical Chemistry has been established in 2000 by Prof. Wolfgang Lubitz after his appointment as a director of the Max Planck Institute for Bioinorganic Chemistry, formerly Radiation Chemistry, which in 2012 was renamed Max Planck Institute for Chemical Energy Conversion (MPI-CEC). At present there are approximately 30 scientists, postdocs, doctoral students and technicians working in the department. Five research groups, each headed by a group leader, are working on specific topics (scheme 1).

“Artificial photosynthesis”, the concept that is explored in the department, is illustrated in Figure 1. More specifically, we are studying native systems (enzymes) to understand the ingenious concepts of Nature with the aim to use this knowledge to design and synthesize chemical systems for efficient light energy capturing, energy conversion and storage in chemical compounds. In this broad research field we are focusing on two biological systems that contain complex transition metal catalysts in their active sites: i) the water oxidizing complex (WOC) - or oxygen evolving complex (OEC) - of oxygenic photosynthesis; and ii) hydrogenases that produce or convert molecular hydrogen. We use a variety of different physical techniques to study these systems, including X-ray crystallography, X-ray spectroscopy, Mössbauer spectroscopy, magnetic resonance (EPR/NMR), optical and vibrational spectroscopy as well as electrochemistry. Particular emphasis is placed on characterizing the magnetic properties of the metal sites and their ligand sphere, for which advanced electron paramagnetic resonance (EPR) techniques are employed. Most of the investigated systems are prepared in-house, allowing sample optimization and modification in an efficient way. The information obtained from such spectroscopies is supplemented by modern quantum chemical approaches, with the aim of understanding the catalytic function at the atomic level (cooperation with Dr. Pantazis, Molecular Theory and Spectroscopy Department of Prof. Neese). In this way, insight into enzymatic water splitting and hydrogen production and consumption in Nature has been obtained, providing new and important design criteria for synthetic bioinspired catalysts for energy conversion (cooperation with the Department Schlögl, Heterogeneous Catalysis). Our recent work has been summarized in overview articles on water oxidation [1-3] and hydrogenases [4].

Instrumentation and Methodologies

A central mission of our department is the development of new instrumentation, methodologies and experimental techniques. In this endeavor we are closely working together with the technicians, engineers and the excellent workshops of the institute. We are recognized as a center for multifrequency EPR and related spectroscopies. The 8 major instrumental EPR stations (Scheme 2) span the microwave frequency range from 2 to 244 GHz at fields between 0 and 12 T, operating in both CW and pulse mode configurations and at temperatures from 1.5 K to significantly above room temperature. To become independent of liquid helium supply we have started to replace all cryostats (for sample cooling) and high field magnets with cryogen-free systems. Accessories for additional MW channels and RF (NMR) irradiation for multiple resonance experiments are available as well as an arbitrary wave form generator (AWG) for pulse shaping and multifrequency MW pulse sequences. Furthermore we are building our own probe heads (MW resonators) adapted to specific applications. Most instruments allow in-situ laser irradiation for studying light-dependent processes. Short-lived paramagnetic species can be studied down to lifetimes of a few nanoseconds. Recently high pressure equipment has been set up that allows high field EPR experiments to be performed at up to 2.5 kbar (4 kbar peak).

These developments in the MPI together with improvements in related microwave technology and data acquisition have led to a substantial increase in the sensitivity and stability of the EPR measurements. This has dramatically expanded the array of chemical systems that can be characterized using EPR techniques, including large protein supercomplexes with multiple paramagnetic centers, fast relaxing spin systems such as transition metal complexes and related materials, species with higher spin states and samples with constrained dimensions, e.g. small single crystals - to name only a few. EPR experiments on single crystals are of particular importance; in the department we are therefore running a crystal growth laboratory. Using microresonators we are now able to investigate very small single crystals with volumes of only a few nanoliters. Short-lived intermediates in reaction cycles (lifetimes of a few milliseconds) can be trapped by a recently implemented rapid freeze-quench system developed in our laboratory. This has been successfully employed for trapping several intermediates (S-states) in the light-driven water splitting clockwork of PS II using laser excitation combined with fast injection of ¹⁷O labeled water in the catalytic cycle (Kutin/Cox et al., to be published).

Another important recent development is the construction of a chemical reactor engineered inside an EPR resonator, allowing the in situ real time detection of the active species in a reaction using a heterogeneous catalyst. This station is combined with analytic gas analysis of the reaction products [5].

Particular emphasis is placed in our EPR laboratory on methods that are able to resolve the electron-nuclear hyperfine couplings between the electron spin and the nuclear spin(s) that are delivering a map of the spin density distribution of the system – unique information that is only available by advanced EPR methods. Next to the more established techniques, electron spin echo modulation (ESEEM) and electron-nuclear double resonance (ENDOR), we have developed and used electron-electron double resonance- (ELDOR) detected NMR (EDNMR) at a range of mw frequencies together with simulation software. In this way even for magnetic nuclei with high nuclear spin like ⁶¹Ni, ⁵⁵Mn, ¹⁷O and ¹⁴N the hfcs could be measured in complex metallobiomolecules with excellent sensitivity. The methodology has been described in recent articles by our group [6-8].

During the last two years we have started to use NMR techniques to determine the structure of metalloproteins in solution. First results have been obtained and published on the ferredoxin (petF) from a green algae that acts as shuttle between the photosynthetic electron transport and other proteins, e.g. hydrogenase (producing hydrogen) [9]. In a subsequent publication we were able to determine a much more complete NMR structure by substituting the paramagnetic iron ions in the [2Fe-2S] cluster in petF by two gallium ions, that are diamagnetic [10]. Very recently we have also started to use paramagnetic NMR to study the active site of various genetically modified and/or labeled, artificially matured [FeFe] hydrogenases (Rumpel et al., to be published).

In recent years we have expanded our activities to obtain also vibrational data that often allow detection of all intermediates in a reaction cycle. For hydrogenase and also photosynthesis research FTIR techniques are very important. We have set up two instruments for experiments covering a wide temperature range (4K to 350K) with light access of the cryostat to follow photoinduced reactions. An ATR (attenuated total reflection) cell for surface IR experiments is also available. Spectroelectrochemistry can be performed in an optical transparent thin layer electrochemical (OTTLE) cell. A similar cell is also used for UV-VIS detection of redox processes for which we have a separate instrument. Furthermore time resolved FTIR experiments are possible in step-scan mode performed on our second FTIR instrument. Another smaller FTIR instrument is placed in a glove box for surface enhanced infrared absorption (SEIRA) spectroscopy in combination with electrochemical control. In the department of Frank Neese a sensitive new Raman instrument has been built that will be used for joint Resonance Raman (RR) experiments. Vibrational data have also been obtained using inelastic Mössbauer scattering (nuclear resonance vibrational spectroscopy, NRVS) in cooperation with Stephen Cramer (UC Davis) on a synchrotron using respective monochromators (<1 meV resolution) at the beamline [11, 12]. This technique allows detection of vibrations that are often not accessible by FTIR or RR, e.g. of metal-hydrides in larger proteins. In the optical regime a new sensitive MCD instrument is available in the Neese Department that we are using together with Eckhard Bill with whom we are also collaborating on Mössbauer spectroscopy [13]. X ray absorption (XAS) and emission (XES) experiments have been started together with Serena DeBeer in the MPI [14].

As mentioned above the extension of our electrochemistry facility has made great progress during the last 3 years. Next to the classical techniques (cyclic voltammetry, coulometry, spectroelectrochemistry etc.) protein film electrochemistry (PFE) can now be performed routinely under controlled environmental conditions in two glove boxes equipped with gas mixers. Furthermore, we have successfully started to perform advanced EPR experiments on electrodes to follow the paramagnetic species and their conversion in the investigated processes (“electrochemical EPR”). This is particularly important for the detection of species (catalysts) on surfaces and embedded in polymer matrices [15-17].

In close collaboration with the Department of Prof. Neese, DFT and ab initio calculations are being performed to relate measured spectroscopic parameters to structure and obtain reliable, unified electronic and geometrical structural models, for example of catalytic intermediates, important for the elucidation of reaction mechanisms, see [11, 18, 19].

Collaborations within the MPI CEC, the Mülheim Chemistry Campus and with Neighboring Universities

Between our Biophysical Chemistry Department and the Molecular Theory and Spectroscopy Department of Frank Neese exist very close and successful ongoing collaborations both for the water oxidation project and the hydrogenases, which is demonstrated by a large number of joint publications. Water oxidation is studied with spectroscopic techniques (Dr. N. Cox) and theoretical methods (Dr. D. Pantazis); the joint effort has led to an atomic level understanding of the structure and the structural changes of the water splitting unit, including an assignment of oxidation and spin states of the individual manganese ions in each of its metastable transition states, as well as an assignment of the sites of substrate water binding, the process of O-O bond formation and O2 release [1-3, 18-20]. Collaboration with Dr. M. van Gastel has led to a significant advancement in the understanding of the structure and function of the catalytic site in [NiFe] hydrogenases [21]. Together with Dr. E. Bill, new important information using Mössbauer and EPR spectroscopy has been obtained for the regulatory hydrogenase, a sensor protein [13]. The work has been complimented by XAS and XES measurements on [NiFe] model systems with Prof. S. DeBeer [14]. With Dr. T. Weyhermüller we are collaborating to synthesize model systems both for water oxidation (manganese clusters) and particularly for hydrogen production [22]. Together with the recent ultra-high resolution crystallographic studies in our department [23] a near complete understanding of the [NiFe] hydrogenase catalytic cycle is within reach.

With the Department Schlögl Heterogeneous Catalysis we have started to set up EPR experiments to detect paramagnetic species in photocatalysis. A close collaboration in a joint project on manganese clusters on surfaces and in solution has been established within the BMBF project “Verbundvorhaben MANGAN” (principal investigators: S. DeBeer, N. Cox, D. Pantazis, A. Knop-Gericke). With Dr. S. Becker’s group functionalized carbon nanotubes for MnO electrocatalysis have been investigated with EPR. With the independent research group leader Dr. Jennifer Strunk (MPI CEC/Universität Duisburg/Essen) an EPR characterization of surface doped TiO2 particles for photocatalysis has been performed.

With the neighboring MPI für Kohlenforschung we have an ongoing collaboration with Dr. C. Farès to obtain protein structures in solution using NMR techniques [9, 10]. We have also initiated a project with Prof. F. Schüth/Dr. Ryan Wang on in situ EPR detection of the catalytically active sites in CuO/CeO2 for the preferential gas phase oxidation of CO to CO2 [5]. This novel technique is highly interesting also for other similar catalytic reactions, e.g. the water-gas shift reaction that is currently under study. Within the Cluster of Excellence (RU Bochum) we are also collaborating with the theory group of Prof. W. Thiel on protein dynamics including the solvent shell (QM/MM) [24].

Since 2012 Prof. W. Lubitz is PI in the Cluster of Excellence “RESOLV”

Hydrogenases

Hydrogenases are Nature´s catalysts for the oxidation of molecular hydrogen or the reverse reaction, the production of H₂ from protons. A basic understanding of the structure, function and dynamics of this class of enzymes is of key importance for a future biologically based hydrogen production technology and for the design and synthesis of bioinspired model systems for hydrogen conversion or production catalysis. In our department both the [NiFe] and the [FeFe] hydrogenases are studied along with appropriate model systems in a combined effort of different groups and by applying a broad range of physical techniques.

[NiFe] Hydrogenase: During the last 3 years the structures of all intermediates in the activation path and catalytic cycle of [NiFe] hydrogenases were finally resolved. The result is shown in Figure 3.

The active species is Ni-SI_a, a diamagnetic complex, Ni(II)Fe(II), with an open bridge between nickel and iron - prepared structurally and electronically to take up H₂. Ni-SI_a has been characterized using FTIR and Mössbauer spectroscopy [13]. This species attaches dihydrogen to yield Ni-R. We have obtained an ultrahigh resolution X-ray crystallographic structure (0.89 Å resolution) [23] of Ni-R in single crystals of the [NiFe] hydrogenase from Desulfovibrio vulgaris Miyazaki F, in which the product of heterolytic splitting of H₂ (H⁺ and H^-) could directly be identified; the hydride is sitting in the bridge between Ni and Fe (closer to Ni) and the proton is attached to the sulfur of one of the terminal cysteines next to the putative proton transfer canal. Furthermore, over 90% of the other hydrogens at ligating cysteines and surrounding amino acids near the active center could be detected including some water molecules.

In this structure the CO and CN- ligands could be distinguished for the first time and the proton transfer channel mapped out. Furthermore, the hydrogen bond network is available in unprecedented precision since the crucial hydrogens could directly be seen in many cases. The loss of an electron and a proton leads to Ni-C that only carries the hydride bridge, as shown in our earlier EPR work [25] and corroborated by DFT calculations on a large model of the active site together with the Neese group [26]. Ni-C is converted back to Ni-SI_a by loss of a proton and an electron, most probably in two steps (via a Ni-L like state). The sequence of these PCET reactions is not yet fully elucidated; it may involve several intermediates, (Ni-L and Ni-R states). The reductive activation of the oxidized state (Ni-B/Ni-A) to Ni-SI_a is done by loss of water (protonation of the OH^- bridge, see Figure 3). The spectroscopic signatures of the two oxidized states present in standard [NiFe] hydrogenases could also be explained by EPR and FTIR experiments together with QC models [21].

[FeFe] Hydrogenase: As discussed above the catalytic H₂ splitting and H₂ formation in [NiFe] hydrogenases is performed by the nickel ion aided by a terminal cysteine sulfur acting as a base. In the [FeFe] hydrogenases an iron ion is employed in concert with a special azadithiolate ligand bridging the two irons, in which the nitrogen is functioning as a base (see Figure 4). The existence of the nitrogen, first shown by pulse EPR and ENDOR in our group [27], was finally proven by the insertion of several biomimetic complexes into the apo-protein of bacterial and algal [FeFe] hydrogenases. This seminal work has been done together with M. Fontecave (Paris), V. Artero (Grenoble) and T. Happe (Bochum) and was published in 2013 [28, 29]. These first experiments on the artificial maturation of [FeFe] hydrogenases had far-reaching consequences for hydrogenase research, since the observed spontaneous cluster assembly could be used for obtaining larger amounts of hydrogenases, for isotopic labeling and changing metals and/or substituents or ligands, and to this end obtaining improved properties and function of the hydrogenase hybrids. Furthermore, the results could offer pathways to probe the theory of geobiochemical evolution of the hydrogenases and other related enzymes.

In Figure 4 a series of compounds with changed ligand sphere is shown that could be incorporated into the apo-protein. It is interesting that all complexes showed much lower activity than the native enzyme both for H₂ oxidation and production; only the compound with one instead of two CN- ligands attained 50% activity of the natural system [30]. In Figure 5 an example is shown demonstrating how specific labeling can lead to new information. Here a hydrogenase with the native cofactor is investigated for which either the [4Fe-4S]H-cluster or the [2Fe]_H-cluster is ⁵⁷Fe labeled. This allows the separate detection and assignment of data from Mössbauer and ⁵⁷Fe EPR/ENDOR spectroscopy for these subsites for different states in the catalytic states [31].

The specific ⁵⁷Fe labeling of the [2Fe]_H-subcluster also allowed the preparation (and stabilization) of the key intermediate that is carrying the hydride end-on at the distal Fe. For the detection vibrational spectroscopy (NRVS) at the synchrotron SPring8 (Hyogo, Japan) was used in collaboration with the group of S. Cramer (UC Davis), employing H/D exchange and a special cofactor that blocks proton transfer and stabilizes the transient intermediate, see Fig. 6 (Reijerse et al., submitted).

Furthermore, the availability of modified (hybrid) [FeFe] hydrogenases opened the possibility to detect and assign the proton nuclei of the active site using paramagnetic NMR, a collaborative research project with C. Farès (KOFO, Mülheim) and C. Luchinat (Florence) (Rumpel et al., in preparation).

Electrochemistry of Hydrogenases: The oxygen sensitivity of the [NiFe] hydrogenases is a major drawback for practical applications in (bio)fuel cells or water electrolysis. Fortunately, several oxygen tolerant [NiFe] hydrogenases are known, e. g, from Knallgas bacteria. How these are dealing with the attack of O₂ has been a topic of intense research in the past 5 years, see [4] for details. Together with the group of W. Schuhmann (RUB) we could show that a special designed smart matrix (a viologen-based polymer/hydrogel) is able to protect an embedded O₂-sensitive [NiFe] hydrogenase against oxygen attack and high potential deactivation [15]. This approach therefore eliminates two of the major problems that prevented the use of hydrogenases in biotechnological devices. Recently we could show that such a protection can also be achieved with the much more O2-sensitive [FeFe] hydrogenases [16]. We currently work on active hydrogenase model systems in cooperation with Wendy Shaw (PNNL, USA). In Figure 7 cyclic voltammograms are shown for H₂ reduction on Pt compared with [NiFe] hydrogenase and a model complex both covalently attached in the same way to the electrode. This demonstrates the excellent performance of both the native and model system - depending on experimental conditions [17].

Hydrogenase Model Systems: In recent years we have started to synthesize new structural and functional model systems for [NiFe] and [FeFe] hydrogenases and characterized them (for an overview see section 6 in ref. [4]). Interesting first results were the demonstration of a reversible protonation of sulfur in a NiFe-model, the design of a complex with Ni(low spin) Fe(high spin) and Fe as active site, and also a mono-iron compound with (P^R₂N^R₂)- and Cp*- ligands for H₂ production, for which an Fe-hydride species could be clearly detected and characterized [22]. We have also performed a large number of spectroscopic experiments on hydrogenase model systems of other groups, see [32] for an example.

Wateroxidase

In photosystem II of oxygenic photosynthesis a protein-bound oxygen-bridged Mn4Ca cluster performs the process of light-induced water oxidation in a complex catalytic cycle, thereby releasing molecular oxygen, protons and electrons. The protons are used to form a gradient across the membrane driving ATP production, whereas the electrons are used to form NADPH; with both molecules (ATP, NADPH) subsequently used in the dark reactions (Calvin cycle) to reduce CO₂ to carbohydrates. During water splitting the cluster passes through five intermediate states S₀ to S₄, where the subscript denoted the number of transiently stored oxidizing equivalents. For many decades, the lack of structural data, the absence of spectroscopic methods with high resolution and sensitivity, and the complexity of the water splitting reaction led to rather slow progress in this highly important research field. With the advent of atomic level X-ray structures in Japan (Shen et al.; Nature, 2011 and 2015), concomitant progress in X-ray spectroscopy and time-resolved X-ray diffraction in USA, and with the development of novel sensitive magnetic resonance techniques here in Mülheim, this field has witnessed an explosion of research activity in recent years. Together with theoretical calculations performed in the Department of Frank Neese an understanding of the process of light-induced water oxidation in Nature is now in sight.

In our department we have used mainly magnetic resonance techniques to study the trapped S-states of the water splitting cycle. Using advanced multifrequency pulse EPR, ENDOR and EDNMR techniques we were able to detect and characterize the flash-generated, freeze-trapped paramagnetic states S₀, S₂ and S₃ (S₁ is diamagnetic and S₄is a transient state). By a careful analysis – backed up by QC calculations – we determine the site oxidation and spin states of all Mn ions and their spin coupling for all intermediates of the catalytic cycle [18, 19].

The binding of the first substrate water and its incorporation into the Mn-cluster had already been measured by us using magnetically labeled water (H₂¹⁷O) and detection by high field ¹⁷O EDNMR [33]. In more recent work the second water binding event was proposed to take place in the S₂ → S₃ state transition; S₃ is the last metastable intermediate of the complex prior to O-O bond formation [20]. In the S₃ state, the two substrate oxygens are ideally located, bound between two Mn sites, allowing highly efficient O-O bond formation in the final S₄ state (Figure 8). This supports an oxo-oxyl coupling model originally proposed by Per Siegbahn (Stockholm).

Figure 8 summarizes the collected knowledge about the water oxidation cycle in oxygenic photosynthesis based on our joint spectroscopic and theoretical results in Mülheim. An interesting aspect is that in the S2 state two structural isomers have been found that allow a low-barrier transition from a low-spin S^A₂ (S_tot = 1/2) to a high-spin S^B₂ (S_tot = 5/2) configuration [34]. The two species are in full agreement with known EPR data. The high spin state, which is a consequence of a closed cubane configuration with the dangling Mn(III) having a vacant coordination site, enables formation of the S₃ (Stot

References

[1] Cox, N., Pantazis, D. A., Neese, F. and Lubitz, W. (2015) Artifical Photosynthesis: Understanding Water Splitting in Nature. Interface Focus, 5, 20150009 dx.doi.org/10.1098/rsfs.2015.0009.

[2] Pérez-Navarro, M., Neese, F., Lubitz, W., Pantazis, D. A. and Cox, N. (2016) Recent Developments in Biological Water Oxidation. Curr. Opin. Chem. Biol., 31, 113.

[3] Cox, N. and Lubitz, W. (2013) Molecular Concepts of Water Splitting: Nature's Approach. Green, De Gruyter Bookshelf, 3, 235.

[4] Lubitz, W., Ogata, H., Rüdiger, O. and Reijerse, E. (2014) Hydrogenases. Chem. Rev., 114, 4081.

[5] Wang, F., Büchel, R., Savitsky, A., Zalibera, M., Widmann, D., Pratsinis, S. E., Lubitz, W. and Schüth, F. (2016) In situ EPR Study of the Redox Properties of CuO–CeO₂ Catalysts for Preferential CO Oxidation (PROX). ACS Catal., 6, 3520.

[6] Cox, N., Lubitz, W. and Savitsky, A. (2013) W-Band ELDOR-Detected NMR (EDNMR) Spectroscopy as a Versatile Technique for the Characterization of Transition Metal-Ligand Interactions. Mol. Phys., 111, 2788.

[7] Nalepa, A., Möbius, K., Lubitz, W. and Savitsky, A. (2014) High-Field ELDOR-Detected NMR Study of a Nitroxide Radical in Disordered Solids: Towards Characterization of Heterogeneity of Microenvironments in Spin-Labeled Systems. J. Magn. Res., 242, 203.

[8] Cox, N., Nalepa, A., Pandelia, M.-E., Lubitz, W. and Savitsky, A. (2015) Pulse Double-Resonance EPR Techniques for the Study of Metallobiomolecules. In: Methods in Enzymology, P. Z. Qin and K. Warncke (eds.), Elsevier, Oxford, pp. 211-249.

[9] Rumpel, S., Siebel, J. F., Farès, C., Duan, J., Reijerse, E., Happe, T., Lubitz, W. and Winkler, M. (2014) Enhancing Hydrogen Production of Microalgae by Redirecting Electrons from Photosystem I to Hydrogenase. Energy Environ. Sci., 7, 3296.

[10] Rumpel, S., Siebel, J. F., Diallo, M., Farès, C., Reijerse, E. and Lubitz, W. (2015) Structural Insight into the Complex of Ferredoxin and [FeFe] Hydrogenase from Chlamydomonas reinhardtii. ChemBioChem., 16, 1663.

[11] Ogata, H., Krämer, T., Wang, H., Schilter, D., Pelmenschikov, V., van Gastel, M., Neese, F., Rauchfuss, T. B., Gee, L. B., Scott, A. D., Yoda, Y., Tanaka, Y., Lubitz, W. and Cramer, S. P. (2015) Hydride Bridge in [NiFe]-hydrogenase Observed by Nuclear Resonance Vibrational Spectroscopy. Nat. Commun., 6, 7890. doi: 10.1038/ncomms8890 (2015)

[12] Wang, H., Yoda, Y., Ogata, H., Tanaka, Y. and Lubitz, W. (2015) A Strenuous Experimental Journey Searching for Spectroscopic Evidence of a Briding Nickel-iron-hydride in [NiFe] Hydrogenase. J. Synchrotron Rad., 22, 1334.

[13] Roncaroli, F., Bill, E., Friedrich, B., Lenz, O., Lubitz, W. and Pandelia, M.-E. (2015) Cofactor Composition and Function of a H₂-sensing Regulatory Hydrogenase as Revealed by Mössbauer and EPR Spectroscopy. Chem. Sci., 6, 4495.

[14] Hugenbruch, S., Shafaat, H. S., Krämer, T., Delgado-Jaime, M. U., Weber, K., Neese, F., Lubitz, W. and DeBeer, S. (2016) In Search of Metal Hydrides: An X-ray Absorption and Emission Study of [NiFe] Hydrogenase Model Complexes. Phys. Chem. Chem. Phys., 18, 10688.

[15] Plumeré, N., Rüdiger, O., Oughli, A. A., Williams, R., Vivekananthan, J., Pöller, S., Schuhmann, W. and Lubitz, W. (2014) A Redox Hydrogel Protects Hydrogenase from High-potential Deactivation and Oxygen Damage. Nat. Chem., 6, 822.

[16] Oughli, A. A., Conzuelo, F., Winkler, M., Happe, T., Lubitz, W., Schuhmann, W., Rudiger, O. and Plumere, N. (2015) A Redox Hydrogel Protects the O₂-Sensitive [FeFe]-Hydrogenase from Chlamydomonas reinhardtii from Oxidative Damage. Angew. Chem., Int. Ed., 54, 12329.

[17] Rodriguez-Macià, P., Dutta, A., Lubitz, W., Shaw, W. and Rüdiger, O. (2015) Direct Comparison of the Performance of a Bio-inspired Synthetic Nickel Catalyst and a [NiFe]-Hydrogenase, Both Covalently Attached to Electrodes. Angew. Chem., Int. Ed., 54, 12303.

[18] Krewald, V., Retegan, M., Cox, N., Messinger, J., Lubitz, W., DeBeer, S., Neese, F. and Pantazis, D. (2015) Metal Oxidation States in Biological Water Splitting. Chem. Sci., 6, 1676.

[19] Krewald, V., Retegan, M., Neese, F., Lubitz, W., Pantazis, D. A. and Cox, N. (2016) Spin State as a Marker for the Structural Evolution of Nature’s Water-Splitting Catalyst. Inorg. Chem., 55, 488.

[20] Cox, N., Retegan, M., Neese, F., Pantazis, D. A., Boussac, A. and Lubitz, W. (2014) Electronic Structure of the Oxygen-evolving Complex in Photosystem II Prior to O-O Bond Formation. Science, 345, 804.

[21] Barilone, J. L., Ogata, H., Lubitz, W. and van Gastel, M. (2015) Structural Differences Between the Active Sites of the Ni-A and Ni-B States of the [NiFe] Hydrogenase: An Approach by Quantum Chemistry and Single Crystal ENDOR Spectroscopy. Phys. Chem. Chem. Phys., 17, 16204.

[22] Weber, K., Weyhermüller, T., Bill, E., Erdem, Ö. F. and Lubitz, W. (2015) Design and Characterization of Phosphine Iron Hydrides: Toward Hydrogen-producing Catalysts. Inorg. Chem., 54, 6928.

[23] Ogata, H., Nishikawa, K. and Lubitz, W. (2015) Hydrogens Detected by Subatomic Resolution Protein Crystallography in a [NiFe] Hydrogenase. Nature, 520, 571.

[24] Decaneto, E., Vasilevskaya, T., Kutin, Y., Ogata, H., Grossman, M., Sagi, I., Havenith, M., Lubitz, W., Thiel, W. and Cox, N. (2017) The Active Site of the Membrane Type-I Matrix Metalloproteinase: Enzyme Regeneration and the Interplay of Solvent Water. Chem. Sci., accepted,

[25] Brecht, M., van Gastel, M., Buhrke, T., Friedrich, B. and Lubitz, W. (2003) Direct Detection of a Hydrogen Ligand in the [NiFe] Center of the Regulatory H₂-sensing Hydrogenase from Ralstonia eutropha in Its Reduced State by HYSCORE and ENDOR Spectroscopy. J. Am. Chem. Soc., 125, 13075.

[26] Krämer, T., Kampa, M., Lubitz, W., van Gastel, M. and Neese, F. (2013) Theoretical Spectroscopy of the Ni^II Intermediate States in the Catalytic Cycle and the Activation of [NiFe] Hydrogenase. ChemBioChem, 14, 1898.

[27] Silakov, A., Wenk, B., Reijerse, E. and Lubitz, W. (2009) ¹⁴N HYSCORE Investigation of the H-Cluster of [FeFe] Hydrogenase: Evidence for a Nitrogen in the Dithiol Bridge. Phys. Chem. Chem. Phys., 11, 6592.

[28] Berggren, G., Adamska, A., Lambertz, C., Simmons, T. R., Esselborn, J., Atta, M., Gambarelli, S., Mouesca, J. M., Reijerse, E., Lubitz, W., Happe, T., Artero, V. and Fontecave, M. (2013) Biomimetic Assembly and Activation of [FeFe]-Hydrogenases. Nature, 499, 66.

[29] Esselborn, J., Lambertz, C., Adamska-Venkatesh, A., Simmons, T., Berggren, G., Noth, J., Siebel, J., Hemschemeier, A., Artero, V., Reijerse, E., Fontecave, M., Lubitz, W. and Happe, T. (2013) Spontaneous Activation of the [FeFe]-Hydrogenases by an Inorganic [2Fe] Active Site Mimic. Nat. Chem. Biol., 9, 607.

[30] Siebel, J. F., Adamska-Venkatesh, A., Weber, K., Rumpel, S., Reijerse, E. J. and Lubitz, W. (2015) Hybrid [FeFe]-hydrogenases with Modified Active Sites Show Remarkable Residual Enzymatic Activity. Biochemistry, 54, 1474.

[31] Gilbert-Wilson, R., Siebel, J. F., Adamska-Venkatesh, A., Pham, C. C., Reijerse, E., Wang, H., Cramer, S. P., Lubitz, W. and Rauchfuss, T. B. (2015) Spectroscopic Investigations of [FeFe] Hydrogenase Maturated with [⁵⁷Fe₂(adt)(CN)₂(CO)₄]^2-. J. Am. Chem. Soc., 137, 8998.

[32] Chambers, G. M., Huynh, M. T., Li, Y., Hammes-Schiffer, S., Rauchfuss, T. B., Reijerse, E. and Lubitz, W. (2016) Models of the Ni-L and Ni-SI_a States of the [NiFe]-Hydrogenase Active Site. Inorg. Chem., 55, 419.

[33] Rapatskiy, L., Cox, N., Savitsky, A., Ames, W. M., Sander, J., Nowaczyk, M. M., Rögner, M., Boussac, A., Neese, F., Messinger, J. and Lubitz, W. (2012) Detection of the Water Binding Sites of the Oxygen-Evolving Complex of Photosystem II Using W-Band ¹⁷O ELDOR-Detected NMR Spectroscopy. J. Am. Chem. Soc., 134, 16619.

[34] Pantazis, D. A., Ames, W., Cox, N., Lubitz, W. and Neese, F. (2012) Two Interconvertible Structures that Explain the Spectroscopic Properties of the Oxygen-Evolving Complex of Photosystem II in the S₂ State. Angew. Chem., Int. Ed., 51, 9935.

Prof. Dr. Karl Wieghardt

Direktor 1994-2010

Vita

Diplom in Chemie	Universität Heidelberg (1967)
Promotion	Universität Heidelberg, Institut für Anorganische Chemie, Prof. Hans Siebert (1969)
Assistent	Universität Heidelberg, Inst. für Anorganische Chemie, Labor Prof. Siebert und Prof. Weiss (1969-1972)
Post-doc	University of Leeds, GB, Prof. A. G. Sykes (1972-1973)
Habilitation	Universität Heidelberg (1974)
Privatdozent	Universität Heidelberg (1974-1975)
Professor, wiss. Rat	Technische Universität Hannover (1975-1981)
Professor	Lehrstuhl für Anorganische Chemie, Ruhr-Universität Bochum (1981-1994)
Founding Director	Max-Planck-Institut für Bioanorganische Chemie (1994-2010)
Emeritus	Max-Planck-Institut für Bioanorganische Chemie (2010)

Publications

full publications Researcher ID

Awards

Französisch-Deutscher Alexander von Humboldt, Gay Lussac Forschungspreis, April 1995
Wilhelm-Klemm-Medaille, Gesellschaft Deutsche Chemiker, 2000
John-Bailar-Medaille, University of Illinois, 2000
Centenary Medal, Royal Society of Chemistry (London), 2002
American Chemical Society Award in Inorganic Chemistry, 2006
Ruhrpreis, 2005

Functions

Gesellschaft Deutscher Chemiker
Deutsche Akademie der Naturforscher, Leopoldina
Auswärtiges Mitglied der Chemical Research Society of India
Mitglied des Auswahlgremiums des Otto Hahn-Preises (Gesellschaft Deutscher Chemiker; Stadt Frankfurt)
Vorsitzender des Gremiums zur Auswahl des Alfred-Stock-Gedächtnispreises (Gesellschaft Deutscher Chemiker)
Fachgutachter der Deutschen Forschungsgemeinschaft, 8 Jahre
Mitglied des Heisenbergausschusses, 6 Jahre

Research - Bioinorganic Chemistry

Fig. 1 Top: Mulliken atom spin densities as derived from BS(3,3)B3LYP DFT calculations: alpha-spin density in red; β-spin density in yellow. Bottom: Qualitative MO-scheme showing the antiferromagnetic coupling between the central Cr(III) ion (d3; SCr=3/2) and three ligand pi-radicals (tbbdt•)1-yielding the observed S=0 ground state.

Fig. 2 Sulfur K-edge X-ray absorption spectra of [Cr(Cl₂-bdt)]^1-,2-,3- showing the presence (blue = 1- species; red = 2- species) and absence (green = 3- species) of the characteristic π-radical pre-edge feature at2469.8 eV

Fig. 3 Calculated atom spin densities for the mono-, di-, and trianionof[CrIII(Cl₂-bdt)₃]^n-. Θ represents a twist angle (Θ=0° in a trigonal prism and 60° in a regular octahedron).

The research of my group focuses on two areas of Inorganic Chemistry, namely Coordination Chemistry of Transition Metal Ions and Bioinorganic Chemistry.

Coordination Chemistry

We continue to extensively study the coordination chemistry of organic p radical ligands with paramagnetic transition metal ions. The main focus is the correct description of the electronic structure of compounds containing open-shell organic ligands and paramagnetic metal ions. In a very simplified picture we have to discern between the following two possibilities:

Mⁿ⁺ — L or M^(n-1)+ — L^•

(1) (2)

The question arises if the two structures (1) and (2) represent

a) two mesomeric resonance structures of a single electronic ground state configuration or

b) two distinctly different ground states with differing chemical reactivities(equilibrium).

We have developed spectroscopic and theoretical methodology (in collaboration with F. Neese) to answer such questions. In fact, computational chemistry has been found to be an extremely powerful tool for the discovery of coordinated radicals. Broken symmetry DFT calculations of the electronic structure of a given compound and calculations of their spectroscopic properties(UV-vis IR-, RR-, EPR-, and Mössbauer spectroscopy) allow to solve complicated electronic structure problems.

Two examples may illustrate this approach: The neutral tris(benzene–1,2-dithiolato)chromium complex is a diamagnetic molecule with a S=0 ground state. There are two extreme electronic structures conceivable: [Cr^VI(bdt^2-)3]⁰ with a central Cr(VI) ion (d⁰, S_Cr=0) and three closed-shell dianionic, diamagnetic (bdt)^2-(S_L=0) ligands or, alternatively the complex could possess a central paramagnetic Cr(III) ion (d³, S_Cr=3/2) and three paramagnetic monoanionic pi-radical ligands (bdt•)^1-(S_L=1/2) the spins of which couple intramolecularly antiferromagnetically yielding the observed S=0 ground state. It is possible to calculate both electronic structures: with

a) a spin-restricted closed-shell S=0 solution or

b) a broken symmetry spin unrestricted Kohn-Sham DFT solution BS(3,3).

It was found that the latter solution is ~20 kcal/mol lower in energy than the former. Thus the [Cr^III (bdt•) ₃]⁰ formulation represents the correct electronic structure and not [Cr^VI (bdt)₃]⁰ (Fig. 1) Experimentally this can be proven by X-ray absorption spectroscopy (measuring CrK-edge and S K-edge energies).

We have established a very close and intense collaboration between Professor Serena DeBeer George of the Stanford Synchrotron Laboratory (SLAC) and our laboratory in Mülheim. Fig. 2 shows the S K-edge spectra of the electron transfer series: [Cr^III(bdt₃)]^3-/2-/1- where the trianion [Cr^III(bdt)₃]^3-(S=3/2) consists of three (bdt)^2-ligands whereas the dianion contains a single pi-radical anion[Cr^III(bdt•)(bdt)_2-]^2-(S=1) and the monoanion [Cr^III(bdt•)₂(bdt)^1-(S=1/2) consists of two (bdt•)^1- radicals and one closed-shell (bdt)^2-. The neutral complex consists of three (bdt•)^1- monoanions and a central Cr^III ion. A characteristic pi-radical pre-edge feature has been identified (of varying intensity) at 2468.8 eV for the mono- and dianion but not for the trianion. Broken symmetry DFT calculations shown in Fig. 3 beautifully confirm these results.

In an extended program we have investigated and successfully determined the electronic structures of such [ML₃]ⁿ electron transfer series of V, Mo, W, Re.

A second example may illustrate the electronic structure problem in organometallic chemistry. [Ni(COD)₂]⁰(COD=cyclooctadiene) is a diamagnetic molecule containing two neutral COD ligands and a central diamagnetic Ni⁰ ion(d₁₀, S^Ni=0). Reaction of this species with alpha-diimines(L1) or 1,2-diketones (L2) produces diamagnetic molecules [Ni(COD) (L1,2)]⁰which in the past have been described as classic Ni⁰ (d¹⁰) complexes with a neutral alpha-diimine or 1,2-diketone ligand.

We have established that both the alpha-diimines and the 1,2-diketones are redox-noninnocent ligands which can exist in three oxidation levels as

a) a neutral ligand (L_1,2) and

b) a monoanionic pi radical (L•_1,2)^1-, and

c) a diamagnetic dianion (L^Red)^2-.

Thus the above diamagnetic complexes can have three different electronic structures:[Ni⁰(COD)(L_1,2)]⁰, [Ni^I(COD)(L•_1,2)]⁰, or [Ni^II(COD)(L_1,2^Red)]⁰.

We have established by computational chemistry and spectroscopy that they are in fact singlet diradicals with a) central Ni^I ion (d⁹, S_Ni=1/2) and a pi-radical monoanion(L•_1,2)^1- which couple antiferromagnetically: S_t=0. This discovery has wide implications in organometallic chemistry. In a third project – in a collaboration with Professor P.Chirik (Cornell University) and funded by the NSF (National Science Foundation, U.S.A.) and the DFG – we investigate the correlation of established electronic structures of some (bis(imino)pyridine) iron complexes and their reactivity. These ligands represent another class of redox-noninnocent ligands which can exist as a neutral species, and as mono-, di-, or trianion when coordinated to a transition metal ion.

Bioinorganic Chemistry

It is well-established that more than one half of all known enzymes are metalloproteins containing one or more transition metal ions in their respective active site (V, [Cr], Mn,Fe, Co, Ni, Cu, Zn, Mo, or W). It is our philosophy that an understanding of their reactivity can only be achieved ift he underlying coordination chemistry (geometry, electronic structure, etc.) is unraveled for all intermediates in the respective catalytic cycle.

We have continued our efforts to synthesize tetranuclear manganese complexes which might oxidize water as model compounds for the water oxidizing center (WOC) in photosystem II.

4hν + 2H₂O 4H⁺ + 4e + O₂

In this area of research a close and successful collaboration between our group and that of Professor Lubitz has been further developed. Thus, we have investigated in great depth the EPR and ENDOR signatures of Mn^IIIMn^IVdimers in Nature (catalases, PSII) and models.

The active sites of non-heme iron metalloenzymes containing one or more iron ions continue to fascinate my group. So-called high-valent iron compounds, where the formal or spectroscopic oxidation state of the central iron ion is > +III, are still of main interest.

Prof. Dr. Kurt Schaffner

Direktor 1976-1999

Vita

Dipl. Ing.-Chem.		Eidg. Technische Hochschule (ETH), Zürich (1954)
Promotion (Dr. sc. techn.)		Lab. Organische Chemie, ETH (1957)
Privatdozent		Lab. Organische Chemie, ETH (1964-71)
Titularprofessor		Lab. Organische Chemie, ETH (1970)
Professeur ord.		Chimie Organique, Université de Genève (1971-76)
Director		Max-Planck-Institut für Strahlenchemie / für Bioanorganische Chemie (1976-99)
Emeritus		Max-Planck-Institut für Strahlenchemie / für Bioanorgansiche Chemie (since 1999)

Awards

1957 Silver Medal of ETH
1965 Swiss Chemical Society Award with Werner Medal
1968 Ruzicka Award, ETH Zürich
1990 Havinga Medal, Leiden
1995 M. L. Dewey and C. H. Kelly Award, University of Nebraska, Lincoln
1997 European Society for Photobiology Award
2001 Theodor Förster Award, Deutsche Bunsengesellschaft and Gesellschaft Deutscher Chemiker

Functions

1966-92 Visiting Professorships (University of California at Riverside and Los Angeles; Weizmann Institute of Science, Rehovot; Universities of Colorado, Boulder, Leiden, and Amsterdam; Japan Society for the Promotion of Science; Academy of Sciences, UdSSR; National Chemical Laboratory for Industry, Tsukuba, Ibaraki)
1970 European Photochemistry Association (Member since 1970; 1970-72 Member, Standing Committee; 1972-1976 President)
1971-2001 IUPAC Organic Chemistry Division (1971-81 Member, Commission on Photochemistry; 1976-81 Chairman; 1983-89 Coopted Member, Division Committee; 1991-2001 Member, Committee on Chemical Weapons Destruction Techniques)
1976 President, VIIth IUPAC Symposium on Photochemistry, Aix-en-Provence
1977 Pacific Coast Lecturer
1977-2000 Int. Photochemistry Foundation (1977-96 Chairman; 1996-2000 Trustee)
1981 Chairman, EUCHEM Conference‚ Intermediates in Organic Chemistry’, Ajaccio
1983-99 Founder, Biannual DFG Round Table Discussions ‘Spectroskopie biologischer Photorezeptoren’, Schloss Ringberg, Rottach-Egern
European Society for Photobiology (Member since 1985; 1985-86 President, Founding Committee; 1986-89 Member, Executive Committee)
Nordrhein-Westfälische Akademie der Wissenschaften, Düsseldorf (Full Member since 1986; 1998-2000 Sekretar and Vice-President)
Since 1989 Member, Academia Europaea
1990-2000 Member, Beirat of the Ladislaus-Farkas Research Centre for the Conversion of Light Energy (Minerva Centre), Hebrew University, Jerusalem
1991 Doctor honoris causa, Institut Químic de Sarrià, Ramon Llull University, Barcelona
Since 1993 Member, Deutsche Akademie der Naturforscher Leopoldina, Halle
Since 1994 Member, New York Academy of Sciences

Research - Synthetic and Mechanistic photochemistry

The traditional research activities of his group – synthetic and mechanistic photochemistry – were soon complemented by a broad entry into the field of photobiology and photobiophysics. Research in photomorphogenesis and photosynthesis eventually became the predominant activities: in particular Structure, function and dynamics of chromoproteins (photoreceptors) with open-chain tetrapyrrole pigments:

photomorphogenesis of phytochromes, the light-driven regulatory pigment in green plants, algae, moss, and cyanobacteria
structure and energy transfer mechanism in phycobilisomes (extramembraneous light harvesting antennae of cyanobacteria and certain algae)
photosynthesis, in particular structure/function relationships in antenna systems (LHC II, PS I-antenna complex), electron transfer processes in photosynthetic reaction centres (PS I and II), etc.