12.07 Photocatalytic carbon chemistry - Engineering light harvesting and charge carrier transport (PCC)

Research

A sustainable C1 carbon chemistry requires new approaches to overcome thermodynamic constraints and steer the kinetics of the associated chemical transformations. Prominent examples are the conversion of C1 sources such as CO2 and methane into valuable, high-energy chemicals driven by (solar) photons. Such processes involve light harvesting, charge-carrier separation and transfer to catalytic sites, as well as the actual chemical conversion of C1 sources at these sites. The current state-of-the-art relies on homogeneous (molecular) photocatalysts and heterogeneous (bulk semiconductor/metal) hybrid systems. In this project, we synergetically combine both approaches to overcome stability and reactivity limitations. This requires a highly interdisciplinary approach including synthetic inorganic chemistry, semiconductor and nanomaterials engineering, advanced spectroscopies and microscopies, which expertise can be found at the TUM Departments of Physics and Chemistry. Three types of innovative hybrid systems will be explored: i) Surface-immobilized caviplexes, i.e. multi-metal centres in stable, spatially defined chemical environments linked to light-harvesting supports; ii) ordered low-dimensional photoactive molecular networks as well as iii) band gap-engineered semiconductor surfaces as light harvesting supports, both coupled to level-aligned metal(oxide) co-catalyst clusters.

Publications

P. Knecht, P. T. P. Ryan, D. A. Duncan, L. Jiang, J. Reichert, P. S. Deimel, F. Haag, J. T. Küchle, F. Allegretti, T.-L. Lee, M. Schwarz, M. Garnica, W. Auwärter, A. P. Seitsonen, J. V. Barth and A. C. Papageoergiou (2021): “The tunable interface of ruthenium porphyrins and silver”, J. Phys. Chem. C, 125, 3215-3224, doi: 10.1021/acs.jpcc.0c10418.

P. Knecht, B. Zhang, J. Reichert, D. A. Duncan, M. schwarz F. Haag, P. T. P. Ryan, T.-L. Lee, P. S. Deimel, P. Feulner, F. Allegretti, W. Auwärter, G. MÉdard, A. P. Seitsonen, J. V. Barth and A. C. Papageoergiou (2021): “Assembly and manipulation of a prototypical N-heterocyclic carbene with a metalloporphyrin pedestal on a solid surface”, J. Am. Chem. Soc., 143, 4433-4439, doi: 10.1021/jacs.1c01229.

P. Knecht, J. Reichert, P. S. Deimel, P. Feulner, F. Haag, F. Allegretti, M. Garnica, M. Schwarz, W. Auwärter, P. T. P. Ryan, T.-L. Lee, D. A. Duncan, A. P. Seitsonen,  J. V. Barth and A. C. Papageoergiou (2021): “Conformational control of chemical reactivity for surface-confined Ru-porphyrins”, Angew. Chem., Int. Ed. 60, 2-9, doi: 10.1002/anie.202104075.

P. S. Deimel, P. Casado Aguilar, M. Paszkiewicz, D. A. Duncan, J. V. Barth, F. Klappenberger, W. Schöfberger and   F. Allegretti (2020): „Stabilisation of tri-valent ions with a vacant coordination site at a corrole–metal interface”, Chem. Commun., 76, 11219-11222, doi: 10.1039/D0CC03947K

X. Jiang, H. Kim, P. S. Deimel, W.Chen, W. Cao, D. Yang, S. Yin, R. Schaffrinna, F. Allegretti, J. V. Barth,M. Schwager, H. Tang, K. Wang, M. Schwartzkopf, S. V. Rothef  and P. Müller-Buschbaum (2020): „Internal nanoscale architecture and charge carrier dynamics of wide bandgap non-fullerene bulk heterojunction active layers in organic solar cells”, Journal of Materials Chem., 44, 23628-23636, doi: 10.1039/D0TA09671G

Z. Wang, K. Qian, M. A. Öner, P. S. Deimel,  Y. Wang, S. Zhang, X. Zhang, V. Gupta, J. Li, H.-J. Gao, D. A. Duncan, J. V. Barth, X. Lin, F. Allegretti, S. Du and C.-A. Palma (2020): „Layer-by-Layer Epitaxy of Porphyrin−Ligand Fe(II)-Fe(III) Nanoarchitectures for Advanced Metal–Organic Framework Growth”, ACS Appl. Nano Mater. 2020, 3, 12, 11752–11759, doi: 10.1021/acsanm.0c02237

P. T. P. Ryan, P. L. Lalaguna, F. Haag, M. M. Braim, P. Ding, D. J. Payne, J. V. Barth, T.-L. Lee, D. P. Woodruff, F. Allegretti and D. A. Duncan (2020): "Validation of the inverted adsorption structure for free-base tetraphenyl porphyrin on Cu(111)", Chem. Commun., 56, 3681-3684, doi: 10.1039/C9CC09638H

P. T. P. Ryan, M. Meier, Z. Jakub, J. Balajka, J. Hulva, D. J. Payne, T.-L. Lee, C. Franchini, F. Allegretti, G. S. Parkinson, and D. A. Duncan (2020): "Probing structural changes upon carbon monoxide coordination to single metal adatoms", J. Chem. Phys., 152, 051102, doi: 10.1063/1.5137904

A. Baklanov, M. Garnica, A. Robert, M.-L. Bocquet, K. Seufert, J. T. Küchle, P. T. P. Ryan, F. Haag, R. Kakavandi, F. Allegretti, W. Auwärter (2020): "On-Surface Synthesis of Nonmetal Porphyrins", J. Am. Chem. Soc., 142, 4, 1871-1881, doi: 10.1021/jacs.9b10711

C. Courtois, M. Eder, K. Schnabl, C. A. Walenta, M. Tschurl, Prof.Dr. U. Heiz (2019): "Reactions in the Photocatalytic Conversion of Tertiary Alcohols on Rutile TiO2(110)", Angewandte Chemie, 58, 40, 14255-14259, doi: 10.1002/anie.201907917

D. A. Duncan, P. S. Deimel, A. Wiengarten, M. Paszkiewicz, P. Casado Aguilar, R. G. Acres, F. Klappenberger, W. Auwärter, A. P. Seitsonen, J. V. Barth, and F. Allegretti (2019): "Bottom-Up Fabrication of a Metal-Supported Oxo–Metal Porphyrin", J. Phys. Chem. C, 123, 51, 31011-31025, doi: 10.1021/acs.jpcc.9b08661

Y.-Q. Zhang, T. Paintner, R. Hellwig, F. Haag, F. Allegretti, P. Feulner, S. Klyatskaya, M. Ruben, A. P. Seitsonen, J. V. Barth, F. Klappenberger (2019): "Synthesizing Highly Regular Single-Layer Alkynyl–Silver Networks at the Micrometer Scale via Gas-Mediated Surface Reaction", J. Am. Chem. Soc., 141, 13, 5087-5091, doi: 10.1021/jacs.8b13547

Team

Project team leader

Dr. habil. Francesco Allegretti
Physics of Surfaces and Interfaces

Doctoral researcher

Johannes Tore Küchle
Physics of Surfaces and Interfaces

Doctoral researcher

Carla Courtois
Chair of Physical Chemistry

Doctoral researcher

Felix Haag
Physics of Surfaces and Interfaces

Doctoral researcher

Nicolas Bock
Chair of Physical Chemistry

Principal investigator

Professor Johannes Barth
Physics of Surfaces and Interfaces

Principal investigator

Professor Ueli Heiz
Chair of Physical Chemistry