Understanding and improving the catalytic activity of transition metal oxide surfaces: Insights from DFT+U calculations

The development and improvement of catalysts for chemical energy conversion, such as (photo-) electrocatalytic water splitting or alcohol oxidation, requires mechanistic understanding at the atomic/molecular level. In my talk I will address several examples for the application of density functional theory calculations to model, understand and tailor the catalytic activity of anode materials for water splitting. To disentangle the role of structural motifs, crystallographic orientation and dopants, I will focus on iron and cobalt containing transition metal oxides with spinel [1-3], corundum [4] vs. perovskite [5] structure. The aim is to establish a link between the energetic trends and the underlying structural and electronic properties and to identify potential active sites. A further topic is the reduction of iron oxide surfaces and bulk via hydrogen adsorption [6] and incorporation.

Funding by the German Research Foundation DFT within SPP 1613 and CRC TRR247 as well as computational time at the Leibniz Rechenzentrum and the supercomputer MagnitUDE at UDE is gratefully acknowledged.

[1] K. Chakrapani, G. Bendt, H. Hajiyani, I. Schwarzrock, T. Lunkenbein, S. Salamon, J. Landers, H. Wende, R. Schlögl, R. Pentcheva, M. Behrens, S. Schulz, ChemCatChem. 9, 2988-2995, (2017)

[2] H. Hajiyani, R. Pentcheva, ACS Catal. 8, 11773-11782 (2018)

[3] Y. Peng, H. Hajiyani, R. Pentcheva, ACS Catal. 11, 5601–5613, (2021)

[4] A.G. Hufnagel, H. Hajiyani, S. Zhang, T. Li, O. Kasian, B. Gault, B. Breitbach, T. Bein, D. Fattakhova-Rohlfing, C. Scheu, R. Pentcheva, Adv. Funct. Mater., 165, 1804472 (2018)

[5] A. Füngerlings, A. Koul, M. Dreyer, A. Rabe, D. M. Morales, W. Schuhmann, M. Behrens, and R. Pentcheva, Chemistry - A European Journal, accepted.

[6] G. S. Parkinson, N. Mulakaluri, Y. Losovyj, P. Jacobson, R. Pentcheva, and U. Diebold, Phys. Rev. B 82, 125413 (2010)