Rational design of novel materials for energy applications demands a deeper understanding at the atomic level of the origin of relevant properties of materials and associated processes. The use of Density Functional Theory (DFT) has resulted in major breakthroughs in those efforts and has had an enormous impact both on fundamental and applied materials research. This paper will describe some of the efficient computational tools, which can be used in concert with experimental approaches to explore various aspects in the design of both platinum group metal and non-platinum group matal based materials for fuel cell applications.

The first part will be a discussion of the capabilities of DFT to model the structure of, and catalytic processes on different catalytic materials. Examples include an explanation of the observed catalytic activity of CuCo₂O₄  ORR/OER bi-functional catalysts by DFT methods, and the structure-property relationships in novel 3D graphene hybrid materials synthetized at UNM [1]. This will be followed by a description of theoretical modeling of the catalyst-ionomer interface, which can identify some key ionomer features of crucial importance for their efficient implementation with the specific electro-catalyst in the anion and proton exchange membrane fuel cells. Examples in this part include the interaction of organic cations with an extended platinum surface and nafion with M-N-C type catalysts. DFT based approaches as a support for spectroscopic measurements of surface phenomena will be discussed in the last part of this talk, including the advantages and disadvantages of DFT in reproducing accurate vibrational spectra of surface bound species [2]. Finally, the use of core level shifts obtained from DFT calculations can facilitate the interpretation of X-ray Photoelectron Spectroscopy (XPS) experiments, and thereby support the effort to determine structure to reactivity relationships that are essential for reaching an understanding of M-N-C catalysts on the molecular level.

[1] A. Serov, N. I. Andersen, A. J. Roy, I. Matanovic, K. Artyushkova, P. Atanassov, CuCo₂O₄ ORR/OER Bi-Functional Catalyst: Influence of Synthetic Approach on Performance. J.Electrochem. Soc.162 (4) F449-F454 (2015).

[2] I. Matanović, P. Atanassov, B. Kiefer, F. H. Garzon and N. Henson, Applicability of Density Functional Theory in Reproducing Accurate Vibrational Spectra of Surface Bound Species. J. Comput. Chem., 35, 1921-1929 (2014).