Towards the computational design of solid catalysts

Abstract

Over the past decade the theoretical description of surface reactions has undergone a radical development. Advances in density functional theory mean it is now possible to describe catalytic reactions at surfaces with the detail and accuracy required for computational results to compare favourably with experiments. Theoretical methods can be used to describe surface chemical reactions in detail and to understand variations in catalytic activity from one catalyst to another. Here, we review the first steps towards using computational methods to design new catalysts. Examples include screening for catalysts with increased activity and catalysts with improved selectivity. We discuss how, in the future, such methods may be used to engineer the electronic structure of the active surface by changing its composition and structure.

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions

“…A theoretical description, preferentially with predictive quality, is equally required. For steady‐state operation conditions molecular‐level modelling and simulation has already taken up the role of such an increasingly valuable, if not indispensable partner in the quest for an atomic‐scale understanding of catalytic function 24, 97, 98. Corresponding approaches are predominantly based on first‐principles electronic structure theory and density‐functional theory (DFT), in particular, with selected aspects also treated on the level of (reactive) force fields.…”

“…Corresponding scaling relations allow to minimize the computationally intensive first‐principles calculations, in particular of reaction barriers, and thereby to make first‐principles rate constants much easier accessible. Over the last decade microkinetic models using or even entirely based on such first‐principles data have correspondingly been devised for reaction networks of ever increasing complexity 23, 24, 97, 98. To date, all such first‐principles microkinetic and computational screening work has focused on steady‐state operation.…”

“…For this purpose, suitable model catalysts have to be selected and thoroughly examined by spectroscopic methods. As demonstrated in the corresponding sections, theory and modelling approaches can then provide valuable information on electronic and structural effects which finally allow designing improved catalyst candidates 24, 104…”

“…With the availability of new analytical methods, it is now possible to gain further insights into (electro‐)catalytic systems and to obtain a deep molecular‐level understanding even for variable reaction conditions 12. Furthermore, theoretical approaches have evolved to an extent that they can now predict active sites and give input for kinetic modeling which will substantially contribute to understanding the complex relationships in dynamically operated systems 23, 24, 25. Deriving such a microscopic understanding will be vital for adapting catalysts and chemical processes to the new boundary conditions.…”

Ab initio GGA+U study of oxygen evolution and oxygen reduction electrocatalysis on the (001) surfaces of lanthanum transition metal perovskites LaBO3(B = Cr, Mn, Fe, Co and Ni)

“…These questions include, e.g., what are the stable surfaces for these perovskites, how different surface orientations/terminations result in different activities, how the bulk electronic structure descriptors can be used to describe activities of various surface terminations, and whether/how surface stability is linked to surface catalytic activities. First principles-based Density Functional Theory (DFT) methods are now able to simulate catalytic reactions at specific metal oxide surfaces and extract surface electronic structure and energetic details, which can provide new insights into structure-activity relationships and strategies for material design and development 7,[14][15][16] . For example, Man et al 14 have performed 1 .…”