Transformations of Organic Molecules over Metal Surfaces: Insights from Computational Catalysis

Abstract

Much-needed progress in catalytic science, in particular regarding heterogeneous catalysis, is associated with the transition from largely empirical research to rational design of new and improved catalysts and catalytic processes. To achieve this goal, fundamental atomic-scale understanding of catalytic processes is required, which can be achieved with the help of theoretical modeling, in particular, using methods based on quantum chemical calculations. In this review we illustrate the current progress by discussing examples from the authors' work in which complex reaction networks involving organic molecules on transition-metal surfaces have been studied using density functional theory. We review some of the success stories where theory helped to interpret experimental observations and provided atomistic insights into the mechanisms, which were not definitively known before. In other cases, partial disagreement between theoretical results and existing experimental evidence calls for further reconciliation studies.

Operando Surface Spectroscopy and Microscopy during Catalytic Reactions: From Clusters via Nanoparticles to Meso‐Scale Aggregates

“…However, in many cases the interpretation and verification of the obtained experimental spectra/images/patterns relies on theoretical support, for example, by simulating test structures of clusters and nanoparticles and their corresponding spectra, calculating adsorption and reaction energies or micro-kinetic modelling. [33,98,159,[199][200][201][202][203][204][205][206][207][208][209][210] Based on its important role in catalysis, DFT is explicitly mentioned here, but without any technical details (which can be found in the references). Clearly, if calculations are performed for realistic gas pressures (coverage) and temperatures, they are even more relevant for operando studies.…”

Guidelines to Achieving High Selectivity for the Hydrogenation of α,β-Unsaturated Aldehydes with Bimetallic and Dilute Alloy Catalysts: A Review

“…As such, the selective hydrogenation of α,β-unsaturated aldehydes is also an ideal case for the study of structure-activity relationships in heterogeneous catalysis. [34][35][36][37][38][39][40][41][42][43][44][45][46][47] Recent works indicate that bimetallic catalysts have the potential to enhance the selectivity in the hydrogenation of many different classes of chemicals, such as alkynes, alkenes, imines, and carbonyl compounds, 21,26,39,46,[48][49][50][51][52][53][54][55][56][57][58][59][60][61][62][63][64][65][66] as well as biomass-derived molecules. [67][68][69][70][71][72][73] In particular, singleatom alloys, in which dilute amounts of catalytically active elements, e.g.…”

Sum frequency generation spectroscopy in heterogeneous model catalysis: a minireview of CO-related processes

“…Much of the fundamental understanding of elementary steps originates from studies of well-defined model catalysts in ultrahigh vacuum (UHV), 1,2 especially when combined with DFT calculations. [13][14][15][16][17][18][19][20] Investigations of metal single crystal surfaces of different crystallographic orientations directly revealed the structure-sensitivity of gas adsorption, co-adsorption and reactivity, focusing on molecular/dissociative adsorption and oxidation/ hydrogenation reactions.…”