Ensembles of Metastable States Govern Heterogeneous Catalysis on Dynamic Interfaces

CONSPECTUS: Heterogeneous catalysis is at the heart of the chemical industry. Being able to tune and design efficient catalysts for processes of interest is of the utmost importance, and for this, a molecular-level understanding of heterogeneous catalysts is the first step and indeed a prime focus of modern catalysis research. For a long time, the single most thermodynamically stable structure of the catalytic interface attained under the reaction conditions had been envisioned as the reactive phase. However, some catalytic interfaces continue to undergo structural dynamics in the steady state, triggered by high temperatures and pressures and binding and changing reagents. Among particularly dynamic interfaces are such widely used catalysts as crystalline and amorphous surfaced supporting (sub)-nanometallic clusters. Recently, it became clear that this dynamic fluxionality causes the supported clusters to populate many distinct structural and stoichiometric states under catalytic conditions. Hence, the catalytic interface should be viewed as an evolving statistical ensemble of many structures (rather than one structure). Every member in the ensemble contributes to the properties of the catalyst differently, in proportion to its probability of being populated. This new notion flips the established paradigm and calls for a new theory, new modeling approaches, operando measurements, and updated design strategies. The statistical ensemble nature of surface-supported subnanocluster catalysts can be exemplified by oxide-supported and adsorbate covered Pt, Pd, Cu, and CuPd clusters, which are catalytic toward oxidative and nonoxidative dehydrogenation. They have access to a variety of 3D and quasi-2D shapes. The compositions of their thermal ensembles are dependent on the cluster size, leading to size-specific catalytic activities and the famous every atom counts phenomenon. The support and adsorbates affect catalyst structures, and the state of the reacting species causes the ensemble to change in every reaction intermediate. The most stable member of the ensemble dominates the thermodynamic properties of the corresponding intermediate, whereas the kinetics can be determined by more active but less populated metastable catalyst states, and that suggests that many earlier studies might have overlooked the actual active sites. Both effects depend on the relative time scales of catalyst restructuring and reaction dynamics. The catalyst may routinely operate off-equilibrium. Ensemble phenomena lead to surprising exceptions from established rules of catalysis, such as scaling relations and Arrhenius behavior. Catalyst deactivation is also an ensemble property, and its extent of mitigation can be predicted through the new paradigm. These findings were enabled by advances in theory, such as global optimization and subsequent utilization of multiple local minima and pathways sampling as well as operando catalyst characterization. The fact that the per-site and per-species resolution is needed for the description and prediction of catalyst properties gives theory the central role in catalysis research, as most experiments provide ensemble-average information and cannot detect the crucial minority species that may be responsible for the catalytic activity.