On the Conceptualization of the Active Site in Selective Oxidation over a Multimetal Oxide Catalyst: From Atomistic to Black-Box Approximation

Catalytic reactor engineering bridges the active-site scale and the industrial-reactor scale, with kinetics as the primary bottleneck in scale-up. The main challenge in kinetics is conceptualizing the active site and formulating the reaction mechanism, leading to multiple approaches without clear guidance on their reliability for industrial-reactor design. This work assesses different approaches to active-site conceptualization and reaction-mechanism formulation for selective oxidation over a complex multi-metal catalyst. It integrates atomistic-scale insights from periodic Density Functional Theory (DFT) calculations into kinetic-model development. This approach contrasts with the macroscopic classical method, which treats the catalyst as a black box, as well as with alternative atomistic methods that conceptualize the active site as a single metal atom on different catalytic-surface regions. As a case study, this work examines ethane oxidative dehydrogenation to ethylene over the multi-metal oxide catalyst MoVTeNbO, which has a complex structure. This analysis provides insights into the ability of DFT to accurately describe reactions on such materials. Additionally, it compares DFT predictions to experimental data obtained from a non-idealized MoVTeNbO catalyst synthesized and assessed under kinetic control at the laboratory scale. The findings indicate that while the black-box active-site conceptualization best describes observed trends, its reaction mechanism and parameters lack reliability compared to DFT calculations. Furthermore, atomistic active-site conceptualizations lead to different parameter sets depending on how the active site and reaction mechanism are defined. Unlike previous studies, our approach determines activation-energy profiles within the range predicted by DFT. The resulting kinetic model describes experimental trends while maintaining phenomenological and statistical reliability. The corrections required for primary parameters remain below 20 kJ mol⁢−1, consistent with the inherent uncertainties in DFT calculations. In summary, this work demonstrates the feasibility of integrating atomistic insights into kinetic modeling, offering different perspectives on active-site conceptualization and reaction-mechanism formulation, paving the way for future studies on rational catalyst and industrial-reactor design.