Real-time dynamics and structures of supported subnanometer catalysts via multiscale simulations

Understanding the performance of subnanometer catalysts and how catalyst treatment and exposure to spectroscopic probe molecules change the structure requires accurate structure determination under working conditions. Experiments lack simultaneous temporal and spatial resolution and could alter the structure, and similar challenges hinder first-principles calculations from answering these questions. Here, we introduce a multiscale modeling framework to follow the evolution of subnanometer clusters at experimentally relevant time scales. We demonstrate its feasibility on Pd adsorbed on CeO2(111) at various catalyst loadings, temperatures, and exposures to CO. We show that sintering occurs in seconds even at room temperature and is mainly driven by free energy reduction. It leads to a kinetically (far from equilibrium) frozen ensemble of quasi-two-dimensional structures that CO chemisorption and infrared experiments probe. CO adsorption makes structures flatter and smaller. High temperatures drive very rapid sintering toward larger, stable/metastable equilibrium structures, where CO induces secondary structure changes only.

Slurry-phase ethylene polymerization processes: a review on multiscale modeling and simulations

Slurry polymerization processes using Zeigler–Natta catalysts, are most widely used for the production of polyethylene due to their several advantages over other processes. Significant advancements have been made in the modeling of these processes to obtain high-quality final products. The modeling work in this field has a very wide scope due to the great diversity of the catalyst types, polymerization processes, polymerization conditions, product qualities and microstructures that exist at the commercial scale. In this article, we have reviewed and discussed the slurry polymerization processes for the production of polyethylene and the multiscale modeling and simulation framework in slurry reactors. The multiscale modeling framework mainly comprises of the kinetic model, single-particle diffusion models, multiphase hydrodynamics, phase equilibria, reactor residence time distribution and the overall mass and heat balances. Guidelines to implement the multiscale mathematical modeling and simulation in slurry-phase olefin polymerization processes are proposed. Special focus is given on the need to reduce the computational effort for the simulation of industrial reactors so that the models can be used as an effective tool-kit for optimization studies using state-of-art algorithms.

Frontiers in the Simulation of Dislocations

Dislocations play a vital role in the mechanical behavior of crystalline materials during deformation. To capture dislocation phenomena across all relevant scales, a multiscale modeling framework of plasticity has emerged, with the goal of reaching a quantitative understanding of microstructure–property relations, for instance, to predict the strength and toughness of metals and alloys for engineering applications. This review describes the state of the art of the major dislocation modeling techniques, and then discusses how recent progress can be leveraged to advance the frontiers in simulations of dislocations. The frontiers of dislocation modeling include opportunities to establish quantitative connections between the scales, validate models against experiments, and use data science methods (e.g., machine learning) to gain an understanding of and enhance the current predictive capabilities.