Stability of heterogeneous single-atom catalysts: a scaling law mapping thermodynamics to kinetics

Abstract

Heterogeneous single-atom catalysts (SACs) hold the promise of combining high catalytic performance with maximum utilization of often precious metals. We extend the current thermodynamic view of SAC stability in terms of the binding energy (Ebind) of single-metal atoms on a support to a kinetic (transport) one by considering the activation barrier for metal atom diffusion. A rapid computational screening approach allows predicting diffusion barriers for metal–support pairs based on Ebind of a metal atom to the support and the cohesive energy of the bulk metal (Ec). Metal–support combinations relevant to contemporary catalysis are explored by density functional theory. Assisted by machine-learning methods, we find that the diffusion activation barrier correlates with (Ebind)2/Ec in the physical descriptor space. This diffusion scaling-law provides a simple model for screening thermodynamics to kinetics of metal adatom on a support.

A DFT Study on Heterogeneous Pt/CeO2(110) Single Atom Catalysts for CO Oxidation

“…[9] The computed cohesive energy of bulk Pt determined with the same computational setup is 6.40 eV. Using machine learning algorithms to predict SAC stability, [10] the diffusion barrier of Pt atom on the CeO 2 (110) surface is estimated to be around 2.8 eV. This indicates that Pt atom has a high stability on the CeO 2 (110) surface.…”

Dimensionality reduction of complex reaction networks in heterogeneous catalysis: From linear‐scalingrelationships to statistical learning techniques

“…LASSO has been applied to homogeneous catalysis for predicting regioselectivities of alkenes, 132 and the electronic structure of transition metal complexes with different organic ligands, 133 and with a L2‐regularization method (Kernel Ridge Regression), to select the best catalysts in cross‐coupling reactions 134 . In heterogeneous catalysis, LASSO has been used for generating a method for screening new possible catalysts 135 and to investigate properties of single atom catalysis 136,137 …”

“…134 In heterogeneous catalysis, LASSO has been used for generating a method for screening new possible catalysts 135 and to investigate properties of single atom catalysis. 136,137 The ENR method is a variation of the LASSO method with quadratic penalty term (L2-regularization). ENR shares the strong points of LASSO, with the extra benefit that solves the issue of the number of features extracted but still has the issue of the correlated variables and with a high computational cost.…”

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

“…Multiple experimental techniques are used to characterize the catalysts but their effect on the catalyst structure and dynamics, e.g., upon exposure the metal to CO for infrared (IR) measurements, is unknown. The catalyst activity and selectivity are dictated in part from their structure controlled by metal-metal, metal-adsorbate, and metal-support interactions 11 , 12 . Mastering the structure evolution at the atomic scale under working conditions is key to understanding structure-reactivity relations and discovering new catalysts.…”