Statistical Modeling of Active Site Distributions on ZrO2-Decorated Copper

Abstract

Inverse catalysts exhibit significant site heterogeneity that challenges traditional single-site descriptions. In this study, a statistical model was developed to describe the distribution of active sites at ZrO2–Cu interfaces using DFT-derived energetics. Five dominant site classes were identified and weighted according to their thermodynamic stability. Ensemble-averaged microkinetic simulations show that interfacial Zr–O–Cu motifs contribute over 65% of the methanol formation rate, despite occupying less than 30% of the surface area. The ensemble model improves agreement with experimentally reported turnover frequencies compared to single-site approximations. This work highlights the necessity of statistical treatments for realistic modeling of inverse catalysts.