Resolving Active Sites in Cu/ZnO Methanol Synthesis via Coupled Modelling of Surface Reconstruction and Coverage-dependent Kinetics
Abstract
Identifying active sites in heterogeneous catalysis is central to fundamental understanding and designing catalysts, yet it becomes challenging when surface structures, adsorbate coverages and reaction kinetics co-evolve under operating conditions. This challenge is exemplified by the enduring controversy over the active site for methanol synthesis over ZnO/Cu catalysts. Here we combine global structure exploration, grand-canonical sampling, a reactive CuZnCHO machine-learning potential and coverage-consistent microkinetics to establish a condition-dependent picture of the active surface. We show that Zn-Cu alloys, ZnO-like overlayers and partially reduced Zn species are not mutually exclusive active-site models, but distinct states within the same dynamic structural landscape. Activity is maximized within an intermediate thermodynamic window, where a Cu-Zn/Cu-Cu bifunctional ensemble forms near a step rim. These findings reconcile seemingly conflicting active-site assignments and establish a general framework for understanding activity in complicated systems. More broadly, our approach provides a paradigm for identifying activity-structure relationships in catalytic systems.
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BibTeX
@misc{fang2026resolving,
title = {{Resolving Active Sites in Cu/ZnO Methanol Synthesis via Coupled Modelling of Surface Reconstruction and Coverage-dependent Kinetics}},
author = {Zhening Fang and Chenyu Wu and Changxi Yang and Wenbo Xie and Zhi Liu and Peijun Hu},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15009405/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009405/v1},
note = {CC BY-NC},
}
RIS
TY - UNPB
TI - Resolving Active Sites in Cu/ZnO Methanol Synthesis via Coupled Modelling of Surface Reconstruction and Coverage-dependent Kinetics
AU - Zhening Fang
AU - Chenyu Wu
AU - Changxi Yang
AU - Wenbo Xie
AU - Zhi Liu
AU - Peijun Hu
PY - 2026
DA - 2026/09/23
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009405/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009405/v1
AB - Identifying active sites in heterogeneous catalysis is central to fundamental understanding and designing catalysts, yet it becomes challenging when surface structures, adsorbate coverages and reaction kinetics co-evolve under operating conditions. This challenge is exemplified by the enduring controversy over the active site for methanol synthesis over ZnO/Cu catalysts. Here we combine global structure exploration, grand-canonical sampling, a reactive CuZnCHO machine-learning potential and coverage-consistent microkinetics to establish a condition-dependent picture of the active surface. We show that Zn-Cu alloys, ZnO-like overlayers and partially reduced Zn species are not mutually exclusive active-site models, but distinct states within the same dynamic structural landscape. Activity is maximized within an intermediate thermodynamic window, where a Cu-Zn/Cu-Cu bifunctional ensemble forms near a step rim. These findings reconcile seemingly conflicting active-site assignments and establish a general framework for understanding activity in complicated systems. More broadly, our approach provides a paradigm for identifying activity-structure relationships in catalytic systems.
ER -