Dynamic Fluxionality of Nickel Clusters Bypasses Linear Scaling Relations in Methane Dry Reforming
6 affiliations
- 1Key Laboratory of Precision and Intelligent Chemistry
- 2University of Science and Technology of China
- 3Suzhou Institute for Advanced Research, University of Science and Technology of China
- 4National Institute of Clean-and-Low-Carbon Energy, China Energy Investment Corporation Ltd.
- 5School of Material Science and Engineering
- 6Northeastern University
Abstract
While oxide-supported Ni-cluster catalysts are highly active and stable for dry reforming of methane, the size-dependent role of metal-support interactions remains elusive. Here, we deploy a comprehensive framework-integrating density functional theory (DFT), Ab initio molecular dynamics (AIMD), and microkinetic modeling-to elucidate the structure-dynamic-reactivity relationship of six Ni clusters (Ni1 to Ni16) under realistic reaction conditions. DFT reveals that increasing cluster size enhances supportto-metal electron transfer and induces electronic segregation, ultimately driving the formation of robust bifunctional interfacial sites. Furthermore, AIMD simulations indicate that while larger clusters maintain structural rigidity, medium-sized clusters exhibit dynamic fluxionality, reconstructing into highly active, transient single-atom-like configurations at elevated temperatures. Using carbon (EC) and hydrogen (EH) adsorption energies as descriptors, the microkinetic models yield distinct volcano plots for CO and H2 formation revealing a fundamental decoupling in their electronic requirements. Coverage analysis highlights a pronounced size effect: mechanistic shift: small clusters are thermodynamically quenched by oxygen poisoning, whereas large clusters are kinetically bottlenecked by inefficient H-H coupling. Ultimately, the Ni8 configuration achieves an optimal balance between these competing constraints, demonstrating that leveraging dynamic fluxionality and cluster nuclearity offers a powerful strategy to bypass static scaling relations in complex reforming reactions.
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BibTeX
@misc{mei2026dynamic,
title = {{Dynamic Fluxionality of Nickel Clusters Bypasses Linear Scaling Relations in Methane Dry Reforming}},
author = {Ziyu Mei and Jielin Chen and Wenjie Du and Quan Lin and Yuping Ren and Yang Wang and Gaowu Qin and Chuangwei Liu and Jun Jiang},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15011095/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011095/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Dynamic Fluxionality of Nickel Clusters Bypasses Linear Scaling Relations in Methane Dry Reforming
AU - Ziyu Mei
AU - Jielin Chen
AU - Wenjie Du
AU - Quan Lin
AU - Yuping Ren
AU - Yang Wang
AU - Gaowu Qin
AU - Chuangwei Liu
AU - Jun Jiang
PY - 2026
DA - 2026/10/27
PB - ChemRxiv
DO - 10.26434/chemrxiv.15011095/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011095/v1
AB - While oxide-supported Ni-cluster catalysts are highly active and stable for dry reforming of methane, the size-dependent role of metal-support interactions remains elusive. Here, we deploy a comprehensive framework-integrating density functional theory (DFT), Ab initio molecular dynamics (AIMD), and microkinetic modeling-to elucidate the structure-dynamic-reactivity relationship of six Ni clusters (Ni1 to Ni16) under realistic reaction conditions. DFT reveals that increasing cluster size enhances supportto-metal electron transfer and induces electronic segregation, ultimately driving the formation of robust bifunctional interfacial sites. Furthermore, AIMD simulations indicate that while larger clusters maintain structural rigidity, medium-sized clusters exhibit dynamic fluxionality, reconstructing into highly active, transient single-atom-like configurations at elevated temperatures. Using carbon (EC) and hydrogen (EH) adsorption energies as descriptors, the microkinetic models yield distinct volcano plots for CO and H2 formation revealing a fundamental decoupling in their electronic requirements. Coverage analysis highlights a pronounced size effect: mechanistic shift: small clusters are thermodynamically quenched by oxygen poisoning, whereas large clusters are kinetically bottlenecked by inefficient H-H coupling. Ultimately, the Ni8 configuration achieves an optimal balance between these competing constraints, demonstrating that leveraging dynamic fluxionality and cluster nuclearity offers a powerful strategy to bypass static scaling relations in complex reforming reactions.
ER -