Methane reforming can convert methane from renewable carbon sources into syngas, a valuable mixture of hydrogen and carbon monoxide used to manufacture fuels and chemicals. However, the nickel catalysts commonly used in this process can lose performance because of carbon buildup, particle aggregation, or the excessive retention of reaction products.
A new computational study provides an atomic-scale explanation of how the material supporting nickel influences these competing effects. The findings could guide the development of more active, stable, and carbon-resistant catalysts for methane reforming.
"The support is not simply a platform that holds the nickel particles in place. It directly changes how reactants, intermediates, and products interact with the catalytic sites," said corresponding author Professor Qiang Lu. "Our calculations show that selecting the right support requires balancing reaction activity with the ability to prevent carbon accumulation and product poisoning."
Researchers compared clusters containing four nickel atoms supported on four common metal oxides: aluminum oxide, zirconium oxide, magnesium oxide, and silicon dioxide. They also compared these supported clusters with a conventional flat nickel surface.
Using density functional theory calculations, the team examined how each catalyst interacted with methane, carbon dioxide, water, hydrogen, carbon monoxide, and several short-lived reaction intermediates. The researchers also analyzed electron transfer and chemical bonding at the interface between nickel and each support.
Aluminum oxide, zirconium oxide, and magnesium oxide generally increased the reactivity of the nickel clusters. These supports strengthened the adsorption of methane and other molecules involved in reforming. The supported clusters also promoted the adsorption of intermediates produced as methane molecules break apart.
Magnesium oxide showed particularly strong interactions with carbon dioxide, suggesting that it could effectively promote methane dry reforming, which uses methane and carbon dioxide to produce syngas. Calculated methane activation barriers were also low for nickel clusters supported on magnesium oxide and aluminum oxide.
However, stronger adsorption was not always beneficial. Magnesium oxide bound carbon atoms and carbon monoxide very strongly. Carbon could therefore become trapped on the catalyst, while carbon monoxide could occupy active sites instead of leaving the surface as a product. Both effects may reduce long-term catalytic performance.
Aluminum oxide also interacted strongly with deposited carbon, but it showed an exceptional ability to retain oxygen species. The researchers described this behavior as an oxygen reservoir that could assist the removal of surface carbon through its conversion into carbon monoxide.
Among the four materials, zirconium oxide provided the most balanced performance. It enhanced the interaction of nickel clusters with reforming reactants while maintaining moderate carbon binding and strong oxygen affinity. This combination could support methane conversion while helping to suppress carbon deposition.
Silicon dioxide behaved very differently. Rather than preserving the four-atom nickel cluster, the surface dispersed the nickel into isolated atoms. These individual sites interacted weakly with methane and carbon dioxide, resulting in substantially lower predicted reforming activity.
The results demonstrate that catalyst design cannot focus only on maximizing reactant adsorption. An effective support must activate methane while allowing products to leave and deposited carbon to be removed.
===
Journal reference: Xia Y, Wang H, Hu B, Sun H, Iqbal T, et al. 2026. An atom-level insight into the oxide support effect of Ni-based catalysts on the syngas production in methane reforming. Sustainable Carbon Materials 2: e023 doi: 10.48130/scm-0026-0018
https://www.maxapress.com/article/doi/10.48130/scm-0026-0018
===
About Sustainable Carbon Materials :
Sustainable Carbon Materials (e-ISSN 3070-3557) is a multidisciplinary platform for communicating advances in fundamental and applied research on carbon-based materials. It is dedicated to serving as an innovative, efficient and professional platform for researchers in the field of carbon materials around the world to deliver findings from this rapidly expanding field of science. It is a peer-reviewed, open-access journal that publishes review, original research, invited review, rapid report, perspective, commentary and correspondence papers.
