Reaction-induced modification of Co nanoclusters driven by Co-Mn interfacial sites to control selectivity in CO<sub>2</sub> hydrogenation.
basic_science · Level V
Where this comes from
- Record sourced from PubMed, PMID 41794835.
- Also identified by DOI 10.1038/s41467-026-70328-z and PMC identifier 13096657.
- Licence recorded as CC BY-NC-ND.
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Abstract
Controlling the selectivity of chemical products on small Co nanoparticles is crucial in many catalytic applications. Reaction-driven structural changes offer an alternative methodology to regulate their properties. Herein, carbon-induced surface restructuring occurs on a 2Co/MnOₓ catalyst (cobalt nanoclusters with 2% mass loading on manganese oxide) during thermal CO<sub>2</sub> hydrogenation, driven by the formation of bridging Co-C-O-Mn interfacial sites. This leads to a shift in selectivity from methane to CO, with a remarkable enhancement of the CO/CH<sub>4</sub> product ratio from 0.89 to 13.4. Such a Co/MnO<sub>x</sub> system has unique interfacial properties, including strong carbonophilic and oxophilic characteristics. It chemisorbs reaction-derived CO and facilitates C-O bond breaking, promoting rapid CO dissociation and subsequent carbon coverage on Co nanoclusters. This restructuring of Co nanoclusters suppresses the hydrogenation of CO intermediates to methane. This effect is unique to 2Co/MnOₓ and absent at higher/lower Co loadings or other oxide supports. This insight shows how structural evolution during catalysis enables precise surface engineering, overcoming the structure-sensitivity limits of Co nanoclusters.