Dynamics of Pd Subsurface Hydride Formation and Their Impact on the Selectivity Control for Selective Butadiene
Esther Asedegbega-Nieto1, Ana Iglesias-Juez2, Marco Di Michiel3
1Dpto. Química Inorgánica y Técnica, Facultad de Ciencias, UNED, Av. de Esparta s/n, 28232 Las Rozas, Madrid, Spain.
Subsurface palladium hydride (PdHx) species, not Pd-C, govern butadiene hydrogenation selectivity. Nanoparticle size controls PdHx formation and decomposition, directly impacting catalytic performance.
Area of Science:
- Catalysis
- Materials Science
- Surface Chemistry
Background:
- Structure-sensitive reactions depend on various parameters.
- Palladium-carbon (Pd-C) species were previously thought to control palladium nanoparticle (Pd NP) catalysis.
- Butadiene partial hydrogenation is a key industrial process.
Purpose of the Study:
- To investigate the role of subsurface palladium hydride (PdHx) species in butadiene partial hydrogenation.
- To determine the influence of Pd nanoparticle dimensions on catalytic reactivity and selectivity.
- To elucidate the reaction mechanism governing Pd NP catalysis.
Main Methods:
- Time-resolved high-energy X-ray diffraction (HEXRD) was employed.
- Experimental evidence was gathered to support the proposed mechanism.
- Pd nanoparticle aggregates of varying dimensions were studied.
Main Results:
- Subsurface PdHx species, not Pd-C, were identified as the key reactive species.
- The formation and decomposition of PdHx are highly sensitive to Pd nanoparticle aggregate size.
- Nanoparticle dimensions directly control the selectivity of the hydrogenation reaction.
Conclusions:
- Subsurface PdHx species are the primary determinants of reactivity in butadiene partial hydrogenation.
- Controlling Pd nanoparticle size is crucial for tuning catalytic selectivity via PdHx dynamics.
- This finding offers a new perspective on designing efficient Pd-based catalysts.
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