Palladium single-atom catalysts prepared via strong metal-support interaction for selective 1,3-butadiene hydrogenation

Abstract

Selective hydrogenation of 1,3-butadiene to butenes is an effective way to eliminate the minor 1,3-butadiene impurities, which can cause intractable issues of catalyst deactivation in the C₄ olefins upgrading processes. To this end, Pd single-atom catalysts (SACs) exhibit remarkable selectivity to desired butene products due to the adsorption configuration of 1,3-butadiene in a mono-π mode. However, it is still a grand challenge to prepare thermally stable Pd SACs with conventional synthetic methods. Herein, we acquired Pd SACs via the selective encapsulation strategy exploiting classical strong metal-support interaction, during which Pd nanoparticles are more prone to be encapsulated by the oxide overlayer than Pd single atoms, thus Pd single atoms exclusively stay exposed to the catalytic environment. Various characterizations, such as aberration-corrected high-angle annular dark-field scanning transmission electron microscopy, electron energy loss spectroscopy, together with CO adsorbed in-situ diffuse reflectance infrared Fourier transform spectra, have collectively demonstrated the successful synthesis of Pd SACs on CeO₂ support when we adjusted the reductive temperature to 600 °C (Pd/CeO₂-H600). The as-obtained Pd/CeO₂-H600 gives excellent catalytic performances in the selective hydrogenation of 1,3-butadiene with conversion of almost 100% and butenes selectivity of above 98% at 100 °C. Moreover, the conversion of 99% and butenes selectivity of 97.5% can also remain nearly unchanged for 60 h at a weight hourly space velocity of 60,000 mL/g_cat/h. This work illustrates the effectiveness of this selective encapsulation strategy to construct Pd SACs and can probably provide a prospective avenue to prepare various SACs for selective hydrogenation processes.

Keywords

Single-atom catalysts / strong metal-support interaction / 1,3-butadiene / selective hydrogenation / palladium

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