Beschreibung:
<jats:p>Shorter chain alcohols, as opposed to longer ones, are beneficial as biomass feedstock for chemicals and fuels, including hydrogen production. More so, it has been demonstrated that carbon–carbon rather than carbon–oxygen bond-cleaving activity determines the product selectivity of a metal catalyst for higher oxygenates reforming. In this report, we investigate the direct C2–C3 bond-cleaving activity of xylitol via first-principles, periodic density functional theory calculations to identify the differences in activities between single-crystal catalysts (SCCs) and single-atom catalysts (SACs). A comparison of the kinetic barriers revealed that xylitol's C–C bond scission appears to be a near-impossible task on SCCs. However, SACs demonstrated higher performance. For example, Ir1/MgO and Ir1/MgO_Ovac (having surface oxygen vacancy) yielded ∼72% and 54% decrease, respectively, in Gibb’s free activation energy compared to Ir (111) at the xylitol reforming operating temperature of 473 K. Furthermore, electronic structure calculations revealed an up-shift in the DOS for the surface M1 atoms in all investigated SACs compared to the surface atoms of their respective SCCs, resulting in M1 higher d-band center and stronger adsorbate (s) binding. This study highlights the importance of SACs for boosting the atom efficiency of costly metals while also offering a new strategy for tuning the activity of catalytic reactions.</jats:p>