CO-Tolerant Pt₁-MoO_<i>x</i>/Mo₂N Catalyst for Efficient Activation of C–H and O–H Bonds toward Alcohol Dehydrogenation

Excessively strong adsorption of CO onto a Pt-based catalyst results in the poisoning effect during numerous CO-containing catalysis reactions, including the dehydrogenation process of alcohols. Traditional strategies via modifying the electronic state of Pt atoms are beneficial for weakening CO adsorption; however, they are normally detrimental to C-H cracking, thereby degrading catalytic efficiency toward alcohol dehydrogenation reaction. In this work, we present a synergistic function of Pt₁ single atoms and heterostructured MoO<i>_<i>x</i></i>/Mo₂N for efficiently dehydrogenating alcohols, allowing high CO resistance along with excellent capacity for C-H and O-H activation. This conjunction renders electron transfer via a strong Pt-MoO<i>_<i>x</i></i>/Mo₂N interaction and thus induces the low 5d occupancy of Pt sites, enabling the facile CO desorption, which thereby boosts the efficiency of entire reaction cycles. Based on <i>in situ</i> structural characterizations and isotopic labeling analysis, we found that the spontaneously formed thin MoO<i>_<i>x</i></i>-O<i>_v</i> layer enables the barrierless breakage of O-H bonds even at as low as room temperature, which further energetically facilitates C-H cracking on interfacial Pt₁ sites. Therefore, this strategy can be applied to fabricate CO-tolerant Pt-based catalysts toward numerous CO-containing reactions without compromising reactivity by coupling the advantages of single-atom and defective support materials.