CO-Tolerant Pt1-MoOx/Mo2N Catalyst for Efficient Activation of C–H and O–H Bonds toward Alcohol Dehydrogenation

Abstract

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_x/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_x/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 in situ structural characterizations and isotopic labeling analysis, we found that the spontaneously formed thin MoO_x-O_v 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.