Platinum–copper single atom alloy catalysts with high performance towards glycerol hydrogenolysis

Abstract

Selective hydrogenolysis of biomass-derived glycerol to propanediol is an important reaction to produce high value-added chemicals but remains a big challenge. Herein we report a PtCu single atom alloy (SAA) catalyst with single Pt atom dispersed on Cu nanoclusters, which exhibits dramatically boosted catalytic performance (yield: 98.8%) towards glycerol hydrogenolysis to 1,2-propanediol. Remarkably, the turnover frequency reaches up to 2.6 × 103 molglycerol·molPtCu–SAA−1·h−1, which is to our knowledge the largest value among reported heterogeneous metal catalysts. Both in situ experimental studies and theoretical calculations verify interface sites of PtCu–SAA serve as intrinsic active sites, in which the single Pt atom facilitates the breakage of central C–H bond whilst the terminal C–O bond undergoes dissociation adsorption on adjacent Cu atom. This interfacial synergistic catalysis based on PtCu–SAA changes the reaction pathway with a decreased activation energy, which can be extended to other noble metal alloy systems.

Enhanced multi-carbon alcohol electroproduction from CO via modulated hydrogen adsorption

“…In the case of adding a small amount of Pd/Pt precursors in the bulk Cu solutions, ultrasound waves consisting of compression and rarefaction cycles not only improve the reaction rate of galvanic replacement but also inhibit the aggregation of Pd/Pt atoms, in agreement with prior works 27,42 . In a typical synthesis process, we first prepared 2 M metal (i.e.…”

On the behaviour of structure-sensitive reactions on single atom and dilute alloy surfaces

“…3 Surface science and catalysis studies underline the excellent catalytic properties of SAAs for a number of chemistries, such as hydrogenation and dehydrogenation reactions, 2,[4][5][6] C-H activation, 7,8 C-C coupling, 9 and catalytic oxidations. 10 Remarkably, studies by Zhang et al 11 have unveiled that Pt/Cu SAA catalysts exhibit an unprecedented catalytic performance (i.e. extremely high activity, selectivity and stability) during the hydrogenolysis of glycerol to 1,2propanediol; we note that the activation of pertinent reactions usually requires the presence of large PGM metal ensembles on the alloy surface.…”

“…The high activity of Cu-based SAAs toward numerous chemical reactions has been experimentally confirmed. 4,11,14 We determine that, among the Cu-based SAAs, Ni/Cu and Rh/Cu bimetallic alloys exhibit the lowest dissociation barriers. The most facile bond cleavage reactions are predicted to occur on Ni/Cu surfaces (Fig.…”

“…extremely high activity, selectivity and stability) during the hydrogenolysis of glycerol to 1,2propanediol; we note that the activation of pertinent reactions usually requires the presence of large PGM metal ensembles on the alloy surface. 12 Accordingly, the work of Zhang et al 11 is a testament to the unique catalytic properties offered by isolated reactive atoms doped on less reactive host materials. 13 In addition, very recent studies by Furukawa and co-workers highlight that Pd/Cu SAA nanoparticles supported on Al 2 O 3 are exceptional catalysts for the catalytic NO reduction by CO. 14 The latter reaction is crucial for stripping out harmful gases from catalytic converters.…”

Recent Advances in Glycerol Catalytic Valorization: A Review

“…As active metals in glycerol hydrogenolysis catalysts, the activity of Ir-, Pd-, Ru-, and Pt-based noble metals has been widely reported [108,139,140]. However, recent advances have focused on catalyst cost reduction, and efforts have especially focused on a supported Cu-based catalyst that has reported nearly complete glycerol conversions and 1,2-PDO yields higher than 80% [122,129,[141][142][143][144]. In this sense, the work of Gatti et al [145], with Ni supported over γ-Al 2 O 3 and a phosphorous-impregnated carbon composite in a consecutive treatment of crude glycerol, reached total conversion and yields of 87% 1,2-PDO in the first reaction with Ni/γ-Al 2 O 3 and, after the second hydrogenolysis reaction, obtained 1-PrOH with a 79% yield.…”