Promoted Glycerol Oxidation Reaction in an Interface‐Confined Hierarchically Structured Catalyst

Abstract

Confined catalysis in a 2D system is of particular interest owing to the facet control of the catalysts and the anisotropic kinetics of reactants, which suppress side reactions and improve selectivity. Here, a 2D‐confined system consisting of intercalated Pt nanosheets within few‐layered graphene is demonstrated. The strong metal–substrate interaction between the Pt nanosheets and the graphene leads to the quasi‐2D growth of Pt with a unique (100)/(111)/(100) faceted structure, thus providing excellent catalytic activity and selectivity toward one‐carbon (C1) products for the glycerol oxidation reaction. A hierarchically porous graphene architecture, grown on carbon cloth, is used to fabricate the confined catalyst bed in order to enhance the mass‐diffusion limitation in interface‐confined reactions. Owing to its unique 3D porous structure, this graphene‐confined Pt catalyst exhibits an extraordinary mass activity of 2910 mA mgPt −1 together with a formate selectivity of 79% at 60 °C. This paves the way toward rational designs of heterogeneous catalysts for energy‐related applications.

An Overview of Glycerol Electrooxidation Mechanisms on Pt, Pd and Au

“…This proposition is based on the fact that glycerol can be fully oxidized to CO 2 on Pt, Pd and Au, together with the observation that glyceric acid and glycolic acid are the most commonly seen products beside DHA [10–12,49,146] . This proposed mechanism also matches the fact that oxalic acid, tartronic acid, and mesoxalic acid are not easily obtained unless a lower ratio of glycerol concentration to the concentration of OH − is used, [2,36,46,112,147] which is likely to involve the electrooxidation of DHA, glyceric acid and glycolic acid. Furthermore, this model also supports the fact that glyoxylic acid, glycoaldehyde and formaldehyde are rarely found in most of the studies.…”

Bromide-Regulated Anisotropic Growth of Desert-Rose-Like Nanostructured Gold onto Carbon Fiber Electrodes as Freestanding Electrocatalysts

“…Table S2 summarizes the performance of nanostructured mono-and bi-metallic catalysts for the electrooxidation of glycerol in basic solutions, which have a peak current density of jp = 20-290 mA cm −2 based on the area of the electrode or jp = 0.2-18 A mgAu −1 , and where metal content is fairly high of 16-500 µgAu cm −2 . 20, 28,[53][54][55][56][57][58] Except for few examples of nanoalloynanoporous AuAg 19 and Pt-PtCo, 53,57 it can, therefore, be deduced that the performance of the asfabricated GDE-Au freestanding material is superior to the relevant activities reported in the literature for gold-, palladium-, and platinum-based electrocatalysts. 20, [54][55][56][58][59][60][61][62] To our knowledge, this is the first time a free-standing electrocatalyst made of desert rose-like nanostructured gold has been obtained directly onto carbon fiber electrode and demonstrate high performance towards the glycerol electrooxidation.…”

WITHDRAWN: Electrocatalytic glycerol oxidation with concurrent hydrogen evolution utilizing an efficient MoOx/Pt catalyst

“…30 The much steeper slope for the The GOR involves complicated oxidation pathways, which would produce C3 products via direct oxidation or C2/C1 products through C-C cleavage. 31 The quantitative analysis of the products from GOR over the different electrodes was performed by high-performance liquid chromatography (HPLC). A typical HPLC spectrum recorded from the product solution of the MoO x /Pt electrode is shown in Supplementary Fig.…”