On the Catalytic Activity of Pt Supported by Graphyne in the Oxidation of Ethanol

Abstract

The adsorption of Pt clusters on β- and γ-graphyne (β-GY, γ-GY), graphdiyne (GDY), and graphene (GP) was extensively investigated with density functional theory. Ethanol adsorption and its partial oxidation on the Pt supported by the GY and GP were then explored to address the influence of the supporting materials on the activity of Pt nanoclusters to ethanol oxidation. Among the examined adsorption sites such as the hollow, Csp-Csp, and Csp-Csp2 bonds, the hollow site consisting of multiple triple bonds is the most attractive one to adsorb Pt and Pt4 regardless of β-GY, γ-GY, and GDY. The binding of Pt4 to the GDY is slightly stronger than those of β-GY and γ-GY (binding energy: −3.64, −3.73, and −4.08eV). It is remarkable that the adsorption of Pt4 on GY is 2–3 times stronger than that on GP (−3.6–4.1 vs −1.3 eV), showing that the GY and GDY are better substracts than the GP for the stability of Pt clusters. Furthermore, the potential energy profiles for the oxidation of ethanol show that in spite of the higher energy barrier for the adsorbed ethanol on Pt4 supported by γ-GY than by GP (1.54 vs 1.19eV), the dehydrogenation product and of ethanol on Pt-graphyne is much stabler than that on Pt-graphene, suggesting that graphyne is thermodynamically more favorable than graphene as a subtract for the Pt catalyst.

Graphynes: indispensable nanoporous architectures in carbon flatland

“…GYs were recently investigated as potential candidates to support Pt for the oxidation of ethanol. 175 The binding energies of Pt on γ-GY, β-GY, GDY and graphene were compared and they follow the order: graphene < GDY < γ-GY < β-GY. Binding on GYs leads to higher binding energies compared to pristine graphene due to more reactive sp carbon atoms present in these systems.…”

Substituent Effects on Electronic Structures and Peroxidase-Mimicking Activities of Graphyne and Palladium-Doped Graphyne: A Computational Study

“…Kim et al have further studied the doping of GY by all 3d, 4d, and 5d transition metals and suggested that all transition metals besides noble metals can be atomically dispersed on the surface . Therefore, GY has been used to design novel metal@graphyne complexes in which the metals are atomically dispersed in the acetylenic holes, behaving as the active centers for catalytic CO , and ethanol oxidations, electrocatalytic water splitting and CO 2 reduction, , a molecule sensing − and storage, − etc.…”

An In Situ Quick X‐ray Absorption Spectroscopy Study on Pt3Sn/Graphene Catalyst for Ethanol Oxidation Reaction

“…Graphene combines a vastly graphitic character with extremely large surface areas, and thus shows superior features to enhance the electrochemical stability and activity of the supported electrocatalysts [26] . The great conductivity (10 3 –10 4 S/m), large surface area (∼2600 m 2 /g) and trigonally bonded carbon atoms arranged in a two‐dimensional sheet of graphene are thus widely applied as a support for electrocatalysts in low‐temperature fuel cells [27,28] . PtSn nanostructures on various carbon supports thus showed greater EOR activity than other reported Pt‐based nanocatalysts, but few investigations are reported of the correlation of electrochemical characteristics and electronic structure of electrocatalysts with EOR activity under varied electrochemical conditions.…”