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Chemical Dopants on Edge of Holey Graphene Accelerate Electrochemical Hydrogen Evolution Reaction.

ABSTRACT: Carbon-based metal-free catalysts for the hydrogen evolution reaction (HER) are essential for the development of a sustainable hydrogen society. Identification of the active sites in heterogeneous catalysis is key for the rational design of low-cost and efficient catalysts. Here, by fabricating holey graphene with chemically dopants, the atomic-level mechanism for accelerating HER by chemical dopants is unveiled, through elemental mapping with atomistic characterizations, scanning electrochemical cell microscopy (SECCM), and density functional theory (DFT) calculations. It is found that the synergetic effects of two important factors-edge structure of graphene and nitrogen/phosphorous codoping-enhance HER activity. SECCM evidences that graphene edges with chemical dopants are electrochemically very active. Indeed, DFT calculation suggests that the pyridinic nitrogen atom could be the catalytically active sites. The HER activity is enhanced due to phosphorus dopants, because phosphorus dopants promote the charge accumulations on the catalytically active nitrogen atoms. These findings pave a path for engineering the edge structure of graphene in graphene-based catalysts.

SUBMITTER: Kumatani A

PROVIDER: S-EPMC6524082 | biostudies-other | 2019 May

REPOSITORIES: biostudies-other

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Chemical Dopants on Edge of Holey Graphene Accelerate Electrochemical Hydrogen Evolution Reaction.

Kumatani Akichika A Miura Chiho C Kuramochi Hirotaka H Ohto Tatsuhiko T Wakisaka Mitsuru M Nagata Yuki Y Ida Hiroki H Takahashi Yasufumi Y Hu Kailong K Jeong Samuel S Fujita Jun-Ichi JI Matsue Tomokazu T Ito Yoshikazu Y

Advanced science (Weinheim, Baden-Wurttemberg, Germany) 20190401 10

Carbon-based metal-free catalysts for the hydrogen evolution reaction (HER) are essential for the development of a sustainable hydrogen society. Identification of the active sites in heterogeneous catalysis is key for the rational design of low-cost and efficient catalysts. Here, by fabricating holey graphene with chemically dopants, the atomic-level mechanism for accelerating HER by chemical dopants is unveiled, through elemental mapping with atomistic characterizations, scanning electrochemica ...[more]

PMID: 31131204

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Project description:Two dimensional (2D) semiconductor materials, such as molybdenum disulfide (MoS2) have attracted considerable interest in a range of chemical and electrochemical applications, for example, as an abundant and low-cost alternative electrocatalyst to platinum for the hydrogen evolution reaction (HER). While it has been proposed that the edge plane of MoS2 possesses high catalytic activity for the HER relative to the "catalytically inert" basal plane, this conclusion has been drawn mainly from macroscale electrochemical (voltammetric) measurements, which reflect the "average" electrocatalytic behavior of complex electrode ensembles. In this work, we report the first spatially-resolved measurements of HER activity on natural crystals of molybdenite, achieved using voltammetric scanning electrochemical cell microscopy (SECCM), whereby pixel-resolved linear-sweep voltammogram (LSV) measurements have allowed the HER to be visualized at multiple different potentials to construct electrochemical flux movies with nanoscale resolution. Key features of the SECCM technique are that characteristic surface sites can be targeted and analyzed in detail and, further, that the electrocatalyst area is known with good precision (in contrast to many macroscale measurements on supported catalysts). Through correlation of the local voltammetric response with information from scanning electron microscopy (SEM) and atomic force microscopy (AFM) in a multi-microscopy approach, it is demonstrated unequivocally that while the basal plane of bulk MoS2 (2H crystal phase) possesses significant activity, the HER is greatly facilitated at the edge plane (e.g., surface defects such as steps, edges or crevices). Semi-quantitative treatment of the voltammetric data reveals that the HER at the basal plane of MoS2 has a Tafel slope and exchange current density (J0) of ∼120 mV per decade and 2.5 × 10-6 A cm-2 (comparable to polycrystalline Co, Ni, Cu and Au), respectively, while the edge plane has a comparable Tafel slope and a J0 that is estimated to be more than an order-of-magnitude larger (∼1 × 10-4 A cm-2). Finally, by tracking the temporal evolution of water contact angle (WCA) after cleavage, it is shown that cathodic polarization has a 'self-cleaning' effect on the surface of MoS2, consistent with the time-independent (i.e., time after cleavage) HER voltammetric response.

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Chemical Dopants on Edge of Holey Graphene Accelerate Electrochemical Hydrogen Evolution Reaction.

Publications

Chemical Dopants on Edge of Holey Graphene Accelerate Electrochemical Hydrogen Evolution Reaction.

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