title: Ultrafast Electron Transfer Kinetics of Graphene Grown by Chemical Vapor Deposition.
abstract: High electrochemical reactivity is required for various energy and sensing applications of graphene grown by chemical vapor deposition (CVD). Herein, we report that heterogeneous electron transfer can be remarkably fast at CVD-grown graphene electrodes that are fabricated without using the conventional poly(methyl methacrylate) (PMMA) for graphene transfer from a growth substrate. We use nanogap voltammetry based on scanning electrochemical microscopy to obtain very high standard rate constants k(0) ≥25 cm s(-1) for ferrocenemethanol oxidation at polystyrene-supported graphene. The rate constants are at least 2-3 orders of magnitude higher than those at PMMA-transferred graphene, which demonstrates an anomalously weak dependence of electron-transfer rates on the potential. Slow kinetics at PMMA-transferred graphene is attributed to the presence of residual PMMA. This unprecedentedly high reactivity of PMMA-free CVD-grown graphene electrodes is fundamentally and practically important.
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA).
authors.forename: Ran
authors.initials: R
authors.lastname: Chen
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA).
authors.forename: Nikoloz
authors.initials: N
authors.lastname: Nioradze
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA).
authors.forename: Padmanabhan
authors.initials: P
authors.lastname: Santhosh
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA).
authors.forename: Zhiting
authors.initials: Z
authors.lastname: Li
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA).
authors.forename: Sumedh P
authors.initials: SP
authors.lastname: Surwade
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA).
authors.forename: Ganesh J
authors.initials: GJ
authors.lastname: Shenoy
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA).
authors.forename: David G
authors.initials: DG
authors.lastname: Parobek
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA).
authors.forename: Min A
authors.initials: MA
authors.lastname: Kim
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA).
authors.forename: Haitao
authors.initials: H
authors.lastname: Liu
authors.affiliation: Department of Chemistry, University of Pittsburgh, 219 Parkman Avenue, Pittsburgh, PA 15260 (USA). amemiya@pitt.edu.
authors.forename: Shigeru
authors.initials: S
authors.lastname: Amemiya
keywords: chemical vapor deposition; electrochemistry; graphene; nanogap voltammetry; scanning electrochemical microscopy