Abstract:<div><div><div><p>Outer-sphere electron transfer (OS-ET) is a cornerstone elementary electrochemical reaction, yet microscopic understanding is largely based on idealized theories, developed in isolation from experiments that themselves are often close to the kinetic (diffusion) limit. Focusing on graphene as-grown on a copper substrate as a model 2D material/metal-supported electrode system, this study resolves the key electronic interactions in OS-ET, and identifies the role of graphe… Show more
“…In Liu et al work the authors tend to believe that ET at the copper/graphene electrode is adiabatic or weakly nonadiabatic. 34 In our previous work, 45 under the assumption of the nonadiabatic limit, we qualitatively explained the electrocatalytic effect of the gold substrate, shown in the experiment of Hui et al 24 Here, we continue this study. We investigate how the type of metal changes the electronic properties of the metal/graphene heterostructure, and how these changes affect the kinetics of the nonadiabatic ET at the graphene surface.…”
Section: Introductionmentioning
confidence: 51%
“…The rate constant values are taken for a distance of 4.5 Å from the graphene surface, which corresponds to the closest approach of the [Ru(NH 3 ) 6 ] 3+/2+ complexes. 34 We see that for platinum, which has the highest r F , such an explanation is quite applicable. Large density of states in Pt is due to the fact that the Fermi level is inside the d-band, while for Au, Cu, Ag the d-band lies below the Fermi level (see Fig.…”
Section: Paper Pccpmentioning
confidence: 87%
“…The calculated rate constant values are taken for a distance of 4.5 Å, which corresponds to the closest approach of the [Ru(NH 3 ) 6 ] 3+/2+ complexes to the graphene surface. 34 Table 2 shows experimental standard rate constants for [Ru(NH 3 ) 6 ] 3+/2+ at the following electrodes: Au/graphene, Cu/graphene, and quasi free graphene supported on semiconductor surface. It can be seen that when gold and copper substrates are used, the rate constants have similar values (B10 À2 cm s À1 ), which is consistent with the calculations in Fig.…”
Section: Paper Pccpmentioning
confidence: 99%
“…31,32 The data on the ET adiabaticity at the graphene surface is contradictory. 31,33,34 Nevertheless, there are many confirmations of the nonadiabatic regime of ET at graphene supported on insulating substrates if large organometallic complexes are used for measurements. In ref.…”
Solid-supported graphene is a typical configuration of electrochemical devices based on single-layer graphene. Therefore, it is necessary to understand the electrochemical features of such heterostructures. In this work, we theoretically...
“…In Liu et al work the authors tend to believe that ET at the copper/graphene electrode is adiabatic or weakly nonadiabatic. 34 In our previous work, 45 under the assumption of the nonadiabatic limit, we qualitatively explained the electrocatalytic effect of the gold substrate, shown in the experiment of Hui et al 24 Here, we continue this study. We investigate how the type of metal changes the electronic properties of the metal/graphene heterostructure, and how these changes affect the kinetics of the nonadiabatic ET at the graphene surface.…”
Section: Introductionmentioning
confidence: 51%
“…The rate constant values are taken for a distance of 4.5 Å from the graphene surface, which corresponds to the closest approach of the [Ru(NH 3 ) 6 ] 3+/2+ complexes. 34 We see that for platinum, which has the highest r F , such an explanation is quite applicable. Large density of states in Pt is due to the fact that the Fermi level is inside the d-band, while for Au, Cu, Ag the d-band lies below the Fermi level (see Fig.…”
Section: Paper Pccpmentioning
confidence: 87%
“…The calculated rate constant values are taken for a distance of 4.5 Å, which corresponds to the closest approach of the [Ru(NH 3 ) 6 ] 3+/2+ complexes to the graphene surface. 34 Table 2 shows experimental standard rate constants for [Ru(NH 3 ) 6 ] 3+/2+ at the following electrodes: Au/graphene, Cu/graphene, and quasi free graphene supported on semiconductor surface. It can be seen that when gold and copper substrates are used, the rate constants have similar values (B10 À2 cm s À1 ), which is consistent with the calculations in Fig.…”
Section: Paper Pccpmentioning
confidence: 99%
“…31,32 The data on the ET adiabaticity at the graphene surface is contradictory. 31,33,34 Nevertheless, there are many confirmations of the nonadiabatic regime of ET at graphene supported on insulating substrates if large organometallic complexes are used for measurements. In ref.…”
Solid-supported graphene is a typical configuration of electrochemical devices based on single-layer graphene. Therefore, it is necessary to understand the electrochemical features of such heterostructures. In this work, we theoretically...
The effect of the gold underlayer on the outer-sphere non-adiabatic electron transfer on the graphene surface is investigated theoretically using both periodic and cluster DFT calculations. We propose the model...
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