TY - JOUR

T1 - Copper underpotential deposition on boron nitride nanomesh

AU - Mertens, S.F.L.

PY - 2017/8/20

Y1 - 2017/8/20

N2 - The boron nitride nanomesh is a corrugated monolayer of hexagonal boron nitride (h-BN) on Rh(111), which so far has been studied mostly under ultrahigh vacuum conditions. Here, we investigate how copper underpotential deposition (upd) can be used to quantify defects in the boron nitride monolayer and to assess the potential window of the nanomesh, which is important to explore its functionality under ambient and electrochemical conditions. In dilute sulfuric acid, the potential window of h-BN/Rh(111) is close to 1 volt, i.e. larger than that of the Rh substrate, and is limited by molecular hydrogen evolution on the negative and by oxidative removal on the positive side. From copper upd on pristine h-BN/Rh(111) wafer samples, we estimate a collective defect fraction on the order of 0.08–0.7% of the geometric area, which may arise from line and point defects in the h-BN layer that are created during its chemical vapour deposition. Overpotential deposition (opd) is demonstrated to have significant consequences on the defect area. We hypothesise that this non-innocent Cu electrodeposition involves intercalation originating at initial defects, causing irreversible delamination of the h-BN layer; this effect may be used for 2D material nanoengineering. On the relevant timescale, upd itself does not alter the defect area on repeated cycling; therefore, metal upd may find use as a general tool to determine the collective defect area in hybrids between 2D materials and various substrate metals. © 2017

AB - The boron nitride nanomesh is a corrugated monolayer of hexagonal boron nitride (h-BN) on Rh(111), which so far has been studied mostly under ultrahigh vacuum conditions. Here, we investigate how copper underpotential deposition (upd) can be used to quantify defects in the boron nitride monolayer and to assess the potential window of the nanomesh, which is important to explore its functionality under ambient and electrochemical conditions. In dilute sulfuric acid, the potential window of h-BN/Rh(111) is close to 1 volt, i.e. larger than that of the Rh substrate, and is limited by molecular hydrogen evolution on the negative and by oxidative removal on the positive side. From copper upd on pristine h-BN/Rh(111) wafer samples, we estimate a collective defect fraction on the order of 0.08–0.7% of the geometric area, which may arise from line and point defects in the h-BN layer that are created during its chemical vapour deposition. Overpotential deposition (opd) is demonstrated to have significant consequences on the defect area. We hypothesise that this non-innocent Cu electrodeposition involves intercalation originating at initial defects, causing irreversible delamination of the h-BN layer; this effect may be used for 2D material nanoengineering. On the relevant timescale, upd itself does not alter the defect area on repeated cycling; therefore, metal upd may find use as a general tool to determine the collective defect area in hybrids between 2D materials and various substrate metals. © 2017

KW - 2D materials

KW - boron nitride

KW - electrodeposition

KW - intercalation

KW - nanomesh

KW - opd

KW - rhodium

KW - upd

KW - Boron nitride

KW - Chemical vapor deposition

KW - Copper

KW - Deposition

KW - Electrodeposition

KW - Electrodes

KW - Intercalation

KW - Monolayers

KW - Nitrides

KW - Point defects

KW - Rhodium

KW - Vapor deposition

KW - Chemical vapour deposition

KW - Cu electrodepositions

KW - Electrochemical conditions

KW - Hexagonal boron nitride (h-BN)

KW - Nanomesh

KW - Overpotential deposition

KW - Ultrahigh vacuum conditions

KW - Underpotential deposition

KW - Defects

U2 - 10.1016/j.electacta.2017.06.082

DO - 10.1016/j.electacta.2017.06.082

M3 - Journal article

VL - 246

SP - 730

EP - 736

JO - Electrochimica Acta

JF - Electrochimica Acta

SN - 0013-4686

ER -