Insights into the transition metal ion-mediated electrooxidation of glucose in alkaline electrolyte

TY - JOUR

T1 - Insights into the transition metal ion-mediated electrooxidation of glucose in alkaline electrolyte

AU - Zheng, Weiran

AU - Li, Yong

AU - Lee, Lawrence Yoon Suk

N1 - Publisher Copyright: © 2019 Elsevier Ltd

PY - 2019/6/10

Y1 - 2019/6/10

N2 - Glucose electrooxidation is of particular interest owing to its broad applications in glucose fuel cell and electrochemical sensing. In pursuit of high atomic utilization of catalytic active sites, we employed homogenously dispersed transition metal ions (Co 2+ , Cu 2+ , and Ni 2+ ) as the electrocatalyst in alkaline electrolyte. Combining cyclic voltammetry, chronoamperometry, impedance spectroscopy, and in situ UV–Vis spectroelectrochemistry, the catalytic activity and reaction mechanism of M(II)-catalyzed glucose electrooxidation are discussed, suggesting a general activity trend of Co(II) > Cu(II) > Ni(II). Using a μM level of Co(II), Cu(II), and Ni(II), the sensitivity values of 1,342, 579, and 38.9 mA M −1 cm −2 are achieved, respectively, toward glucose sensing. The coordination between metal sites and glucose plays the critical role of lowing the oxidation potential of M(II) to higher valent forms. A homogenous reaction mechanism is suggested: Co(II)-catalyzed reaction shows potential-dependent electrooxidation via the formation of Co(III)-glucose and Co(IV)-glucose complex, while both Cu(II) and Ni(II) feature the intermediate of M(III)-glucose. The Co(II)-glucose electrooxidation presents the smallest charge transfer resistance and the highest transfer coefficient, accounting for its high activity.

AB - Glucose electrooxidation is of particular interest owing to its broad applications in glucose fuel cell and electrochemical sensing. In pursuit of high atomic utilization of catalytic active sites, we employed homogenously dispersed transition metal ions (Co 2+ , Cu 2+ , and Ni 2+ ) as the electrocatalyst in alkaline electrolyte. Combining cyclic voltammetry, chronoamperometry, impedance spectroscopy, and in situ UV–Vis spectroelectrochemistry, the catalytic activity and reaction mechanism of M(II)-catalyzed glucose electrooxidation are discussed, suggesting a general activity trend of Co(II) > Cu(II) > Ni(II). Using a μM level of Co(II), Cu(II), and Ni(II), the sensitivity values of 1,342, 579, and 38.9 mA M −1 cm −2 are achieved, respectively, toward glucose sensing. The coordination between metal sites and glucose plays the critical role of lowing the oxidation potential of M(II) to higher valent forms. A homogenous reaction mechanism is suggested: Co(II)-catalyzed reaction shows potential-dependent electrooxidation via the formation of Co(III)-glucose and Co(IV)-glucose complex, while both Cu(II) and Ni(II) feature the intermediate of M(III)-glucose. The Co(II)-glucose electrooxidation presents the smallest charge transfer resistance and the highest transfer coefficient, accounting for its high activity.

KW - Cobalt

KW - Copper

KW - Glucose electrooxidation

KW - In situ UV–Vis spectroelectrochemistry

KW - Nickel

UR - http://www.scopus.com/inward/record.url?scp=85064159528&partnerID=8YFLogxK

U2 - 10.1016/j.electacta.2019.04.007

DO - 10.1016/j.electacta.2019.04.007

M3 - 文章

AN - SCOPUS:85064159528

SN - 0013-4686

VL - 308

SP - 9

EP - 19

JO - Electrochimica Acta

JF - Electrochimica Acta

ER -