Characterization of electrochemically pretreated glassy carbon electrodes

Engstrom, Royce C.; Strasser, Vernon A.

doi:10.1021/ac00266a005

Cited by 437 publications

(322 citation statements)

References 27 publications

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“…Common strategies include surface derivatization of metal oxides by carboxylate, phosphonate, and siloxane bindings (24)(25)(26)(27), carbongrafted electrodes (28)(29)(30), and electropolymerization (31)(32)(33). These approaches provide a useful bridge to the interface and a way to translate mechanistic understanding and ease of synthetic modification of solution catalysts to heterogeneous applications with a promise of higher reactivity under milder conditions.…”

mentioning

confidence: 99%

Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation

Vannucci

Alibabaei

Losego

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

136

154

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Enhancing the surface binding stability of chromophores, catalysts, and chromophore-catalyst assemblies attached to metal oxide surfaces is an important element in furthering the development of dye sensitized solar cells, photoelectrosynthesis cells, and interfacial molecular catalysis. Phosphonate-derivatized catalysts and molecular assemblies provide a basis for sustained water oxidation on these surfaces in acidic solution but are unstable toward hydrolysis and loss from surfaces as the pH is increased. Here, we report enhanced surface binding stability of a phosphonate-derivatized water oxidation catalyst over a wide pH range (1-12) by atomic layer deposition of an overlayer of TiO 2 . Increased stability of surface binding, and the reactivity of the bound catalyst, provides a hybrid approach to heterogeneous catalysis combining the advantages of systematic modifications possible by chemical synthesis with heterogeneous reactivity. For the surface-stabilized catalyst, greatly enhanced rates of water oxidation are observed upon addition of buffer bases −H 2 PO − 4 /HPO 2− 4 , B(OH) 3 /B(OH) 2 O − , HPO 2− 4 /PO 3− 4 − and with a pathway identified in which O-atom transfer to OH − occurs with a rate constant increase of 10 6 compared to water oxidation in acid.electrocatalysis | surface stabilization H eterogeneous catalysis plays an important role in industrial chemical processing, fuel reforming, and energy-producing reactions. Examples include the Haber-Bosch process, steam reforming, Ziegler-Natta polymerization, and hydrocarbon cracking (1-8). Research in heterogeneous catalysis continues to flourish (9-15) but iterative design and modification are restricted by limitations in materials preparation and experimental access to surface mechanisms. By contrast, synthetic modification of molecular catalysts is possible by readily available routes; a variety of experimental techniques is available for monitoring rates and mechanism in solution for the investigation of homogeneous catalysis (16-23). Transferring this knowledge and the reactivity of homogeneous molecular catalysts to a surface could open the door to heterogeneous applications in fuel cells, dye sensitized photoelectrochemical cells, and multiphase industrial reactions.Procedures are available for immobilization of organometallic and coordination complexes on the surfaces of solid supports. Common strategies include surface derivatization of metal oxides by carboxylate, phosphonate, and siloxane bindings (24-27), carbongrafted electrodes (28-30), and electropolymerization (31-33). These approaches provide a useful bridge to the interface and a way to translate mechanistic understanding and ease of synthetic modification of solution catalysts to heterogeneous applications with a promise of higher reactivity under milder conditions. A significant barrier to this approach arises from the limited stability of surface binding. Surface-bound carboxylates are typically unstable to hydrolysis in water, whereas phosphonates are unstable in neutral or basic...

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mentioning

confidence: 99%

Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation

Vannucci

Alibabaei

Losego

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

136

154

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“…1), leading to enhanced electrochemical performance. 9,[12][13][14][15][16] The present paper describes the resisting ability against adsorption of various In order to improve electrochemical performance of a glassy carbon (GC) electrode anodized in triethylene glycol (TEG), a GC electrode was anodized in H2O prior to TEG anodization. The effect of this pretreatment was evaluated by comparing electrochemical responses of acetaminophen on HPLC using the following electrodes: a GC electrode anodized in both H2O and TEG (double modified GC electrode); an unmodified GC electrode; GC electrodes anodized in either H2O or TEG.…”

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confidence: 99%

Surface Improvement of Glassy Carbon Electrode Anodized in Triethylene Glycol and Its Application to Electrochemical HPLC Analysis of Protein-Containing Samples

et al. 2000

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“…[11][12][13][14][15][16] Furthermore, accumulation of oxidation products involving radical intermediates, such as dimer from the one-electron oxidation product NAD +. , 17,18 can cause deactivation and fouling of the electrode surface.…”

Section: 10mentioning

confidence: 99%

Investigation of Direct Electrooxidation Behavior of NADH at a Chemically Modified Glassy Carbon Electrode

Jin

Peng

et al. 2015

J. Electrochem. Soc.

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In this study, the composite material that made up polyglycine/3d-4f hybrid-metallic cyano-bridged mixed coordination polymers (CyMCP) was successfully decorated onto a glassy carbon rotating disk electrode (GC RDE) using electrodeposition. The voltammetric behavior of NADH showed typical direct electrooxidation characteristics on the modified GC electrode. Our polyglycine/CyMCP-modified GC RDE was able to measure the apparent heterogeneous electron transfer rate constant of NADH during its direct electrooxidation by preventing fouling effects on the working electrode, which would generally cause a decrease in the oxidative peak current of NADH. In addition, differential pulse voltammetry provided a large linear range between the oxidative peak current and the concentration of NADH from 2-1500 μM at the polyglycine/CyMCP/GC electrode. Finally, the apparent heterogeneous electron transfer rate constant (k s NADH ) of NADH was determined to be 1.73 × 10 −2 cm · s −1 using the polyglycine/CyMCP-modified GC RDE. Both reduced and oxidized forms of β-nicotinamide adenine dinucleotide (NADH and NAD + , respectively) are the coenzymes for a large number of dehydrogenase enzymes (>300) and components of biomarker systems.1 In fact, because of its very important role in the field of analytical electrochemistry, 2,3 bioelectrocatalysis 4-6 and biofuel cells, 7,8 the electrochemical investigation for the formal potential of NADH/NAD + redox couple has attracted much attention. 9,10Therefore, direct oxidation of NADH at untreated or unmodified classical solid electrodes is known to appear poor reversibility and occurs with considerable overpotential (e.g., 1.1 V on carbon and 1.3 V on platinum). [11][12][13][14][15][16] Furthermore, accumulation of oxidation products involving radical intermediates, such as dimer from the one-electron oxidation product NAD +. , 17,18 can cause deactivation and fouling of the electrode surface. Such contamination of the working electrode can largely lower the sensitivity and reproducibility of voltammetric measurements. Consequently, considerable effort has been devoted with a strategy of surface modification on the substrate of conventional materials electrode to attain the electrode's long term stability for determination of NADH at a lower potential. 2,[19][20][21] Over the last few decades, various carbon nanomaterial 22-24 and redox-active mediator materials [25][26][27][28][29][30][31][32][33][34][35] have been modified onto the electrode surface in order to alleviate and/or prevent higher overpotential and fouling problems of the electrode. Therefore, there exist two kinds of catalytic model for the electrooxidation of NADH: one is a direct electro-catalysis 13,15,16,36 and the other is called a redox mediator electro-catalysis. [25][26][27][28][29][30][31][32]37 Though these redox mediators are very efficient electron shuttles for NADH oxidation processes, hydrodynamic voltammetry on the mediator-modified electrode remains a challenge for examining the kinetic parameters of NADH elect...

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Characterization of electrochemically pretreated glassy carbon electrodes

Cited by 437 publications

References 27 publications

Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation

Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation

Surface Improvement of Glassy Carbon Electrode Anodized in Triethylene Glycol and Its Application to Electrochemical HPLC Analysis of Protein-Containing Samples

Investigation of Direct Electrooxidation Behavior of NADH at a Chemically Modified Glassy Carbon Electrode

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