Nanostructured palladium doped nickel electrodes for immobilization of oxidases through nickel nanoparticles

doi:10.1016/j.electacta.2019.04.143

Electrochimica Acta

Volume 315, 20 August 2019, Pages 102-113

https://doi.org/10.1016/j.electacta.2019.04.143 Get rights and content

Highlights

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Palladium doped nickel electrodes and nickel nanoparticles.
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Benefits from the catalytic effect of Pd and the magnetic properties of Ni.
•
Oxidase immobilization solely through magnetic interactions.
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Palladium doped nickel electrodes for the detection of H₂O₂.
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Biosensor operates at low potential values avoiding interfering compounds.

Abstract

The present investigation deals with the development, characterization and application of nanostructured Pd doped Ni electrodes (Pd@Ni), which uses the electrochemical properties of Pd in synergy with the magnetic properties of Ni for biosensors development. The Pd@Ni electrodes have been characterized by X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. It has been shown that palladium presented spherical assemblies ranging 150–200 nm medium diameter size that covers large areas of the electrode surface while metallic nickel, which confers magnetic properties, showed a uniform granular structure with sizes between 20 and 50 nm. Cyclic voltammetry and electrochemical impedance spectroscopy were performed to understand the electrochemical process at the Pd@Ni electrodes in neutral media. The Pd@Ni electrodes were applied for the electrochemical detection of H₂O₂. Finally, Ni nanoparticles (NiNP) functionalized with the model enzyme glucose oxidase (GOx-NiNP) have been attached to the Pd@Ni electrode solely through magnetic interactions, and the obtained GOx-NiNP/Pd@Ni biosensor applied for glucose determination in aqueous solutions by fixed potential amperometry at −0.05 V (vs Ag/AgCl) with reduced interferences.

Graphical abstract

Introduction

The development of interference free amperometric biosensors requires effective catalysts that enable their use at very low overvoltages, close to 0.0 V. In the case of oxidase-based biosensors, where hydrogen peroxide is the by-product of the enzyme-catalyzed reaction, its electrochemical detection dictates the overvoltage required for the biosensor functioning. It is known that aqueous H₂O₂ can be reduced to water in a two-electron transfer electrochemical process, which is slow and requires large overpotentials at conventional electrodes. In order to enhance electron transfer and reduce the overpotential, noble metal catalysts are frequently involved, including electrodes modified with nanoparticles (NPs) [1], with Pt-based materials being predominant [2,3]. Their use is however restricted by the high cost and limited supply. In this context, Pd-based materials emerged as an alternative, since Pd presents high affinity for hydrogen, which enables its utilization as catalysts in several applications, including hydrogen peroxide reduction [4,5]. Pd nanostructured materials, such as nanowires and nanoparticles electrochemically synthesized have been thoroughly characterized [6,7], and hence applied alone [4,5,8,9] or in the presence of graphene materials [[10], [11], [12], [13], [14], [15], [16]], TiO₂ [17], TiO₂ together with graphene [18], with graphite [19], with magnetic nanoparticles [20] and on mesoporous silica [21] for several analytical applications. Also, alloys of Pd with Au [10], Ag [22], Pt [15], or Cu [23] were obtained as NP and applied for hydrogen peroxide detection.

In the context of emerging nanotechnology for improved biosensor performance, some crucial aspects are the enhanced sensitivity and selectivity, as well as the immobilization procedure [24, 25]. In search of new substrates for simple enzyme immobilization, our recent results make use of magnetic Ni nanoparticles (NiNP) as a scaffold for the enzyme immobilization on Ni electrodes, without externally applied magnetic field. This principle was tested for glucose biosensors that operated at both negative and positive potentials, through the detection of H₂O₂ generated during the enzymatic reaction.

The two objectives of this investigation are related to the development of an electrode surface: i) for immobilization of oxidase enzymes solely through magnetic forces and ii) capable to operate at low potential values in order to avoid interfering compounds. In this context, Pd was employed for doping Ni electrodes (Pd@Ni), so as to benefit from both the catalytic effect of the Pd towards H₂O₂ reduction and the magnetic properties of Ni. The Pd@Ni electrodes were characterized by X-ray diffraction, scanning electron microscopy with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy. Electrochemical techniques, such as cyclic voltammetry and electrochemical impedance spectroscopy, allowed to determine the nature of the electrochemical process at the Pd@Ni electrodes. By using electrochemical methods, the Pd@Ni electrodes were applied for: i) the detection of H₂O₂ and ii) immobilization of the model enzyme glucose oxidase (GOx) functionalized with NiNP solely through magnetic interactions. The obtained GOx-NiNP/Pd@Ni biosensor was used for glucose determination in aqueous solutions by fixed potential amperometry at −0.05 V (vs. Ag/AgCl).

Section snippets

Reagents and solutions

All reagents were of analytical grade and were used without further purification. All solutions were prepared with Millipore Milli-Q nanopure water (resistivity≥18 MΩ cm).

Palladium chloride, nickel chloride, sodium chloride, hydrazine hydrate and polyvinylpyrrolidone (PVP), hydrogen peroxide, glucose oxidase from Aspergillus niger (>100 kU/g solid), glucose, ascorbic acid, uric acid, mannose, xylose and galactose and BSA were from Sigma-Aldrich. Phosphate buffer saline (NaPB) at pH 7.0

X-ray diffraction

The crystalline status of Ni and Pd@Ni electrodes was initially investigated by XRD, Fig. 1. The electrode patterns were assessed by grazing incidence XRD being dominated by maxima of Ni 111 superimposed with Au 200, and Ni 200. The structure of the Pd@Ni was also studied and, apart from an evident decrease of the Ni related diffraction maxima, the patterns are featured by the main diffraction maxima of Pd 111 and Pd 200. A similar analysis was performed after deposition of NiNP onto the Pd@Ni

Conclusions

The research describes the characterization and applications of nanostructured palladium doped nickel electrode for the immobilization of oxidase enzymes solely through magnetic forces and detect their activity at low potential values in order to avoid interfering compounds.

The nanostructured electrode surface was characterized by scanning electron microscopy with energy dispersive X-ray spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy and it has been shown that palladium

Acknowledgments

Financial support from the Romanian Ministry of Research and Innovation through Operational Programme Competitiveness 2014–2020, Project: NANOBIOSURF-SMIS 103528 and PN19-03 (contract no. 21 N/08.02.2019). The authors thank Dr. George Stan for XRD measurements.

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Nanostructured palladium doped nickel electrodes for immobilization of oxidases through nickel nanoparticles

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Reagents and solutions

X-ray diffraction

Conclusions

Acknowledgments

J. Electroanal. Chem.

Talanta

Biosens. Bioelectron.

J. Phys. Chem. Solids

Biosens. Bioelectron.

Sensor. Actuator. B Chem.

J. Solid State Chem.

Surfaces and Interfaces

Sensor. Actuator. B Chem.

Anal. Chim. Acta

Biosens. Bioelectron.

Nucl. Instruments Methods Phys. Res. Sect. A Accel. Spectrometers, Detect. Assoc. Equip.

Surf. Sci.

Electrochim. Acta

Nanoparticles of noble metals as effective platforms for the fabrication of amperometric biosensors on hydrogen peroxide

Sens. Lett.

Selectivity enhancement of amperometric nitric oxide detection via shape-controlled electrodeposition of platinum nanostructures

Analyst