Nanostructures in Hydrogen Peroxide Sensing

Abstract

In recent years, several devices have been developed for the direct measurement of hydrogen peroxide (H2O2), a key compound in biological processes and an important chemical reagent in industrial applications. Classical enzymatic biosensors for H2O2 have been recently outclassed by electrochemical sensors that take advantage of material properties in the nano range. Electrodes with metal nanoparticles (NPs) such as Pt, Au, Pd and Ag have been widely used, often in combination with organic and inorganic molecules to improve the sensing capabilities. In this review, we present an overview of nanomaterials, molecules, polymers, and transduction methods used in the optimization of electrochemical sensors for H2O2 sensing. The different devices are compared on the basis of the sensitivity values, the limit of detection (LOD) and the linear range of application reported in the literature. The review aims to provide an overview of the advantages associated with different nanostructures to assess which one best suits a target application.

Keywords: biosensors; enzymes; hydrogen peroxide; nanostructures; sensors.

Figure 1

Electrochemical hydrogen peroxide (H${}_2$O${}_2$) sensor based on palladium nanowires (PdNWs). (a) SEM micrograph of the PdNWs electrode, (b) basic diagram of the sensor operation. With permission from [8].

Figure 2

Characteristics of Prussian blue nanoparticles (PBNPs). (a) SEM micrograph of the PBNPs deposited by drop casting over an electrode; (b) Prussian blue crystalline structure. With permission from [18].

Figure 3

Electrochemical characterization of the electrodes with electrodeposited Prussian blue nanoparticles (PBNPs) layers. (Left) mechanism of the catalytic H${}_2$O${}_2$ reduction mediated by Prussian blue (PB), (Right) calibration curve of H${}_2$O${}_2$ on PBNP screen printed electrodes (SPEs). (a) Detail in the concentration range between 0 and 25 $\mathsf{\mu }$M and (b) raw amperometric data from 0 to 4.5 mM. With permission from [29].

Figure 4

(A) SEM image of Ag urchin-like NWs on an SPC electrode (inset: enlarged view of a single cluster of urchin-like Ag NWs; (B) calibration curves of amperometric tests. Adapted with permission from [9].

Figure 5

A general scheme for the synthesis of silver particles (a), their immobilization on the carbon rod electrode (b), and electrode utilization as a H${}_2$O${}_2$ sensor (c). With permission from [55].

Figure 6

Chrono–amperometric response (left) of N-Co-MOF/GCE for the successive addition of 10 $\mathsf{\mu }$M of H${}_2$O${}_2$ in 0.1 M PBS (pH = 7) under constant stirring, −0.35 V. To the (right), the figure shows the change in current at different concentrations of H${}_2$O${}_2$, the inset shows a TEM image of the Nitrogen-enriched MOF. Adapted with permission from [61].

Figure 7

Scheme of the synthesis and application of a $\delta$-MnO${}_2$ nanocomposite with carbon nanotubes ($\delta$-MnO${}_2$/CNTs) as an enzyme-free sensor for the detection of hydrogen peroxide (H₂O₂) through an electroreduction reaction. (Left) carbon nanotubes; (Middle) synthesis of the $\delta$-MnO${}_2$/CNTs nanocomposite by a simple one-step hydrothermal process in an alkaline solution without using surfactants or templates; (Right) investigation of the electrochemical properties of $\delta$-MnO${}_2$/CNTs in a glassy carbon electrode by cyclic voltammetry and amperometry. With permission from [71].

Figure 8

Modified glassy carbon electrode made of multilayer Cu/molybdenum disulfide (CuNFs-MoS${}_2$/GCE) with 3D nano-flower shape for non-enzymatic sensing. (Left) schematic representation of the fabrication of the CuNFs-MoS₂/GCE, and (Right) possible reaction mechanisms at the electrode during the analysis for H${}_2$O${}_2$ and glucose. With permission from [81].

Figure 9

Schematic representation of a hydrogen peroxide H${}_2$O${}_2$ biosensor based on MoS${}_2$ nanoparticles. With permission from [82].

Figure 10

Schematic representation (A–D), of the construction of a chemically modified vitreous carbon electrode biosensor of impure multi-walled carbon nanotubes (MWCNT-Fe)-chitosan biopolymer (H${}_2$N-CHIT) (GCE/[MWCNT-Fe:H${}_2$N-CHIT]) for the electrocatalytic and electrochemical detection of hydrogen peroxide (H${}_2$O${}_2$) in phosphate buffer (PBS) pH 7. With permission from [95].

Figure 11

Amperometric responses of sequential additions of H${}_2$O${}_2$ at the MWCNT–PEDOT/GCE in pH 7 PBS. Rotating speed = 2000 rpm, E${}_{app.}$ = −0.5 V. The blank amperometric response of MWCNT–PEDOT/GCE is tested during 0–200 s. Inset: (A) scale-up amperometric response to the first H${}_2$O${}_2$ additions; (B) calibration plot of H${}_2$O${}_2$ concentration; (C) amperometric response to H${}_2$O${}_2$; (D) complete calibration plot. With permission from [96].

Figure 12

Schematic representation of the functionalization of graphene. (A) graphene oxide sheet; (B) PEI-funtionalized graphene. This composite was prepared firstly by stirring PEI and graphene in KOH at 80 ${}^{\circ }$C during 24 h. Then, NaBH${}_4$ was added to the mixture and kept at 80 ${}^{\circ }$C for 2 h. The PEI-functionalized graphene was collected by centrifugation and wash with distilled water. With permission from [97].

Figure 13

Electrochemical operation of the sensor built by the layer-by-layer complexation method. (A) Cyclic voltammograms of [PB/PEI–graphene]${}_{10}$ multilayer (a) in N${}_2$-saturated potassium hydrogen phthalate (0.1 M, pH = 4), [PB/PEI–graphene]${}_{10}$ multilayer; (b) and [PB/PEI]${}_{10}$ multilayer; (c) in the presence of 5 mM H${}_2$O${}_2$ in N${}_2$-saturated potassium hydrogen phthalate. Scan rate: 10 mV/s; (B) spectroscopic monitoring of potential switching for [PB/PEI–graphene]${}_{16}$ multilayer film immersed in a quiescent cuvette cell. Switching occurred between −0.2 V (Prussian white, low absorbance) and 0.6 V (Prussian blue, high absorbance). With permission from [97].

Figure 14

(A) Schematic representation of the biosensor based on HRP and the one based on TOP enzymes; (B) calibration curves for both biosensors in a FIA System with PBS buffer at pH 7 with 0.1 M KCl as carrier, and 20 $\mathsf{\mu }$L sample injection volume, −0.1 V vs. Ag|AgCl (0.1 M KCl). The inset shows the linear section of the curves. With permission from [110].

Figure 15

Schematic representation of the Cyt c modified single-layered graphene FET sensor for ultrasensitive H${}_2$O${}_2$ detection. (a) the overall fabrication process for graphene FET sensor platform. The fabrication strategy is first performed to obtain single-layered graphene-based FET platform for a high-performance sensor. The second step involves the conjugation of the Cyt c with surface-modified graphene via 1,5-diaminoaphthanlene (DAN). Then, this sensor platform was utilized for the detection of the H${}_2$O${}_2$ in real-time manner; (b) Cyt c-conjugated graphene FET sensor. Cyt c, which contains a heme structure as a catalytic site, is able to convert the value of the current via electron transport by H₂O₂-induced oxidation. With permission from [111].