Electrochemical H2O2 Sensor Research Articles

Enzyme‐free Electrochemical Detection of Hydrogen Peroxide Based on the Three‐Dimensional Flower‐like Cu‐based Metal Organic Frameworks and MXene Nanosheets†

Main observation and conclusionCu‐based metal organic frameworks (MOFs) are regarded as promising sensing materials, which have abundant metal sites, large surface area and simple synthesis processes. In this work, a novel three‐dimensional flower‐like Cu‐MOF was synthesized, which was combined with ultra‐thin MXene nanosheets to construct a novel electrochemical sensor for H2O2. During the electrocatalytic reduction of H2O2, the catalytic activity of Cu‐MOF/MXene/GCE results in the ultra‐sensitive detection of H2O2 owing to the structure properties of MOFs, the nature of Cu‐contained nanomaterials as well as the high electrical conductivity of MXene. The Cu‐MOF/MXene/GCE showed a wide linear range from 1 μmol/L to 6.12 mmol/L using chronoamperometry at the detection potential of –0.35 V, and the detection limit is estimated to be 0.35 μmol/L. The sensor also shows good anti‐interference due to the lower detection potential, specific catalysis of Cu‐MOF to H2O2, which promises the sensor good selectivity in complexed samples. Meanwhile, the electrochemical sensor is capable to detect H2O2 in milk and serum samples with satisfactory recoveries. The ultra‐sensitivity, rapid detection, and easy operation of the proposed sensor present significant prospect for real‐time analysis and monitoring of H2O2 in foods and biological samples.

An Electrochemical Sensor for H2O2 Based on Au Nanoparticles Embedded in UiO-66 Metal–Organic Framework Films

An Electrochemical Sensor for H₂O₂ Based on Au Nanoparticles Embedded in UiO-66 Metal–Organic Framework Films

Three-Dimensional Carbon Foam Supported Co3O4/NiO Nanosheets As Non-Enzymatic Electrochemical H2O2 Sensors

In the present work, we successfully in-situ synthesized a three-dimensional (3D) carbon foam (CF) supported two-dimensional (2D) cobaltosic oxide/nickel oxide nanosheets through a facile solvothermal reaction assisted with a subsequent annealing procedure. Scanning electron microscopy (SEM) measurements showed that Co3O4/NiO nanosheets were uniformly grown on the 3D carbon framework at 180 °C for 1h which was labled as Co3O4/NiO-NSs/CF-1801. Due to the micron-level porous architecture and the high conductivity of the 3D carbon foam, the obtained composites possess large surface area, fast mass transport and high electronic conductivity. The Co3O4/NiO-NSs/CF-1801 showed a relative low limit of detection (LOD=5.51 µM) and the wide linear detection range (0.20–4.00 mM) with a sensitivity of 7.67 mA mM-1 cm-2. This excellent performance is due to the synergetic effect of micron-level porous architecture of 3D carbon foam and the in-situ uniformly growth of Co3O4/NiO nanosheets, which make them to be promising materials as electrochemical H2O2 sensing catalysts.

Back Cover: A Nonenzymatic Hydrogen Peroxide Electrochemical Sensing and Application in Cancer Diagnosis (Small Methods 5/2021)

In article number 2001212, Yan Yu, Jinrong Peng, Zhiyong Qian, and co-workers developed a biologically sensitive and efficient H2O2 electrochemical sensor based on PtNi-N-rGO nanocomposites. Using this sensing can successfully capture H2O2 from cancer cells after fMLP added. This sensing is capable of tumor diagnosis at high sensitivity, fast rate, and cheap.

Gold Nanowires – Assisted Prussian Blue Enhancing Peroxidase – Like Activity for the Non‐enzymatic Electrochemically Sensing H2O2 Released From Living Cells

AbstractPrussian blue nanoparticles (PBNPs) have peroxidase‐like activity for H2O2. However, PB alone have poor electrochemical performances. Herein, a strategy was proposed by direct in‐situ growth PBNPs onto gold nanowires (AuNWs) surface to obtain the peroxidase‐like activity with about 4.05 times higher than that of PBNPs alone. PBNPs@AuNWs was employed to construct a non ‐ enzymatic electrochemical H2O2 sensor with the detection limit of 5.3×10−9 mol/L (S/N=3). The sensor was successfully used to detect H2O2 in human serum samples or secreted from living HeLa cells. It may be a competitive candidate for H2O2 assaying in biological samples or cellular investigation.

A Nonenzymatic Hydrogen Peroxide Electrochemical Sensing and Application in Cancer Diagnosis.

The diagnosis of malignant tumors is essential for informing clinical decisions regarding therapeutic options. Current imaging and pathological diagnostic methods do not provide quantitative molecular information that is important in tumor identification. Moreover, pathological tissue analysis is dependent on unevenly distributed pathological features. The tumor microenvironment has been documented to have hydrogen peroxide (H2 O2 ). This study presents a biologically sensitive and efficient H2 O2 electrochemical sensor based on PtNi nanoparticle-doped N-reduced graphene oxide (PtNi-N-rGO) with a low detection limit (2.8× 10-9 m), a fast response time (<6 s) and desirable anti-interference characteristics. Herein, H2 O2 is used as molecular biomarker. The sensor successfully captures H2 O2 from cancer cells. In addition, it efficiently detects tumor tissues, adjacent tissues, and normal tissues. This study demonstrates the H2 O2 sensor potential to rapidly detect tumor tissues. This technique provides a complementary method for pathological tumor diagnosis that is independent of the traditional pathology labs.

Recent advances in enzyme-free electrochemical hydrogen peroxide sensors based on carbon hybrid nanocomposites

The article gives an overview of the recent advances of the enzyme-free electrochemical H2O2 sensors based on carbon hybrid nanocomposites in the hope of suggesting feasible approaches to further enhance the sensitivity of carbon hybrid materials.

Preyssler-type polyoxometalate-based crystalline materials for the electrochemical detection of H2O2

Four Preyssler-type polyoxometalate-based organic–inorganic hybrid materials were synthesized as non-enzymatic H2O2 electrochemical sensors, with high sensitivity and low detection limit.

Reasonable design of an MXene-based enzyme-free amperometric sensing interface for highly sensitive hydrogen peroxide detection

Sensitive detection of H2O2 in the nano- to micromolar range is critical for health monitoring and disease diagnosis. Two-dimensional transition metal carbides or/and nitrides (called MXenes, MXs) have excellent potential applications in the electrochemical field due to their outstanding electrical conductivity and catalytic properties. In this work, Ti3C2Tx (MX) was employed for the construction of a sensitive and enzyme-free electrochemical sensing interface for the detection of hydrogen peroxide (H2O2) through a simple and effective method. Prussian blue (PB) was electrochemically deposited on the surface of a glassy carbon electrode (GCE). Chitosan (CS) and MX were sequentially dripped onto the PB modified GCE surface. The reasonable fabrication of the MX/CS/PB/GCE sensing interface presented good electrochemical sensing performance towards H2O2 with a low limit of detection (4 nM), a wide linear range from 50 nM to 667 μM and good selectivity. The proposed MX/CS/PB/GCE has been proven to monitor H2O2 in food samples and biological samples with recoveries between 94.7% and 100.3%. This work has made a beneficial attempt and research for exploring and expanding the application of MXs in the field of electrochemical sensing.

Three-dimensional carbon foam supported NiO nanosheets as non-enzymatic electrochemical H2O2 sensors

In this work, we successfully in situ fabricated two-dimensional (2D) nickel oxide nanosheets (NiO-NSs) uniformly grown on a three-dimensional (3D) carbon foam (CF) network by using a facile solvothermal reaction assisted with a subsequent annealing procedure. The nanoporous NiO nanosheet structures can be size-controlled by simply tuning the reaction temperature and time (90 °C for 10 and 20 h, 120 °C for 10 h, 180 °C for 1 h). Among the studied composites, the obtained NiO-NSs/CF-1801 modified electrode exhibited the highest performance for non-enzymatic detecting H2O2. It showed the lowest limit of detection (LOD = 13.03 nM) and the largest linear detection range (0.20–3.75 mM) with a sensitivity of 23.30 μA mM−1 cm−2. This excellent performance is due to the synergetic effect of 3D micron-level porous structure of carbon foam and the in-situ uniformly growth of NiO nanosheets. The present results demonstrate that NiO-NSs/CF is a promising sensing candidate for quantitative electrochemical detecting H2O2.

Simple Electrochemical Synthesis of Polyethylenimine-Encapsulated Ag Nanoparticles from Solid AgCl Applied in Catalytic Reduction of H2O2

We report a simple and environmentally friendly synthesis of polyethylenimine (PEI)-encapsulated Ag nanoparticles (AgNPs) by a direct electroreduction of solid AgCl. The AgNPs, characterized by field-emission scanning electron microscopy (FE-SEM), X-ray photoelectron spectroscopy (XPS), and energy dispersive X-ray spectroscopy (EDS), revealed that AgNPs diameters (100–500 nm) depended on the loading of the AgCl precursor. Using cyclic voltammetry (CV), it was confirmed that the AgNPs had a catalytic effect on the electrochemical reduction of H2O2. The obtained AgNPs were subsequently used to construct an electrochemical H2O2 sensor exhibiting a low detection limit (1.66 μM) and a wide linear response range, with real-life tests indicating an insensitivity to common interferents and confirming the potential use of the developed technique in diverse applications.

Fabrication of Pt/CeO2/NCNFs with embedded structure as high-efficiency nanozyme for electrochemical sensing of hydrogen peroxide

The construction of nanozyme with stable structure and excellent analytical properties is urgently needed for non-enzymatic electrochemical sensing of H2O2. Herein, we prepared Pt particles/CeO2 plates embedded in N-doped carbon nanofibers (Pt/CeO2/NCNFs) by heat-treating electrospun composites as nanozyme for the detection of H2O2. Characterization results showed that Pt nanoparticles dispersed on or around CeO2 nanoplates and the composite embedded homogeneously in NCNFs matrix, which improved the structure stability and contributed to the synergistic effect of Pt, CeO2 and NCNFs, and further enhanced the enzyme-like electrocatalytic activity of as-prepared nanozyme for H2O2 reduction. Pt/CeO2/NCNFs-based sensors exhibited superior H2O2 analytical performances of low detection limit (0.049 μM), high sensitivity (185.6 μA mM−1 cm−2) and wide linear range (0.0005–15 mM). In addition, the sensor was possessed of high selectivity, anti-interference, excellent reproducibility and stability. These above results were attributed to the embedded structure and the synergistic effect of Pt nanoparticles, CeO2 nanoplates and NCNFs. More interestingly, the fabricated sensor showed satisfactory recoveries and RSD for H2O2 detection in cosmetics. These attractive properties manifested that Pt/CeO2/NCNFs had potential to be a candidate for fabricating H2O2 electrochemical sensor.

Co-Cr mixed spinel oxide nanodots anchored on nitrogen-doped carbon nanotubes as catalytic electrode for hydrogen peroxide sensing

Hydrogen peroxide (H2O2) is a significant biomarker in physiological processes. Abnormal levels of H2O2 are considered to be closely related to some acute diseases. Therefore, it is important to monitor the H2O2 levels in bio-samples. Herein, we present a novel non-enzymatic electrochemical H2O2 sensor based on the excellent electrocatalytic performance of a composite comprising Zn-Cr-Co ternary spinel metal oxide nanodots (ZnCrCoO4) anchored on the surface of nitrogen-doped carbon nanotubes (NCNTs), denoted as ZnCrCoO4/NCNTs, toward H2O2 reduction. ZnCrCoO4/NCNTs were synthesized using a facile one-pot hydrothermal strategy. The enhanced electrocatalytic performance of ZnCrCoO4 is resulted from the partial substitution of Co in spinel zinc cobaltate (ZnCo2O4) with Cr, which modifies the CoO electronic structure and enhances electroconductivity. The ZnCrCoO4/NCNTs-based H2O2 sensor exhibited a wide quantitative detection range from 1 to 7330 μM with a detection limit of 1 μM. The sensor showed excellent reproducibility and selectivity for H2O2 sensing. In addition, remarkable recoveries were obtained for H2O2-spiked fish serum samples. These results demonstrated that the as-developed sensor has a great potential in monitoring H2O2 levels in practical applications.

Highly defective carbon nanotubes for sensitive, low-cost and environmentally friendly electrochemical H2O2 sensors: Insight into carbon supports

We employed the oxidative dehydrogenation of C2H2 by CO2 and the C2H2 decomposition to prepare carbon nanotubes (CNTs) and carbon nanofibers (CNFs). The use of a small amount of Ni catalyst made it possible to produce CNTs and CNFs having a highly defective structure at a relatively low temperature compared to the one typically used for the CNT synthesis. The synthesized CNTs and CNFs were decorated with about 10 nm-gold nanoparticles (AuNPs) via an electrostatic self-attachment. The electrode with CNTs synthesized via the C2H2–CO2 reaction exhibits superior electrochemical reactivity with H2O2 when compared to the ones with CNTs synthesized via C2H2 decomposition, commercial CNTs, CNFs, and other more common carbon supports e.g. carbon black and activated charcoal. It demonstrates a rapid response, high sensitivity (104.9 μA mM−1 cm−2), wide linear working range (5 μM–23 mM), low detection limit (0.138 μM), good selectivity, reproducibility, and stability. The CNTs synthesized via the C2H2–CO2 reaction are suggested as energy-saving, cost-effective and environmentally friendly supporting material candidates for practical applications. The electrodes with CNTs show a high electrochemically active surface area, low charge transfer resistance and fast mass transfer at the electrode surface that are key factors for H2O2 detection.

One-Step Electrodeposition of Silver Nanostructures on 2D/3D Metal-Organic Framework ZIF-67: Comparison and Application in Electrochemical Detection of Hydrogen Peroxide.

Metal-organic frameworks (MOFs) have been widely used as supporting materials to load or encapsulate metal nanoparticles for electrochemical sensing. Herein, the influences of morphology on the electrocatalytic activity of Co-containing zeolite imidazolate framework-67 (ZIF-67) as supporting materials were studied. Three types of morphologies of MOF ZIF-67 were facilely synthesized by changing the solvent because of the influence of the polar solvent on the nucleation and preferential crystal growth. Two-dimensional (2D) ZIF-67 with microplate morphology and 2D ultrathin ZIF-67 nanosheets were obtained from pure H2O (H-ZIF-67) and a mixed solution of dimethylformamide and H2O (D-ZIF-67), respectively. Three-dimensional ZIF-67 with rhombic dodecahedron morphology was obtained from pure methanol (M-ZIF-67). Then, one-step electrodeposition of silver nanostructures on ZIF-67-modified glassy carbon electrode (Ag/ZIF-67/GCE) was performed for the reduction of hydrogen peroxide (H2O2). Cyclic voltammetry can be used to investigate the electrocatalytic activity of Ag/ZIF-67/GCE, and Ag/H-ZIF-67/GCE displayed the best electrocatalytic property than Ag/D-ZIF-67/GCE and Ag/M-ZIF-67/GCE. The electrochemical H2O2 sensor showed two wide linear ranges of 5 μM to 7 mM and 7 to 67 mM with the sensitivities of 421.4 and 337.7 μA mM-1 cm-2 and a low detection limit of 1.1 μM. In addition, the sensor exhibited good selectivity, high reproducibility, and stability. Furthermore, it has been utilized for real-time detection of H2O2 from HepG2 human liver cancer cells. This work provides a novel strategy for enhancing the detection performance of electrochemical sensors by changing the crystalline morphologies of supporting materials.

An electrochemical hydrogen peroxide sensor for applications in nuclear industry

Hydrogen peroxide is a radiolysis product of water formed under gamma-irradiation; therefore, its reliable detection is crucial in the nuclear industry for spent fuel management and coolant chemistry. This study proposes an electrochemical sensor for hydrogen peroxide detection. Cysteamine (CYST), gold nanoparticles (GNPs), and horseradish peroxidase (HRP) were used in the modification of a gold electrode for fabricating Au/CYST/GNP/HRP sensor. Each modification step of the electrode was investigated through electrochemical and physical methods. The sensor exhibited strong sensitivity and stability for the detection and measurement of hydrogen peroxide with a linear range of 1–9 mM. In addition, the Michaelis–Menten kinetic equation was applied to predict the reaction curve, and a quantitative method to define the dynamic range is suggested. The sensor is highly sensitive to H2O2 and can be applied as an electrochemical H2O2-sensor in the nuclear industry.

Ionic liquid supported nickel-based metal-organic framework for electrochemical sensing of hydrogen peroxide and electrocatalytic oxidation of methanol

Since metal-organic frameworks (MOFs) have low electrical conductivity, the application of single MOFs as electrochemical sensor materials is very rare, and the construction of high-performance hydrogen peroxide (H2O2) sensors based on MOFs is still a difficult challenge. In this paper, a nickel-based MOF (Ni-MOF) material was synthesized using an ionic liquid as both solvent and ligand through an ionothermal method. The morphological and structural characterizations were studied by scanning electron microscopy, X-ray diffraction, attenuated total reflectance Fourier transform infrared spectroscopy and thermogravimetric analysis. Electrochemical sensing performance of the Ni-MOF modified glassy carbon electrode towards H2O2 was evaluated by cyclic voltammogram and chronoamperometry in an alkaline solution. The electrochemical H2O2 sensor was found to lead to a linear response from 0.5 μM to 2.0 mM with a detection limit of 0.18 μM. Moreover, the sensor also revealed good anti-interference ability and stability. To further assess the electrochemical properties, electrochemical activity of the Ni-MOF to oxidation of methanol was investigated by cyclic voltammetry. During the methanol oxidation reaction measurement, the Ni-MOF not only exhibited a high current density, but also found a good electrochemical activity for intermediate oxidation products. The above studies proved that the Ni-MOF material synthesized using the ionic liquid as a ligand can be used not only as an electrochemical H2O2 sensor but also as an electrocatalyst for methanol oxidation.

A novel Fe-hemin-metal organic frameworks supported on chitosan-reduced graphene oxide for real-time monitoring of H2O2 released from living cells

Herein, a kind of novel hemin-based metal organic frameworks (Fe-hemin-MOFs) with unique peroxidase-like bioactivity was developed for the first time. The synthesized Fe-hemin-MOFs exhibited satisfactory catalytic activity toward hydrogen peroxide (H2O2). When it was further supported on Chitosan-reduced graphene oxide (CS-rGO), amplified electrochemical signal could be obtained. The Fe-hemin-MOFs/CS-rGO composite was used to construct a novel H2O2 electrochemical sensor. The electrocatalytic reduction of H2O2 displayed two segments linearity range from 1 to 61 μM and 61–1311 μM, as well as a low detection limit of 0.57 μM. Furthermore, the proposed sensor was successfully used for real-time monitoring of H2O2 released from living cells, which extended the practical application of MOFs-based sensors in monitoring the pathological process in living cells.

Hierarchically porous carbon nanofibers embedded with cobalt nanoparticles for efficient H2O2 detection on multiple sensor platforms

Hydrogen peroxide (H2O2) detection is essential in many industrial and biological processes. Current applications of H2O2 electrochemical sensors are often limited by the high cost of precious metal electrocatalysts and sophisticated instrumentation requirements. Here, we demonstrate a highly active non-precious metal cobalt/carbon nanocomposite electrocatalyst for efficient H2O2 sensing on multiple sensor platforms, including conventional glassy carbon electrodes (GCEs), free-standing film electrodes, and screen-printed electrodes (SPEs). This nanocomposite was synthesized by carbonation of electrospun polyacrylonitrile nanofibers containing zeolitic imidazole framework (i.e., ZIF-67) particles. The resulting hierarchically porous nitrogen-doped carbon nanofiber film contains hollow mesoporous carbon particles and exposed cobalt nanoparticles, which has sufficient mechanical strength as a self-standing film and is also electrically highly conductive. Consequently, when tested using GCEs, it exhibits an ultrahigh sensitivity of 300 μA/cm2 mM and a detection limit of 10 μM below the permissible H2O2 residual limit in food packaging permittable by the US FDA. When utilized as free-standing film electrodes, its linear detection range extends an order higher to 50 mM. It is also highly specific toward H2O2 sensing without responses to multiple interfering analytes. Further, it enables mobile H2O2 detection on SPEs when integrated with a portable potentiostat and mobile phone. This new nanocomposite electrocatalyst can open various new opportunities for practical H2O2 sensing applications.

Bovine serum albumin fibrous biofilm template synthesis of metallic nanomeshes for surface-enhanced Raman scattering and electrocatalytic detection

Porous metallic architectures with well-defined networks possess multiple reactivity center and large specific surface area, offer improved catalytic activity, adsorption capacity, and sensing abilities than bulk materials, thus be an increasingly popular materials in various fields. However, it is challenging to synthesis porous metallic structures in a green, facile and scalable way. Using bovine serum albumin (BSA) nanofibrous biofilms as sacrificial templates, a variety of porous metallic nanomeshes were readily formed through the adsorption of ions following by air calcination. The microstructures of the metallic nanomeshes are controllable, with pores ranging from 10−2 to 100 μm and particle diameter of 30–270 nm. Specifically, the Au nanomeshes displayed not only high plasmonic resonance properties as SERS substrates, but also multiple reactivity centers as electrochemical sensor for dopamineand H2O2.