Synthesis of Ag Nanoparticle Doped MnO2/GO Nanocomposites at a Gas/Liquid Interface and its Application in H2O2 Detection

Ag/MnO₂/GO nanocomposites were synthesized via the method of gas/liquid interface based on silver mirror reaction, and a non‐enzymatic H₂O₂ sensor was fabricated through immobilizing Ag/MnO₂/GO nanocomposites on GCE. The composition and morphology of the nanocomposites were studied by energy‐dispersive X‐ray spectroscopy (EDS), X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Electrochemical investigation indicated that it exhibited a favorable performance for the H₂O₂ detection. Its linear detection range was from 3 μM to 7 mM with a correlation coefficient of 0.9960; the sensitivity was 105.40 μA mM^?1 cm^?2 and the detection limit was estimated to be 0.7 μM at a signal‐to‐noise ratio of 3.     

The Hybrid of Gold Nanoparticles and 3D Flower‐like MnO2 Nanostructure with Enhanced Activity for Detection of Hydrogen Peroxide

3D Flower‐like manganese dioxide (MnO₂) nanostructure with the ability of catalysis for hydrogen peroxide (H₂O₂) and super large area that can support gold nanoparticles (AuNPs) with enhanced activity of electron transfer have been developed. The nanostructure of hybrids was prepared by directly mixing citric‐capped AuNPs and 3‐aminopropyltriethoxysilane (3‐APTES)‐capped nano‐MnO₂ using an electrostatic adsorption strategy. The Au‐MnO₂ composite was extensively characterized by scanning electron microscope (SEM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), the Brunauer‐Emmett‐Teller (BET) method and X‐ray photoemission spectroscopy (XPS). Electrochemical properties were evaluated through cyclic voltammetry (CV) and amperometric method. The prepared sensor showed excellent electrochemical properties towards H₂O₂ with a wide linear range from 2.5×10⁻³∼1.39 mM and 3.89∼13.89 mM. The detection limit is 0.34 μM (S/N=3) with the sensitivities of 169.43 μA mM⁻¹ cm⁻² and 55.72 μA mM⁻¹ cm⁻². The detection of real samples was also studied. The result exhibited that the prepared sensor can be used for H₂O₂ detection in real samples.     

Synthesis of MnO2/MWNTs Nanocomposites Using a Sonochemical Method and Application for Hydrazine Detection

A sonochemical method has been successfully used to synthesize MnO₂/MWNTs nanocomposites. The structure and nature of the resulting MnO₂/MWNTs composite were characterized by scanning electron microscopy (SEM), energy‐dispersive X‐ray diffraction (EDX), X‐ray photoelectron spectroscopy (XPS).The results show that the sonochemically synthesized MnO₂ nanoparticles were homogeneously dispersed on the modified MWNT surfaces. The performance of the MnO₂/MWNTs nanocomposites modified electrode was characterized using cyclic voltammetry (CV) and Nyquist plots. The electrode exhibits efficient electron transfer ability and high electrochemical response towards hydrazine. This may be attributed to the small particle size, high dispersion of MnO₂ particles. The fabricated hydrazine sensor showed a wide linear range of 5.0×10^?7–1.0×10^?3 M with a response time less than 5 s and a detection limit of 0.2 μM. Taking the advantage of the unique properties of both MWNTs and MnO₂, it would greatly broaden the applications of MWNTs and MnO₂.     

Electrochemically Prepared Three‐dimensional Porous Nitrogen‐doped Graphene Modified Electrode for Non‐enzymatic Detection of Hydrogen Peroxide

A facile and green electrochemical method for the fabrication of three‐dimensional porous nitrogen‐doped graphene (3DNG) modified electrode was reported. This method embraces two consecutive steps: First, 3D graphene/polypyrrole (ERGO/PPy) composite was prepared by electrochemical co‐deposition of graphene and polypyrrole on a gold foil. Subsequently, the ERGO/PPy composite modified gold electrode was annealed at high temperature. Thus 3DNG modified electrode was obtained. Scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS) and Raman spectroscopy were used to characterize the structure and morphology of the electrode. The electrode exhibits excellent electroanalytical performance for the reduction of hydrogen peroxide (H₂O₂). By linear sweep voltammetric measurement, the cathodic peak current was linearly proportional to H₂O₂ concentration in the range from 0.6 μM to 2.1 mM with a sensitivity of 1.0 μA μM⁻¹ cm⁻². The detection limit was ascertained to be 0.3 μM. The anti‐interference ability, reproducibility and stability of the electrode were carried out and the electrode was applied to the detection of H₂O₂ in serum sample with recoveries from 98.4 % to 103.2 %.     

Electrodeposition of TiO2 Nanoparticles on Multiwalled Carbon Nanotube Arrays for Hydrogen Peroxide Sensing

In this work, an amperometric H₂O₂ sensor based on TiO₂/MWCNTs electrode is reported. TiO₂ nanoparticles were synthesized on vertically aligned multiwalled carbon nanotube (MWCNT) arrays by electrodeposition. The morphology of the TiO₂/MWCNTs was characterized by scanning electron microscopy (SEM). The electrochemical performance of the TiO₂/MWCNTs electrode for detection of H₂O₂ was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry. The TiO₂/MWCNTs electrode displays high electrocatalytic activity towards oxidation of H₂O₂ in 0.1 M phosphate buffer solution (PBS, pH 7.4). At an applied potential of +0.40 V, the TiO₂/MWCNTs electrode exhibits a linear dependence (R=0.998) in the H₂O₂ concentration up to 15.0×10^?3 M with a sensitivity of 13.4 μA mM^?1 and detection limit of 4.0×10^?7 M with signal/noise=3. The optimal response time is less than 5 s with addition of 1 mM H₂O₂. The TiO₂/MWCNTs electrode presents stable, high sensitivity and also exhibits fast amperometric response to the detection of H₂O₂, which is promising for the development of H₂O₂ sensor.     

Synthesis of Ferrocene Based Naphthoquinones and its Application as Novel Non‐enzymatic Hydrogen Peroxide

At present, a highly sensitive hydrogen peroxide (H₂O₂) sensor is fabricated by ferrocene based naphthaquinone derivatives as 2,3‐Diferrocenyl‐1,4‐naphthoquinone and 2‐bromo‐3‐ferrocenyl‐1,4‐naphthoquinone. These ferrocene based naphthaquinone derivatives are characterized by H‐NMR and C‐NMR. The electrochemical properties of these ferrocene based naphthaquinone are investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS) on modified glassy carbon electrode (GCE). The modified electrode with ferrocene based naphthaquinone derivatives exhibits an improved voltammetric response to the H₂O₂ redox reaction. 2‐bromo‐3‐ferrocenyl‐1,4‐naphthoquinone show excellent non‐enzymatic sensing ability towards H₂O₂ response with a detection limitation of 2.7 μmol/L a wide detection range from 10 μM to 400 μM in H₂O₂ detection. The sensor also exhibits short response time (1 s) and good sensitivity of 71.4 μA mM^?1 cm^?2 and stability. Furthermore, the DPV method exhibited very high sensitivity (18999 μA mM^?1 cm^?2) and low detection limit (0.66 μM) compared to the CA method. Ferrocene based naphthaquinone derivative based sensors have a lower cost and high stability. Thus, this novel non‐enzyme sensor has potential application in H₂O₂ detection.     

Self‐Assembled Prussian Blue Nanoparticles Based Electrochemical Sensor for High Sensitive Determination of H2O2 in Acidic Media

In this paper, self‐assembled Prussian blue nanoparticles (PBNPs) on carbon ceramic electrode (CCE) were developed as a high sensitive hydrogen peroxide (H₂O₂) electrochemical sensor. The PBNPs film was prepared by a simple dipping method. The morphology of the PBNPs‐modified CCE was characterized by scanning electron microscopy (SEM). The self‐assembled PB film exhibited sufficient mechanical, electrochemical stability and high sensitivity in compare with other PB based H₂O₂ sensors. The sensor showed a good linear response for H₂O₂ over the concentration range 1 μM–0.26 mM with a detection limit of ca. 0.7 μM (S/N=3), and sensitivity of 754.6 mA M^?1 cm^?2. This work demonstrates the feasibility of self‐assembled PBNPs‐modified CCE for practical sensing applications.     

MnO2/Graphene Nanocomposites for Nonenzymatic Electrochemical Detection of Hydrogen Peroxide

MnO₂/graphene nanocomposites with different morphologies were synthesized and the petal‐shaped nanosheet MnO₂/graphene composite was developed as an electrode material for nonenzymatic hydrogen peroxide (H₂O₂) sensor. The morphology, structure, composition, and hydrophilicity of the resulting products were characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD), thermogravimetric analysis (TGA), and the contact angle tests. In addition, the fabricated MnO₂/graphene composites could be used as catalysts for the electrochemical oxidation of H₂O₂. Cyclic voltammogram (CV) experiments indicated that MnO₂/graphene‐modified electrode showed good electrocatalytic activity towards both the oxidation and reduction of H₂O₂ in a neutral environment. Amperometric response results illustrated that this nonenzymatic sensor had excellent anti‐interference ability and displayed two linear ranges from 10 to 90 µM and from 0.2 to 0.9 mM with a detection limit of 2 µM.     

SnFe2O4 Nanocrystals as Highly Efficient Catalysts for Hydrogen‐Peroxide Sensing

SnFe₂O₄ nanocrystals (NC), prepared with a simple one‐step carrier‐solvent‐assisted interfacial reaction process, were developed as highly efficient catalysts for hydrogen peroxide sensing. These NCs, with a size of around 7 nm, served as the sensing catalyst and were decorated onto the pore surfaces of a porous fluorine‐doped tin oxide (PFTO) host electrode, prepared from commercial FTO glass with a simple anodic treatment, to form the sensing electrode for hydrogen peroxide. The SnFe₂O₄ NCs‐loaded PFTO electrode exhibited an ultra‐high sensitivity of 1027 mA m ^?1 cm^?2 toward hydrogen peroxide, outperforming Pt NCs‐loaded PFTO electrodes. The SnFe₂O₄ NCs‐loaded PFTO electrode proved a promising relatively low cost, high performance sensing electrode for hydrogen peroxide.     

A Photoelectrochemical Biosensor Fabricated using Hierarchically Structured Gold Nanoparticle and MoS2 on Tannic Acid Templated Mesoporous TiO2

In a tannic acid assisted synthesis of mesoporous TiO₂, tannic acid was used as a cost effective and non‐toxic template for pore formation. Meanwhile, a gold nanoparticles (Au NPs) deposited TiO₂ nanocomposite was coated on an indium tin oxide electrode for the fabrication of a photoelectrochemical (PEC) biosensing system. Upon the formation of anatase structure, the electrode was coated with MoS₂ for effective visible light absorption. The mesoporous structure led to an enhanced surface area by improving Au NPs and glucose oxidase adsorption. Incorporation of Au NPs led to an enhanced photonic efficiency due to the generation of Schottky barriers. The obtained nanocomposite was used for the light‐driven, real‐time, and selective PEC glucose sensing. Under visible light irradiation, the enzyme immobilized electrodes yielded significant photocurrent improvement owing to the releasing electron donor H₂O₂. The obtained PEC biosensor demonstrated acceptable reproducibility and stability with a sensitivity of 4.42 μA mM^?1 cm^?2 and a low detection limit of 1.2 μM glucose. Also, the linear measurement range was found to be 0.004–1.75 mM glucose. The results indicated that the proposed production method of mesoporous TiO₂ will pave the way for a green chemistry based porous material production, along with the extension of the implementation of semiconductors in PEC biosensing systems.     

Novel Nonenzymatic Hydrogen Peroxide Sensor Based on Ag/Cu2O Nanocomposites

The nanocomposites of Ag nanoparticles supported on Cu₂O were prepared and used for fabricating a novel nonenzymatic H₂O₂ sensor. The morphology and composition of the nanocomposites were characterized using the scanning electron microscope (SEM), transmission electron microscope (TEM), energy‐dispersive X‐ray spectrum (EDX) and X‐ray diffraction spectrum (XRD). The electrochemical investigations indicate that the sensor possesses an excellent performance toward H₂O₂. The linear range is estimated to be from 2.0 μM to 13.0 mM with a sensitivity of 88.9 μA mM^?1 cm^?2, a response time of 3 s and a low detection limit of 0.7 μM at a signal‐to‐noise ratio of 3. Additionally, the sensor exhibits good anti‐interference.     

MnO2‐TiO2 Nanocomposite and 2‐(3,4‐Dihydroxyphenethyl) Isoindoline‐1,3‐Dione as an Electrochemical Platform for the Concurrent Determination of Cysteine,Tryptophan and Uric Acid

A novel modified carbon paste electrode (CPE) based on an MnO₂‐TiO₂ nanocomposite and 2‐(3,4 dihydroxyphenethyl) isoindoline‐1,3‐dione (DPID) as the modifier for the simultaneous analysis of cysteine (Cys), tryptophan (Trp) and uric acid (UA), as three key biochemicals present in human body. The MnO₂/TiO₂ nanocomposite was synthesized through a chemical co‐precipitation approach and the resulting electrode (MnO₂‐TiO₂/DPID/CPE) was used for studying the electrochemical oxidation of cysteine (Cys), tryptophan (Trp) and uric acid. As opposed to conventional CPEs, the oxidation peak potential of cysteine on MnO₂‐TiO₂/DPID/CPE had a 600.0 mV decrease in overpotential and could be observed at 30.0 mV, and the signals were linear from 0.025 to 200.0 μM, and a lower detection limit of 0.013 μM was reached. The MnO₂‐TiO₂/DPID/CPE was satisfactorily used for the concurrent analysis of Cys, Trp and UA in pharmaceutical and biological samples.     

Low‐Potential Sensitive Hydrogen Peroxide Detection Based on Nanotubular TiO2 and Platinum Composite Electrode

In this work, a novel sensor for detecting hydrogen peroxide was constructed on the base of nanotubular TiO₂ and platinum nanoparticles. The morphology, structural, and electrochemical properties of the Pt/TiO₂ nanocomposite electrodes were characterized by SEM, XRD and electrochemical methods. With an operating potential of +0.3 V versus Ag/AgCl, the sensor produces catalytic oxidation currents at the nanocomposite electrode, which can be exploited for quantitative determinations. The amperometric signals are linearly proportional to hydrogen peroxide concentration in the range 4×10^?6 to 1.25×10^?3 M. The regression equation is I (μA)=0.85 c (mM)+0.16 with a correction coefficient of 0.997. At a signal‐to‐noise ratio of 3, a detection limit of 4.0 μM H₂O₂ can be observed for the nanocomposite electrode. In addition, the sensor has a good stability and reproducibility. The construction process is simple and inexpensive. The results demonstrated that nanotubular TiO₂ exhibits great prospect for developing a class of ideal and novel bioreactors and biosensors.     

Sensitive and Selective Sensing of Hydrogen Peroxide with Iron‐Tetrasulfophthalocyanine‐Graphene‐Nafion Modified Screen‐Printed Electrode

We developed a novel iron‐tetrasulfophthalocyanine‐graphene‐Nafion (FeTSPc‐GR‐Nafion) modified screen‐printed electrode to determine hydrogen peroxide (H₂O₂) with high sensitivity and selectivity. The nanocomposite film (FeTSPc‐GR‐Nafion) exhibits an excellent electrocatalytic activity towards oxidation of H₂O₂ at a potential of +0.35 V in the absence of enzyme. A comparative study reveals that the FeTSPc‐GR complexes play a dual amplification role. Amperometric experiment indicates that the sensors possess good sensitivity and selectivity, with a linear range from 2.0×10^?7 M to 5.0×10^?3 M and a detection limit of 8.0×10^?8 M. This sensor has been successfully used to develop the glucose biosensor and has also been applied to determine H₂O₂ in sterile water.     

A Glucose Biosensor Based on Immobilization of Glucose Oxidase into 3D Macroporous TiO2

3D macroporous TiO₂ inverse opals have been derived from a sol‐gel procedure using polystyrene colloidal crystals as templates. EDS and SEM showed a face‐centered cubic (FCC) structure TiO₂ inverse opal was obtained. Glucose oxidase (GOx) was successfully immobilized on the surface of indium‐tin oxide (ITO) electrode modified by TiO₂ inverse opal (TiO_2(IO)). Electrochemical properties of GOx/TiO_2(IO)/ITO electrode were characterized by using the three electrodes system. The result of cyclic voltammetry showed that a couple of stable and well‐defined redox peaks for the direct electron transfer of GOx in absence of glucose, and the redox peak height enhanced in presence of 0.1 μM glucose. Compare with the ordinary structured GOx/TiO₂/ITO electrode, inverse opal structured GOx/TiO_2(IO)/ITO electrode has a better respond to the glucose concentration change. Under optimized experimental conditions of solution pH 6.8 and detection potential at 0.30 V versus saturated calomel electrode (SCE), amperometric measurements were performed. The sensitivity and the detection limit of glucose detection was 151 μA cm^?2 mM^?1 and 0.02 μM at a signal‐to‐noise ratio of 3, respectively. The good response was due to the good biocompatibility of TiO₂ and the large effective surface of the three‐dimensionally ordered macroporous structure.     

Enzyme‐free Cu2O@MnO2/GCE for Hydrogen Peroxide Sensing

A novel composite material of copper (I) oxide at manganese (IV) oxide (Cu₂O@MnO₂), was synthesized and applied for modification on the glassy carbon electrode (GCE) surface (Cu₂O@MnO₂/GCE) as a hydrogen peroxide (H₂O₂) sensor. The composite material was characterized regarding its structural and morphological properties, using field emission scanning electron microscopy (FE‐SEM), energy‐dispersive X‐ray spectroscopy (EDX), X‐ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The Cu₂O@MnO₂/GCE showed an excellent electrocatalytic response to the oxidation of H₂O₂ which provided a 0.56 s^?1 charge transfer rate constant (K_s), 1.65×10^?5 cm² s^?1 diffusion coefficient value (D), 0.12 mm² electroactive surface area (A_e) and 1.04×10^?8 mol cm^?2 surface concentration ( ). At the optimal condition, the constructed sensor exhibited a wide linear range from 0.5 μM to 20 mM with a low limit of detection (63 nM, (S/N=3) and a good sensitivity of 256.33 μA mM^?1 cm^?2. It also presented high stability (ΔI_response±15 %, n=100), repeatability (1.25 %RSD, n=10) and reproducibility (3.55 %RSD, n=10). The results indicated that the synthesized Cu₂O@MnO₂ was successfully used as a new platform for H₂O₂ sensing.     

Synthesis and Characterization of Nanostructured Manganese Dioxide Used as Positive Electrode Material for Electrochemical Capacitor with Lithium Hydroxide Electrolyte

A nanostructured manganese dioxide electrode material was prepared using a solid‐reaction route starting with MnCl₂·4H₂O and NH₄HCO₃, and its electrochemical performance as a positive electrode for MnO₂/activated carbon hybrid supercapacitor with 1 mol·L^?1 LiOH electrolyte was reported. The material was proved to be a mixture of nanostructured γ‐MnO₂ and α‐MnO₂ containing some bound water in the structure, which was characterized by X‐ray diffraction analysis, infrared spectrum analysis, and transmission electron microscope observation. Electrochemical properties of the MnO₂ electrode and the MnO₂/AC capacitor were investigated by cyclic voltammetry, ac impedance and galvanostatic charge/discharge methods. Experimental results showed that the MnO₂ electrode exhibited faradaic pseudocapacitance behavior and higher specific capacitance in 1 mol·L^?1 LiOH electrolyte. The MnO₂/AC hybrid capacitor with 1 mol·L^?1 LiOH electrolyte presented excellent rate charge/discharge ability and cyclic stability.     

A Simple Electrochemical Approach Based on Inexpensive Wall‐Jet Screen‐Printed Ring Disk Electrode to Evaluate Oxygen Reduction Catalysts

A simple electrochemical approach to evaluate oxygen reduction catalysts using an inexpensive screen‐printed ring disk carbon electrode system, consisting of a ring electrode deposited with MnO₂ and a disk electrode modified with the catalysts for study, is developed in this study. The as‐prepared MnO₂ is selective and sensitive for H₂O₂ oxidation in the presence of O₂ and is crucial to the proposed approach. By coupling with a wall‐jet electrochemical cell, the product generated from the reduction reaction at the disk electrode can effectively be monitored at the MnO₂‐deposited ring electrode. Model catalysts of nano‐Au and nano‐Pd representing 2e^? reduction of O₂ to H₂O₂ and 4e^? reduction to H₂O, respectively, were evaluated as electrode materials in oxygen reduction reaction to demonstrate the applicability of the proposed method.     

Urchin‐like Ag Nanowires as Non‐enzymatic Hydrogen Peroxide Sensor

Urchin‐like Ag nanowires were prepared by reacting AgNO₃(aq) with Cu metal in the presence of cetyltrimethylammonium chloride and HNO₃(aq) on a screen printed carbon electrode at room temperature. The diameters of the nanowires were about 100 nm, while the lengths were up to 10 μm. Cyclic voltammetric experiments using the Ag nanowires as the working electrode showed electrocatalytic H₂O₂ reduction. The electrode exhibited a high sensitivity of 4705 μA mM^‐1 mg^‐1 cm^‐2 from 50 μM to 10.35 mM and a measurable detection limit of 10 μM in amperometric detection. This is the first report on Ag NWs for non‐enzymatic H₂O₂ sensing.     

Mesoporous Foam TiO2 Nanomaterials for Effective Hydrogen Production

Hydrolysis of TiCl₄ in a diether‐functionalized imidazolium ionic liquid (IL), namely 1‐methyl‐3‐[2‐(2‐methoxy(ethoxy)ethyl]imidazolium methane sulfonate (M(MEE)I ? CH₃SO₃), results in a heterostructured organic/inorganic and sponge‐like porous TiO₂ material. The thermal treatment (300 °C) followed by calcination (500 °C) affords highly porous TiO₂. The characterization of the obtained samples (with and without IL, before and after calcination) by XRD, SEM, and TEM reveals TiO₂ anatase crystalline phases and irregular‐shaped particles with different porous structures. These hierarchical‐structured mesoporous TiO₂ nanomaterials were employed as efficient photocatalysts in the water‐splitting process, yielding up to 1304 μmol g^?1 on hydrogen production.