Hydrogen generation from H<Subscript>2</Subscript>O/H<Subscript>2</Subscript>O<Subscript>2</Subscript>/MnWO<Subscript>4</Subscript> system

Hydrogen gas as a clear energy resource was found to be largely bubbled from a H₂O/H₂O₂/MnWO₄ system. MnWO₄ powder was fabricated by an aqueous reaction method. The powder was characterized with X-ray diffraction (XRD), transmission electron microscope (TEM), and X-ray photoelectron spectrometry (XPS). The efficiency of the hydrogen generation increases with an increase in initial pH in the appropriate range, H₂O₂ proportion, MnWO₄ proportion, and intensity of light resource. Calcining at 400 °C for 1 h can make the MnWO₄ powder synthesized by an aqueous reaction more effective for H₂ generation and more stable in higher initial pH. The MnWO₄ catalyst shows a long-term stability for photocatalytic H₂ generation. A mechanism was suggested for the hydrogen generation from the H₂O/H₂O₂/MnWO₄ system together with XPS analysis.     

In-situ growth of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanoparticles on mesoporous carbon nanofibers: a new nanocomposite for nonenzymatic amperometric sensing of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The paper describes a nonenzymatic amperometric H₂O₂ sensor that uses a nanocomposite consisting of Co₃O₄ nanoparticles (NPs) and mesoporous carbon nanofibers (Co₃O₄-MCNFs). The Co₃O₄ NPs were grown in situ on the MCNFs by a solvothermal procedure. The synergetic combination of the electrocatalytic activity of the Co₃O₄ NPs and the electrical conductivity of MCNFs as an immobilization matrix enhance the sensing ability of the hybrid nanostructure. The oxidation current, best measured at 0.2 V (vs. SCE) is linear in the 1 to 2580 μM H₂O₂ concentration range, with a 0.5 μM lower detection limit (at an S/N ratio of 3). The sensor is highly selective even in the presence of common electroactive interferents. It was applied to the determination of H₂O₂ in spiked milk samples.

Open image in new window

Graphical abstract Schematic of the synthesis of a nanocomposite consisting of Co₃O₄ nanoparticles (NPs) and mesoporous carbon nanofibers (Co₃O₄-MCNFs) by a solvothermal procedure. It was used as electrocatalyst for direct oxidation of H₂O₂.

     

Laser-induced formation of Au/Pt nanorods with peroxidase mimicking and SERS enhancement properties for application to the colorimetric determination of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

Platinum nanoparticles (PtNPs) were uniformly grown on the surface of gold nanorods (AuNRs) by a laser irradiation procedure. Transmission electron microscopy confirmed that the PtNPs are uniformly grown on the surface of the AuNRs. The formation of PtNPs on the AuNRs leads to a red-shift of the absorption maximum from 734 nm to 766 nm. In addition, the efficiency of surface enhanced Raman scattering (SERS) is increased, but the photothermal conversion efficiency is decreased compared to pure AuNRs. The result indicates that electron transfer occurs between gold and platinum. The peroxidase mimicking effect of PtNPs, AuNRs and Au/Pt NRs by catalyzing the oxidation of colorless 3,3’,5,5’-tetramethylbenzidine (TMB) to blue oxidized 3,3’,5,5’-tetramethylbenzidine (oxTMB; a quinone) in the presence of H₂O₂. The catalytic activity of Au/Pt NRs is higher than that of sole AuNRs or PtNPs by factors of 4.2 and 2.1, respectively. Thus, Au/Pt NRs have been used for the detection of peroxide and the limit of detection is 0.04 μM. This work provides an approach to integrate the peroxidase mimicking effect with SERS enhancement for potential application in detection.

Open image in new window

Graphical abstract A schematic diagram for the laser-induced growth of Au/Pt NRs and the colorimetric determination of hydrogen peroxide concentration with their peroxidase mimicking properties. The limit of detection is 0.04 μM based on the use of Au/Pt NRs as a catalyst.

     

Synthesis of peroxy-radical condensates from mixtures of H<Subscript>2</Subscript>+O<Subscript>2</Subscript>

One of the methods for the synthesis of peroxy-radical condensates is the condensation at liquid nitrogen temperature of an H₂+O₂ mixture dissociated in an electrical discharge at low pressure. Peroxy-radical condensates are thought to contain substantial quantities of higher hydrogen peroxides H₂O₃ and H₂O₄. The present work investigates the influence of experimental parameters on the synthesis of peroxy-radical condensates from an H₂+O₂ mixture, analyses the relevant literature, and recommends the optimal experimental conditions for the synthesis. The synthesis is carried out in a U-tube electrical discharge reactor (inner diameter ∼15 mm), immersed in liquid nitrogen, at rather low pressure (0.5–1 Torr). The maximum conversion of initial O₂ into higher hydrogen peroxides was observed at a composition of initial gas mixture of 66.7% H₂ + 33.3% O₂.     

Improved peroxidase mimetic activity of a mixture of WS<Subscript>2</Subscript> nanosheets and silver nanoclusters for chemiluminescent quantification of H<Subscript>2</Subscript>O<Subscript>2</Subscript> and glucose

It is reported that a mixture of WS₂ nanosheets (WS₂ NS) and silver nanoclusters (AgNCs) displays strongly enhanced peroxidase-mimicking activity. The catalytic effect of the mixture was studied by colorimetry, fluorometry, chemiluminescence (CL) and electrochemistry. The effect is interpreted in terms of a difference between the Fermi energy level of the two nanomaterials. This leads to the formation of charge separation regions which act as active sites for enzyme mimetic interaction with the substrates. The mixture of WS₂ NS and AgNCs was exploited for the non-enzymatic determination of H₂O₂ and glucose. A stopped-flow method was applied as a sensitive CL detection system using the bicarbonate-H₂O₂ reaction. The mixture has a powerful peroxidase mimicking activity on the bicarbonate-H₂O₂ CL reaction, and this effect is much larger than that of any single constituent. In addition, the CL emission is improved several times by using the stopped-flow technique. Under optimum condition, H₂O₂ can be determined in the 2.5–1500 nM concentration range. Moreover, glucose levels in human serum can be quantified via glucose oxidase based oxidation which leads to the generation of H₂O₂. Using this CL assay, a linear relationship was obtained between the intensity of the CL emission and glucose concentration in the range of 0.03–20 μM, with a limit of detection (3S) of 13 nM.

Open image in new window

Graphical abstract An enhanced peroxidase-like catalytic activity for WS₂ nanosheets (WS₂ NS) was revealed in the presence of silver nanoclusters (AgNCs), and was exploited for the non-enzymatic determination of H₂O₂, and of glucose (via glucose oxidase; GOx) using a stopped-flow CL method.

     

Magnetic carbon nitride nanocomposites as enhanced peroxidase mimetics for use in colorimetric bioassays,and their application to the determination of H<Subscript>2</Subscript>O<Subscript>2</Subscript> and glucose

Graphite-like carbon nitride ? Fe₃O₄ magnetic nanocomposites were synthesized by a chemical co-precipitation method. The nanocomposites were characterized by transmission electron microscopy, X-ray diffraction, FTIR spectroscopy, X-ray photoelectron spectroscopy and magnetization hysteresis loops. The nanocomposites exhibit enhanced peroxidase-like activity (compared to that of graphite-like carbon nitride or Fe₃O₄ NPs). More specifically, they are capable of catalyzing the oxidation of different peroxidase substrates (such as TMB, ABTS or OPD) by H₂O₂ to produce the typical color reactions (blue, green or orange). The nanocomposites retain their magnetic properties and can be separated by an external magnet. On the basis of these findings, a highly sensitive and selective method was applied to the determination of H₂O₂ and glucose (by using glucose oxidase). It was successfully applied to the determination of glucose in (spiked) human serum. Compared to other nanomaterial-based peroxidase mimetics, the one described here provides distinctly higher sensitivity for both H₂O₂ and glucose, with detection limits as low as 0.3 μM and 0.25 μM, respectively.

Open image in new window

Graphical abstract The magnetic carbon nitride nanocomposite exhibits enhanced peroxidase-like activity that is much larger than that of graphite-like carbon nitride or Fe₃O₄ NPs alone. This finding was applied to design a highly sensitive and selective colorimetric assay for H₂O₂ and glucose.

     

Study on chemisorption of H<Subscript>2</Subscript>, O<Subscript>2</Subscript>, CO and C<Subscript>2</Subscript>H<Subscript>4</Subscript>on Pt-Ag/SiO<Subscript>2</Subscript>catalysts by microcalorimetry and FTIR

Adsorption microcalorimetry has been employed to study the interaction of ethylene with the reduced and oxidized Pt-Ag/SiO₂catalysts with different Ag contents to elucidate the modified effect of Ag towards the hydrocarbon processing on platinum catalysts. In addition, microcalorimetric adsorption of H₂, O₂, CO and FTIR of CO adsorption were conducted to investigate the influence of Ag on the surface structure of Pt catalyst. It is found from the microcalorimetric results of H₂and O₂adsorption that the addition of Ag to Pt/SiO₂leads to the enrichment of Ag on the catalyst surface which decreases the size of Pt surface ensembles of Pt-Ag/SiO₂catalysts. The microcalorimetry and FTIR of CO adsorption indicates that there still exist sites for linear and bridged CO adsorption on the surface of platinum catalysts simultaneously although Ag was incorporated into Pt/SiO₂. The ethylene microcalorimetric results show that the decrease of ensemble size of Pt surface sites suppresses the formation of dissociative species (ethylidyne) upon the chemisorption of C₂H₄on Pt-Ag/SiO₂. The differential heat vs. uptake plots for C₂H₄adsorption on the oxygen-preadsorbed Pt/SiO₂and Pt-Ag/SiO₂catalysts suggest that the incorporation of Ag to Pt/SiO₂could decrease the ability for the oxidation of C₂H₄.     

A review on nanomaterial-based electrochemical sensors for H<Subscript>2</Subscript>O<Subscript>2</Subscript>, H<Subscript>2</Subscript>S and NO inside cells or released by cells

The incorporation of nanomaterials into electrochemical sensors is an attractive approach towards the improvement of the sensitivity of amperometry and also can provide improved sensor selectivity and stability. This review (with 137 references) details the current state of the art and new trends in nanomaterial-based electrochemical sensing of hydrogen peroxide (H₂O₂), hydrogen sulfide (H₂S) and nitric oxide (NO) in cells or released by cells. The article starts with a discussion of the significance of the three analytes, and this is followed by three sections that summarize the electrochemical detection schemes for H₂O₂, H₂S and NO. Each section first summarizes the respective physiological roles, and then reviews electrochemical sensors based on the use of carbon nanomaterials, noble metal nanomaterials, metal oxide nanomaterials, and layered doubled hydroxides. The materials are compiled in three tables along with figures of merit for the various sensors.

Open image in new window

Graphical abstract Nanomaterial-based electrochemical sensors for Reactive oxygen species (H₂O₂), Reactive nitrogen species (NO) and Reactive hydrogen sulfide species (H₂S) inside cells or released by cells.

     

Application of spinel-structured MgFe<Subscript>2</Subscript>O<Subscript>4</Subscript> nanoparticles for simultaneous electrochemical determination diclofenac and morphine

The paper describes a sensitive method for simultaneous sensing of morphine (MOR) and diclofenac (DCF). The surface of a MgFe₂O₄/graphite paste electrode was modified with multi-walled carbon nanotubes, and the resulting sensor was characterized by cyclic voltammetry, differential pulse voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. The electrode showed an efficient synergistic effect in term of oxidation of DCF and MOR, with sharp oxidation peaks occurring at +0.370 and 0.540 V (vs Ag/AgCl) at pH 7.0. The calibration plot for MOR is linear in the 50 nM to 920 μM concentration range, and the detection limit is 10 nM (at a signal-to-noise ratio of 3). The respective data for DCF are 100 nM to 580 μM, with a 60 nM LOD. The sensor was applied to the determination of MOR and DCF in spiked serum and urine samples, with recoveries ranging between 91.4 and 100.7 %.

Open image in new window

Graphical abstract A sensitive method for simultaneous sensing of morphine (MOR) and diclofenac (DCF) is described. The surface of MgFe₂O₄/graphite paste electrode was modified with multi-walled carbon nanotubes, and the resulting sensor showed an efficient synergistic effect in terms of oxidation of DCF and MOR. The calibration plot for MOR is linear in the 50 nM to 920 μM concentration range, and the detection limit is 10 nM. The respective data for DCF are 100 nM to 580 μM, with a 60 nM LOD.

     

Preparation and electrochemical properties of V<Subscript>2</Subscript>O<Subscript>5</Subscript> submicron-belts synthesized by a sol–gel H<Subscript>2</Subscript>O<Subscript>2</Subscript> route

One-dimensional (1D) submicron-belts of V₂O₅ have been prepared by a sol–gel route using V₂O_5, H₂O₂ and aniline as starting materials. Thermogravimetric and differential thermal analysis, X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy were employed to characterize the samples. Electrochemical behaviors as cathode material in rechargeable lithium-ion batteries were investigated by galvanostatic charge–discharge measurement and cyclic voltammeter. The results showed that the synthesized V₂O₅ appeared to be submicron-belts and orthorhombic structure. The V₂O₅ submicron-belts exhibited a high initial discharge capacity of 346 mAh/g and stayed 240 mAh/g after 20 cycles at 0.1 C discharge rate in the potential region 1.8–4.0 V.     

Kinetic method for acetylsalicylic acid determination based on its inhibitory effect upon the catalytic decomposition of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

The catalytic reaction of catalase was investigated, by means of a Clark oxygen sensor, in the presence of various concentrations of acetylsalicylic acid. Michaelis-Menten kinetic parameters were determined from Lineweaver-Burk plots, obtained in the absence and in the presence of the inhibitor. The inhibition pattern, suggested by the Lineweave-Burk plots, corresponds to a fully mixed inhibition mechanism. A kinetic method, based on the indicator reaction: , was developed for the quantitative determination of acetylsalicylic acid. Calibration graphs of the reciprocal value of first-order rate constant versus acetylsalicylic concentration covered the concentration range (2.99–19.98)×10^–4 mol/L, while the detection limit was 4.12×10^–4 mol/L acetylsalicylic acid with a standard deviation of 2.1×10^–5 mol/L.     

X-ray photoelectron study of the interaction of H<Subscript>2</Subscript> and H<Subscript>2</Subscript>+O<Subscript>2</Subscript> mixtures on the Pt/MoO<Subscript>3</Subscript> model catalyst

The effects of H₂ and H₂ + O₂ gas mixtures of varying composition on the state of the surface of the Pt/MoO₃ model catalyst prepared by vacuum deposition of platinum on oxidized molybdenum foil were investigated by X-ray photoelectron spectroscopy (XPS) at room temperature and a pressure of 5–150 Torr. For samples with a large Pt/Mo ratio, the XP spectrum of large platinum particles showed that the effect of hydrogen-containing mixtures on the catalyst was accompanied by the reduction of molybdenum oxide. This effect results from the activation of molecular hydrogen due to the dissociation on platinum particles and subsequent spill-over of hydrogen atoms on the support. The effect was not observed at low platinum contents in the model catalyst (i.e., for small Pt particles). It is assumed for the catalyst that the loss of its hydrogen-activating ability is a consequence of the formation of platinum hydride. Possible participation of platinum hydride as intermediate in hydrogen oxidation to H₂O₂ is discussed.     

Model of the catalytic reaction 2H<Subscript>2</Subscript> + O<Subscript>2</Subscript> → H<Subscript>2</Subscript>O with the participation of molecules in a precursor state

The absence of experimental evidence for the occurrence of the catalytic reaction 2H₂ + O₂ → 2H₂O on platinum in accordance with the Langmuir-Hinshelwood mechanism was established. It was found that the heterogeneous process can be described more adequately and its nature can be better understood with consideration for chemical transformations involving molecules in a precursor state in a model of the above reaction. The inverse kinetic problem was solved. It was found that the model in which an unambiguously specified set of rate constants for the elementary steps of the reaction was used provided an opportunity to describe experimental data obtained by various authors concerning the oxidation of hydrogen on platinum over the detonating gas pressure range 10^?3-10⁵ Pa. The signs of the occurrence of heterogeneous reactions by an adsorption mechanism were found.     

H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript> anchored on graphene-grafted silica-coated MnFe<Subscript>2</Subscript>O<Subscript>4</Subscript> as magnetic catalyst for Mannich reaction

In this study, a three-component nanocomposite consisted of graphene, manganese ferrite and phosphotungstic acid (PTA) has been prepared. This composite, which is designated as Graphene/MnFe₂O₄@PTA, was synthesized through anchoring of PTA–imidazolium ionic liquid on magnetic graphene sheets. The structural and magnetic properties of the fabricated nanocomposite were studied by employing FT-IR, SEM, EDX, TEM, ICP, VSM, P-XRD and BET techniques. The synthesized magnetic nanocomposite was examined as an efficient and recyclable acidic catalyst for Mannich reaction under solvent-free conditions. The products of this reaction, which are an important class of potentially bioactive compounds, were obtained with good to excellent yields, and the catalyst could be readily recycled without any significant loss of its activity.     

The activation characteristics of the decomposition of H<Subscript>2</Subscript>O<Subscript>2</Subscript> on palladium-carbon catalysts

The kinetics of catalytic decomposition of H₂O₂ on palladium-carbon catalysts with various deposited metal distributions in carrier (active carbon) porous granules was studied. The activation parameters (E _a and A ₀) of the process were calculated by the Arrhenius equation. A determining factor for the catalytic process was found to be the entropy factor (A ₀), which characterized the formation and dissociation of activated transition complexes. A quantum-chemical study of the electronic structure of palladium-carbon catalysts showed the occurrence of electron density transfer from the carbon matrix to metal clusters and collectivization of their electronic systems. This increased the donor-acceptor ability of the synthesized materials and, as a consequence, their catalytic activity.     

Glass formation in the CaO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> and SrO-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> systems

A physicochemical study of glasses based on the MO-Bi₂O₃-B₂O₃ and SrO-Bi₂O₃-B₂O₃ systems was performed. Glass formation regions were found. The structural and optical properties, as well as the thermal behavior of the glasses, were studied.     

ZrO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> binary oxides as promising supports for palladium catalysts of hydrodechlorination

Deposited palladium catalysts of the hydrodechlorination of 1,3,5-trichlorobenzene were studied. Pure zirconium and aluminum oxides and ZrO₂-Al₂O₃ mixtures with 1, 5, and 10 mol % Al₂O₃ prepared by coprecipitation were used as supports. Palladium was deposited by the precipitation of its hydroxide on supports. Catalysts on binary supports (ZrO₂ + 1% Al₂O₃ and ZrO₂ + 5% Al₂O₃) exhibited higher activity and stability in hydrodechlorination compared with catalysts on pure supports. The suggestion was made that the high activity and stability of these systems in hydrodechlorination was related to the formation of binary oxide in the interaction of ZrO₂ with palladium oxide at the stage of annealing of the catalyst precursor. Binary oxide, which was a center of the activation of the C-Cl bond, was simultaneously a source of active hydrogen. The presence of various palladium states in catalysts was substantiated by the temperature programmed reduction method.     

Synthesis of nanocrystalline ZnO by the thermal decomposition of [Zn(H<Subscript>2</Subscript>O)(O<Subscript>2</Subscript>C<Subscript>5</Subscript>H<Subscript>7</Subscript>)<Subscript>2</Subscript>] in isoamyl alcohol

It was studied how the conditions of heat treatment of a [Zn(H₂O)(O₂C₅H₇)₂] solution in isoamyl alcohol at 120–140°C for 2–60 min affect the precursor decomposition mechanism and the characteristics of the obtained nanocrystalline zinc oxide. In all the cases, the product was a crystalline substance with the wurtzite structure and a size of crystallites of 14–18 nm, which was independent of the synthesis conditions. The thermal behavior and microstructure of the separated and dried nanostructured ZnO powder were investigated. It was determined how the duration and temperature of the heat treatment of the precursor solution affects the microstructure of ZnO coatings dip-coated onto glass substrates using dispersions produced at 120 and 140°C. The nanosized ZnO application procedure was shown to be promising for creating a gas-sensing layer of chemical gas sensors for detecting 1% H₂ (\(R_0 /R_{H_2 } \) was 58 ± 2 at an operating temperature of 300°C) and 4 ppm NO₂ (\(R_{NO_2 } /R_0\) were 15 ± 1 and 1.9 ± 0.1 at operating temperatures of 200 and 300°C, respectively).     

Catalytic decomposition of H<Subscript>2</Subscript>O<Subscript>2</Subscript> in hydrophilic solvents: The kinetic aspect

Decomposition of hydrogen peroxide in organic hydrophilic solvents, catalyzed by cobalt(II) palmitate [Co(palm)₂], was studied by the method of inhibitors.