Adsorption and diffusion behaviors of H2, H2S,NH3, CO and H2O gases molecules on MoO3 monolayer: A DFT study

Molybdenum trioxide (MoO₃) with α-phase is a promising material for gas sensing because of its high sensitivity, fast response and thermodynamic stability. To probe the mechanism of superior gas detection ability of MoO₃ monolayer, the adsorption and diffusion of H₂, H₂S, NH₃, CO and H₂O molecules on two-dimensional (2D) MoO₃ layer are studied via density functional theory (DFT) calculations. Based on calculated adsorption energies, density of states, charge transfer, diffusion barriers and diffusion coefficient, MoO₃ shows a superior sensitive and fast response to H₂ and H₂S than CO, NH₃, H₂O, which is consistent with experimental conclusions. Moreover, the response of MoO₃ to H₂S and H₂ will be obviously enhanced at high gas concentration, and the incorporation of H₂ and H₂S results in an obvious increasing in DOS near Fermi level. Our analysis provides a conceptual foundation for future design of MoO₃-based gas sensing materials.     

A hydrogen peroxide electrochemical sensor based on Ag nanoparticles grown on ITO substrate

In this article, the Ag nanoparticles were synthesized on indium tin oxide conducting glass (ITO) substrate using the electrochemical deposition method. The morphology analysis of the deposits using scanning electron microscope (SEM) reveals that the sizes and densities of the Ag nanoparticles were tuned by varying the time of electrodeposition. The structure of the deposits was characterized by X-ray diffraction (XRD). The prepared Ag nanoparticles electrode was then applied to detect hydrogen peroxide (H₂O₂) in 0.01 M pH 7.0 phosphate buffer medium. The present electrochemical sensing platform exhibited good electrocatalytic activity towards the reduction of H₂O₂. The detection sensitivity of the sensor was 0.237 mA mM⁻¹. This method is very simple, inexpensive, and undemanding, thus it should be extensively applied in many fields for the detection of H₂O₂.     

Coumarin-based Fluorescent Probes for H2S Detection

Although hydrogen sulfide (H₂S) has been known as a toxic gas with unpleasant rotten egg smell, the correlation between H₂S and physiological processes has attracted scientists to develop brand new methods to monitor such a gaseous molecule in vitro and in vivo. Herein, we described a couple of coumarin-based fluorescent probes (1a and 1b) that can be activated by reduction of azide to amine in the presence of H₂S. It should be emphasized that probe 1b demonstrated high selectivity and sensitivity for H₂S over other relevant reactive sulfur species in vitro, as well as identified exogenous H₂S in living cells.     

Cantilever enhanced photoacoustic spectrometry: Quantitative analysis of the trace H2S produced by SF6 decomposition

As one of the key characteristic components that result from sulfur hexafluoride (SF₆) decomposition in SF₆ gas-insulated equipment, hydrogen sulfide (H₂S) can reflect the severity of the internal insulation faults and indicate whether or not such faults involve solid insulation material effectively. The decomposition of SF₆ and its reaction with other impurities to form H₂S are simulated in this study via Materials Studio. The simulation verifies that H₂S is generated only when serious faults occur in the equipment; thus, the online monitoring of the trace H₂S is highly necessary. To achieve a high detection accuracy and avoid cross interference, the spectral line R (8) of the H₂S ν₁ + ν₂ + ν₃ co-frequency absorption band is taken as the absorption line for the gas detection by online simulation based on the HITRAN on the Web. In addition, this study develops a cantilever-enhanced photoacoustic spectrometry trace gas detection platform and conducts experimental research on the quantitative detection of trace H₂S/SF₆ and H₂S/N₂. Experimental results show that the detection sensitivity of the detection platform to trace H₂S under the background gas N₂ and SF₆ is 0.84 and 1.75 μL/L, respectively, and a strong linear relationship exists between the trace H₂S concentration and its corresponding PA signal. Moreover, based on both the theoretical simulation and experiment, the influence of temperature and pressure on the detection platform is discussed and analyzed. The results indicate that the change in the PA signal amplitude decreases with an increase in the pressure or temperature of the PA cell, and the detection platform is more sensitive to pressure.     

Spectroscopic studies of the corrosion of model iron electrodes in carbonate and phosphate buffer solutions

We have extended our unenhanced (non-SERS) Raman spectroscopic investigations to include a study of the corrosion of an iron electrode in carbonate and phosphate buffer solutions. The measurements have been supported by electrochemical investigations (via cyclic voltammetry), enabling oxidation and reduction reactions to be systematically followed at variable applied potentials. In a carbonate buffer (pH = 9.4) the surface oxidation led to the formation of a ‘green rust’ (a hydrated hydroxy-carbonate), followed by the α- and β-forms of FeOOH and an underlying magnetite layer formed on the cathodic (reduction) cycle. In a phosphate buffer (pH = 7.7) the surface was passivated by hydrated phosphates of iron [identified as FePO₄ · xH₂O and Fe₃(PO₄)₂·8H₂O]. The formation of oxides (Fe₂O₃ and Fe₃O₄) were inferred from voltammetry, but spectral identification was more difficult because of broad, ill-defined spectra. Despite the challenges of using unenhanced Raman spectroscopy, we believe that the effort was worthwhile, the reactions identified being more likely to be relevant to real electrochemical environments. Copyright © 2008 John Wiley & Sons, Ltd.     

Kinetic of Copper(III)/(II) Tetraglycine Reactions with Sulfite. Analytical Potentialities

Abstract

The oxidation of Cu(II)/tetraglycine complex in borate buffer (pH=9.2) in aqueous medium, by dissolved oxygen is strongly accelerated by S(IV). The reaction is adequate for S(IV) determination as the concentration of (Cu(H_-3G₄)]^? formed is proportional to SO₃2- concentration. The [Cu(H_-3G₄)]^? presents a maximum absorbance at 365 nm (? = 7400 mol^?1.L.cm^?1) and it was followed spectrophotometrically by flow injection analysis procedure. The detection limit was 7×10^?6 mol.L^?1 and the linear regression showed a standard deviation of 0.02% (n=5). Kinetics studies showed the catalytic effect of some transition metal ions, “which can be present in environmental samples, in the oxidation of S(IV). The pseudo-first-order rate constants were determined in the presence of formaldehyde.     

Synthesis and electrocatalytic activities of Co<Subscript>3</Subscript>O<Subscript>4</Subscript> nanocubes

In this article, a hydrothermal method was developed to synthesize Co₃O₄ nanocubes using hydrogen peroxide (H₂O₂) as oxidant, Co(NO₃)₂·6H₂O as a cobalt source. The products are characterized in detail by multiform techniques including X-ray diffraction (XRD), energy dispersive X-ray analysis (EDS), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results show that the obtained products are Co₃O₄ nanocubes with size ranging between 20 and 40 nm. The effects of the hydrogen peroxide concentration on the size of the products have been studied. The electrocatalytic activities of H₂O₂ reduction on Co₃O₄ nanocubes in phosphate buffer were also evaluated.     

Core–Shell Poly (Ionic Liquid)@Mesoporous Silica Chemiluminescent Nanoprobes for Sensitive Intracellular Hydrogen Peroxide Imaging

Despite significant developments in spatial distribution imaging of H₂O₂ as one the most important nonradical reactive oxygen species, novel background‐free, highly sensitive, and selective probes that allow intracellular sensing are still imperative. This is mainly because the fluorescent probes usually suffer some drawbacks such as, fluorescence bleaching and requirement of bulky light sources. In this study, the rational design and fabrication of a nonenzymatic nanoprobe (c‐PIL@mSiO₂) with dramatically improved sensitivity for chemiluminescent (CL) imaging of intracellular and in vivo H₂O₂ at nano molar level is presented. The limit of detection is lower than the endogenous H₂O₂ concentration, and is significantly better than that of some recently reported fluorescent and CL probes. Structurally, the nanoprobe is composed of a unique amphiphilic poly(ionic liquid) core for preserving H₂O₂ responsive reagents, and a mesoporous silica shell acts as an “exoskeleton” to provide hydrophilic nature. The multiple alternating hydrophobic and hydrophilic nanodomains of the poly(ionic liquid) core increase mass transfer dynamics, which increase the sensitivity of H₂O₂ imaging. RAW264.7 macrophages and mice models of inflammations experiment show that the c‐PIL@mSiO₂ is capable of imaging H₂O₂ intracellular and in vivo. This probe for the first time achieves CL detection of endogenous intracellular H₂O₂ without disruption of cells.     

The Influence of Phosphate on the Determination of Calcium by Flame Methods of Analysis—A New Approach

The depression of the analytical signal of calcium by phosphate ion when using turbulent (H₂/0₂ and H₂/A/entrained air) and laminar (C₂/H₂/air) flames in flame spectro-ietry is studied. Measurements of flame emission of calcium as a function of calcium to phosphate and pyrophosphate molar ratios for various flame heights in both turbulent and laminar flames are made. The phosphate interference when using turbulent flames is shown to be a result of a slow vaporization of the calcium phosphate particles. The phosphate interference when using laminar flames with chamber type aspirators is only important at high calcium and phosphate concentrations. The cause of the interference is probably a result of either slow vaporization of the calcium phosphate particles or a slow rate of change of the orthophosphate to pyrophosphate during the decomposition step.     

An Immunonanogold Resonance Scattering-Quenching Probe for Rapid and Sensitive Assay of Microalbumin

A novel and sensitive immunonanogold resonance scattering (RS) spectral probe was obtained for rapid detection of microalbumin (Malb), using 10 nm gold nanaoparticle to label goat anti-human Malb. It was based on that the gold-labeled anti-Malb took place nonspecific aggregation and exhibited a strong RS peak at 577 nm in pH 5.2 C₆H₈O₇–Na₂HPO₄ buffer solution containing polyethylene glycol (PEG), and the immunocomplex formed after specific reaction of gold-labeled anti-Malb with Malb, which led to a decrease in the intensity of RS peak at 577 nm considerably. The decreased RS intensity at 577 nm (ΔI _577nm) was linear to the concentration of Malb in the range of 4–128 ng/mL, with a detection limit of 3.2 ng/mL. The proposed method was applied to detect Malb in healthy human urine samples with satisfactory results.     

Multiplex CARS measurements in supersonic H2/air combustion

2 and O₂ multiplex coherent anti-stokes Raman spectroscopy (CARS) employing a single dye laser has been explored to simultaneously determine the temperature and concentrations of H₂ and O₂ in a hydrogen-fueled supersonic combustor. Systematic calibrations were performed through a well-characterized H₂/air premixed flat-flame burner. In particular, temperature measurement was accomplished using the intensity ratio of the H₂ S(5) and S(6) rotational lines, whereas extraction of the H₂ and O₂ concentrations was obtained from the H₂ S(6) and O₂ Q-branch, respectively. Details of the calibration procedure and data reduction are discussed. Quantification of the supersonic mixing and combustion characteristics applying the present technique has been demonstrated to be feasible. The associated detection limits as well as possible improvements are also identified. Received: 1 July 1997/Revised version: 29 September 1998     

Detection of acetylene by electronic resonance-enhanced coherent anti-Stokes Raman scattering

We report the detection of acetylene (C₂H₂) at low concentrations by electronic resonance-enhanced coherent anti-Stokes Raman scattering (ERE-CARS). Visible pump and Stokes beams are tuned into resonance with Q-branch transitions in the v₂ Raman band of acetylene. An ultraviolet probe beam is tuned into resonance with the – electronic transition of C₂H₂, resulting in significant electronic resonance enhancement of the CARS signal. The signal is found to increase significantly with rising pressure for the pressure range 0.1–8 bar at 300 K. Collisional narrowing of the spectra appears to be important at 2 bar and above. A detection limit of approximately 25 ppm at 300 K and 1 bar is achieved for our experimental conditions. The signal magnitudes and the shape of the C₂H₂ spectrum are essentially constant for UV probe wavelengths from 233.0 to 238.5 nm, thus indicating that significant resonant enhancement is achieved even without tuning the probe beam into resonance with a specific electronic resonance transition. PACS 42.65.Dr; 42.62.Fi; 42.65.-k     

Line strength and collisional broadening studies of hydrogen sulphide in the 1.58 μm region using diode laser spectroscopy

High resolution diode laser spectroscopy has been applied to the detection of hydrogen sulphide at ppm levels utilizing different transitions within the region of the ν ₁+ν ₂+ν ₃ and 2ν ₁+ν ₂ combination bands around 1.58 μm. Suitable lines in this spectral region have been identified, and absolute absorption cross sections have been determined through single-pass absorption spectroscopy and confirmed in the Doppler linewidth regime using cavity enhanced absorption spectroscopy (CEAS). The desire for a sensitive system potentially applicable to H₂S sensing at atmospheric pressure has led to an investigation on suitable transitions using wavelength modulation spectroscopy (WMS). The set-up sensitivity has been calculated as 1.73×10⁻⁸ cm⁻¹ s^1/2, and probing the strongest line at 1576.29 nm a minimum detectable concentration of 700 ppb under atmospheric conditions has been achieved. Furthermore, pressure broadening coefficients for a variety of buffer gasses have been measured and correlated to the intermolecular potentials governing the collision process; the H₂S–H₂S dimer well depth is estimated to be 7.06±0.09 kJ mol⁻¹.     

Fluorescent Detection of Phosphate in Aqueous Solution Based on Near Infrared Emission Ag<Subscript>2</Subscript>S QDs/Metal − Organic Shell Composite

A novel fluorescence method for sensitive and selective detection of phosphate was developed based on near infrared emission Ag₂S QDs/ Metal ? Organic Shell Composite via the deposition of metal-organic (zinc-nitrogen) coordination shell around Ag₂S QDs . Under optimal conditions described, the fluorescence intensity of the composite was decreased at 685 nm in the presence of phosphate, which was linearly related to the concentration of phosphate in the range of 0. 7 to 4.2 μM and 11.2 to 88.2 μM with the relative correlation coefficient of R² = 0.998 and 0.987 respectively and detection limit as low as 6 nM. In addition, the proposed method was successfully utilized in serum samples, tap water and Yangtze River water samples with the recoveries ranged from 94.76 to 100.86 %, which presaged more opportunities for application in related bioassay and water sample researches.     

Adsorption and electrochemistry of hemoglobin on Chi-carbon nanotubes composite film

This study describes the noncovalently functionalization of carbon nanotubes (CNTs) with natural biopolymer chitosan (Chi) as substrate for hemoglobin (Hb) immobilization. The noncovalently Chi-functionalized CNTs possessed an improved solubility in aqueous solution and was beneficial to form three-dimensional configuration of the CNTs film electrode. The adsorbed Hb in Chi-CNTs interface showed a pair of quasi-reversible redox peak with a formal potential of −0.34 V (vs. SCE) in 0.10 M pH 7.0 phosphate buffer solution and possessed good bioelectrochemical catalytic activities toward the reductions of H₂O₂.     

Determination of lead in Yellow River using ammonium molybdate as a molecular probe by resonance light scattering technique

A novel method for the determination of trace lead in Yellow River using ammonium molybdate (AM) as a molecular probe based on resonance light scattering (RLS) has been developed. In the presence of KHC₈H₄O₄-NaOH buffer solution, Pb²⁺ can react with AM to form an association, which results in the significant enhancement of RLS intensity and the appearance of the corresponding RLS characteristics. The enhanced RLS intensity is directly proportional to the concentration of Pb²⁺ in the range of 0.01-1.0 μg mL⁻¹. The detection limit can achieve 1.89 ng mL⁻¹. Moreover, the characteristics of RLS spectra of the complexes, the optimum conditions and the influencing factors have been investigated. The method has high selectivity and sensitivity, and was applied to the determination of Pb²⁺ in Yellow River with satisfactory results, which was in agreement with that of atomic absorbance spectrometry (AAS).     

硫酸羟胺及亚硝酸钠对高碳钢表面锌系磷化涂层的组织和摩擦性能的影响

研究了在锌系磷化液中添加环保型促进剂-硫酸羟胺与常规促进剂-亚硝酸钠以便在高碳钢表面形成锌系磷化涂层．用X射线衍射分析了磷化涂层的相结构的变化,结果发现,形成的磷化膜主要由Zn₃Fe(PO₄)₂·4H₂O(H膜)和Zn₂Fe(PO₄)₂·4H₂O(P膜)组 成．运用扫描电镜分析了磷化涂层的显微组织与磷化时间之间的变化规律．四球摩擦实验结果表明,与亚硝酸钠相比,在锌系磷化液中添加硫酸羟胺能有效降低润滑后的磷化涂层的摩擦系数．     

Rapid electrochemical determination of dissolved sulphur in liquid copper by solid-sulphide electrolytes

The application of solid-sulphide electrolyte sulphur sensing cells to measure directly dissolved sulphur in molten copper has been investigated using an immersion probe with the Cas-2wt% ZrS₂ solid solution electrolyte and the Mo+Mo₂S₃ two-phase mixture reference electrode. The emf measurements were carried out at 1473 K for the liquid copper with sulphur concentrations from 0.43 to 2.20 at %. Steady potentials were attained within ≈10 min after dipping the probe. The equilibrium partial pressures of sulphur in molten copper calculated from the observed emfs were in agreement with those from the H₂-H₂S gas equilibrium investigations.     

Adsorption of H2S at Stone–Wales defects of graphene-like BC3: a computational study

We employed density functional theory to characterise H₂S adsorption, and dissociation on the pristine and Stone–Wales (SW) defected BC₃ graphenes. H₂S is predicted to be weakly adsorbed on the pristine graphene with the adsorption energy of about 7.11 kcal/mol. Two types of SW defects were generated by rotating a C–C bond (SW-CC) or a B–C bond (SW-BC) by about 90°. We predict that, in contrast to SW-BC, dehydrogenation of H₂S is energetically more favourable on the SW-CC compared to the associative adsorption. It is also found that SW-CC formation is more favourable than the formation of SW-BC. Molecular adsorption of H₂S on both of the SW defected sheets is more favourable than that on the pristine sheet. The preferable adsorption process on the SW-BC and SW-CC defected graphene sheets is via associative and dissociative mechanisms, respectively. Furthermore, the highest occupied molecular orbital and lowest unoccupied molecular orbital energy gap of the SW-BC defected sheet is highly sensitive to the adsorption process which may be used for the detection of H₂S.     

Interaction mechanism among CO,H2S and CuO oxygen carrier in chemical looping combustion: A density functional theory calculation study

When using coal-derived syngas or coal as fuel in chemical looping combustion (CLC), CO as a representative pyrolysis/gasification product and H₂S as the main sulfurous gas coexist in fuel reactor. Either CO or H₂S can absorb on the surface of CuO (the active component of Cu-based oxygen carriers), and reactions will occur among them. In this study, density functional theory (DFT) calculations are conducted to investigate the interaction among H₂S, CO, and CuO, including: the reaction between CO and H₂S over CuO particle, the influence of CO on the H₂S dissociation and further reaction process, and the impact of H₂S dissociation products on CO oxidation. Firstly, the co-adsorption results suggest that H₂S might directly react with CO to produce COS via the Eley–Rideal mechanism, while CO prefers to react with HS* or S* via the Langmuir–Hinshelwood mechanism. This means that the reaction mechanisms between CO and H₂S will change as the H₂S dissociation proceeds, which has already been forecasted by the co-adsorption energies and verified by all of potential Eley–Rideal and Langmuir–Hinshelwood reaction pathways. Then, the influence of CO on the H₂S dissociation process is examined, and it is noted that the presence of CO greatly limits the dissociation of H₂S due to the increased energy barrier of the rate-determining dehydrogenation step. Furthermore, the impact of H₂S dissociation products on CO oxidation by CuO is also investigated. The presence of H₂S and S* significantly supresses the CO oxidation activity, while the presence of HS* slightly promotes the CO oxidation activity. Finally, the complete interaction mechanisms among H₂S, CO, and CuO are concluded. It should be noted that COS will be inevitably produced via the Langmuir–Hinshelwood reaction between surface S* and CO*, which is prior to H₂O generation and subsequent sulfidation reaction.