Pd gate MOS sensor for hydrogen detection

The performance of Pd gate MOS hydrogen sensor was studied using C–V and G–V characteristics. The device was fabricated on p-type <100> (1–6Ω cm.) silicon with thermal oxide layer of about 100 Å. The C–V and G–V responses of sensor were measured at different frequencies (1 kHz, 10 kHz, and 100 kHz) upon exposure to hydrogen (conc. 1–8%) at room temperature. It was observed that value of zero bias capacitance decreases with increase in frequency as well as hydrogen concentration. The inversion potential (V_inv.) and flat band voltage (V_FB) of the device approach higher values as frequency is reduced. Interface trap density (N_it) was also determined corresponding to the peak in the conductance curve, using a bias scan conductance method at fixed frequency. N_it was found to be decreasing with increasing concentrations of hydrogen. The sensor showed better sensitivity at lower frequency.     

Hydrogen atom yield in RF and microwave hydrogen discharges

The hydrogen atom yield in pure-H₂ RF and microwave-sustained discharges is investigated both theoretically and experimentally. A particle balance model is developed that provides the concentrations of the H, H₂, H⁺, H ₂ ⁺ , and H ₃ ⁺ species. It is also shown that an approximate solution of this model is adequate for calculating the concentration of H atoms (required, for instance, in diamond film deposition) in the 0.1–10 torr range. Next, the validity of the actinometry technique applied to the determination of the H-atom density in pure-H₂ discharges is examined. Using this diagnostic, it is observed that the H-atom concentration decreases when the vessel wall temperature increases, owing to the increased efficiency of atomic hydrogen recombination on the wall. To overcome this effect, the discharge tube wall is cooled off with dimethyl polysiloxane, a low-loss dielectric liquid. It improves significantly the H-atom concentration at 2450 MHz provided the pressure is typically below a few torr and the power density is not too high.     

SAW hydrogen gas sensor based on WO3 and Pd nanostructures

Bi-layer nanostructures of WO₃ (～100 nm and 150 nm) with a very thin film of palladium (Pd～10 nm) on the top, have been studied for hydrogen gas-sensing application at ～700C and medium hydrogen concentrations (1 – 4%) in air. The structures were obtained by vacuum deposition (first the WO₃ and then the Pd film) onto a LiNbO₃ Y- cut Z-propagating substrate and were tested by means of Surface Acoustic Wave method in a three channel delay line configuration. Very repeatable results have been observed for these two nanostructures with changes in frequency on the level of 500 to 1800 Hz for hydrogen concentration from 1 to 4 % in air. The absolute response value depends on the WO₃ film thickness and hydrogen gas concentration and is greater for the nanostructure with a thicker WO₃ film.     

Influence of atmospheric oxygen on hydrogen detection on Pd using Kelvin probe technique

Influence of oxygen concentration in the measurement atmosphere on detection of hydrogen using Kelvin probe was studied. The studied material was a 100-μm-thick palladium foil, which was mounted in a 3D printed electrochemical flow cell. The used setup enables hydrogen loading with in-situ contact potential measurement of the hydrogen exit side of the Pd electrode. The hydrogen loading and unloading procedure, including insertion of different amounts of hydrogen into the Pd membrane and recording resulting values of contact potential difference, was performed at distinct oxygen concentrations ranging between 1 and 80 vol%. An increasing amount of oxygen in the atmosphere surrounding the hydrogen-loaded Pd electrode resulted in an accelerated removal of hydrogen from the Pd. The kinetics of this reaction was studied based on Kelvin probe measurements, and a reaction mechanism is discussed.     

Effect of oxygen addition on the hydrogen production from ethanol steam reforming in a Pd–Ag membrane reactor

In this communication, a porous stainless steel (PSS) tube was electrolessly plated into Pd–Ag membrane reactor which was used for separating hydrogen produced in an ethanol steam reforming reaction with the addition of oxygen, which has not been reported before. Palladium and silver were deposited on porous stainless steel tube via the sequential electroless plating procedure with an overall film thickness of 20 μm and Pd/Ag weight ratio of 78/22. Ethanol–water mixture (n_water/n_ethanol = 1 or 3) and oxygen (n_oxygen/n_ethanol = 0.2 or 0.7) were fed concurrently into the membrane reactor packed with MDC-3. The reaction temperatures were set at 593–723 K and the pressures 3–10 atm. The effect of oxygen addition plays a vital role on the ethanol steam reforming reaction, especially for the Pd–Ag membrane reactor in which a higher flux of hydrogen is required. If oxygen in the feed is not sufficient, it would be possible that steam reforming reaction prevails. Inversely, high O₂ addition will shift the reaction scenario to be partial oxidation dominating, and selectivity of CO₂ increases with increasing oxygen feed. At high pressure, autothermal reaction of ethanol would be easily reached.     

Pd-gate MOS sensor for detection of methanol and propanol

The present paper focused on the detection of methanol and propanol using Pd-gate metal-oxide-semiconductor (MOS) sensor. Surface mor- phology and composition of the gate film were studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The response of the sensor for propanol and methanol was measured as shift in capacitance-voltage (C-V) and conductance-voltage (G-V) curves of the MOS structure. The sensitivity of the sensor towards methanol was found to be greater than that towards propanol. It was 58.2% for methanol and 32% for propanol (at 0.6 V, 1 MHz) in terms of capacitance measurements, while in terms of conductance results the sensitivity was found to be 57.2% for methanol and 38.9% for propanol at 1 kHz. The discontinuities or cracks present in the microstructure of the gate material are believed to be mainly responsible for the high sensitivity of the sensor, going with the decomposition of gas molecules and subsequent hydrogen permeation through Pd.     

Water formation on Pd(111) by reaction of oxygen with atomic and molecular hydrogen

In this work we have studied the steady-state reaction of molecular and atomic hydrogen with oxygen on a Pd(111) surface at a low total pressure (<10(-7) mbar) and at sample temperatures ranging from 100 to 1100 K. Characteristic features of the water formation rate Phi(pH2; pO2; TPd) are presented and discussed, including effects that are due to the use of gas-phase atomic hydrogen for exposure. Optimum impingement ratios (OIR) for hydrogen and oxygen for water formation and their dependence on the sample temperature have been determined. The occurring shift in the OIR could be ascribed to the temperature dependence of the sticking coefficients for hydrogen (SH2) and oxygen (SO2) on Pd(111). Using gas-phase atomic hydrogen for water formation leads to an increase of the OIR, suggesting that hydrogen abstraction via hot-atom reactions competes with H2O formation. The velocity distributions of the desorbing water molecules formed on the Pd(111) surface have been measured by time-of-flight spectroscopy under various conditions, using either gas-phase H atoms or molecular H2 as reactants. In all cases, the desorbing water flux could be represented by a Maxwellian distribution corresponding to the surface temperature, thus giving direct evidence for a Langmuir-Hinshelwood mechanism for water formation on Pd(111).     

Reactions of hydrogen peroxide vapor dissociated in a microwave plasma

Analysis of the plasma emission from a low-pressure microwave cavity discharge through flowing hydrogen peroxide vapor showed that both H and OH were produced in proportions which varied with the applied power. When the dissociated vapor was condensed at 195 K only water was obtained; at 77 K, H₂O₂ and H₂O₄ were also obtained. Their formation could not be increased by increasing the H atom or OH radical concentration in the plasma. When the reaction time of the dissociated vapor between the plasma exit and the cold surface was increased, the rate of H₂O₂ formation increased mostly at the expense of water formation. It appears that, as in the case of the reaction of H with O₂, the rate of H₂O₂ formation is dependent on the concentration of O₂ produced in the spatial afterglow by the gas-phase reactions of the hydroxyl radicals.     

Characteristics of Pd/Nafion oxygen sensor modified with polypyrrole by chemical vapor deposition

In this study, Pd/Nafion electrodes were prepared by impregnation-reduction methods in sensing oxygen. To prolong the electrode's life in practical use, a polypyrrole (PPy) film was chemically deposited onto the Pd/Nafion electrode. The sensitivities of PPy-modified Pd/Nafion electrodes are 0.00671 and 0.0117 μA/ppm obtained in O₂ concentration regions of 0–5000 and 5000–50,000 ppm, respectively. Generally, the response time and the recovery time decreases and increases significantly with increasing O₂ concentrations. After continuous aging tests for 48 h, the sensitivities of the Pd/Nafion and the PPy-modified Pd/Nafion electrodes decrease by 97% and 53%, respectively. Electronic Publication     

Promotional effect of nitrogen-doped and pore structure for the direct synthesis of hydrogen peroxide from hydrogen and oxygen by Pd/C catalyst at ambient pressure

Nitrogen-doped porous carbon is potential support for directly synthesizing H₂O₂ from H₂ and O₂. Here, density functional theory (DFT) was used to study the effect of N-doped porous carbon on H₂O₂ directly synthesized. The theoretical calculation results showed that N-doped improved H₂O₂ productivity and H₂ conversion by increasing the dispersion of Pd nanoparticles and the Pd⁰/Pd²⁺ ratio. However, N-doped decreased H₂O₂ selectivity by reducing oxygen's dissociation energies. The experimental results showed that adjusting the pore structure of N-doped porous carbon could improve the adverse effects of N-doping for H₂O₂ selectivity. The H₂O₂ productivity and selectivity of Pd/C catalyst with a macropore-mesoporous-microporous hierarchical porous structure were up to 328.4 mol_H2O2·kg_cat^-1·h^?1 and 71.9 %, respectively, at ambient pressure. The macropore structure enhances the transfer and diffusion performance of the catalyst and effectively inhibits the effect of N-doping on OO bond dissociation, which improves H₂O₂ productivity and selectivity. This research provides a possible solution for designing a high-performance Pd/C catalyst to directly synthesize H₂O₂ from H₂ and O₂ at ambient pressure.     

载体性质对Pd催化剂加氢脱硫性能的影响

以Si O2、全硅MCM-41(Si-MCM-41)、通过机械混合Si-MCM-41与ZSM-5得到的Z-MCM-41-M以及通过在ZSM-5外部包覆MCM-41制备得到的Z-MCM-41四种材料为载体,制备了四种负载型Pd催化剂。采用XRD、HRTEM、N2吸附-脱附、NH3-TPD手段对Pd催化剂进行了表征;以二苯并噻吩(DBT)为模型化合物,在固定床反应器上对四种催化剂的加氢脱硫(HDS)活性、加氢路径选择性和加氢裂化活性进行了考察,研究了不同类型载体对Pd催化剂加氢脱硫性能的影响。结果表明,载体的性质会显著影响负载型Pd催化剂的加氢脱硫性能。载体的比表面积对负载型Pd催化剂加氢脱硫活性影响不大,但是HYD路径的选择性与载体的孔道结构有关;具有介孔孔道结构有利于加氢路径选择性的提高。酸性载体负载的Pd催化剂表现出较好加氢脱硫活性和加氢选择性,这与氢溢流有关。介孔材料的孔道结构与微孔沸石的酸性有机结合,所得到的Z-M CM-41复合材料是是潜在的贵金属Pd加氢脱硫催化剂优良载体,可有效提升其加氢脱硫活性。     

Stability of polycarbonate and polystyrene surfaces after hydrophilization with high intensity oxygen RF plasma

A general drawback observed with plasma treatment is the limited stability of the hydrophilic-treated surfaces toward washing, storage, or heating. It has recently been found that oxygen, air, or argon radiofrequency plasmas with higher intensities than normally used can give hydrophilic surfaces having good wash stability. High intensity oxygen plasma treatment of polystyrene and polycarbonate surfaces was therefore carried out using two different capacitively coupled RF reactors with internal shelf electrodes. The obtained surface characteristics and stability were evaluated using contact angle measurements, XPS, AFM, and nanoindentation. For both materials, low water contact angles were found to correlate with high surface oxygen content. Only the surfaces exposed to relatively intense treatments, with self-bias voltages above 140 V (polystyrene) or 240 V (polycarbonate), could withstand washing in ethanol and remain highly hydrophilic. Substantial amounts of nonsoluble material were observed on the plastic substrates after treatment. Furthermore, for polycarbonate Young's modulus of the surface was found to increase with increasing intensity of the plasma. These observations were taken as an indication that extensive cross-linking of the surface layer took place. After more than 6 months of storage, the samples treated with the most intense plasmas (self-bias voltages in the range of 480-600 V) still had water contact angles around 20 degrees .     

Temporally resolved laser diagnostic measurements of atomic hydrogen concentrations in RF plasma discharges

Ground-state atomic hydrogen produced in radio-frequency plasma discharges (20 KHz-5 MHz) has been detectedin situ using two-photon absorption laser-induced fluorescence (TALIF). Atomic ground-state concentration measurements have demonstrated excellent spatial resolution in the interelectrode gap of a planar discharge configuration with 10 nsec temporal resolution at all phases of the RF driving voltage waveform. Concentrations were measured in gas mixtures of helium and hydrogen down to 2×10¹³ H atoms/cm³.     

Influence of oxygen plasma treatment on hydrogen chloride removal of activated carbon fibers

The oxygen plasma treatment of activated carbon fibers (ACFs) was carried out to introduce oxygen-containing groups onto carbon surfaces. Surface properties of the ACFs were determined by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). N2/77 K adsorption isotherms were investigated by BET and D-R plot methods to characterize specific surface area, pore volume, and pore size distribution. The efficiency of hydrochloride removal was confirmed by two kinds of methods; one is detecting tubes (range: 1-40 ppm), and the other is a gas chromatography technique. As experimental results, the hydrochloride removal efficiency of the ACFs was increased with the number of plasma treatment times up to around 300%, resulting from newly formed oxygen-containing functional groups (especially phenolic and carboxylic) on carbon surfaces, in the decreased specific surface areas or pore volumes. These results indicate that the plasma treatment leads to the increase of hydrochloride removal due to the improvement of surface functional groups containing oxygen on the carbon surfaces.     

The electromagnetic performance of a surfatron-based coaxial microwave plasma torch

Low power microwave plasma torches are of particular interest to analytical chemists. The torch design investigated herein, called TPS, is based on the known surfatron structure to which a coaxial section is added consisting of an impedance transformer followed by the metallic nozzle at the tip of which the discharge occurs. A series of experiments illustrate the main electromagnetic features and performance of this novel coaxial microwave plasma torch operating at 2.45 GHz and with input power in the range 10–180 W. A specially devised slotted coaxial line with a movable probe arrangement can be inserted into the torch in place of the transformer section to provide in situ measurements of the plasma impedance. Analyzing these results, we show that the shape of the torch tuning characteristics can be controlled to improve the power transfer to the plasma and stability of operation with respect to changes in discharge conditions; under these conditions, the design of the device can be simplified. The procedures presented have a general character and can be applied to various torch configurations.     

An ESCA investigation of the inductively coupled RF plasma polymerization of fluoronaphthalene and fluoronaphthalene/hydrogen mixtures

1-Fluoronaphthalene was plasma polymerized and its composition and structure, as a function of position, power, and temperature, were examined by ESCA. The F:C ratio of the deposited film was lower than that of the starting monomer both at room temperature and at 150°C. An asymmetry of the main C_1s photoionization peak was noted. Plasmas were also excited in fluoronaphthalene/hydrogen mixtures where extensive fluorine elimination and hydrogen incorporation occurred. This gave direct evidence that the height of step function or asymmetry of the main C_1s peak is related to the degree of saturation in the compound.     

A magnetically excited microwave plasma source for atomic emission spectroscopy with performance approaching that of the inductively coupled plasma

A novel magnetically excited microwave plasma emission source was developed and tested. Unlike previous microwave plasma sources which couple energy from the microwave electric field, this source couples energy from the magnetic field. The resultant plasma shape allows easy entrainment of wet sample aerosol, such as is produced by a conventional inductively coupled plasma (ICP) nebulizer and spray chamber, into the core of the plasma. Plasma support gas can be either nitrogen or air although better sensitivity is achieved using nitrogen. Good stability of operation was observed for both aqueous and organic solvents over a wide range of sample flows. The measured performance when used as a spectroscopic source in conjunction with an echelle polychromator showed detection limits approaching those of commercial ICP sources.     

Characterization of an argon-hydrogen microwave discharge used as an atomic hydrogen source. Effect of hydrogen dilution on the atomic hydrogen production

This work is devoted to the study of an argon-hydrogen microwave plasma used as an atomic hydrogen source. Our attention has focused on the effect of the hydrogen dilution in argon on atomic hydrogen production. Diagnostics are performed either in the discharge or in the post-discharge using emission spectroscopy (actinometry) and mass spectrometry. The agreement between actinometry and mass spectrometry diagnostics proves that actinometry on the Ha(656.3 nm) and Hβ(486.1 nm) hydrogen Balmer lines can be used to measure the relative atomic hydrogen density within the microwave discharge. Results show that the atomic hydrogen density is maximum for a gas mixture corresponding to the partial pressure ratioP _{H 2}/P _Ar range between 1.5 and 2. The variation of atomic hydrogen density can be explained by a change of the dominant reactive mechanisms. At a low hydrogen partial pressure the dominant processes are the charge transfers with recombinations between Ar⁺ and H₂ which lead to ArH⁺ and H ₂ ⁺ ion formation. Both ions are dissociated in dissociative electron attachment processes. At a low argon partial pressure the electron temperature and the electron density decrease with increasing partial pressure ratio. The dominant mechanisms become direct reactions between charged particles (e, H⁺, H ₂ ⁺ , and H ₃ ⁺ ) or excited species H(n=2) with H₂ producing H atoms.     

Cu triggered fluorescence sensor based on fluorescein derivative for Pd detection

This Letter describes the synthesis of a novel fluorescein-based derivative used as the fluorescence sensor for Pd²⁺ detection. The sensor can show highly selective and sensitive ‘off-on’ fluorescence response only in the presence of Cu²⁺ as a synergic trigger, which presents a new strategy for Pd²⁺ detection method.     

Effect of reduction method on the performance of Pd catalysts supported on activated carbon for the selective oxidation of glucose

The effect of the reduction method on the catalytic properties of palladium catalysts supported on activated carbon for the oxidation of D-glucose was examined. The reduction methods investigated include argon glow discharge plasma reduction at room temperature, reduction by flowing hydrogen at elevated temperature, and reduction by formaldehyde at room temperature. The plasma-reduced catalyst shows the smallest metal particles with a narrow size distribution that leads to a much higher activity. The catalyst characteristics show that the plasma reduction increases the amount of oxygen-containing functional groups, which significantly enhances the hydrophilic property of the activated carbon and improves the dispersion of the metal.