Facial fabrication of an inorganic/organic thermoelectric nanocomposite based gas sensor for hydrogen detection with wide range and reliability

A novel method for fabrication of a thermochemical hydrogen (TCH) gas sensor composed of platinum (Pt)-decorated graphene sheets and a thermoelectric (TE) polymer nanocomposite was investigated. The hydrogen sensing characterization for the device included gas response, response time (T₉₀), recovery time (D₁₀), and reliability testing, which were systematically conducted at room temperature with a relative humidity of 55%. Here, the Pt-decorated graphene sheets act as both an effective hydrogen oxidation surface and a heat-transfer TE polymer nanocomposite having low thermal conductivity. This property plays an important role in generating output voltage signal with a temperature difference between the top and bottom surfaces of the nanocomposite. As a result, our TCH gas sensor can detect the range of hydrogen from 100 ppm to percentage level with good linearity. The best response and recovery time revealed for the optimized TCH gas sensor were 23 s and 17 s under 1000 ppm H₂/air, respectively. This type of sensor can provide an important component for fabricating thermoelectric-based gas sensors with favorable gas sensing performance.     

Characteristics of resistivity-type hydrogen sensing based on palladium-graphene nanocomposites

We describe the characteristics of resistivity-type hydrogen (H₂) sensors made of palladium (Pd)-graphene nanocomposites. The Pd-graphene composite was synthesized by a simple chemical route capable of large production. Synthesis of Pd nanoparticles (PdNPs) of various sizes decorated on graphene flakes were easily controlled by varying the concentration of Pd precursors. Resistivity H₂ sensors were fabricated from these Pd-graphene composites and evaluated with various concentrations of H₂ and interfering gases at different temperatures. Characteristics for sensitivity, selectivity, response time and operating life were studied. The results from testing the Pd-graphene indicated a potential for hydrogen sensing materials at low temperature with good sensitivity and selectivity. Specifically H₂ was measurable with concentrations ranging from 1 to 1000 ppm in laboratory air, with a very low detection limit of 0.2 ppm. The response of the sensors is almost linear. The resistivity of sensors changed approximately 7% in its resistance with 1000 ppm H₂ even at room temperature. The robust mechanical properties of graphene, which supported these PdNPs, exhibit structural stability and durability in H₂ sensors for at least six months. Moreover, the advantages in this work are experimental reproducibility in synthesis Pd-graphene composite and sensor fabrication process.     

Ultra-sensitive hydrogen gas sensors based on Pd-decorated tin dioxide nanostructures: Room temperature operating sensors

We have investigated the fabrication of hydrogen gas sensors based on networks of Pd nanoparticles (NPs) deposited tin dioxide nanowires (NWs). SnO₂ NWs with tin NPs attached on the surface were obtained by a simple thermal evaporation of SnO crystalline powders. The tin dioxide NWs were decorated with Pd NPs by the reduction process in Pd ion solution. The sensors showed ultra-high sensitivity (∼1.2 × 10⁵%) and fast response time (∼2 s) upon exposure to 10,000 ppm H₂ at room temperature. These sensors were also found to enable a significant electrical conductance modulation upon exposure to extremely low concentrations (40 ppm) of H₂ in the air. Our fabrication method of sensors combining with Pd NPs, Sn NPs and n-type semiconducting SnO₂ NWs allows optimized catalytic and depletion effect and results the production of highly-sensitive H₂ sensors that exhibit a broad dynamic detection range, fast response times, and an ultra-low detection limit.     

Hydrogen sensor using the Pd film supported on anodic aluminum oxide

Highly sensitive hydrogen gas sensors were fabricated using a microelectromechanical system (MEMS) and anodic aluminum oxides (AAOs) process. MEMS based gas sensor platform was designed with the multi-layer type for Pd film morphology manipulations. The operating temperature of the micro heater was positively correlated with the heater. Hydrogen sensing response of the sensor showed a good positive linearity as the gas sensitivity increased with increasing hydrogen concentration. The hydrogen sensitivity (defined as ratio of sensor resistances in air and after the hydrogen gas injection) was 0.638% at hydrogen concentration of 2000 ppm. The H₂ sensitivity was very dependent on the thickness and morphology of Pd-nanosized film. The gas sensitivity and response properties showed different behaviors when palladium film was deposited on the anodic aluminum oxide (AAO) layer. The hydrogen sensitivity for the Pd on AAO layer was about 0.783% at the hydrogen concentration of 2000 ppm. The sensitivity of the Pd-AAO layer improved with respect to the pure Pd thin film due to nanoporous nature of AAO.     

Hydrogen gas sensing based on polyaniline/anatase titania nanocomposite

Polyaniline (emeraldine)/anatase TiO₂ nanocomposite (PA-NC) was prepared by a chemical oxidative polymerization. The thin films of PA-NC for hydrogen gas sensing application were deposited on Cu-interdigited electrodes by spin coating technique. A study on characteristics of PA-NC thin films was demonstrated by a porous cylindrical morphology. The response and response/recovery time of sensors for hydrogen gas were evaluated by the change of TiO₂ wt% at environmental conditions. Resistance-sensing measurement was exhibited a high sensitivity about 1.63, a good Long-term response, low response time and recovery time about 83 s and 130 s, respectively, at 0.8 vol% hydrogen gas for PA-NC including 25% wt of anatase nanoparticles. The current–voltage characteristics of PA-NC gas sensors before and after hydrogen gas injection showed a nonlinear ohmic current. Moreover, we studied the formation of PA-NCs and their hydrogen gas sensing mechanism based on contact regions in PA-NC.     

On a transistor-type hydrogen gas sensor prepared by an electrophoretic deposition (EPD) approach

A Pd/GaN/AlGaN heterostructure field-effect transistor (HFET)-type hydrogen gas sensor, based on an electrophoretic deposition (EPD) approach, is fabricated and studied. Due to the formation of good Schottky gate contact by an EPD approach, the studied HFET shows improved DC performance including the suppressed gate current and better thermal stabilities on current–voltage (I–V) characteristics. This is mainly attributed to the reduction of interface trap density and improved Pd morphology. The EPD-based Pd morphologies are examined by X-ray diffraction, energy dispersive spectroscopy, Auger electron spectroscopy, scanning electron microscopy, and atomic force microscopy. For the used gate-dimension of 1 μm × 100 μm, an EPD-based HFET shows low gate current of 2.9 nA, maximum drain saturation current of 490 mA/mm, and maximum extrinsic transconductance of 78.9 mS/mm at room temperature. Also, solid thermal stabilities on maximum drain saturation current (−0.46 mA/mm K) and maximum extrinsic transconductance (−0.08 mS/mm K) are found as the temperature is increased from 300 to 600 K. For hydrogen gas sensing application, at 370 K, the maximum hydrogen sensitivity of 600.1 μA/mm ppm H₂/air under a 5 ppm H₂/air ambiance and fast response time (30 s) and recovery time (47 s) under a 10,000 ppm H₂/air ambiance are obtained. The EPD approach also demonstrates advantages of low cost, simple apparatus, easy process, little restriction on the shaped substrate, composited deposition, and adjustable alloy grain size. Therefore, the proposed EPD approach gives the promise for fabricating high-performance HFET devices and hydrogen gas sensors.     

Hydrogen and electricity co-production plant integrating steam-iron process and chemical looping combustion

In this paper, steam-iron process (Fe looping) and NiO-based chemical looping combustion (Ni looping) are integrated for hydrogen production with inherent separation of CO₂. An integrated combined cycle based on the Fe and Ni loopings is proposed and modeled using Aspen Plus software. The simulation results show that at Fe-SR 815 °C, Fe-FR 815 °C, Ni-FR 900 °C and Ni-AR 1050 °C without supplementary firing, the co-production plant has a net power efficiency 14.12%, hydrogen efficiency 33.61% and an equivalent efficiency 57.95% without CO₂ emission. At a supplementary firing temperature of 1350 °C, the net power efficiency, hydrogen efficiency and the equivalent efficiency are 27.47%, 23.39% and 70.75%, respectively; the CO₂ emission is 365.36 g/kWh. The plant is attractive because of high-energy conversion efficiency and relatively low CO₂ emission; moreover, the hydrogen/electricity ratio can be varied in response to demand. The influences of iron oxide recycle rate, supplementary firing temperature, inert support addition and other parameters on the system performance are also investigated in the sensitive analyses.     

Pd–WO3/reduced graphene oxide hierarchical nanostructures as efficient hydrogen gas sensors

Pd–WO₃ nanostructures were incorporated on graphene oxide (GO) and partially reduced graphene oxide (PRGO) sheets using a controlled hydrothermal process to fabricate effective hydrogen gas sensors. Pd–WO₃ nanostructures showed ribbon-like morphologies and Pd–WO₃/GO presented an irregular nanostructured form, while Pd–WO₃/PRGO exhibited a hierarchical nanostructure with a high surface area. Gas sensing properties of thin films of these materials were studied for different hydrogen concentrations (from 20 to 10,000 ppm) at various temperatures (from room temperature to 250 °C). Although adding GO in the Pd–WO₃, after hydrothermal process could increase the film conductivity, gas sensitivity was reduced to half, due to lower surface area of the irregular morphology in comparison with the ribbon-like morphology. The Pd–WO₃/PRGO films showed an optimum sensitivity (∼10 folds better than the sensitivity of Pd–WO₃/GO), and a fast response and recovery time (<1 min) at low temperature of 100 °C. Moreover, the Pd–WO₃/PRGO-based gas sensor was sensitive to 20 ppm concentration of hydrogen gas at room temperature. The results confirmed the effect of residual oxygen-containing functional groups of PRGO on the growth and morphology of Pd–WO₃ as well as gas sensing properties of metal oxide/graphene based hybrid nanostructures.     

VO2 nanostructures based chemiresistors for low power energy consumption hydrogen sensing

Mott-type VO₂ oxide nanobelts are demonstrated to be effective hydrogen gas sensors at room temperature. These nanobelts, synthesized by hydrothermal process and exhibiting the VO₂ (A) crystallographic phase, display room temperature H₂ sensitivity as low as 0.17 ppm. The nanobelts (ultralong belt-like) nanostructures could be an ideal system for fully understanding dimensionally confined transport phenomena in functional oxides and for building functional devices based on individual nanobelts.     

Robust hydrogen detection system with a thermoelectric hydrogen sensor for hydrogen station application

A prototype hydrogen detection system using the micro-thermoelectric hydrogen sensor (micro-THS) was developed for the safety of hydrogen infrastructure systems, such as hydrogen stations. We have designed a detection part with a pressure proof enclosure adoptable for the international standard of Exd II CT3, and carried out an explosion strength test, explosion and fire hazard tests, and an impact test. The hydrogen sensing performance of the detection part of this prototype system showed a good linear relationship between the sensing signal and hydrogen concentrations in air, for a wide range of hydrogen concentrations from 10 ppm to 40,000 ppm (4 vol.%). This prototype detection system was installed in the outdoor field of the hydrogen station and the response for H₂ gas in air of 100 ppm, 1000 ppm, and 10000 ppm was tested monthly for 1 year.     

Comprehensive investigation on planar type of Pd–GaN hydrogen sensors

This paper reviews both static and dynamic characteristics of a planar-type Pd–GaN metal–semiconductor–metal (MSM) hydrogen sensor. The sensing mechanism of a metal–semiconductor (MS) hydrogen sensor was firstly reviewed to realize the sensing mechanism of the proposed sensor. Symmetrically bi-directional current–voltage characteristics associated with our sensor were indicative of easily integrating with other electrical/optical devices. In addition to the sensing current, the sensing voltage was also used as detecting signals in this work. With regard to sensing currents (sensing voltages), the proposed sensor was biased at a constant voltage (current) in a wide range of hydrogen concentration from 2.13 to 10,100 ppm H₂/N₂. Experimental results reveal that the proposed sensor exhibits effective barrier height variations (sensing responses) of 134 (173) and 20 mV (1) at 10,100 and 2.13 ppm H₂/N₂, respectively. A sensing voltage variation as large as 18 V was obtained at 10,100 ppm H₂/N₂, which is the highest value ever reported. If an accepted sensing voltage variation is larger than 3 (5) V, the detecting limit is 49.1 (98.9) ppm. Moreover, voltage transient response and current transient response to various hydrogen-containing gases were experimentally studied. The new finding is that the former response time is shorter than the latter one. Other dynamic measurements by switching voltage polarity and/or continuously changing hydrogen concentration were addressed, showing the proposed sensor is a good candidate for commonly used MS sensors.     

Combustion characteristics of mixture of anode off gas and LNG in reformer

Fuel processing system which converts hydrocarbon fuel into hydrogen rich gas (by stream reforming, partial oxidation, auto-thermal reforming) needs high temperature environment (600-1000 °C). Generally, anode off gas or mixture of anode off gas and LNG are used as input gas for a fuel reformer. In order to constitute efficient and low emission burner system for fuel reformer, it is necessary to elucidate the combustion and emission characteristics of fuel reformer burner. In this study, lean flat flame using the ceramic porous burner was analyzed numerically and experimentally. Burning velocity of anode off gas calculated by CHEMKIN simulation was 51.8 cm, which was faster than that of LNG having 40.63 cm/s at the stoichiometric ratio because of high composition of hydrogen in anode off gas. As composition of LNG in mixture of anode off gas + LNG is increased, the burning velocity decreases and in the other hand the adiabatic temperature increases. CO, NO_x were measured below 50 ppm in operating load range of the reformer. Blue flame pattern was found as stable flame region for design of fuel reformer and anode off gas flame was maintained in blue flame pattern at equivalence ratio 0.55-0.62 under 1-5 kW power range.     

Hydrogen production from carbon dioxide reforming of methane over Ni-Co/MgO-ZrO2 catalyst: Process optimization

Greenhouse gases, carbon dioxide and methane are utilized in the production of hydrogen through carbon dioxide reforming of methane catalyzed by Ni-Co/MgO-ZrO₂ catalyst. Design of Experiments (DOE) was used to study the effects of process variables such as, carbon dioxide to methane ratios (1-5), gas hourly space velocity (8400-200,000 mL/g/h), oxygen concentration in the feed (3-8 mol%) and reaction temperature (700-800 °C) over methane conversion and yield of hydrogen. The ANOVA analysis indicated that the effect of each process variable was significant to its respective responses in the proposed quadratic model. The response surface methodology (RSM) was used to find the optimum value of the process variables by maximizing the hydrogen yield in the process model. The optimum space velocity as 145,190 mL/g/h at reaction temperature 749 °C with carbon dioxide to methane ratio of 3 and 7 mol% of oxygen in the feed gave 88 mol% of CH₄ conversion and 86 mol% of hydrogen yield, respectively. The experiments were run at the optimum condition gave 87.7 mol% methane conversion and 85.5 mol% of hydrogen yield, which were in good agreement with the simulated values obtained from the model. The catalyst stability and its regeneration characteristics were studied at the optimum condition by monitoring methane conversion and hydrogen yield with time on stream.     

Electrical and hydrogen gas sensing properties of Co1-xZnxFe2O4 nanoparticles; effect of the sputtered palladium thin layer

Hydrogen gas sensing of Co_1-xZn_xFe₂O₄ (x = 0–0.45) nanoparticles synthesized by a simple hydrothermal process has been investigated. An n→p crossover in the electrical conductivity toward hydrogen gas was observed. However, no such charge carrier reversal is noticed at higher x values. In both cases, the related mechanisms are proposed. It has been found that reversal is temperature and doping ratio dependent. In this regard, the more compatible and realistic model is presented which explains the nature of our observations. By analyzing the adsorption kinetics of the surface, it is identified that at a higher percentage of Zn (x = 0.45) the sensor response deviates from the Freundlich isotherm and falls under the category of the Langmuir adsorption model toward H₂ gas exposure. These strong correlations between the results of gas sensing measurements and those calculated based on the DC electric resistivity would pave the way for further investigation of the gas sensors from a fundamental point of view. Deposition of Palladium nano-structures (possibly island-like) on the surface of the CoFe₂O₄ sensor appeared to be effective in speeding up the response time and increasing the sensitivity. The remarkable response time, as low as 3 s, is obtained after modifying the sensor surface with the palladium deposition.     

Effect of mechanical activation process parameters on the properties of LiFePO4 cathode material

Pure, nano-sized LiFePO₄ and carbon-coated LiFePO₄ (LiFePO₄/C) positive electrode (cathode) materials are synthesized by a mechanical activation process that consists of high-energy ball milling and firing steps. The influence of the processing parameters such as firing temperature, firing time and ball-milling time on the structure, particle size, morphology and electrochemical performance of the active material is investigated. An increase in firing temperature causes a pronounced growth in particle size, especially above 600 °C. A firing time longer than 10 h at 600 °C results in particle agglomeration; whereas, a ball milling time longer than 15 h does not further reduce the particle size. The electrochemical properties also vary considerably depending on these parameters and the highest initial discharge capacity is obtained with a LiFePO₄/C sample prepared by ball milling for 15 h and firing for 10 h at 600 °C. Comparison of the cyclic voltammograms of LiFePO₄ and LiFePO₄/C shows enhanced reaction kinetics and reversibility for the carbon-coated sample. Good cycle performance is exhibited by LiFePO₄/C in lithium batteries cycled at room temperature. At the high current density of 2C, an initial discharge capacity of 125 mAh g⁻¹ (73.5% of theoretical capacity) is obtained with a low capacity fading of 0.18% per cycle over 55 cycles.     

Hydrogen production by sorption enhanced steam reforming of oxygenated hydrocarbons (ethanol, glycerol, n-butanol and methanol): Thermodynamic modelling

Thermodynamic analysis of steam reforming of different oxygenated hydrocarbons (ethanol, glycerol, n-butanol and methanol) with and without CaO as CO₂ sorbent is carried out to determine favorable operating conditions to produce high-quality H₂ gas. The results indicate that the sorption enhanced steam reforming (SESR) is a fuel flexible and effective process to produce high-purity H₂ with low contents of CO, CO₂ and CH₄ in the temperature range of 723-873 K. In addition, the separation of CO₂ from the gas phase greatly inhibits carbon deposition at low and moderate temperatures. For all the oxygenated hydrocarbons investigated in this work, thermodynamic predictions indicate that high-purity hydrogen with CO content within 20 ppm required for proton exchange membrane fuel cell (PEMFC) applications can be directly produced by a single-step SESR process in the temperature range of 723-773 K at pressures of 3-5 atm. Thus, further processes involving water-gas shift (WGS) and preferential CO oxidation (COPROX) reactors are not necessary. In the case of ethanol and methanol, the theoretical findings of the present analysis are corroborated by experimental results from literature. In the other cases, the results could provide an indication of the starting point for experimental research. At P = 5 atm and T = 773 K, it is possible to obtain H₂ at concentrations over 97 mol% along with CO content around 10 ppm and a thermal efficiency greater than 76%. In order to achieve such a reformate composition, the optimized steam-to-fuel molar ratios are 6:1, 9:1, 12:1 and 4:1 for ethanol, glycerol, n-butanol and methanol, respectively, with CaO in the stoichiometric ratio to carbon atom.     

Study of a GaN Schottky diode based hydrogen sensor with a hydrogen peroxide oxidation approach and platinum catalytic metal

A platinum (Pt) catalytic metal and a hydrogen peroxide oxidation approach are utilized to fabricate a hydrogen sensor based on a GaN Schottky diode. The presence of a gallium oxide dielectric layer between the Pt metal and the GaN surface can increase the adsorption sites for dissociated hydrogen species, thereby improving the related sensing ability towards hydrogen gas. Experimentally, under introduced 1% hydrogen/air gas, the studied device shows a high sensing response ratio of 1.03 × 10⁵ at 300 K. In addition, the lowest detecting level of 1 ppm hydrogen at 300 K is obtained. This device also exhibits good high-temperature durability (≥573 K) and a high sensing speed. The response (recovery) time constant at 300 K is only 74 (103) sec even under a very low hydrogen concentration of 1 ppm; these time constant values are much smaller than those of palladium metal-based sensors. Under the 1% hydrogen/air, the response (recovery) time constant at 300 K is drastically reduced to 15 (19) sec. Furthermore, in order to improve the feasibility of transmitting the sensing data, the concept of linear differentiation method is employed to eliminate redundant data. The simulation result shows that the average of the reduced ratios can achieve 77.88%. Therefore, this Schottky diode device not only shows promise to detect hydrogen gas, but also can be utilized effectively in the transmission of sensing data.     

Hydriding/dehydriding properties of MgH2/5 wt.% Ni coated CNFs composite

In this paper, we reported that the prepared nickel coated carbon nanofibers (NiCNFs) by electroless plating method exhibited superior catalytic effect on hydrogen absorption/desorption of magnesium (Mg). It is demonstrated that the nanocomposites of MgH₂/5 wt.% NiCNFs prepared by ball milling could absorb hydrogen very fast at low temperatures, e.g. absorb ∼6.0 wt.% hydrogen in 5 min at 473 K and ∼5.0 wt.% hydrogen in 10 min even at a temperature as low as 423 K. More importantly, the desorption of hydrogen was also significantly improved with additives of NiCNFs. Diffraction scanning calorimetry (DSC) measurement indicated that the peak desorption temperature decreased 50 K and the on-set temperature for desorption decreased 123 K. The composites also desorbed hydrogen fast, e.g. desorb 5.5 wt.% hydrogen within 20 min at 573 K. It is suggested that the new phase of Mg₂Ni, and the nano-sized dispersed distribution of Ni and carbon contributed to this significant improvement. Johnson–Mehl–Avrami (JMA) analysis illustrated that hydrogen diffusion is the rate-limiting step for hydrogen absorption/desorption.     

Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation—Model simulations

One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. In a membrane reactor process, the thermal energy needed for the endothermic hydrocarbon reforming may be provided by combustion of the membrane reject gas. The energy efficiency of the overall hydrogen generation is maximized by controlling the hydrogen product yield such that the heat value of the membrane reject gas is sufficient to provide all of the heat necessary for the integrated process. Optimization of the system temperature, pressure and operating parameters such as net hydrogen recovery is necessary to realize an efficient integrated membrane reformer suitable for compact portable hydrogen generation. This paper presents results of theoretical model simulations of the integrated membrane reformer concept elucidating the effect of operating parameters on the extent of fuel conversion to hydrogen and hydrogen product yield. Model simulations indicate that the net possible hydrogen product yield is strongly influenced by the efficiency of heat recovery from the combustion of membrane reject gas and from the hot exhaust gases. When butane is used as a fuel, a net hydrogen recovery of 68% of that stoichiometrically possible may be achieved with membrane reformer operation at 600 °C (873 K) temperature and 100 psig (0.791 MPa) pressure provided 90% of available combustion and exhaust gas heat is recovered. Operation at a greater pressure or temperature provides a marginal improvement in the performance whereas operation at a significantly lower temperature or pressure will not be able to achieve the optimal hydrogen yield. Slightly higher, up to 76%, net hydrogen recovery is possible when methanol is used as a fuel due to the lower heat requirement for methanol reforming reaction, with membrane reformer operation at 600 °C (873 K) temperature and 150 psig (1.136 MPa) pressure provided 90% of available combustion and exhaust gas heat is recovered.     

Co-production of hydrogen and carbon black from solar thermal methane splitting in a tubular reactor prototype

This study addresses the solar thermal decomposition of natural gas for the co-production of hydrogen and carbon black (CB) as a high-value nano-material with the bonus of zero CO₂ emission. The work focused on the development of a medium-scale solar reactor (10 kW) based on the indirect heating concept. The solar reactor is composed of a cubic cavity receiver (20 cm-side), which absorbs concentrated solar irradiation through a quartz window by a 9 cm-diameter aperture. The reacting gas flows inside four graphite tubular reaction zones that are settled vertically inside the cavity. Experimental results in the temperature range 1740-2070 K are presented: acetylene (C₂H₂) was the most important by-product with a mole fraction of up to about 7%, depending on the gas residence time. C₂H₂ content in the off-gas affects drastically the carbon yield of the process. The effects of temperature and residence time are analyzed. A preliminary process study concerning a 55 MW solar chemical plant is proposed on the basis of a process flow sheet. Results show that 1.7 t/h of hydrogen and 5 t/h of CB could be produced with an hydrogen cost competitive to conventional steam methane reforming.