High performance hydrogen sensor based on Pd/TiO2 composite film

Hydrogen sensors with fast response and recovery rate based on nanoporous palladium (Pd) and titanium dioxide (TiO₂) composite films supported by anodic aluminum oxide (AAO) template have been demonstrated. Nanoporous TiO₂ film was sprayed on the porous AAO templates, followed by Pd film deposited on TiO₂ layer by DC magnetron sputtering. We have researched the detection performance of the hydrogen sensors depending on different thickness of TiO₂ layer from 6 to 30 nm with keeping the thickness of Pd as 30 nm. The results have demonstrated the sensors with 10 nm thickness of TiO₂ achieve the best performance with a response/recovery time as short as 4/8s at 0.8% and 0.4% hydrogen concentration, respectively. The sensors exhibited very good performance under hydrogen concentrations from 0.4% to 1.8%.     

A novel yttria-doped ZrO2 based conductometric sensor for hydrogen leak monitoring

Pure and (8%)Y₂O₃-doped zirconium oxide commercial samples were investigated for developing a high performance conductometric hydrogen sensor. The morphological, microstructural, optical, and electrical characteristics of the samples were studied and compared. Conductometric sensors based on these samples were fabricated using a planar platform in alumina provided with interdigitated electrodes, and sensing tests were carried at different operating temperatures and hydrogen concentrations. Sensing tests revealed that the fabricated sensor based on the tetragonal ZrO₂–Y₂O₃ (8%) showed the best performances in terms of sensor response (R₀/R_H2 = 7.3@10000 ppm of hydrogen), response and recovery time (5 and 10 s, respectively), and low operating temperature (150 °C). These characteristics have been exploited for developing the first hydrogen leak conductometric sensor based on ZrO₂ so far reported.     

Highly sensitive hydrogen sensor based on a new suspended structure of cross-stacked multiwall carbon nanotube sheet

In this research, we proposed a highly sensitive hydrogen sensor based on a new suspended structure of cross-stacked multiwall carbon nanotube (MWCNT) sheet. MWCNT sheet is a kind of CNT film which has a super-high CNT alignment and can be easily prepared by drawing from the spinnable CNT array in large scales. By stacking the sheets onto an electrode with a 1 × 1 cm hole in mutually perpendicular directions, sensors with suspended cross-stacked structure were realized. Afterwards, a two-side Pd functionalization was introduced. The effects of suspended structure, cross-stacked structure and two-side Pd functionalization were investigated respectively. It was observed that the sample with 2 + 1 layers of cross-stacked MWCNT sheet and two-side 3 nm Pd deposition showed the best gas sensing performance with a relative resistance change of 35.30% at 4% H₂. This result indicates that the proposed sensor is one of the best among all reported MWCNT based hydrogen sensors. The method demonstrated in this research gives a potential solution for the mass production of CNT-based sensors with high sensitivity and reliability.     

Effect of Pd overlayer and mixed gases on hydrogen permeation of Pd/Nb30Hf35Co35/Pd composite membranes

Effect of Pd overlayer and mixed gases on hydrogen permeation of Pd/Nb₃₀Hf₃₅Co₃₅/Pd composite membranes was investigated. The diameter of Pd particle increases with increasing sputtering power. With this change, the membrane shows a signification reduction in hydrogen permeability/or flux, but its durability and stability increases significantly, which can be mainly attributed to a decrease in hydrogen solubility coefficient. In addition, H₂S impurity in mixed gases can greatly degrade membrane performance, especially the hydrogen permeability, whereas the Ar impurity content has less effect in the temperature range of 523–673 K. Lowering of permeability caused by the change of gas purity can be attributed to a decrease in hydrogen solubility, which is closely related to the stronger adsorption of H₂S molecules to the Pd overlayer of the membrane. Thus, it is concluded that aside from the optimum design for composition of Nb-based hydrogen permeable alloy to improve their permeability, the control of Pd overlayer film on membrane surface and gas purity in the feed gas is important.     

Preparation of a novel Pd/layered double hydroxide composite membrane for hydrogen filtration and characterization by thermal cycling

A layered double hydroxide (LDH) layer was grown directly on a porous stainless steel (PSS) surface to reduce the pore opening of the PSS and to be a middle layer retarding Pd/Fe interdiffusion. A thin Pd film (∼7.85 μm) was plated on the modified PSS tube by an electroless plating method. A helium leak test proved that the thin Pd on the LDH-modified PSS substrate was free of defects. The membrane had a H₂ flux of 28–36 m³/(m² h) and H₂/He selectivity larger than 2000 at a pressure difference of 1 bar. Thermal cycling between room temperature and 673 K was performed and showed that the membrane exhibited good permeance and selectivity. Long-term evaluation (1500 h) of the membrane at 673 K showed static results of H₂ flux (∼30 m³/(m² h)) and H₂/He selectivity (∼2000) over the 1500 h test period.     

Fabrication and electrochemical hydrogen storage performance of Ti49Zr26Ni25 alloy covered with Cd/Pd core/shell particles

A facile two-step reduction method is employed to obtain the Cd/Pd core/shell particles. Mechanical alloying and subsequent annealing are used to fabricate the Ti₄₉Zr₂₆Ni₂₅ quasicrystal. Composite materials of Ti₄₉Zr₂₆Ni₂₅ mixed with different contents of Cd/Pd particles are obtained via ball-milling. The electrochemical performance and kinetics properties of the alloy electrodes for Ni/MH secondary batteries are studied. Ultimately, a maximum discharge capacity of 272.9 mA h/g is achieved for 7% additive content of Cd/Pd. Ti₄₉Zr₂₆Ni₂₅ + Cd/Pd shows higher capacity than Ti₄₉Zr₂₆Ni₂₅ + Pd (246.8 mA h/g) and original Ti₄₉Zr₂₆Ni₂₅ (212.5 mA h/g). Moreover, the composites also exhibit improved cyclic stability and high-rate dischargeability. The Cd/Pd particles with special core/shell microstructure can enhance the electro-catalytic activity of Pd. The Cd/Pd material covered on the surface of alloy can further decrease the charge-transfer resistance and accelerate the hydrogen transmission, thus improving the electrochemical properties and reaction kinetics of the electrode.     

Fast response of hydrogen sensor using palladium nanocube-TiO2 nanofiber composites

In this work, we investigated the properties of resistivity type hydrogen (H₂) sensor for monitoring in H₂ gas. The H₂ sensor was made of Pd nanocube (NCs) and TiO₂ nanofiber (NFs) composites. The Pd NCs was synthesized by seed-mediated growth and TiO₂ nanofiber was synthesized via electrospinning method. The two nanomaterials are then converted into nanocomposites by ultrasonication process. Pd NCs-TiO₂ NFs composite was characterized by scanning electron microscope (SEM) and high resolution transmission electron microscope (HRTEM). The H₂ sensing properties including the response/recovery time, the response value and linearity of the synthesized samples were investigated toward to various H₂ concentrations (0.6, 0.8 and 1%). The response of H₂ sensor is S = 40.8% and the response/recovery time are 25/1 s with 0.6% at working temperature of 150 °C. Moreover, the H₂ sensor has excellent cross-selectivity for H₂ compared to ethanol, nitrogen dioxide and isopropyl alcohol.     

Controllable electrodeposition synthesis of Pd/TMxOy-rGO/CFP composite electrode for highly efficient methanol electro-oxidation

A novel and high-efficiency Pd/TM_xO_y-rGO/CFP (TM_xO_y = Co₃O₄, Mn₃O₄, Ni(OH)₂) electrocatalyst for directly integrated membrane electrode was synthesized by controllable cyclic voltammetry electrodeposition combined with hydrothermal process. The results showed excellent performance towards methanol oxidation reduction. The Pd/Co₃O₄-rGO/CFP as-prepared catalyst has the best electrocatalytic activity, and mass activity is 5181 mA·mg⁻¹_Pd, which is about 40 times and 4.3 times that of the commercial Pd/C and Pt/C catalyst (JM). It can be attributed that the small size of Pd nanoparticle, uniformity of distribution, and the synergistic interaction between transition metal oxide on the support surface and Pd nanoparticles. The prepared Pd/TM_xO_y-rGO/CFP composite electrode is a promising catalyst for integrated membrane electrode assembly of proton exchange membrane fuel cells in the future.     

Novel non-alloy Ru/Pd composite membrane fabricated by electroless plating for hydrogen separation

This study presents a new non-alloy Ru/Pd composite membrane fabricated by electroless plating for hydrogen separation. It shows that palladium and ruthenium can be deposited on an aluminum-oxide-modified porous Hastalloy by using our new EDTA-free plating bath at room temperature and 358 K, respectively. A 6.8 μm thick non-alloy Ru/Pd membrane film could be plated and helium leak test confirmed that the membrane was free of defects. Hydrogen permeation test showed that the membrane had a hydrogen permeation flux of 4.5 × 10⁻¹ mol m⁻² s⁻¹ at a temperature of 773 K and a pressure difference of 100 kPa. The hydrogen permeability normalized value with thickness of the membrane was 1.4 times higher than our pure Pd membrane having similar structure. The EDX profiles of the front and back side membrane, cross-sectional EDX line scanning and XRD profile show that there was no alloying progress between the palladium and ruthenium layer after hydrogen permeation test at 773 K.     

Palladium dispersed multiwalled carbon nanotube based hydrogen sensor for fuel cell applications

Palladium nanocatalysts supported on surface-oxidized multiwalled carbon nanotubes (MWNT) were prepared by the aqueous solution reduction of _PdCl2${\mathrm{PdCl}}_2$. MWNT have been synthesized by catalytic chemical vapor deposition (CCVD) technique. Pyrolysis of acetylene using a fixed-bed catalytic reactor over rare earth (RE) based _AB2${\mathrm{AB}}_2$ alloy hydride catalyst, obtained through hydrogen decrepitation technique, has been performed to synthesize MWNT. Structural, morphological and vibrational characterizations have been carried out using XRD, SEM, TEM and Raman spectroscopy, respectively. In situ electrical resistance measurements for thin films of MWNT obtained by spin coating samples were carried out by two-probe technique in a chamber with provision to introduce known concentration of hydrogen in constant air flow. Investigations of hydrogen sensing properties of Pd–MWNT ensembles have been carried out. The stability of Pd–MWNT thin films after several cycles of adsorption and desorption was studied. The change in electrical resistance due to hydrogen adsorption is reversible, with increase to saturation on exposure to hydrogen gas. The results demonstrate that chemically treated MWNT functionalized with nanostructured Pd show good _H2${\mathrm{H}}_2$ sensing response at room temperature.     

Hydrogen gas sensor based on mesoporous In2O3 with fast response/recovery and ppb level detection limit

Hydrogen gas sensors were fabricated using mesoporous In₂O₃ synthesized using hydrothermal reaction and calcination processes. Their best performance for the hydrogen detection was found at a working temperature of 260 °C with a high response of 18.0 toward 500 ppm hydrogen, fast response/recovery times (e.g. 1.7 s/1.5 s for 500 ppm hydrogen), and a low detection limit down to 10 ppb. Using air as the carrier gas, the mesoporous In₂O₃ sensors exhibited good reversibility and repeatability towards hydrogen gas. They also showed a good selectivity for hydrogen compared to other commonly investigated gases including NH₃, CO, ethyl alcohol, ethyl acetate, styrene, CH₂Cl₂ and formaldehyde. In addition, the sensors showed good long-term stability. The good sensing performance of these hydrogen sensors is attributed to the formation of mesoporous structures, large specific surface areas and numerous chemisorbed oxygen ions on the surfaces of the mesoporous In₂O₃.     

Resistive-type hydrogen gas sensor based on TiO2: A review

Owing to its high energy density and environmentally friendly nature, hydrogen has already been regarded as the ultimate energy of the 21st century and gained significant attention from the worldwide researchers. Meanwhile, there are increasing concerns about its safe use, storage and transport as, despite being colorless and odorless, after certain concentration level it becomes flammable and explosive in air. Therefore, it is imperative to develop H₂ sensors for real-time monitoring of the H₂ leakage for an early warning. This paper firstly introduces the general hydrogen gas sensing mechanism of TiO₂-based hydrogen sensors. Then we summarize and comment on the current hydrogen gas sensor based on various TiO₂ materials, which include pristine TiO₂, metal-assisted TiO₂, organic-TiO₂ composites, carbon-TiO₂ composites, MOX-TiO₂ composites and novel sensor concept with effective top-bottom electrode configuration. Finally, we briefly discuss the obstacles that TiO₂-based H₂ sensors have to overcome in the progress of the systematically practical application, possible solutions, and future research perspectives that can be focused in this area.     

Hydrogen sensing properties of a Pd/oxide/InAlAs metamorphic-based transistor

A Pd/oxide/InAlAs metal–oxide–semiconductor (MOS) type metamorphic high electron mobility transistor (MHEMT)-based hydrogen sensor is fabricated and investigated. In comparison with the conventional HEMT-based sensors, the MOS MHEMT-based sensor exhibits significantly high sensitivity to the hydrogen. The found hydrogen sensing response is as high as 300%. Using the thermodynamic analysis to estimate the enthalpy value of hydrogen adsorption, the value for the proposed sensor is much lower than that for the other reported HEMT-based sensors. The MHEMT-based sensors are demonstrated to have a relatively fast response as comparing to other HEMT-based ones. The response time of the device is approximately 10 s under exposure to a 1% H₂/air gas. Consequently, the performance of the studied sensors shows the promise characteristics for practical applications.     

A low cost optical hydrogen sensing device using nanocrystalline Pd grating

A Pd grating of periodicity of 1.5 μm comprising of 1 μm wide nanocrystalline Pd lines has been obtained by a direct micromolding method to serve as Hydrogen sensor element in an optical diffraction set up. The device uses a low power diode laser and a photodetector and works with sensitivity of ∼20%. The hydrogen sensing action is based on monitoring the changes in the diffraction efficiency (DE) which is defined as the ratio of the first and the zeroth order diffracted beam intensities. The diffraction efficiency undergoes large and sudden changes as the nanocrystalline grating becomes disordered due to PdH_x formation, as monitored using in-situ microscopy and optical profilometric measurements. This is truly a low cost, portable hydrogen sensor meant for large installations.     

Reliability of hydrogen sensing based on bimetallic Ni–Pd/graphene composites

Graphene-supported nickel–palladium (Ni–Pd) bimetallic nanoparticles (Ni–Pd/Gr) were synthesized using a simple chemical method, followed by a post-thermal annealing process. The characteristics of resistivity-type hydrogen (H₂) sensors composed of Pd–Gr composites (with small amounts of Ni added to the Pd nanoparticles (Pd NPs)) were investigated in detail. Pd NPs with various amounts of Ni embedded into the Pd lattice were synthesized by varying the molar ratios of the Ni/Pd precursors. The results from this work indicate that the addition of Ni not only enhances performance, but also reduces the hysteresis behavior of the Pd–Gr composite based H₂ sensors. H₂ was detectable from 1 to 1000 ppm based on a rapid recovery response with suitable Ni/Pd percentages. At the optimal Ni/Pd percentage of 7% (Ni/Pd ∼7%), sensors showed a small enhancement of sensitivity, fast recovery, and minimum hysteresis effect. From our experiment, the addition of Ni to Pd NPs results in a reduction of the hysteresis effect and reliability on H₂ sensors based on Pd–Gr composites.     

Fabrication and characterization of Pd/Nb40Ti30Ni30/Pd/porous nickel support composite membrane for hydrogen separation and purification

A porous nickel support was successfully prepared by uniaxial compression of nickel powders. Microstructures and mechanical properties of Nb₄₀Ti₃₀Ni₃₀ membranes fabricated by magnetron sputtering were investigated. Deposited and annealed Nb₄₀Ti₃₀Ni₃₀ membranes consisted of amorphous and crystalline phases, respectively. Higher base temperature was shown to increase the hardness and elastic modulus of the Nb₄₀Ti₃₀Ni₃₀ membrane. Pd/Nb₄₀Ti₃₀Ni₃₀/Pd/porous nickel support composite membranes were then fabricated using a multilayer magnetron sputtering method. The hydrogen permeability of the composite membranes with amorphous and crystallized Nb₄₀Ti₃₀Ni₃₀ metal layer was measured and compared with that of self-supported Nb₄₀Ti₃₀Ni₃₀ and Pd alloys. Solid-state diffusion was shown to be the rate-controlling factor when the thickness of the Nb₄₀Ti₃₀Ni₃₀ layer was about 12 μm or greater, while other factors were in effect for thinner layers (such as 6 μm). The Pd/Nb₄₀Ti₃₀Ni₃₀/Pd/porous nickel support composite membrane exhibited excellent permeation capability and satisfactory mechanical properties. It is a promising new permeation membrane that could replace Pd and PdAg alloys for hydrogen separation and purification.     

SrS/CdS composite powder as a novel photocatalyst for hydrogen production under visible light irradiation

In this paper a novel SrS/CdS composite powders were prepared by coprecipitation method. The physicochemical properties of the photocatalysts were analyzed by XRD, UV–Vis, BET, PL and SEM. Photocatalytic hydrogen production results showed that these composite powders can work efficiently under visible light without loading noble metal, and it was found that the ratio of SrS/CdS equaling to 2/8 has the best performance among various SrS/CdS composite powders, and the hydrogen evolution rate amounted to 123 μmol/h under visible light irradiation. The apparent quantum yield for this photocalyst was calculated to be 2.85%, 4.59%, 9.63% at 420 nm, 440 nm and 480 nm respectively, and the apparent quantum yield under visible light was 5.83%. The reason for its high activity was analyzed.     

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.     

H2 production via water gas shift in a composite Pd membrane reactor prepared by the pore-plating method

In this work, H₂ production via catalytic water gas shift reaction in a composite Pd membrane reactor prepared by the ELP “pore-plating” method has been carried out. A completely dense membrane with a Pd thickness of about 10.2 μm over oxidized porous stainless steel support has been prepared. Firstly, permeation measurements with pure gases (H₂ and N₂) and mixtures (H₂ with N_2, CO or CO₂) at four different temperatures (ranging from 350 to 450 °C) and trans-membrane pressure differences up to 2.5 bar have been carried out. The hydrogen permeance when feeding pure hydrogen is within the range 2.68–3.96·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5, while it decreases until 0.66–1.35·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 for gas mixtures. Furthermore, the membrane has been also tested in a WGS membrane reactor packed with a commercial oxide Fe–Cr catalyst by using a typical methane reformer outlet (dry basis: 70%H₂–18%CO–12%CO₂) and a stoichiometric H₂O/CO ratio. The performance of the reactor was evaluated in terms of CO conversion at different temperatures (ranging from 350 °C to 400 °C) and trans-membrane pressures (from 2.0 to 3.0 bar), at fixed gas hourly space velocity (GHSV) of 5000 h⁻¹. At these conditions, the membrane maintained its integrity and the membrane reactor was able to achieve up to the 59% of CO conversion as compared with 32% of CO conversion reached with conventional packed-bed reactor at the same operating conditions.     

Pd/Ag alloy as an application for hydrogen sensing

A highly sensitive H₂ gas sensor was fabricated using a Micro Electromechanical Systems (MEMS) procedure having an embedded micro-heater. The palladium-silver (Pd/Ag having stoichiometric ratios 77:23) thin film was deposited by the RF/DC magnetron sputtering and used as the hydrogen sensing layer designed as a zig-zag pattern. Morphological and structural properties of the Pd/Ag thin film was studied by Field emission scanning electron microscope (FESEM), Atomic force microscopy (AFM) and Energy Dispersive Analysis of X-rays respectively. The working temperature of the micro heater showed a linear relation with variations of the heater voltage. The electro thermal properties of the H₂ sensor were studied by finite element method (FEM). The sensing properties of the fabricated H₂ sensor as the change of electrical resistance were studied with respect to hydrogen concentration and temperature. Experimental results showed high sensor response and response time after application of the heater voltage. The sensing properties of the alloyed Pd/Ag thin film were more improved than those of pure palladium. The maximum sensor response (R_s) of the fabricated H₂ sensor was 14.26% for 1000 ppm H₂. The sensor response of the fabricated H₂ sensor showed linear behavior with the heater voltage (operating temperature) and positively corresponded with the hydrogen concentration.