Hydrogen permeation through the Pd-Nb-Pd composite membrane: Surface effects and thermal degradation

The composite membranes based on Group 5 metals are capable of H₂ separation with the high speed and infinite selectivity. The chemical and thermal stability are critical issues for the application of such membranes in the field of hydrogen energy. In order to understand the degradation mechanisms, the H₂ permeation through composite Pd_2μm-Nb_100μm-Pd_2μm membranes was investigated in a very wide pressure range: (10⁻⁵-10⁴) Pa. At higher pressures the surface contaminations only moderately decreased the permeation. However the permeation experiments at lower pressures demonstrated that an orders of magnitude change in the probability of H₂ molecule dissociative sticking is actually hidden behind this relatively moderate effect. The membranes poisoned by the surface contaminations could be recovered by their exposure to O₂ at (300-400) °C. Heating at temperature higher than 500 °C resulted in the irreversible decrease of permeation and in the pronounced change of permeation behavior at the variation of H₂ pressure. An extremely high permeation was observed at lower pressures at the clean surface of Pd coating. That allows developing an effective membrane pump for hydrogen isotopes.     

Improved hydrogen permeation through thin Pd/Al2O3 composite membranes with graphene oxide as intermediate layer

Here we proposed the decreasing in the roughness of asymmetric alumina (Al₂O₃) hollow fibers by the deposition of a thin graphene oxide (GO) layer. GO coated substrates were then used for palladium (Pd) depositions and the composite membranes were evaluated for hydrogen permeation and hydrogen/nitrogen selectivity. Dip coating of alumina substrates for 45, 75 and 120 s under vacuum reduced the surface mean roughness from 112.6 to 94.0, 87.1 and 62.9 nm, respectively. However, the thicker GO layer (deposited for 120 s) caused membrane peel off from the substrate after Pd deposition. A single Pd layer was properly deposited on the GO coated substrates for 45 s with superior hydrogen permeance of 24 × 10⁻⁷ mol s⁻¹m⁻² Pa⁻¹ at 450 °C and infinite hydrogen/nitrogen selectivity. Activation energy for hydrogen permeation through the Al₂O₃/GO/Pd composite membrane was of 43 kJ mol⁻¹, evidencing predominance of surface rate-limiting mechanisms in hydrogen transport through the submicron-thick Pd membrane.     

Transient dynamic of hydrogen permeation through a palladium membrane

Transient dynamic of hydrogen permeation through a palladium membrane is studied in the present study. Three different pressure differences between the two sides of the membrane are considered; they are 3, 5 and 8 atm. The experimental results indicate that the variation in the hydrogen permeation process is notable at the selected pressure differences. When the pressure difference is relatively low (i.e. 3 atm), the hydrogen permeation process proceeds from a time-lag period, then to a concave up period and eventually to a concave down period. Therefore, the transient hydrogen permeation is characterized by a three-stage mass transfer process. When the pressure difference is increased to 5 atm, the time-lag period disappears, thereby evolving the three-stage mass transfer process into a two-stage one. However, the concave up period withers significantly. Once the pressure difference is as high as 8 atm, the transient hydrogen permeation is completely characterized by a concave down curve, yielding a single-stage mass transfer process. A quasi-steady state of hydrogen permeation is defined to evaluate the period of the transient mass transfer process. It suggests that, within the investigated conditions of operation, the time required for hydrogen permeation to reach the steady value is around or over 1 h. For the low pressure difference cases, the transient period is especially long, resulting from the time-lag characteristic. Once the hydrogen permeation is in the steady state, over 80% of hydrogen can be recovered from the membrane.     

Improvement in high temperature stability of Pd coating on Nb by Nb2C intermediate layer

Niobium subcarbide (Nb₂C) was chosen as a material for non-porous intermediate layer to improve the high temperature durability of Pd–Nb composite membranes for hydrogen separation. A layer of Nb₂C was prepared between Nb substrate and thin Pd films (100 nm), and the stability of Pd coating at elevated temperatures (573–773 K) was examined by hydrogen absorption experiments. Hydrogen permeability through the Nb₂C layer appeared to be sufficiently high, and no noticeable deterioration was observed in hydrogen absorption rate under as-prepared conditions. The degradation in coating effect of Pd at elevated temperatures was substantially mitigated by Nb₂C layer. Such improved durability was ascribed to retardation of open porosity development by Nb₂C caused as a consequence of impeded interdiffusion between Pd and Nb.     

Tight-binding study of hydrogen adsorption on palladium decorated graphene and carbon nanotubes

In this work we report a theoretical study on the atomic and molecular hydrogen adsorption onto Pd-decorated graphene monolayer and carbon nanotubes by a semi-empirical tight-binding method. We first investigated the preferential adsorption geometry, considering different adsorption sites on the carbon surface, and then studied the evolution of the chemical bonding by evaluation of the overlap population (OP) and crystal orbital overlap population (COOP). Our results show that strong C–Pd and H–Pd bonds are formed during atomic hydrogen adsorption, with an important role in the bonding of C 2p_z and Pd 5s, 5p_z and 4d_z² orbitals. The hydrogen storage mechanism in Pd-doped carbon-based materials seems to involve the dissociation of H₂ molecule on the decoration points and the bonding between resultant atomic hydrogen and the carbon surface.     

Efficient composite bipolar plate reinforced with carbon fiber and graphene for proton exchange membrane fuel cell

The composite bipolar plates are developed using natural graphite, carbon black, and carbon fiber, along with 1% graphene with phenol formaldehyde (resole) resin. The graphene is developed by thermo-chemical exfoliation of natural graphite and characterized by XRD, Raman, FESEM, and AFM analyses. The synthesized graphene is monolayer graphene with a minimum thickness of 1 Å. The bipolar plates are developed using compression molding technique and thoroughly characterized considering stringent benchmarks (US-DOE and Plug Power Inc.) for PEMFC viz., electrical conductivity, flexural strength, deflection at mid-point, and corrosion current density. The composite bipolar plate showed excellent corrosion resistance to the rigorous fuel cell environment. All the required properties are achieved by the developed composite bipolar plate for PEMFC application. The fuel cell is fabricated with the developed bipolar plate and the performance of the fuel cell is studied. The incorporation of graphene has improved the fuel cell performance significantly.     

Experimental and theoretical studies of hydrogen generation by binary metal (oxide)-graphene oxide composite materials

Theoretical and experimental studies with focuse on hydrogen generation through the hydrolysis of graphene oxide (GO) functionalized with magnesium (GOMg), titanium (GOTi), and niobium (GONb) were performed. Thermogravimetric (TGA) results reveal variable thermal decomposition profiles for the composites, in agreement with the decomposition of the labile oxygenated groups of GO. X-ray photoelectron spectroscopy (XPS) results show variable oxygen content (%) for the composites and the formation of MgO, TiO₂, and NbO₂ layers on the GO surface. The hydrogen generation studies suggest that the formation of a Mg(OH)₂ layer on the GO surface is a critical limiting factor for the hydrolysis of GOMg, whereas TiO₂ and NbO₂ catalyze the hydrolysis of GONb and GOTi. The hydrogen generation results reveal that GONb produced the highest H₂ yield of 2 L in 2 h compared to 1.5 L for GOTi and 1.3 L for GOMg. The results support the claim that the hydrolysis of GO functionalized with niobium and titanium are promising candidates for on-board H₂ generation applications.     

Unexpected large hydrogen adsorption by Nb cluster films under mild conditions of pressure and temperature

Hydrogen absorption in several cluster assembled films was investigated by the optical and electrical response of the films when modified by hydrogen adsorption. The films were grown by deposition of niobium clusters and by co-deposition of niobium clusters with manganese or palladium clusters on sapphire and then capped by a thin Pd film. Unusual high adsorption of hydrogen by Nb clusters and thin metal oxide reductions at room temperature can be inferred by changes in optical transmission and resistance of the film. On the other hand, no hydrogen absorption can be inferred in the same experiments with co-deposited clusters of Nb and Pd and co-deposited clusters of Nb and Mn. The technique used in this work allows fast screening and detection of potential perm-selective materials for hydrogen.     

Si-doping effect on the enhanced hydrogen storage of single walled carbon nanotubes and graphene

We identified several parameters that correlate with the hydrogen physisorption energy and physicochemical properties of heteronuclear bonding in single-walled carbon nanotubes (SWCNT) and graphene. These parameters were used to find the most promising heteronuclear doping agents for SWCNTs and graphene for enhanced hydrogen storage capacity. Si-doping was showed to increase the amount of physisorbed hydrogen on such surfaces. Grand Canonical Ensemble Monte Carlo (GCMC) simulations showed that the hydrogen storage capacity of 10 at% Si-doped SWCNT (Si-CNT10) could reach a maximum of 2.5 wt%, almost twice the storage capacity of undoped SWCNTs, which were showed to reach a maximum capacity of 1.4 wt% at room temperature. To achieve this capacity, debundling effects of the uneven surfaces of Si-doped SWCNTs were found to be necessary. Similarly, 10 at% Si-doping on graphene (Si-GR10) was showed to increase the hydrogen storage capacity from 0.8 to 2.4 wt%.     

Palladium composite membrane fabricated on rough porous alumina tube without intermediate layer for hydrogen separation

A thin palladium composite membrane without any modified layer was successfully obtained on a rough porous alumina substrate. Prior to the fabrication of palladium membrane, a poly(vinyl) alcohol (PVA) layer was first coated onto the porous substrate by dip-coating technique to improve its surface roughness and pore size. After deposition of palladium membrane on the PVA modified substrate, the polymer layer can be completely removed from the composite membrane by heat treatment. The microstructure of the palladium composite membrane was characterized in detail using SEM, EDXS and XRD analysis. Permeation measurements were carried out using H₂ and N₂ at temperatures of 623 K, 673 K, 723 K and 773 K. The results indicated that the hydrogen permeation flux of 0.238 mol m^?2 s^?1 with H₂ separation factor α(H₂/N₂) of 956 for the as-prepared palladium membrane was obtained at 773 K and 100 kPa. Furthermore, the good membrane stability was proven during the total operation time of 160 h at the temperature range of 623 K–773 K and gas exchange cycles of 30 between hydrogen and nitrogen at 723 K.     

Modeling of transient hydrogen permeation process across a palladium membrane

Transient mass transfer processes of hydrogen permeating through a Pd membrane are modeled to aid in predicting the hydrogen transport behavior. The model is established in terms of the quasi-steady time and the steady permeation rate. Meanwhile, four important parameters are considered; they are the permeation lag time, the initial permeation rate, the concave up period and the concave down period. A unit step function is embedded in the model to account for the effect of the hydrogen permeation lag at a lower pressure difference. Corresponding to the lower, the moderate and the higher pressure differences (i.e. 3, 5 and 8 atm), though the hydrogen permeation undergoes a three-stage, a two-stage and a one-stage processes, respectively, these processes can be predicted well by an arc tangential function. By introducing an adjusting parameter in the arc tangential function, there exists an optimal value of the adjusting parameter when the pressure difference is lower. In regard to the moderate and higher pressure differences, the predictions agree with experiments well if the adjusting parameter is sufficiently large. Physically, the unit step function is used to account for the controlling mechanisms of hydrogen diffusion toward the membrane and the spillover of the hydrogen across the membrane. The initial jump parameter represents the rapid response of the initial hydrogen permeation. The adjusting parameter can be used to describe the relative importance of the concave up and the concave down periods.     

Enhanced hydrogen permeance through graphene oxide membrane deposited on asymmetric spinel hollow fiber substrate

Membranes of graphene oxide (GO) present suitable application for hydrogen (H₂) purification. The deposition of a selective and high permeable GO membrane on a proper substrate is still a challenge. Here we applied the vacuum-assisted method to deposit a GO layer on asymmetric spinel (MgAl₂O₄) hollow fibers. The synthetized GO showed a nanosheeted morphological structure and a relative high degree of oxidation. The hollow fibers were produced with dolomite and alumina as the ceramic starting material and showed the desired asymmetric pore size distribution, in addition to suitable bending strength, 54.88 ± 4.25 MPa, and average surface roughness, 180 ± 8.2 nm. A continuous GO layer of 1.7 ± 0.2 μm was deposited onto the fiber outer surface. The composite MgAl₂O₄/GO membrane presented H₂ permeance of 8.2 ± 0.0 × 10^?7 mol s^?1 m^?2 Pa^?1 at room temperature (approximately 25 °C) and 0.3 MPa of transmembrane pressure. Ideal hydrogen/nitrogen and hydrogen/carbon dioxide selectivity values were of 3.3 ± 0.0 and 11.4 ± 0.1, respectively.     

Preparation and characterization of palladium ceramic alumina membrane for hydrogen permeation

In this study, a tubular palladium membrane has been prepared by an electroless plating method using palladium II chloride as a precursor with the intent of not having a completely dense film since its application does not require high hydrogen selectivity. The support used was a 15 nm pore sized tubular ceramic alumina material that comprised of 77% alumina and 33% titania. It has dimensions of 7 mm inner and 10 mm outer diameters respectively. The catalyst was deposited on the outside tube surface using the electroless deposition process. The membrane was morphologically characterized using scanning electron microscopy/energy dispersive x-ray analysis (SEM/EDXA) and liquid nitrogen adsorption/desorption analysis (BET) to study the shape and nature of the palladium plating on the membrane. The catalytic membrane was then inserted into a tubular stainless-steel holder which was wrapped in heating tapes so as to enable the heating of the membrane in the reactor. The gases used for permeation tests comprised H₂, N₂, O₂ and He. Permeation tests were out at 573 K and at pressure range between 0.05 and 1 barg. The results showed that hydrogen displayed a higher permeation when compared to other gases that permeated through the membrane and its diffusion is also thought to include solution diffusion through the dense portions of the palladium in addition to Knudsen, convective and molecular sieving mechanisms occurring through cracks and voids along the grain boundaries. While high hydrogen selectivity is critically important in connection with hydrogen purification for fuel cells and in catalytic membrane reactors used to increase the yield of thermodynamically limited reactions such as methane steam reforming and water–gas shift reactions whereby the effective and selective removal of the H₂ produced from the reaction zone shifts the equilibrium, it is not so important in situations in which the membrane has catalytic activity such that it is possible to carryout the reaction in situations where the premixed reactants are forced-through the membrane on which the catalysts is attached. This type of catalytically active membranes is novel and has not been tested in gas-solid-liquid reactions and liquid-solid reactions before. With such a reactor configuration, it is possible to achieve good feed stream distribution and an optimal usage of the catalytic material. The preparation and characterization of such membrane catalysts has gained increased interest in the process industries because it can be adapted to carryout the chemical reactions if one of the reactants is present in low concentration and an optimal reactant distribution results in a better utilization of the active catalytic material. However, there are concerns in terms of the high cost of palladium membranes and research on how to fabricate membranes with a very low content of the palladium catalyst is still ongoing. Work is currently underway to deploy the Pd/Al₂O₃ membrane catalysts for the deoxygenating of water for downhole injection for pressure maintenance and in process applications.     

Methane steam reforming operation and thermal stability of new porous metal supported tubular palladium composite membranes

In 2009 cooperation between Plansee SE, Austria (PSE), Karlsruhe Institute of Technology, Germany (KIT) and the Engineering Division of Linde AG, Germany (LE) was set up with the aim to develop new tubular palladium composite membranes and a membrane reformer system for small scale on-site hydrogen production.     

A comparison of the performance and stability of Pd/BCC metal composite membranes for hydrogen purification

Composite membranes were fabricated by sputtering 100 nm of Pd on to both sides of dense BCC metal foils (V, Ta, Nb). Under pure H₂ gas testing at 500 °C the maximum permeability of all three metals exceeds previously reported values and closely approach theoretical limits. However, the stability of each membrane varied significantly due to unique failure mechanisms. Pd/V membranes failed quickly (<20 h) due to a combination of Pd–V interdiffusion and high susceptibility to oxidation as shown through microscopy and compositional analysis. The Pd/Ta membranes were the most resilient to oxygen, but their mechanical integrity was relatively poor and they failed within 48 h due to Pd–Ta interdiffusion. In contrast, Pd/Nb membranes exhibited high permeability throughout the 168 h of testing, with no Pd–Nb interdiffusion observed. The decline in permeability observed during testing was attributed to partial Pd delamination as a result of membrane deformation. These results provide pathways for further development of these membranes.     

The effect of mixture gas on hydrogen permeation through a palladium membrane: Experimental study and theoretical approach

Hydrogen permeation through a palladium membrane has been measured in the presence of several gases, such as CO, _N2${\mathrm{N}}_2$, _CO2${\mathrm{CO}}_2$, and Ar, both in the feed side and in the shell side of the (membrane) module. It has been found that CO molecules, remarkably inhibit hydrogen permeation. In particular, in the presence of carbon monoxide the permeation decreases with two different slopes: (I) for low CO concentrations, the hydrogen permeation decreases quickly (surface effects), whereas (II) for higher ones it decreases smoothly (dilute effect). Permeation of hydrogen, in the presence of the other gases, i.e. _N2${\mathrm{N}}_2$, _CO2${\mathrm{CO}}_2$ and Ar, always decreases with the same slope (dilute effect). In order to describe the CO inhibition, a theoretical investigation has been proposed. In particular, the framework of the Density Functional Theory has been used. CO and _N2${\mathrm{N}}_2$ Density Functional full optimisations on palladium clusters show that CO and _N2${\mathrm{N}}_2$ molecules present two minima on the cluster surfaces with bond lengths of 2.0 and 3.8 Å, respectively. The CO minima are much stable than _N2${\mathrm{N}}_2$ minima, resulting in a surface effect on the hydrogen permeation through the membrane.     

Analysis of adsorption equilibrium of hydrogen on graphene sheets

The adsorption equilibrium of hydrogen on graphene sheets (GS) was studied based on a sample of GS with S_BET = 300 m²/g at the temperatures of 77.15 K–293.15 K and the pressures of 0 MPa–6 MPa. In the meantime, the adsorptions (Excess adsorption measurements) of hydrogen on granular coconut shell SAC-02 activated carbon (S_BET = 2074 m²/g) and carbon nanofiber (CNFs, S_BET = 205 m²/g) were investigated at the pressures of 0–8 MPa and the temperature of 77.15 K. The outcomes from experiments were used to determine the parameters in Toth equation by way of Non-linear fit. The absolute adsorption amounts of hydrogen on the GS, which were calculated from the equation, were used to calculate the isosteric heat of hydrogen adsorption by use of adsorption isosteres.     

Assessment of the effect of electrophoretic deposition parameters on hydrogen storage performance of graphene oxide layer applied on nickel foam

In this study, the hydrogen storage capacity of the graphene oxide layer was studied electrochemically. The graphene oxide was synthesized by modified Hummers' method and applied on the nickel foam by electrophoretic deposition (EPD) method at different potentials (20 and 60 V) and times (20 and 60 min) to determine the effect of applied potential and time of deposition on the hydrogen adsorption performance. The hydrogen adsorption tests including charge-discharge test, electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were conducted in 6 M KOH solution and at room temperature. Based on the achieved CV curves, the graphene oxide (GO) layer achieved at 60 V within 20 min has a higher electrochemical hydrogen adsorption capability compared to other obtained samples. The calculated hydrogen storage capacity is obtained 50.9 mA. h. g^?1. The rosette flower like morphology of the obtained GO layers at optimum condition, has an impressive effect on the improving electrochemical hydrogen adsorption based on morphology study by field emission scanning electron microscopy.     

Time and frequency domain analysis of hydrogen permeation across PdCu metallic membranes for hydrogen purification

Hydrogen permeation is a process used in the industry for purification purposes. Palladium alloys (PdAg and PdCu) are commonly used as membrane material. In this communication, we report on the kinetics of hydrogen permeation across Pd_0.47Cu_0.53 metallic membranes which can be used in catalytic crackers of biofuels. The permeation mechanism is a multi-step process including surface chemisorption of molecular hydrogen (upstream side of the membrane), hydrogen diffusion across bulk regions, hydrogen recombination (downstream side of the membrane) and evolution. The role of different operating parameters (temperature, surface state, sample microstructure) is analyzed and discussed using both time and frequency domain experiments. Experimental pneumato-chemical impedance diagrams show that there is no significant rate-limitation at surfaces, except at low temperatures close to room temperature. Diffusion-controlled transport of hydrogen across the membrane is rate-determining. However, the value of the hydrogen diffusion coefficient does not rise exponentially with operating temperature in the 40–400 °C temperature range under investigation, as expected for a thermally activated diffusion process. At temperatures as low as 300 °C, new rate-limitations appear. They can be attributed to recrystallization and/or phase transformation processes induced by temperature and the presence of hydrogen.