Search Results (8)

Ammonia (NH₃) represents a promising zero-emission fuel in hydrogen fuel cells. Membrane reactors for NH₃ decomposition based on Pd-alloys have demonstrated high NH₃ conversion, high hydrogen diffusivity, and high hydrogen selectivity, which allows for the production of high-purity H₂ without the need for gas separation or purification. However, it is observed that Pd-alloy membranes are to a various degree prone to H₂ flux inhibition in the presence of NH₃. Hence, finding proper means to tailor the surface adsorption properties through, e.g., alloying is imperative to further improve the technology. In the current work, hydrogen and ammonia co-adsorption phenomena on M(1 1 1) and Pd₃M(1 1 1) (M = Pd, Ru, Ag, Au, Cu) surfaces are studied using density functional theory calculations. It is shown that the surface adsorption properties are strongly dependent on the surface composition, which can be linked to the corresponding electronic structure at the membrane surface. Full article

Hydrogen purification is a critical industrial process, and there are ongoing efforts to develop low-cost alternatives to palladium foil membranes. Titanium nitride (TiN) is studied as an interdiffusion barrier to enable hydrogen permeation in composite palladium–vanadium membranes. TiN was deposited via reactive sputtering, and films with the desired (200) orientation were obtained in the metallic regime at 400 °C under a 200 V bias to the substrate. The permeability of thin-film TiN was determined with palladium-based sandwich structures. TiN layers up to 10 nm resulted in a minimal decrease in flux (~20%) relative to a freestanding PdCu foil, which was attributed to the interfacial resistance. At greater thicknesses, the TiN layer was rate-limiting, and it was found that the effective permeability of the sputtered TiN thin films was ~6 × 10⁻¹² mol s⁻¹ m⁻¹ Pa^−0.5. Composite Pd|TiN|V|TiN|Pd membranes exhibited permeability values up to three times greater than pure palladium, exhibiting stability at 450 °C for over 100 h, with the lack of intermetallic diffusion and alloy formation being confirmed with XRD. The membranes were unstable at 500 °C, which was attributed to the instability of the thin Pd layer and loss of catalytic activity. Full article

Thin-film membranes of Pd-Ag and Pd-Cu alloys capable of releasing hydrogen in a wide temperature range have been developed. The surface activation of the membranes with a nanostructured coating made it possible to intensify hydrogen transport through Pd-containing membranes at low temperatures. This effect was achieved by accelerating limiting surface processes by increasing the active area of the membrane. Surface-activated membranes demonstrated the highest values of hydrogen flux over the entire temperature range, which reached up to 49.4 mmol s⁻¹ m⁻² for Pd-Ag membranes and up to 32.9 mmol s⁻¹ m⁻² for Pd-Cu membranes. Membranes modified with filiform nanoparticles demonstrated a hydrogen flux up to 12 times higher than that of membranes with a smooth surface. Based on the results obtained, a theoretical model of hydrogen transport through metal membranes was developed, taking into account the effect of the state of the membrane surface on hydrogen transport at low temperatures. This model makes it possible to predict hydrogen flows in the entire temperature range much more accurately compared to other existing models. The selectivity and stability of the developed membranes over a long period of operation have been confirmed. The study of the effect of the surface activation of Pd-based membranes on the intensification of hydrogen permeability has shown the success of the method developed, which in turn opens up wide opportunities for creating low-temperature, highly efficient membrane hydrogen filters based on palladium and other devices based on them. Full article

The development of stable and durable hydrogen (H₂) separation technology is essential for the effective use of H₂ energy. Thus, the use of H₂ permeable membranes, made of palladium (Pd), has been extensively studied in the literature. However, Pd has considerable constraints in large-scale applications due to disadvantages such as very high cost and H₂ embrittlement. To address these shortcomings, copper (Cu) and Pd were deposited on Ta to fabricate a composite H₂ permeable membrane. To this end, first, Pd was deposited on a tantalum (Ta) support disk, yielding 7.4 × 10⁻⁸ mol_H2 m⁻¹ s⁻¹ Pa^−0.5 of permeability. Second, a Cu–Pd alloy on a Ta support was synthesized via stepwise electroless plating and plasma sputtering to improve the durability of the membrane. The use of Cu is cost-effective compared with Pd, and the appropriate composition of the PdCu alloy is advantageous for long-term H₂ permeation. Despite the lower H₂ permeation of the PdCu/Ta membrane (than the Pd/Ta membrane), about two-fold temporal stability is achieved using the PdCu/Ta composite. The degradation process of the Ta support-based H₂ permeable membrane is examined by SEM. Moreover, thermocatalytic H₂ dissociation mechanisms on Pd and PdCu were investigated and are discussed numerically via a density functional theory study. Full article

Owing to exceptionally high selectivity, membranes based on palladium alloys are widely used for obtaining high-purity hydrogen. An important issue for providing high hydrogen permeability of the membranes is to form the required phase composition. The structural organization of the solid solutions consisting of Cu–36.4 at .% Pd and Cu–50 at .% Pd were studied by X-ray diffraction (XRD), electron diffraction (ED), high-resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDXS). It was found that the former composition can be ordered in the temperature range of 300–400 °C and in the heating (up to 800 °C)–cooling cycle. In the presence of excess Cu atoms (27.2%), this structure can be represented by CsCl type structural units (β-phase) and distributed body center cubic (BCC) copper structural units in the corresponding concentration dose. The formation of a single crystal ordered phase within the mosaic blocks of the disordered phase was established. Experimental evidence was obtained for the separation of the α-phase solid solution in the elemental composition; the very low rate of ordering inherent in this system was attributed to this effect. The hydrogen permeability of a foil of the equiatomic composition was described. Full article

The study of methanol steam reforming (MSR) over a Pt-Rh/TiO₂-In₂O₃ catalyst was carried out in traditional and membrane reactors using Pd-Cu foil treated by various methods. This catalyst showed the highest catalytic activity in a conventional reactor. The best results (hydrogen yield) are achieved in a membrane reactor with the use of the Pt-Rh/TiO₂-In₂O₃ catalyst and Pd-Cu membrane after hard rolling. At the same time, the hydrogen recovery degree on the permeate zone on this membrane reached 60%. Full article

A thin Pd-based H₂-permeable membrane is required to produce high-purity H₂ with high efficiency. In this study, a porous Ni-supported Pd₆₀Cu₄₀ composite H₂-permeable membrane was developed using a reverse build-up method to produce economical H₂ purification. The thickness of the Pd₆₀Cu₄₀ alloy layer produced by the improved membrane production process reached 1.0 μm; it was thinner than the layer obtained in a previous study (3.7 μm). The membrane was characterized by scanning electron microscope, inductively coupled plasma optical emission spectrometer, H₂ permeation test, and Auger microprobe analysis. The permeation tests were performed at 300–320 °C and 50–100 kPa with H₂ introduced from the primary side. The H₂ permeation flux was stable up to ~320 °C. The n-value was determined to be 1.0. The H₂ permeance of the membrane was 2.70 × 10⁻⁶ mol m⁻² s⁻¹ Pa^−1.0 at 320 °C, after 30 h, similar to those of other 2.2-µm-thick and 3.7-µm-thick Pd₆₀Cu₄₀ composite membranes, suggesting that the adsorption and dissociation reaction processes on the PdCu alloy surface were rate-limiting. The Pd cost of the membrane was estimated to be ~1/30 of the Pd cost of the pure Pd₆₀Cu₄₀ membrane. Full article

Dense metal membranes that are based on palladium (Pd) are promising for hydrogen separation and production due to their high selectivity and permeability. Optimization of alloy composition has normally focused on bulk properties, but there is growing evidence that grain boundaries (GBs) play a crucial role in the overall performance of membranes. The present study provides parameters and analyses of GBs in the ternary Pd-Ag-Cu system, based on first-principles electronic structure calculations. The segregation tendency of Cu, Ag, and vacancies towards 12 different coherent ∑ GBs in Pd was quantified using three different procedures for relaxation of supercell lattice constants, representing the outer bounds of infinitely elastic and stiff lattice around the GBs. This demonstrated a clear linear correlation between the excess volume and the GB energy when volume relaxation was allowed for. The point defects were attracted by most of the GBs that were investigated. Realistic atomic-scale models of binary Pd-Cu and ternary Pd-Cu-Ag alloys were created for the ∑5(210) boundary, in which the strong GB segregation tendency was affirmed. This is a starting point for more targeted engineering of alloys and grain structure in dense metal membranes and related systems. Full article