Graphite coating on alumina substrate for the fabrication of hydrogen selective membranes

Development of composite membranes is a suitable alternative to improve the hydrogen flux through palladium membranes. The porous substrate should not represent a barrier to gas permeation, but the roughness of its surface should be sufficiently smooth for the deposition of a thin and defect-free metal layer. In this study, the performances of the modification of the outer surface of an asymmetric alumina hollow fibre substrate by the deposition of a graphite layer were evaluated. The roughness of the substrate outer surface was reduced from 120 to 37 nm after graphite coating. After graphite coating, the hydrogen permeance through the composite membrane produced with 2 Pd plating cycles was of 1.02 × 10^?3 mol s^?1 m^?2 kPa^?1 at 450 °C and with infinite H₂/N₂ selectivity. Similar hydrogen permeance was obtained with the composite membrane without graphite coating, also at infinite H₂/N₂ selectivity, but 3 Pd plating cycles were necessary. Thus, graphite coating on asymmetric alumina hollow fibres is a suitable alternative to reduce the required palladium amount to produce hydrogen selective membranes.     

Preparation of palladium membrane on Pd/silicalite-1 zeolite particles modified macroporous alumina substrate for hydrogen separation

A palladium composite membrane was successfully fabricated by electroless plating on a macroporous alumina tube. Pd/silicalite-1 zeolite particles were employed to reduce the pore size of the alumina support and improve its surface roughness. Moreover, the Pd⁰ existed in the Sil-1 particle can avoid the time consuming sensitization and activation steps for palladium seeding. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDXS) and X-ray diffraction (XRD) analysis were conducted for analyzing the detailed microstructure of the palladium composite membrane. The hydrogen permeation performance of the resulting palladium membrane was investigated at temperatures of 623 K, 673 K, 723 K and 773 K. The hydrogen permeance of 1.95 × 10⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ with an H₂/N₂ ideal selectivity of 1165 for the palladium membrane was obtained at 773 K. Furthermore, the resulting palladium membrane was stable for a long-term operation of 15 days at 673 K.     

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 of thin Pd membrane on porous stainless steel tubes modified by a two-step method

Thin Pd membranes for hydrogen filtration were deposited on modified porous stainless steel (PSS) tubes using an electroless plating technique. Alumina oxide (Al₂O₃) particles of two different sizes were subsequently used to modify the non-uniform pore distribution and the surface roughness of the PSS tubes. The principle of the modification was to use large Al₂O₃ particles (∼10 μm) to fill larger pores on the surface, and leave the smaller pores intact. Small Al₂O₃ particles (∼1 μm) were then used to further decrease the surface roughness. The detailed manufacturing steps of the Al₂O₃ modification were investigated and optimized to achieve a continuous dense Pd membrane with a minimum thickness of 4.4 μm on the modified PSS tubes. The highest hydrogen permeance of the membrane was 2.94 × 10⁻³ mol/m²-s-kPa^0.5 at 773 K, with a selectivity coefficient (H₂/He) of 1124 under a pressure difference of 800 kPa. In comparison, the thickness and hydrogen permeance of a dense Pd membrane on unmodified PSS tubes were 31.5 μm and 5.97 × 10⁻⁴ mol/m²-s-kPa^0.5, respectively, at 773 K under an 800 kPa pressure difference. The stability of the membranes at high temperatures was also investigated. The hydrogen permeation flux at 773 K was stable during a test period of 500 h. These results demonstrate that the two-step method modifies the surface of PSS tubes in a relatively simple way and results in thin, dense Pd membranes with high hydrogen permeance and good thermal stability.     

Silica-zirconia membrane supported on modified alumina for hydrogen production in steam methane reforming unit

A hydrogen-selective and hydrothermally stable membrane composed of silica-zirconia layer deposited on a modified alumina sub layer was successfully prepared. The composite membrane was used for hydrogen purification from synthesis gas in steam methane reforming process. Silica-zirconia layer was synthesized using the CVD method at 923K and atmospheric pressure while the alumina base layer was prepared via sol-gel procedure. DLS, XRD, SEM/EDX, and BET characterization techniques were used to prove that γ-alumina base and silica-zirconia layer are fabricated successfully. Using the composite membrane, hydrogen selectivity toward other gases has improved significantly. Moreover, H₂/CH₄, H₂/CO, and H₂/CO₂ selectivity have been increased from 700, 350 and 70 in 5 h CVD synthesized membrane to 1600, 750 and 570 for 12 h CVD synthesized membrane respectively. The synthesized Silica-Zirconia membrane successfully altered gases permeability tendency order from H₂ > CH₄ > CO₂ > CO to H₂ > CO₂ > CO > CH₄ which leads to better separation of the product from methane feed. Finally, hydrothermal stability test demonstrated that permeability loss in silica-zirconia CVD coated membrane for H₂ is 45.7% after 48 h, while for silica CVD coated on the modified alumina approaches 92.5%.     

In-situ repair of composite palladium membranes with macro defects: A case study

A new method was developed for repairing Pd/Al₂O₃ membranes with macro defects without the need of disassembling the membrane from the module. In order to target and fill the membrane defect automatically with solid particles, a TiO₂ powder was firstly tested by flowing high-pressure nitrogen as a carrier gas, followed by a heat treatment. A filter cake was found on the membrane defect but still porous. A glass powder was selected instead of TiO₂, and the membrane defect was successfully sealed by glazing. The in-situ repair of a waste commercial Pd/Al₂O₃ membrane separator was carried out with the glass powder, and the hydrogen flux and H₂/N₂ selectivity of the membrane separator at 450 °C under 100 kPa reached 12.6 m³m⁻²h⁻¹ and 1600, respectively.     

Pd–Cu alloy membrane deposited on CeO2 modified porous nickel support for hydrogen separation

In this study, the hydrogen permeation behavior of a Pd₉₃–Cu₇ alloy membrane deposited on ceria-modified porous nickel support (PNS) was evaluated. PNS, which has an average pore size of 600 nm, was modified by alumina sol. Alumina sol was prepared using precursors that had a mean particle size of 300 nm. Alumina-modified PNS was further treated with ceria sol modification to produce a smoother surface morphology and narrow surface pores. A 7 μm thick Pd₉₃–Cu₇ alloy membrane was made on an alumina-modified PNS and a ceria-finished membrane was fabricated by magnetron sputtering followed by Cu-reflow at 700 °C for 2 h. SEM analysis showed that the membrane deposited on a ceria-finished PNS contained more clear grain boundaries than the membrane deposited on the alumina-modified PNS. The membrane was mounted in a stainless steel permeation cell with a gold-plated stainless steel O-ring. Permeation tests were then conducted using pure hydrogen and helium at temperatures ranging from 673 to 773 K and feed side pressures ranging from 100 to 400 kPa. These tests showed that the membrane had a hydrogen permeation flux of 2.8 × 10⁻¹ mol m⁻² s⁻¹ with H₂/He selectivity of >50,000 at a temperature of 773 K and pressure difference of 400 kPa.     

Fabrication,characterization, and application of palladium composite membrane on porous stainless steel substrate with NaY zeolite as an intermediate layer for hydrogen purification

Palladium composite membrane with excellent stability was successfully prepared using the electroless plating (ELP) route on a porous stainless steel (PSS) support for hydrogen separation. In order to modify the average pore size of PSS support and to prevent inter-metallic diffusion, the NaY zeolite layer was coated on the PSS support with the seeding and secondary growth method. A high-temperature membrane module was designed by Solid work software and fabricated from 316 L stainless steel with a knife-edge seal. The microstructures and morphologies of the samples were analyzed using XRD, BET, AFM, FESEM and EDX techniques. Permeation experiments were carried out with binary mixtures of H₂/N₂ with various ratios (90/10, 75/25 and 50/50) and pure H₂ and N₂ at different temperatures (350, 400 and 450 °C) and feed pressures (200–400 kPa). Hydrogen permeation tests showed that the membrane with a thickness of about 7 μm had a hydrogen permeance of 6.2 × 10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 with an ideal H₂/N₂ selectivity of 736, at 450 °C. In addition, the results of stability tests revealed that the membrane could remain stable during a long-term operation by varying temperature and feed gases.     

Fabrication,permeation, and corrosion stability measurements of silica membranes for HI decomposition in the thermochemical iodine–sulfur process

In this study, a corrosion-stable silica membrane was developed to be used in H₂ purification during the hydrogen iodide decomposition (2HI → H₂ + I₂), which is a new application of the silica membranes. From a practical perspective, the membrane separation length was enlarged up to 400 mm and one end of the membrane tubes was closed to avoid any thermal variation along the membrane length and sealing issues. The silica membranes consisted of a three-layer structure comprising a porous α-Al₂O₃ ceramic support, an intermediate layer, and a top silica layer. The intermediate layer was composed of γ-Al₂O₃ or silica, and the top silica layer that is H₂ selective was prepared via counter-diffusion chemical vapor deposition of a hexyltrimethoxysilane.To the best of our knowledge, this is the first report of 400-mm-long closed-end silica membranes supported on Si-formed α-Al₂O₃ tubes produced via chemical vapor deposition method. A 400-mm-long closed-end membrane using a Si-formed α-Al₂O₃ tube exhibited a higher H₂/SF₆ selectivity of 1240 but lower H₂ permeance of 1.4 × 10⁻⁷ mol Pa⁻¹ m⁻² s⁻¹ with compared with the membrane using a γ-Al₂O₃-formed α-Al₂O₃ tube (907 and 5.6 × 10⁻⁷ mol Pa⁻¹ m⁻² s⁻¹, respectively). The membrane using the Si-formed α-Al₂O₃ tube was more stable in corrosive HI gas than a membrane with a γ-Al₂O₃-formed α-Al₂O₃ tube after 300 h of stability tests. In conclusion, the developed silica membranes using the Si-formed α-Al₂O₃ tubes seem suitable for membrane reactors that produce H₂ on large scale using HI decomposition in the thermochemical iodine–sulfur process.     

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.     

An improvement of the hydrogen permeability of C/Al2O3 membranes by palladium deposition into the pores

The development of compact hydrogen separator based on membrane technology is of key importance for hydrogen energy utilization, and the Pd-modified carbon membranes with enhanced hydrogen permeability were investigated in this work. The C/Al₂O₃ membranes were prepared by coating and carbonization of polyfurfuryl alcohol, then the palladium was introduced through impregnation–precipitation and colloid impregnation methods with a PdCl₂/HCl solution and a Pd(OH)₂ colloid as the palladium resources, and the reduction was carried out with a N₂H₄ solution. The resulting Pd/C/Al₂O₃ membranes were characterized by means of SEM, EDX, XRD, XPS and TEM, and their permeation performances were tested with H₂, CO₂, N₂ and CH₄ at 25 °C. Compared with the colloid impregnation method, the impregnation–precipitation is more effective in deposition of palladium clusters inside of the carbon layer, and this kind of Pd/C/Al₂O₃ membranes exhibits excellent hydrogen permeability and permselectivity. Best hydrogen permeance, 1.9 × 10⁻⁷ mol/m² s Pa, is observed at Pd/C = 0.1 wt/wt, and the corresponding H₂/N₂, H₂/CO₂ and H₂/CH₄ permselectivities are 275, 15 and 317, respectively.     

Porous stainless steel support for hydrogen separation Pd membrane; fabrication by metal injection molding and simple surface modification

We prepared a disc-shaped porous stainless steel (PSS) support for hydrogen separation Pd membrane via metal injection molding (MIM) method to facilitate the mass production of porous substrates. MIMed PSS supports obtained in a batch showed relatively higher apparent porosity (from 32.75% to 39.28%) than that reported for commercially available PSS substrate. In addition, the surface morphologies of the MIMed PSS, surface roughness of 1.119 μm and pore depth of 8.6 μm, indicate its suitability as a membrane support than the commercially available one. Pd membrane prepared over MIMed PSS, which was modified by a simple axial pressing method to control the surface morphologies, had a thinner Pd layer, 2.94 μm, and showed an extremely higher ideal H₂/N₂ selectivity with a hydrogen permeation flux of 21.3 ml/min/cm² at del-P = 1 bar and 400 °C, compared with Pd membrane over MIMed PSS modified with conventional surface modification.     

Fabrication of Pd/ceramic membranes for hydrogen separation based on low-cost macroporous ceramics with pencil coating

Increasing hydrogen energy utilization has greatly stimulated the development of the hydrogen-permeable palladium membrane, which is comprised of a thin layer of palladium or palladium alloy on a porous substrate. This work chose the low-cost macroporous Al₂O₃ as the substrate material, and the surface modification was carried out with a conventional 2B pencil, the lead of which is composed of graphite and clay. Based on the modified substrate, a highly permeable and selective Pd/pencil/Al₂O₃ composite membrane was successfully fabricated via electroless plating. The membrane was characterized by SEM (scanning electron microscopy), field-emission SEM and metallographic microscopy. The hydrogen flux and H₂/N₂ selectivity of the membrane (with a palladium thickness of 5 μm) under 1 bar at 723 K were 25 m³/(m² h) and 3700, respectively; the membrane was found to be stable during a time-on-stream of 330 h at 723 K.     

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.     

Influence of the type of siliceous material used as intermediate layer in the preparation of hydrogen selective palladium composite membranes over a porous stainless steel support

In this work, several composite membranes were prepared by Pd electroless plating over modified porous stainless steel tubes (PSS). The influence of different siliceous materials used as intermediate layers was analyzed in their hydrogen permeation properties. The addition of three intermediate siliceous layers over the external surface of PSS (amorphous silica, silicalite-1 and HMS) was employed to reduce both roughness and pore size of the commercial PSS supports. These modifications allow the deposition of a thinner and continuous layer of palladium by electroless plating deposition. The technique used to prepare these silica layers on the porous stainless steel tubes is based on a controlled dip-coating process starting from the precursor gel of each silica material. The composite membranes were characterized by SEM, AFM, XRD and FT-IR. Moreover they were tested in a gas permeation set-up to determine the hydrogen and nitrogen permeability and selectivity. Roughness and porosity of original PSS supports were reduced after the incorporation of all types of silica layers, mainly for silicalite-1. As a consequence, the palladium deposition by electroless plating was clearly influenced by the feature of the intermediate layer incorporated. A defect free thin palladium layer with a thickness of ca. 5 μm over the support modified with silicalite-1 was obtained, showing a permeance of 1.423·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 and a complete ideal permselectivity of hydrogen.     

Evaluation of electrochemical hydrogen storage capability of graphene oxide multi-layer coating

Due to its unique physical and chemical properties, graphene oxide (GO) has excellent potential in energy-saving applications, especially in hydrogen storage materials such as bulk and layer coatings. A three-layer GO/Ni/GO coating was applied successfully on the Ni-foam through the hybrid coating process. GO was firstly synthesized by modified Hummers' method and then deposited on Ni-Foam using an electrophoretic deposition (EPD) method at 40, 60, and 80 V at various times (1 and 2 h). Furthermore, Ni-layer was applied on the first applied to GO layer using a Ni-electroplating bath at 3 V for 3 min. For evaluation of the electrochemical hydrogen storage performance, cyclic voltammetry (CV), galvanostatic charge-discharge (GCD), and electrochemical impedance spectroscopy (EIS) were carried out in 1 M NaOH solution at room temperature. Obtained results showed a significant improvement in the amount of adsorbed hydrogen. The hydrogen storage capacity was increased from 88 to 741 F. g^?1, and load transfer resistance decreased from 260 to 35 Ω for uncoated and coated porous substrates, respectively, which is due to the achieved high specific area. Based on the hydrogen storage capacity, the optimum EPD method is 60 V and 2 h.     

Coating the porous Al2O3 substrate with a natural mineral of Nontronite-15A for fabrication of hydrogen-permeable palladium membranes

Substrate surface modification is a key pretreatment during fabrication of composite palladium membranes for hydrogen purification in hydrogen energy applications. The suspension of a natural porous material, Nontronite-15A mineral, without any organic additives was employed in dip-coating of the porous Al₂O₃ substrate. The Nontronite-15A mineral was characterized by SEM, XRD, TG−DSC and granulometry analysis. The surface and cross-section of the coated porous Al₂O₃ tubes were observed by SEM, and their pore size distribution and nitrogen flux were also measured. Palladium membranes were fabricated over the coated Al₂O₃ tubes by a suction-assisted electroless plating. The optimal loading amount of the Nontronite-15A mineral is just to fill in and level up the surface cavities of the Al₂O₃ substrate rather than to form an extra continuous layer. A thin and selective palladium membrane was successfully obtained, and its permeation performances were tested. The kinetic analyses on the hydrogen flux indicate that the hydrogen permeation behavior exhibits typical characteristics for most of the palladium membranes. During the stability test at 450 °C for 192 h, no membrane damage was detected, and the hydrogen flux increased slightly.     

Thermal stability and effect of typical water gas shift reactant composition on H2 permeability through a Pd-YSZ-PSS composite membrane

This work comprises a study of hydrogen separation with a composite Pd-YSZ-PSS membrane from mixtures of H₂, N₂, CO and CO₂, typical of a water gas shift reactor. The Pd layer is extended over a tubular porous stainless steel support (PSS) with an intermediate layer of yttria-stabilized-zirconia (YSZ). YSZ and Pd layers were incorporated over the PSS using Atmospheric Plasma Spraying and Electroless Plating techniques, respectively. The Pd and YSZ thickness values are 13.8 and 100 μm, respectively, and the Pd layer is fully dense. Permeation measurements with pure, binary and ternary gases at different temperatures (350–450 °C), trans-membrane pressures (0–2.5 bar) and gas composition have been carried out. Moreover, thermal stability of the membrane was also checked by repeating permeation measurements after several cycles of heating and cooling the system. Membrane hydrogen permeances were calculated using Sieverts' law, obtaining values in the range of 4·10⁻⁵–4·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5. The activation energy of the permeance was also calculated using Arrhenius' equation, obtaining a value of 16.4 kJ/mol. In spite of hydrogen selectivity being 100% for all experiments, the hydrogen permeability was affected by the composition of feed gas. Thus, a significant depletion in H₂ permeate flux was observed when other gases were in the mixture, especially CO, being also more or less significant depending on gas composition.     

Pre-activation of SBA-15 intermediate barriers with Pd nuclei to increase thermal and mechanical resistances of pore-plated Pd-membranes

Thermal and mechanical resistances of palladium composite membranes prepared by Electroless Pore-Plating (ELP-PP) and containing SBA-15 as intermediate layer were improved by doping the silica material with Pd nuclei before its incorporation on the composite membrane. Textural properties of synthesized SBA-15 materials (both raw and doped ones) were analyzed by XRD, N₂ adsorption-desorption at 77 K and TEM, while the main properties of the composite membrane were determined by SEM and gravimetric analyses. Moreover, membrane permeation tests were also carried out with pure gases, hydrogen and nitrogen, and binary mixtures of them at temperature of 400 °C and pressure driving forces in the range of 0.5–2.5 bar. The use of bare SBA-15 intermediate layer leads to the appearance of cracks on the Pd layer during permeation experiments at high temperature. In contrast, the use of Pd-doped SBA-15 particles avoids this problem, thus improving both thermal and mechanical resistances of the composite ELP-PP Pd-membrane. Following this preparation method, an estimated Pd thickness of 7.1 μm was obtained, reaching a hydrogen permeance of 3.81·10^?4 mol s^?1 m^?2 Pa^?0.5 and ensuring an ideal H₂/N₂ separation factor higher than 2550 at 400 °C.     

Tuning the alloy degree for Pd-M/Al2O3 (M=Co/ Ni /Cu) bimetallic catalysts to enhance the activity and selectivity of dodecahydro-N-ethylcarbazole dehydrogenation

Hydrogen is a promising candidate to substitute the fossil fuels. However, the efficient hydrogen storage technologies restrict the commercial applications. Developing new catalysts with high activity and selectivity is important for the dehydrogenation reaction in N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NECZ/12H-NECZ) hydrogen storage system. In this work, a series of Pd-M/Al₂O₃ (M = Co, Ni and Cu) bimetallic catalysts are synthesized successfully and show good performance in the dehydrogenation reaction of 12H-NECZ than the commercial Pd/Al₂O₃ catalyst. The Pd₁Co₁/Al₂O₃ catalyst (Practical Pd content = 2.4136 wt%) showed the highest catalytic performance with 95.34% H₂ release amount, TOF of 230.5 min⁻¹ and 85.4% selectivity of NECZ. Combined with the characterization analysis, it can be proposed that the dehydrogenation performance of 12H-NECZ is dependent on the alloy phases, reasonable electronic structures and nanoparticle size of catalysts. The fine-tuned alloy degree and appropriate nanoparticle size of Pd₁Co₁/Al₂O₃ bring the 17.7% increase of H₂ release amount and 99.5% increase of NECZ selectivity than those of Pd/Al₂O₃. For the bimetallic catalysts, the enhancement of selectivity of NECZ is mainly from the increase of the kinetic constant of rate-limiting step.