High active pd@mil-101 catalyst for dehydrogenation of liquid organic hydrogen carrier

Highly dispersed Pd nanoparticles immobilized in MIL-101 (Pd@MIL-101) were prepared and used for the catalytic dehydrogenation of Liquid organic hydrogen carriers (LOHC). The as-synthesized catalysts were characterized and it was found that 3 wt% of Pd@MIL-101 embodied smaller and highly dispersed Pd NPs. The catalytic activities of as-synthesized catalysts were investigated by the dehydrogenation of a representative LOHC compound, perhydro-N-propylcarbazole (12H-NPCZ). The results indicated that 3 wt% Pd@MIL-101 catalyst exhibited good catalytic activity and good reusability for the dehydrogenation of 12H-NPCZ, which is superior to that of commercial 5 wt% Pd/Al₂O₃ catalyst. This study demonstrates that Pd@MIL-101 is a promising dehydrogenation catalyst for the application of LOHC technology.     

Study on reversible hydrogen uptake and release of 1,2-dimethylindole as a new liquid organic hydrogen carrier

Indole derivatives have been considered as promising liquid organic hydrogen carriers (LOHCs) for onboard hydrogen storage applications. Here a new member of indole family, 1,2-dimethylindole (1,2-DMID), was reported as a potential liquid organic hydrogen carrier with a hydrogen storage content of 5.23 wt%, a meting point of 55 °C and a boiling point of 260 °C. Full hydrogenation and dehydrogenation of 1,2-DMID can be achieved with fast kinetics under mild conditions. The hydrogenation of 1,2-DMID followed the first order kinetics with an apparent activation energy of 85.1 kJ/mol. Dehydrogenation of fully hydrogenated product, octahydro-1,2-DMID was conducted over 5 wt% Pd/Al₂O₃ at 170–200 °C. The stored hydrogen can be completely released at 180 °C in 3 h and at 200 °C in 1 h. The energy barrier of dehydrogenation of octahydro-1,2-DMID was calculated to be 111.9 kJ/mol 3 times cycles of hydrogenation and dehydrogenation were employed to test the recycle ability of 1,2-DMID. The structures of intermediates were also discussed by means of Material Studio calculations.     

7-ethylindole: A new efficient liquid organic hydrogen carrier with fast kinetics

We report a discovery of a new member of the liquid organic hydrogen carrier (LOHC) family, 7-ethylindole (7-EID), with a low melting point of ?14 °C and a decent hydrogen content of 5.23 wt%. Hydrogenation of the compound was carried out over a commercial 5 wt% Ru/Al₂O₃ catalyst in the H₂ pressure range of 5–8 MPa and a temperature range of 120–160 °C, respectively. It was found that the hydrogenation rate positively correlates with the reaction temperature. However, the rate was barely effected by the H₂ pressure if the pressure exceeds 6 MPa. The estimated apparent activation energy of 7-EID hydrogenation is 51.5 kJ/mol. The fully hydrogenated product, octahydro-7-ethylindole (8H-7-EID), was used as the reactant for the dehydrogenation reaction at 170–200 °C over a 5 wt% Pd/Al₂O₃ catalyst. Full dehydrogenation of 8H-7-EID to 7-EID can be achieved within 270 min at 190 °C. The apparent activation energy of 8H-7-EID dehydrogenation was calculated to be 101.9 kJ/mol at 170–200 °C. The liberated H₂ was found to be of high purity, which meets the requirement of proton exchange membrane fuel cells.     

A YH3 promoted palladium catalyst for reversible hydrogen storage of N-ethylcarbazole

N-ethylcarbazole (NEC) is a promising liquid organic hydrogen carrier, while sluggish kinetics of hydrogen absorption and desorption restrict its application. To overcome that, a YH₃ promoted palladium catalyst Pd/Al₂O₃-YH₃ is developed in this work by taking advantage of the fast reversible hydrogenation and dehydrogenation kinetics of YH₃. With the Pd/Al₂O₃-YH₃, NEC can reversibly store 5.5 wt% hydrogen in 4 h below 473 K. The performance is the best compared to that of all the reported catalysts for both hydrogen absorption and desorption. Moreover, there are no gaseous impurities produced and no performance decay during three hydrogen storage cycles. The excellent performance derives from the intrinsic high catalytic activity of Pd/Al₂O₃ and the promoting effect of YH₃ by providing a new hydrogen transfer path, making NEC more attractive for practical application.     

A highly adaptable Ni catalyst for Liquid Organic Hydrogen Carriers hydrogenation

Reducing the cost of hydrogenation/dehydrogenation catalysts and improving the catalytic activity are essential steps to promote the commercial application of Liquid Organic Hydrogen Carriers (LOHCs) technology. We reported a series of highly adaptable 70 wt% Ni supported catalysts prepared by a facile co-precipitation method. The as-prepared catalysts were used in the hydrogenation of several promising LOHCs candidates, including benzene, N-propylcarbazole, N-ethylcarbazole and dibenzyltoluene. By adjusting the ratio of Al and Si, the Ni₇₀/AlSiO-1/1 catalyst with Al and Si in a molar ratio of 1:1 presents highest catalytic activity for hydrogenation of the above LOHCs, indicating the catalyst is highly adaptable for different LOHCs. The characterization results proved that the presence of SiO₂ could significantly weaken the interaction between metal and carrier and decrease the formation of NiAl₂O₄ species, which is beneficial to the reducibility of Ni. The introduced Al₂O₃ can inhibit the agglomeration of Ni and increase the dispersion of the metal. Besides, the Ni₇₀/AlSiO-1/1 catalyst was used to hydrogenate N-propylcarbazole by 5 cycles. In the fifth cycle, the hydrogen uptake reached the theoretical hydrogenation storage within 1.5 h, which suggested the excellent stability of the catalyst. Because of its low cost, high efficiency, high adaptation and highly stable, the self-made Ni catalyst has potential prospect in large-scale LOHCs application.     

Wet-impregnated bimetallic Pd-Ni catalysts with enhanced activity for dehydrogenation of perhydro-N-propylcarbazole

Palladium/platinum-based catalysts are widely used in the dehydrogenation process of Liquid Organic Hydrogen Carriers (LOHCs). The cost of noble metal has become a main drawback for LOHCs large-scale application. Partial replacement of Pd/Pt by other transition metals can be an effective solution. In this paper, we synthesize the bimetallic Pd–Ni catalyst by incipient wet impregnation and the catalytic dehydrogenation performance of perhydro-N-propylcarbazole (12H-NPCZ) as a LOHC candidate. Ni and Pd were impregnated on mesoporous alumina to obtain both monometallic and bimetallic catalysts, i.e. Pd/Al₂O₃, Ni/Al₂O₃ and Pd–Ni/Al₂O₃ (Pd:Ni = 1:1) with total metal loading of 5 wt%, respectively. The above catalysts were characterized by N₂-adsorption/desorption, H₂-temperature programmed reduction, X-Ray diffraction, X-Ray photoelectron spectroscopy, Inductively coupled plasma - optical emission spectrometer, CO pulse adsorption and Transmission electron microscopy. The catalytic dehydrogenation results indicated that the bimetallic Pd–Ni/Al₂O₃ showed best catalytic activity, followed by Pd/Al₂O₃, commercial Pd/Al₂O₃ and Ni/Al₂O₃. Notably, the catalytic activity of bimetallic was well maintained after 5 cycles at 200 °C with no degradation, indicating this bimetallic catalyst has potential prospect for large-scale application.     

Pt/CeO2 catalyst synthesized by combustion method for dehydrogenation of perhydro-dibenzyltoluene as liquid organic hydrogen carrier: Effect of pore size and metal dispersion

Liquid organic hydrogen carrier (LOHC) is a chemical hydrogen storage method that stores hydrogen in the form of liquid organics. Dibenzyltoluene (DBT) is a promising LOHC material due to its high storage density, low ignitability, and low cost. In this study, Pt/Al₂O₃ and Pt/CeO₂ catalysts are synthesized using a combustion nanocatalyst synthesis method called the glycine nitrate process (GNP) to obtain high catalytic activity for the dehydrogenation of perhydro-dibenzyltoluene (H18-DBT). Pt/CeO₂ exhibits much faster dehydrogenation than Pt/Al₂O₃, 80.5%/2.5 h versus 3.5%/2.5 h. To investigate the causes of the difference in the dehydrogenation rates, microstructural characterization by N₂ physisorption, CO chemisorption and transmission electron microscopy analysis are conducted, and the catalytic activities are evaluated at various liquid hourly space velocities (LHSVs). The differences in dehydrogenation can be attributed to the mass transport of liquid H18-DBT into the catalyst pores being slow due to the small pores in Pt/Al₂O₃, which is a rarely addressed issue for other LOHC materials. This is because many LOHC materials are dehydrogenated at the gas phase, which has higher diffusivity than that of the liquid phase. Pt/CeO₂ synthesized by the GNP is also compared with a commercial Pt/Al₂O₃ catalyst. The commercial Pt/Al₂O₃ catalyst shows a dehydrogenation of 17.8%/2.5 h, which is much slower than that of Pt/CeO₂ synthesized by the GNP, at 80.5%/2.5 h.     

Preparation of Ni-based egg-shell-type catalyst on cylinder-shaped alumina pellets and its application for hydrogen production via steam methane reforming

Nickel-based ‘egg-shell-type’ catalysts were prepared using cylinder-shaped alumina pellets as supports. In the egg-shell-type catalysts, nickel was selectively located in the outer region of the alumina pellets. Ethylene glycol or 1-octanol were used as hydrophobic solvents to retard internal penetration of the alumina pellets by the nickel nitrate solution. Without hydrophobic solvent, a ‘homo-type’ catalyst with even nickel distribution inside the alumina pellets was achieved. Cross-sectional images and SEM-EDS analysis of the cylinder-shaped alumina pellets showed that nickel concentration in the egg-shell-type catalyst was higher in the outer region and decreased towards the inner region of the alumina pellets. The egg-shell-type nickel distribution was maintained after subsequent magnesium impregnation and calcination processes. X-ray diffraction patterns and temperature programmed reduction profiles showed that the only difference between homo-type and egg-shell type catalysts, when their nickel loading was the same, was the nickel distribution inside pellets; and this was shown to cause significant difference in their catalytic activity in the steam methane reforming (SMR) reaction. For the homo-type catalyst, nickel loading of 3.5 wt% was insufficient for the SMR reaction, as metallic nickel particles were evenly distributed through the entire alumina pellet. However, nickel loading of 3.5 wt% was sufficient for the egg-shell-type catalyst, because active sites with metallic nickel particles were concentrated in the outer region of the pellets. These experimental results confirmed that the egg-shell-type nickel distribution is a favorable design for an SMR reaction catalyst.     

Theoretical evaluation of N-alkylcarbazoles potential in hydrogen release

Alkyl chain effect (ethyl, propyl and butyl) on the dehydrogenation mechanism of H₁₂-N-alkylcarbazoles has been investigated theoretically under various different conditions. Gibbs energies of activation of about 107.88 kcal mol^?1 have been determined as the least energy barriers among the studied dehydrogenation processes for dehydrogenation of H₁₂-N-ethylcarbazole to H₄-N-ethylcarbazole in decalin and 57.44 kcal mol^?1 for dehydrogenation of H₁₂-N-propylcarbazole to H₈-N-propylcarbazole under the experimental conditions. Kinetic and thermodynamic studies have shown that the route of H₄-N-alkylcarbazoles formation passes through a higher barrier than that of the H₈-N-alkylcarbazoles. Natural bond orbital (NBO) analysis showed a decrease in electron transfer between π_C–C and σ*_C–H at the center of the reaction. The electron density of the C–H bonds of the transition states was evaluated as evidence of hydrogen release via quantum theory of atoms in the molecules (QTAIM) procedure. Based on this analysis, a change in the nature of C–H bonds was confirmed from covalence to electrostatic interactions during the reaction.     

Dehydrogenation of perhydro-dibenzyltoluene for hydrogen production in a microchannel reactor

A preliminary study regarding the dehydrogenation of perhydro-dibenzyltoluene as a liquid organic hydrogen carrier with switching from a stirred tank reactor to a continuous flow microchannel reactor is presented. The hydrogen production percentage in the case of a continuous flow microchannel reactor was found greater when compared to that of a stirred tank reactor. The hydrogen production was increased from 64.1% to 82.2% with the increase in bottom plate temperature from 260 to 320 °C for 0.01 mL/min flow rate. A maximum of 88% of hydrogen was generated for a 40 hours of operation, at a bottom wall temperature of 290 °C. The kinetic model for the microchannel reactor dehydrogenation was presented with a pre-exponential factor of 3.272 s^?1 and activation energy of 13.79 kJ/mol. The results revealed that a continuous microchannel reactor can be an appropriate technology for the dehydrogenation of perhydro-dibenzyltoluene.     

Evaluation of catalyst activity for release of hydrogen from liquid organic hydrogen carriers

This contribution investigate the effect of parameters for production of hydrogen by catalytic dehydrogenation of perhydrodibenzyltoluene (H18-DBT). The sensitivity of the dehydrogenation reaction to temperature (290–320 °C) is justified by an increase in degree of dehydrogenation (DoD) from 40 to 90% when using 1 wt % Pt/Al₂O₃ catalyst. However, the increase in temperature increases the hydrogen production rate and decreases the hydrogen purity by increasing the formation of by-products. In addition, the DoD of 96% is obtained when 2 wt % Pt/Al₂O₃ is used at 320 °C. The DoD obtained for Pd, Pt, and Pt–Pd catalysts is 11, 82 and 6%, respectively. Therefore, Pd is not a metal of choice for dehydrogenation of H18-DBT, in both monometallic and bimetallic system. The ab-initio density functional theory (DFT) calculations are consistent with this observation. Furthermore, dehydrogenation of H18-DBT followed 1st order reaction kinetics and the activation energies for 1 wt % Pt/Al₂O₃, 1 wt % Pd/Al₂O₃ and 1:1 wt % Pt–Pd/Al₂O₃ catalysts are: 205, 84 and 66 kJ/mol, respectively.     

Co-P nanoparticles supported on dandelion-like CNTs-Ni foam composite carrier as a novel catalyst for hydrogen generation from NaBH4 methanolysis

We used the chemical vapor deposition method to prepare dandelion-like CNTs-Ni foam composite carrier, and then the electroless plating method was used to deposit Co-P nanoparticles on the CNTs of the CNTs-Ni foam. The CNTs-Ni foam and Co-P/CNTs-Ni foam were characterized by BET, SEM, XRD, XPS, and EDS. The results showed that CNTs were uniformly and densely grown in situ on the surface of Ni foam and were further successfully coated with Co-P nanoparticles. The Co-P/CNTs-Ni foam catalysts still maintained the dandelion-like structure and reached a maximum hydrogen production rate of 2430 mL min⁻¹ g⁻¹ at 25 °C. Furthermore, the Co-P/CNTs-Ni foam catalysts also exhibit a remarkable cycling performance and low activation energy (49.94 kJ mol⁻¹) for the methanolysis of sodium borohydride.     

Effect of surface hydrophilization on Pt/Sibunit catalytic activity in bicyclohexyl dehydrogenation in hydrogen storage application

The dehydrogenation of bicyclohexyl as a liquid organic hydrogen carrier on supported Pt/Sibunit catalysts based on the neutral and partially oxidized supports at a temperature of 320 °C and a space velocity of up to 1.5 h^?1 was studied. The oxidized Sibunit is a more effective support for Pt catalyst in terms of TOF, conversion and selectivity than the neutral carrier. The 3 wt% Pt catalyst shows a higher conversion and selectivity to biphenyl than the 0.5 wt% Pt catalyst on both carriers, but TOF of 0.5 wt% Pt catalyst reaches 238 and 182 mol(H₂)/(gPt * min) for 4 h of the reaction on oxidized Sibunit and neutral Sibunit, respectively. The TOF are 47 and 42 mol(H₂)/(gPt * min) for the corresponding catalysts with a 3 wt% Pt loading.     

Catalytic dehydrogenation study of dodecahydro-N-ethylcarbazole by noble metal supported on reduced graphene oxide

Through systematical experiments, a comparative study was conducted concerning several graphene-supported noble metal catalysts for dehydrogenation of dodecahydro-N-ethylcarbazole (12H-NEC). It was found that the catalytic activity of the prepared graphene-supported noble metal catalysts was following the order of Pd > Pt > Rh > Ru > Au for the dehydrogenation process. Pd supported on reduced graphene oxide (rGO) prepared by one-pot in situ synthesis has much more excellent catalytic performance than other kinds of catalysts investigated for comparison, simultaneously the using amount of noble metals can obviously be decreased. To be specific, at 453 K, the final dehydrogenation product catalyzed by the novel catalyst of Pd/rGO is N-ethylcarbazole (NEC) and the process selectivity was increased from 44.77% (commercial Pd/Al₂O₃) to 97.65%, as well as the dehydrogenation ratio reached 99.14%. In addition, the novel catalyst is also superior to other reported catalysts in terms of dehydrogenation performance of 12H-NEC. Its dehydrogenation activity at 443 and 433 K of Pd/rGO was tested and the catalytic performance keeps stable at the two temperatures. Based on the experimental data, kinetic calculation was carried out and some fundamental parameters regarding reaction kinetics was obtained.     

Hydrogen production by steam reforming of liquefied natural gas over a nickel catalyst supported on mesoporous alumina xerogel

Mesoporous alumina xerogel (A-SG) is prepared by a sol–gel method for use as a support for a nickel catalyst. The Ni/A-SG catalyst is then prepared by an impregnation method, and is applied to hydrogen production by steam reforming of liquefied natural gas (LNG). The effect of the mesoporous alumina xerogel support on the catalytic performance of Ni/A-SG catalyst is investigated. For the purpose of comparison, a nickel catalyst supported on commercial alumina (A-C) is also prepared by an impregnation method (Ni/A-C). Both the hydroxyl-rich surface and the electron-deficient sites of the A-SG support enhance the dispersion of the nickel species on the support during the calcination step. The formation of the surface nickel aluminate phase in the Ni/A-SG catalyst remarkably increases the reducibility and stability of the catalyst. Furthermore, the high-surface area and the well-developed mesoporosity of the Ni/A-SG catalyst enhance the gasification of surface hydrocarbons that are adsorbed in the reaction. In the steam reforming of LNG, the Ni/A-SG catalyst exhibits a better catalytic performance than the Ni/A-C catalyst in terms of LNG conversion and hydrogen production. Moreover, the Ni/A-SG catalyst shows strong resistance toward catalyst deactivation.     

Organic chemical hydride dehydrogenation over nickel catalysts supported with SiO2 for hydrogen recovery

Dehydrogenation of organic chemical hydrides has been investigated with catalysts in which the economical Ni was adopted as catalytic component and SiO₂ as support. In this work dehydrogenation of methylcyclohexane was performed as organic chemical hydride in a fixed-bed catalytic reactor in the temperature range of 653–713 K, having 5, 10, 15, and 20 wt.% Ni content.     

Controllable synthesis of carbon nanofiber supported Pd catalyst for formic acid electrooxidation

Carbon nanofiber (CNF) supported Pd nanoparticles are synthesized with sodium citrate and sodium borohydride served as stabilizing agent and reducing agent, respectively. The size and distribution of the supported Pd nanoparticles are controlled by adjusting the pH value of the synthesis solution. Analyses of the obtained Pd/CNF catalysts indicate that the supported Pd nanoparticles become more uniform in size and the average particle size is decreased from 5.85 to 3.62 nm with pH value of the synthesis solution increasing from 3.2 to 6.0. However, the further increasing of the pH value to 6.5 leads to an increased particle size and the formation of PdO phase in the synthesized Pd/CNF catalyst. The Pd/CNF catalyst synthesized at the pH value of 6.0 exhibits superior catalytic activity and stability for formic acid electrooxidation due to its small particle size and uniform size distribution.     

Hydrocarbon hydrogen carriers for catalytic transfer hydrogenation of guaiacol

Polycyclic hydrocarbons are known to be efficient hydrogen carriers capable of yielding high purity H₂ upon dehydrogenation. Due to their high hydrogen density, high boiling point, and stability, these compounds demonstrate the potential to be used as hydrogen donors under catalytic transfer hydrogenation (CTH) conditions. In this work, the potential of a suite of hydrogen carriers to donate hydrogen, as well as the mechanisms affecting their hydrogen transfer, are assessed through the CTH of guaiacol, on Pd/Al₂O₃, as a model system. The results indicated the following descending order of transfer hydrogenation rate: bicyclohexyl > tetralin » hydrogenated terphenyl (HTP) > cyclohexylbenzene. Among the products, cyclohexanone and phenol are the most abundant, directly resulting from CTH. Detailed analysis of the hydrogen carrier conversion and selectivity clearly shows that the potential for CTH is highly linked to the molecular structure of the donor, rather than the amount of hydrogen available for transfer. A density functional theory (DFT) study, supported by experimental data, reveals that when unsaturated hydrocarbons are utilized, such as tetralin, cyclohexylbenzene, and HTP, the effective CTH rate to guaiacol is limited, despite dehydrogenation being more favorable for those molecules than from fully saturated donors, such as bicyclohexyl.     

Thermodynamic assessment of carbazole-based organic polycyclic compounds for hydrogen storage applications via a computational approach

Liquid organic hydrogen carriers (LOHCs) are promising candidates for storage and transport of renewable energy due to their reversible reaction characteristics. For the proper assessment of candidate molecules, various thermochemical properties are required, and significant experimental efforts are necessary. In this work, we suggest a systematic method for the estimation of thermochemical properties for LOHC candidate molecules combining Density Functional Theory (DFT) calculations, Conductor-like Screening Model (COSMO) and Molecular Dynamics (MD) simulations. We applied the suggested method for the assessment of previously reported LOHC materials. Based on the analysis, new candidates of carbazole-derivative compounds (N-acetylcarbazole, N-phenylcarbazole, N-benzoylcarbazole, and 4-methyl-4H-benzocarbazole) are suggested, and their properties are estimated and reviewed. Calculation results show that these candidates can provide high theoretical hydrogen uptake capacities above 6 wt% and optimal heats of dehydrogenation in the liquid phase. Analysis on the stereoisomerism showed that the structure-selectivity toward less stable stereoisomers of the hydrogen-rich form is preferable for the dehydrogenation process.