Comparative Studies on Full Dehydrogenation of Dodecahydro-N-Ethylcarbazole on Pd(111) and Ni(111) Surfaces: Mechanism and Catalytic Enhancement.

Dodecahydro-N-ethylcarbazole (12H-NEC) is regarded as the most promising liquid organic hydrogen carrier for hydrogen storage and transportation. Understanding the mechanism of 12H-NEC dehydrogenation and developing cost-effective catalysts are significant. Pd is a high-performance catalyst for 12H-NEC but is not cost-effective, and Ni is just the opposite. How to understand the whole process of full dehydrogenation and improve the performance of Ni become two key questions. Herein, we systematically investigated the mechanism of the full dehydrogenation of 12H-NEC on Pd(111) and Ni(111) for the first time. By calculating all the barriers in the whole dehydrogenation process, we identified that 3H-NEC to 2H-NEC is the rate-determining step and Ni is catalytically less effective than Pd, which is attributed to its narrower d-band distribution and a 0.32 eV higher d-band center than that of Pd. To improve the performance of Ni, we further introduced dopants of Au, Ag, Cu, Pd, Pt, Ru, Rh, Zn, and Al. We found that Ag doping brings a downshift of the d-band center from -1.29 to -1.67 eV and reduces the barrier of 4H-NEC to NEC from 0.94 to 0.76 eV. This study provides new insights into the catalytic mechanism and performance-tuning strategy to help future experimental synthesis.

Ultrasound-assisted preparation of PdCo bimetallic nanoparticles loaded on beta zeolite for efficient catalytic hydrogen production from dodecahydro-N-ethylcarbazole.

Research and development of high-performance catalysts is a key technology to realize hydrogen energy storage and transportation based on liquid organic hydrogen carriers. Co/beta was prepared using beta zeolite as a carrier via an electrostatic adsorption (ESA)-chemical reduction method, and it was used as the template and reducing agent to prepare bimetallic catalysts via an ultrasonic assisted galvanic replacement process (UGR). The fabricated PdCo/beta were characterized by TEM, XPS, FT-IR, XRD, H2-TPR, and H2-TPD. It was shown that the ultrafine PdCo nanoparticles (NPs) are evenly distributed on the surface of the beta zeolite. There is electron transfer between metal NPs and strong-metal-support-interaction (SMSI), which results in highly efficient catalytic dodecahydro-N-ethylcarbazole (12H-NEC) dehydrogenation performance of PdCo bimetallic catalysts. The dehydrogenation efficiency reached 100 % in 4 h at 180 °C and 95.3 % in 6 h at 160 °C. The TOF of 146.22 min-1 is 7 times that of Pd/beta. The apparent activation energy of the reaction is 66.6 kJ/mol, which is much lower than that of Pd/beta. Under the action of ultrasonic waves, the galvanic replacement reaction is accelerated, and the intermetal and metal-carrier interactions are enhanced, which improves the catalytic reaction performance.

Ultrasonic-assisted preparation of ultrafine Pd nanocatalysts loaded on Cl--intercalated MgAl layered double hydroxides for the catalytic dehydrogenation of dodecahydro-N-ethylcarbazole.

N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NEC/H12-NEC) is a promising LOHC, and the development of a catalyst with high activity and stability is the key to realizing its reversible hydrogen storage process. In this paper, ultrafine Pd nanocrystalline catalysts (Pd/LDHs-us) supported on Cl--intercalated MgAl LDHs were prepared by a simple ultrasonic-assisted reduction method and applied in the dehydrogenation of 12H-NEC. In the process of ultrasonic-assisted reduction, the instantaneous high temperature generated by cavitation decomposed part of the CO32- in LDHs interlayer, and promoted PdCl42- to enter the interlayer and become new intercalated ions. At the same time, hydroxyl groups on the surface of LDHs were excited to generate hydrogen radicals (•H) with strong reducibility, which reduced PdCl42- to Pd nanoparticles (PdNPs) in situ. The remaining Cl- ions continued to exist in the interlayer as intercalated ions. The agglomeration of PdNPs was effectively inhibited, and the average particle size was 1.8 nm, which was uniformly dispersed on LDHs, which improved the catalytic activity of Pd/LDHs-us. The coordination between PdNPs and oxygen in the hydroxyl groups on the surface of LDHs improved its catalytic stability. Using Pd/LDHs-us catalyst, the conversion rate of H12-NEC was 100.0 %, and the dehydrogenation efficiency was 99.3 % at 180℃. When the reaction temperature drops to 170℃, the dehydrogenation efficiency can still reach 94.6 %, showing excellent catalytic performance. The study of dehydrogenation kinetics shows that the apparent activation energy of Pd/LDHs-us catalyst is only 90.97 kJ/mol. This provides a new method and idea for the preparation of efficient dehydrogenation catalysts in the future.

Preparation of highly dispersed Pd/SBA-15 catalysts for dodecahydro-N-ethylcarbazole dehydrogenation reaction by ion exchange-glow discharge.

Dehydrogenation reactions are critical in hydrogen storage based on a liquid organic hydrogen carrier (LOHC) system. Speeding up the dehydrogenation rate and lowering the reaction temperature are the main focuses of LOHC dehydrogenation catalysts. In this paper, Pd/SBA-15 catalysts (Pd-IP/S15) were prepared by NaOH treatment of surface hydroxyl groups on SBA-15, the ion exchange of Na+ with Pd(NH3)42+, and then reduction of Pd ions via glow discharge plasma. The dehydrogenation performance of dodecahydro-N-ethylcarbazole on the prepared catalysts is studied. The turnover frequency of Pd-IP/S15 is 13.94 min-1 at 170°C, which is 10.25 times that of commercial Pd/C. It is ensured via the ion exchange method that Pd(NH3)42+ could be precisely targeted at the Si-OH of SBA-15 to form Si-O-Pd(NH3)42+, which effectively prevents the aggregation and uncontrollable growth of Pd nanoparticles (NPs) during the in situ reduction by plasma. Pd NPs with high dispersion are obtained on SBA-15, which enhances the catalytic activity of Pd-IP/S15. The coordination of Pd NPs with O of Si-OH on SBA-15 enabled Pd-IP/S15 to exhibit excellent catalytic stability. After 7 dehydrogenation cycles at 180°C, the dehydrogenation efficiency remained above 97%.

Hydrogen production from the catalytic dehydrogenation of dodecahydro-N-ethylcarbazole: effect of Pd precursor on the catalytic performance of Pd/C catalysts.

In this paper, Pd/C catalysts are synthesized via Ar glow-discharge plasma reduction using activated carbon as the support and Pd(acac)2, Pd(NO3)2, K2PdCl4, and H2PdCl4 as the Pd precursors, and their catalytic performances are investigated by hydrogen production from dodecahydro-N-ethylcarbazole (H12-NEC). Pd/C-A, prepared from Pd(acac)2, which has the smallest palladium nanoparticles (1.7 nm), the highest dispersion (34%) and no residue of inorganic ions, exhibits the best catalytic activity with a hydrogen release of 5.28 wt.%, which is 2.2 times that of Pd/C-H. The order of the apparent activation energies of the prepared Pd/C catalysts, according to the kinetics of the H12-NEC dehydrogenation reaction, is as follows: Pd/C-A ≈ Pd/C-N < Pd/C-K < Pd/C-H. When Pd(acac)2 with a large ligand acts as a cation Pd precursor, the effect of coulombic attraction to Pd2+ during the plasma reduction process makes it difficult for Pd nanoparticles (NPs) to migrate, which leads to the formation of ultrafine Pd NPs.

Catalytic dehydrogenation of liquid organic hydrogen carrier dodecahydro-N-ethylcarbazole over palladium catalysts supported on different supports.

The system based on liquid organic hydrogen carrier (LOHC) is one of the technologies to solve the problem of hydrogen storage and transportation capacity in large-scale applications. In this paper, the catalytic dehydrogenation of LOHC dodecahydro-N-ethylcarbazole (H12-NEC) over supported Pd nanoparticles (NPs) catalyst on four kinds of different supports, such as Pd/C, Pd/Al2O3, Pd/TiO2, and Pd/SiO2, was studied. It was found from catalyst characterization and dehydrogenation reaction that the volcano-type dependence of the activity on the Pd particle size, catalytic activity improvement with large specific surface area, and high Pd reduction degree indicated that the structure, particle size, and reduction degree of Pd NPs and textural properties of supports had a synergistic effect on the catalytic performance. Among all the catalysts, Pd/C displayed outstanding catalytic performance with the H12-NEC conversion of 99.9% and hydrogen storage capacity of 5.69 wt% at 180 °C after 12 h. The particle size of Pd/C distributes in the range of 1.5-6.0 nm with an average size of 3.0 nm. The results of dehydrogenation reaction kinetics showed that the rate limiting step and rate constant for different catalysts were mainly related to the physicochemical properties and adsorption and activation abilities towards the reactants and intermediates. In terms of the stationarity of dehydrogenation process, Pd/Al2O3 was excellent, indicating that it was best for dehydrogenation of H12-NEC.