Dehydrogenation Of Ammonia Borane Research Articles

Two-dimensional molybdenum boride coordinating with ruthenium nanoparticles to boost hydrogen generation from hydrolytic dehydrogenation of ammonia borane

The coordination between carrier and active metal is critical to the catalytic efficiency of ammonia borane (AB) hydrolysis reaction. In the present study, we report a new type of catalytic support based on molybdenum boride (MBene) MoAl1-xB and demonstrate that the effective combination of MoAl1-xB with Ru nanoparticles can realize the significantly enhanced performance for hydrogen generation. Owing to the efficient activation and dissociation of reactants, the optimal Ru/MoAl1-xB catalyst achieves the large turnover frequency of 494 molH2 molRu-1 min−1, high hydrogen generation rate of 119817 mL min−1 gRu-1 and favorable apparent activation energy of 39.2 kJ mol−1 for the catalytic hydrolysis of AB under alkaline-free condition. The isotopic test suggests the cleavage of OH bond in H2O is the rate-determining step for hydrolysis reaction, while the fracture of B–H bond in AB is also well revealed by attenuated total reflectance (ATR)-Fourier transform infrared (FTIR) spectroscopy. Significantly, the flexible on-demand hydrogen generation is achieved by using chemical switches for on–off AB hydrolysis. This study provides a new support platform based on two-dimensional MBene to exploit efficient catalysts to boost AB dehydrogenation.

Ultrafine Ni-MoOx Nanoparticles Anchored on Nitrogen-Doped Carbon Nanosheets: A Highly Efficient Noble-Metal-Free Catalyst for Ammonia Borane Hydrolysis.

The development of low-cost and high-efficiency catalysts for the hydrolytic dehydrogenation of ammonia borane (AB, NH3BH3) is still a challenging technology. Herein, ultrafine MoOx-doped Ni nanoparticles (~3.0 nm) were anchored on g-C3N4@glucose-derived nitrogen-doped carbon nanosheets via a phosphate-mediated method. The strong adsorption of phosphate-mediated nitrogen-doped carbon nanosheets (PNCS) for metal ions is a key factor for the preparation of ultrasmall Ni nanoparticles (NPs). Notably, the alkaline environment formed by the reduction of metal ions removes the phosphate from the PNCS surface to generate P-free (P)NCS so that the phosphate does not participate in the subsequent catalytic reaction. The synthesized Ni-MoOx/(P)NCS catalysts exhibited outstanding catalytic properties for the hydrolysis of AB, with a high turnover frequency (TOF) value of up to 85.7 min-1, comparable to the most efficient noble-metal-free catalysts and commercial Pt/C catalyst ever reported for catalytic hydrogen production from AB hydrolysis. The superior performance of Ni-MoOx/(P)NCS can be ascribed to its well-dispersed ultrafine metal NPs, abundant surface basic sites, and electron-rich nickel species induced by strong electronic interactions between Ni-MoOx and (P)NCS. The strategy of combining multiple modification measures adopted in this study provides new insights into the development of economical and high-efficiency noble-metal-free catalysts for energy catalysis applications.

Exploring Enhanced Hydrolytic Dehydrogenation of Ammonia Borane with Porous Graphene-Supported Platinum Catalysts.

Graphene is a good support for immobilizing catalysts, due to its large theoretical specific surface area and high electric conductivity. Solid chemical converted graphene, in a form with multiple layers, decreases the practical specific surface area. Building pores in graphene can increase specific surface area and provide anchor sites for catalysts. In this study, we have prepared porous graphene (PG) via the process of equilibrium precipitation followed by carbothermal reduction of ZnO. During the equilibrium precipitation process, hydrolyzed N,N-dimethylformamide sluggishly generates hydroxyl groups which transform Zn2+ into amorphous ZnO nanodots anchored on reduced graphene oxide. After carbothermal reduction of zinc oxide, micropores are formed in PG. When the Zn2+ feeding amount is 0.12 mmol, the average size of the Pt nanoparticles on PG in the catalyst is 7.25 nm. The resulting Pt/PG exhibited the highest turnover frequency of 511.6 min-1 for ammonia borane hydrolysis, which is 2.43 times that for Pt on graphene without the addition of Zn2+. Therefore, PG treated via equilibrium precipitation and subsequent carbothermal reduction can serve as an effective support for the catalytic hydrolysis of ammonia borane.

High performance catalyst for metal catalysis coupled with photocatalysis and its catalytic ammonia borane methanolysis for hydrogen production

In the study, the influence and mechanisms of metal and non-metal dopants on the photochemical properties of the semiconductor catalyst g-C3N4 are investigated. The results reveal that doping Ni, Ru, and B on g-C3N4 results in significant alterations to the energy band structure, the band gap value decreases to 0.78 eV (Ru@g-C3N4), 0.69 eV (Ni@g-C3N4), 0.5 eV (RuB@B-g-C3N4), and 0.1 eV (NiB@B-g-C3N4) from the original value of 1.139 eV. The doping of metal and non-metal atoms can significantly enhance the light absorption capability and photothermal conversion efficiency of B-g-C3N4. The mechanism of ammonia borane (AB) dehydrogenation follows the stepwise dehydrogenation principle. AB molecules adsorb onto the active metal centers, and with the assistance of the catalytic sites, CH3OH molecules activate and attack the B–N bond in AB molecules, leading to the initial breakage of the B–N bond, the interaction between O atoms in CH3OH and N atoms in AB continues, forming NH3BH2(OCH3). Interactions between H(B) and H(O) result in the production of H2, the energy barrier for this reaction is 34.14 kcal/mol. Compared to dark conditions, RuB@B-g-C3N4 exhibits higher catalytic activity under light irradiation, the reaction time from 9′20″ reduce to 8′. This shows that there is a synergistic effect between photocatalytic AB methanolysis and conventional metal catalyzed AB methanolysis in the RuB@B-g-C3N4 catalytic system. The study provides the novel way for the development of dual-function catalysts combining metal catalysis and photocatalysis through Ru and B modification of g-C3N4.

Gamma-ray-irradiated preparation and performance of magnetothermally responsive hybrid materials towards the tandem hydrogenation of halonitrobenzenes

Novel magneto-thermo dual responsive organic-inorganic hybrid materials (PdCu/Fe3O4@SiO2@PNIPAM) were successfully prepared under γ-ray irradiation in this work. The γ-ray irradiation simultaneously induced the grafting of the polymer PNIPAM, and the in-situ anchoring of metallic Pd and Cu via an irradiation reduction. The catalytic performance of the prepared PdCu/Fe3O4@SiO2@PNIPAM hybrid material (abbr. PdCu/FSP) was investigated for the dehydrogenation of ammonia borane (AB) and the tandem hydrogenation of halonitrobenzenes. The results showed that the as-prepared PdCu/FSP exhibited more excellent catalytic performance in the tandem hydrogenation reaction of halonitrobenzenes in comparison with a controlled sample by a traditional preparation method. Furthermore, the PdCu/FSP catalyst prepared at a radiation dose of 25 kGy achieved excess 99 % yield of m-chloroaniline (m-CAN) at room temperature within 5 min. The PdCu/FSP hybrid material could be easily recycled by simple magnetic separation, and increasing temperature led to obvious time-shortening behavior for facile magnetic separation. Owing to lack of the intrinsic drawbacks of conventional chemical reductants and radical initiators, the gamma-ray irradiation method provides an available strategy for the construction of hybrid catalytic materials towards the hydrogenated reduction of halonitrobenzenes.

RuCo@P Core-Shell Nanoparticles Filled with Carbon Nanotubes for Highly Effective Catalytic Hydrolysis of Ammonia Borane

The doping of nonmetals in multiphase metal catalysts can effectively improve the catalytic performance and reduce the catalyst cost. In this study, we synthesized transition metal phosphide (RuCo@P/CNT) catalysts loaded on carbon nanotubes (CNT) using sodium borohydride (NaBH4) as the reducing agent. The microstructure and phase composition of RuCo@P/CNT nanoparticles were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), and BET. RuCo@P/CNT nanoparticles show superior catalytic activity and cycle stability in the catalytic ammonia borane hydrolysis process compared to Ru/CNT and RuCo/CNT nanoparticles, retaining 65.74% of their initial catalytic activity after 5 reaction cycles. The test yielded values for turnover frequency and activation energy of 327.33 min-1 and 36.77 kJ·mol-1, respectively. Additionally, a kinetic isotope effect value of 2.61 for H2O/D2O showed that O-H bond breaking in proportional acceptor water is the decisive step in the dehydrogenation of ammonia borane, and based on this discovery, a specific mechanism for the catalytic hydrolysis of AB by RuCo@P NPs is postulated.

0D Model for the Comparative Analysis of Hydrogen Carriers in Ship’s Integrated Energy Systems

Hydrogen carriers are attractive alternative fuels for the shipping sectors. They are zero-emission, have high energy densities, and are safe, available, and easy to handle. Sodium borohydride, potassium borohydride, dibenzyltoluene, n-ethylcarbazole, and ammoniaborane are interesting hydrogen carriers, with high theoretical energy densities. The exact energy density of these hydrogen carriers depends on the integration of heat and mass with the energy converters. This combination defines the energy efficiency and, thus, the energy density of the system. Using a 0D model, we combined the five carriers with two types of fuel cells (PEM and SOFC), an internal combustion engine and a gas turbine. This resulted in 20 combinations. Despite the limitations of the 0D model and the occasional difficulty of validating input values, this model still produces exciting findings, which are valuable for further research. For the dehydrogenation of both dibenzyltoluene and n-ethylcarbazole, an external hydrogen burner is required if no waste heat resources from the integrated system are available. For the borohydrides, on the other hand, energy integration is essential for reducing cooling power. Dehydrogenation produces substantial energy, but only a fraction of this energy can be used for internal preheating. Dehydrogenation of ammoniaborane produces less energy. Among all hydrogen carriers, both ammoniaborane and sodium borohydride provide energy densities comparable to that of marine diesel oil. In particular, ammoniaborane possesses a remarkably high energy density. Thus, we conclude, that hydrogen carriers are attractive alternative fuels that deserve more attention, including their potential performance for hydrogen imports.

Synthesis of amorphic and hexagonal boron nitride via high temperature treatment of NH3BH3 and Li(BH3NH2BH2NH2BH3).

Thermal decomposition of NH3BH3 and Li(BH3NH2BH2NH2BH3) was investigated at temperatures up to 1000 °C under various conditions with an inert atmosphere. It was found that complete dehydrogenation of ammonia borane towards amorphous boron nitride (a-BN) occurs at 850 °C when using monel reactors or at 1000 °C with the hot isostatic pressing method (HIP), which is significantly lower than was earlier reported. Li(BH3NH2BH2NH2BH3) was found to decompose towards hexagonal boron nitride (h-BN) at 1000 °C with the HIP method but at 850 °C in monel reactors towards a mixture of a-BN and h-BN. The findings are confirmed by Fourier-transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM).

Selective dehydrogenation of ammonia borane to polycondensated BN rings catalysed by ruthenium olefin complexes.

Dehydrogenation of ammonia borane to well-defined products is an important but challenging reaction. A dinuclear ruthenium complex with a Ru-Ru bond bearing a diazadiene (dad) unit and olefins as non-innocent ligands catalyzes the highly selective formation of conjugated polycondensed borazine oligomers (BxNxHy), predominantly B21N21H18, the BN analogue of superbenzene.

CoNi Nanoparticles Supported on Hierarchical SAPO-34 Zeolite as a Catalyst for the Hydrolytic Dehydrogenation of Ammonia Borane

CoNi Nanoparticles Supported on Hierarchical SAPO-34 Zeolite as a Catalyst for the Hydrolytic Dehydrogenation of Ammonia Borane

An evidence for electron transfer of hydrolytic dehydrogenation of ammonia borane over ruthenium ultra-fine nanoparticles

Hydrogen production from ammonia-borane hydrolysis has been widely studied for its high efficiency and many catalytic mechanisms with different viewpoints have been proposed. However, no attention has been paid to electron transfer during catalytic reactions to form H2 in these catalytic mechanisms. In the present contribution, we propose two possible electron transfer pathways for hydrogen production from AB hydrolysis, which were validated by hydrogen evolution reaction (HER) tests. The electrochemical characterization correlates with the AB hydrolysis test results, where Ru4/Fe–N–C catalyst has the largest active surface area and the smallest charge transfer resistance, along with the largest turnover frequency (298.7 molH2 molRu−1 min−1). These results indicate that Ru4/Fe–N–C catalyst not only provides the adsorption/desorption sites but also provides an effective approach for electron transfer in hydrogen production from AB hydrolysis.

Reducible tungsten(VI) oxide-supported ruthenium(0) nanoparticles: highly active catalyst for hydrolytic dehydrogenation of ammonia borane.

Reducible WO3 powder with a mean diameter of 100 nm is used as support to stabilize ruthenium(0) nanoparticles. Ruthenium(0) nanoparticles are obtained by NaBH4 reduction of ruthenium(III) precursor on the surface of WO3 support at room temperature. Ruthenium(0) nanoparticles are uniformly dispersed on the surface of tungsten(VI) oxide. The obtained Ru0/WO3 nanoparticles are found to be active catalysts in hydrolytic dehydrogenation of ammonia borane. The turnover frequency (TOF) values of the Ru0/WO3 nanocatalysts with the metal loading of 1.0%, 2.0%, and 3.0% wt. Ru are 122, 106, and 83 min-1, respectively, in releasing hydrogen gas from the hydrolysis of ammonia borane at 25.0 °C. As the Ru0/WO3 (1.0% wt. Ru) nanocatalyst with an average particle size of 2.6 nm provides the highest activity among them, it is extensively investigated. Although the Ru0/WO3 (1.0% wt. Ru) nanocatalyst is not magnetically separable, it has extremely high reusability in the hydrolysis reaction as it preserves 100% of initial catalytic activity even after the 5th run of hydrolysis. The high activity and reusability of Ru0/WO3 (1.0% wt. Ru) nanocatalyst are attributed to the favorable metal-support interaction between the ruthenium(0) nanoparticles and the reducible tungsten(VI) oxide. The high catalytic activity and high stability of Ru0/WO3 nanoparticles increase the catalytic efficiency of precious ruthenium in hydrolytic dehydrogenation of ammonia borane.

Exposed Facet Tailoring of Ni/Cu Catalysts for Boosting Dehydrogenation of Ammonia Borane

Exposed Facet Tailoring of Ni/Cu Catalysts for Boosting Dehydrogenation of Ammonia Borane

Design of Ammonia Borane Dehydrogenation Catalysts Using Previous Study Data, Public Data, and Machine Learning

Design of Ammonia Borane Dehydrogenation Catalysts Using Previous Study Data, Public Data, and Machine Learning

Visible-light-induced electron density enrichment of the active sites in the core-satellite structured CuWO4@NiO for fast hydrogen generation from ammonia borane methanolysis

Catalytic dehydrogenation of ammonia borane (AB) is an integrated technology for producing hydrogen with promising applications in mobile fuel cells. However, its commercial prospect is significantly hampered by the high expenditure of precious metal catalysts. Herein, a low-cost and efficient Z-schemed core-satellite structured CuWO4@NiO nanocomposite catalyst was developed for the methanolysis of AB for fast hydrogen production. The experimental and theoretical calculation results revealed charge transfer between CuWO4 (core) and NiO (satellite), thus creating active Ni and Cu sites for the adsorption and activation of methanol and AB, respectively. When the CuWO4@NiO catalyst was irradiated with visible light, numerous photogenerated electrons were accumulated in the conduction band of NiO of CuWO4@NiO by virtue of the special Z-scheme heterojunction, resulting in the electron density enrichment of Ni sites. The electron-enriched Ni sites effectively activated the adsorbed methanol, thus making the O–H bond cleavage easier, which was identified as the rate-determining step in AB methanolysis using kinetic isotope effect experiments. Based on the special electronic and energy band structures, our CuWO4@NiO catalyst exhibited outstanding catalytic activity with a turnover frequency of 26.5 min−1 in AB methanolysis, surpassing most noble-metal-free catalysts reported in the literature. Our findings show that visible light can be applied as a useful tool to optimize the electronic states of both active sites of catalysts and adsorbed reactants. This study provides insight into the design of more efficient catalytic systems toward AB methanolysis for fast hydrogen evolution.

Cobalt-free CuO catalyst for hydrolytic dehydrogenation of sodium borohydride and ammonia borane

The environmental and economic impact of Co-based catalysts necessitates the use of a more environmentally friendly and less expensive catalyst, such as CuO. A cobalt-free CuO catalyst was developed via a simple low-temperature hydrothermal process. The efficiency of the catalyst was analysed for the dehydrogenation of NaBH4 as well as NH3BH3. Compared with the commercial particulate CuO, hydrothermally prepared CuO nanoplate (CuO HT) exhibits a good hydrogen evolution rate, the rate of hydrogen evolution for CuO_Commercial and CuO HT was experimentally measured to be 240 ml H2/min/g and 470.5 ml H2/min/g respectively for 0.2 g catalyst for the dehydrogenation of NaBH4. At a 10 times lower concentration of NaBH4 with 0.2 g of CuO HT catalyst, the rate of HER recorded was 1086 ml H2/min/g. The high catalytic activity of CuO HT could be related to the surface oxygen vacancies or defects generated due to the participation of high molar concentrations of NaOH during the reaction. The stability of both catalysts was investigated, and the rate of hydrogen evolution reaction after three cycles was determined to be 492 ml H2/min/g for CuO_Commercial and 925.1 ml H2/min/g for CuO HT. Despite the fact that the rate of hydrogen evolution was observed to be increased for the third cycle, the volume of water displaced was decreased when compared to the first cycle, which could be due to the presence of a less active Cu2O phase retained after temperature treatment. Similarly, with the best catalyst concentration of CuO HT (0.2 g), the hydrogen evolution rate of NH3BH3 was also measured to be 1175 ml H2/min/gm. The result evokes a new insight into the evolution of sustainable and eco-friendly catalysts for a better hydrogen economy.

Spatially confined synthesis of bimetal phosphide nanoparticles encapsulated metal–organic framework architectures via localized phosphorization for efficient ammonia borane dehydrogenation

Spatially confined synthesis of bimetal phosphide nanoparticles encapsulated metal–organic framework architectures via localized phosphorization for efficient ammonia borane dehydrogenation

Amino-functionalized CuFe2O4 supported Pd nanoparticles as magnetically catalyst for H2 production from methanolysis of ammonia borane and hydrogenation of nitro aromatics

Small and equally distributed Pd nanoparticles (NPs) are tightly anchored on the surface of magnetic and amino (–NH2) functionalized CuFe2O4 to obtain magnetically separable CuFe2O4–NH2@Pd catalyst with core-shell structure. Compared to the inherent catalytic activity of CuFe2O4, the catalytic performance of CuFe2O4–NH2@Pd for dehydrogenation of ammonia-borane (AB) and concurrent hydrogenation of different nitro aromatics by H2 generated from AB methanolysis can be boosted more effectively than that of CuFe2O4@Pd, which is the control catalyst and is prepared by loading Pd NPs on pristine CuFe2O4. As electron donating groups, the –NH2 groups covalently bonded to the surface of CuFe2O4 play vital roles in stabilizing Pd NPs, providing strong metal-support interaction and rendering enhanced catalytic activity. However, we find that the catalytic performance of CuFe2O4, CuFe2O4@Pd and CuFe2O4–NH2@Pd for the hydrogenation reduction of mercapto-substituted nitro aromatics (p-nitrothiophenol, p-NTP) is far inferior to that for the reduction of nitroarenes that do not contain a sulfur substituent. Therefore, it is quite essential to research and develop the new-type catalysts with more excellent catalytic performance.

MCM-41 supported NiPCeOx nanoparticles as highly efficient non-noble metal catalyst for hydrolytic dehydrogenation of ammonia borane

Efficient and controllable hydrogen release from ammonia borane (NH3BH3, AB) hydrolysis is a secure and effective way to generate hydrogen on-demand. The development of high-efficiency and low-cost catalysts is of important but still remains a great challenge. Herein, uniformly dispersed NiPCeOx nanoparticles (NPs) with narrow size distribution supported on mesoporous MCM-41 were prepared by incipient wetness impregnation followed by NaBH4 reduction. Attributing to the ordered mesoporous structure of the support as well as the efficiently enhancement of electron density on the Ni active sites brought by the electron transfers, the NiPCeOx/MCM-41 catalyst exhibits exceptional catalytic performance towards AB hydrolysis with a high turnover frequency (TOF) value of 47.3 molH2(molNi·min)−1 at 298 K and a low apparent activation energy (Ea) of 35.86 kJ mol−1. Furthermore, the NiPCeOx/MCM-41 catalyst shows excellent durability with 76.5% of the initial TOF value remained after five cycles.

Strong Electronic Metal–Support Interaction Augments Hydrogen Evolution over hcp-Ni/In2O3 with Ultrasound-Assisting Dehydrogenation of Ammonia Borane

Rational design of highly efficient catalysts for the dehydrogenation of ammonia borane (AB) to produce hydrogen is still challenging. The size and shape effects of catalysts on the performance have been well documented in the past decades. Nevertheless, there is still much space for study on the crystal structure-dependent catalytic performance. Herein, In2O3-supported hexagonal-close-packed (hcp) Ni (hcp-Ni/In2O3) has been prepared via impregnation of corresponding nanoparticles onto In2O3. The stronger electronic metal–support interaction in hcp-Ni/In2O3 than in fcc-Ni/In2O3 endows it with high capacity to activate AB molecules. It exhibits excellent hydrogen evolution activity from catalytic dehydrogenation of AB with a rate of 7.5 molH2 mol–1Ni min–1, which is 1.7 times that of the supported fcc sample. The systematic experiments and DFT calculations demonstrate that the hcp catalyst possesses stronger hydrophilicity and lower activation energy for the dissociation of H2O than the fcc counterpart. Moreover, the assistance with sonication enhances the process of mass and heat transfer and accelerates the reaction. This work provides a new way for the achievement of efficient metastable catalytic systems and promotes the construction of advanced devices toward various applications.