A experimental study on the dehydrogenation performance of dodecahydro-N-ethylcarbazole on M/TiO2 catalysts

Liquid organic hydrogen carrier (LOHC) is considered as a promising candidate for large-scale hydrogen storage. In this work, we found that Pt/TiO₂ catalysts exhibited better catalytic activity and selectivity compared to Pd/TiO₂ and commercial Pd/Al₂O₃ catalysts in the dehydrogenation of dodecahydro-N-ethylcarbazole (12H-NECZ) at 453 K. The catalytic activity of the noble metal catalysts followed the trend of Pt/TiO₂ > Pd/TiO₂ > Rh/TiO₂ > Au/TiO₂ > Ru/TiO₂. Compared with the commercial Pd/Al₂O₃, Pt/TiO₂ greatly improved the selectivity and conversion rate, the reaction time was also shortened. In addition, kinetics calculation was carried out to obtain fundamental reaction parameters. It was found that the third step of 4H-NECZ dehydrogenation to NECZ was the rate-limiting step of the entire dehydrogenation reaction for all catalysts.     

Enhancing selectivity and reducing cost for dehydrogenation of dodecahydro-N-ethylcarbazole by supporting platinum on titanium dioxide

N-ethylcarbazole/dodecahydro-N-ethylcarbazole (NECZ/12H-NECZ) was a promising system for hydrogen storage applications. 1.0 wt% Pt/TiO₂ was regarded as the optimal loading in Pt/TiO₂ catalyst applied in the 12H-NECZ dehydrogenation reaction. The hydrogen release amount, selectivity to NECZ and TOF of 12H-NECZ dehydrogenation are 5.75 wt %, 98% and 229.73 min⁻¹ at 453 K. Compared with the commercial 5.0 wt% Pd and Pt-based catalysts, it exhibited very high activity, selectivity and stability for 12H-NECZ dehydrogenation with low Pt loading. Combined with the XRD, XPS, HRTEM, TPR analysis, it was indicated that the enhanced catalytic performance was due to the SMSI (strong metal-supporting interaction) between Pt and TiO₂ support, which accelerated the rate-limiting step and enhanced the whole dehydrogenation reaction. This work may be beneficial for the commercial application of Pt/TiO₂ catalysts in the Liquid Organic Hydrogen Carrier (LOHC) system.     

Tungsten(VI) oxide supported rhodium(0) nanoparticles; highly efficient catalyst for H2 production from dimethylamine borane

It reports the preparation and characterization of tungsten(VI) oxide supported rhodium(0) nanoparticles (Rh⁰/WO₃ NPs) being used as catalysts in releasing H₂ from dimethylamine borane (DMAB). The reducible nature of WO₃ plays a significant role in the catalytic efficiency of rhodium(0) nanoparticles in the dehydrogenation of DMAB. The Rh⁰/WO₃ NPs were in-situ generated from the reduction of Rh²⁺ ions on the surface of WO₃ during the catalytic dehydrogenation of dimethylamine borane in toluene and isolated from the reaction solution after the dehydrogenation to be characterized by using SEM, TEM, XPS, ATR-IR and XRD. The results reveal the formation of Rh⁰ NPs with a mean particle size of 1.92 ± 0.34 nm dispersed on the surface of tungsten(VI) oxide. Rh⁰/WO₃ NPs are found to be very active catalyst releasing 1.0 equiv. H₂ per mole of dimethylamine borane under ambient conditions. Among the various WO₃ supported Rh⁰ NPs with different metal loadings, the sample with 0.1% wt. Rh provide the record catalytic activity (TOF = 2816 h^?1) which is one of the highest value ever reported for rhodium-based catalysts in H₂ generation from DMAB at 60.0 ± 0.5 °C. Rh⁰/WO₃ NPs were also reusable catalyst in dehydrogenation of DMAB retaining 55% of their initial catalytic activity in the 3rd run of the dehydrogenation reaction. Control experiments were performed at various catalyst concentrations and temperatures to investigate the kinetics of dehydrogenation and to calculate the activation parameters for the reaction.     

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.     

Engineering PdCu and PdNi bimetallic catalysts with adjustable alloying degree for the dehydrogenation reaction of dodecahydro-N-ethylcarbazole

The NECZ/12H-NECZ (N-ethylcarbazole/dodecahydro-N-ethylcarbazole) system is regarded as the most potential liquid organic hydrogen carrier. However, the low activity, selectivity of NECZ and high cost of catalysts for the dehydrogenation reaction restrict its efficiency and commercial applications. In this work, a series of bimetallic Pd-M(M = Cu, Ni)/SiO₂ catalysts were prepared and employed to enhance catalytic activity and selectivity of NECZ for the 12H-NECZ dehydrogenation reaction. Pd₃Ni₁/SiO₂ exhibited high catalytic performance with 100% conversion, 91.1% selectivity of NECZ and 5.63 wt% hydrogen release amount at 453 K, 101.325 kPa for 8 h. The TOF (turnover frequency) of Pd₃Ni₁/SiO₂ is enhanced by 42.4% compared with Pd/SiO₂. Combined with the characterization analysis, it was found that adjusting the alloying degree or the alloy phase in the PdCu and PdNi bimetallic catalysts could significantly enhance the dehydrogenation activity and selectivity, which were dependent on the component of bimetallic catalysts. This work may provide theoretical guidance for designing the efficient and low-cost bimetallic catalysts for the dehydrogenation of 12H-NECZ, which could boost the commercial applications of liquid organic hydrogen carriers.     

Bamboo fungus-derived magnetic porous carbon encapsulated nickel stabilized Rh nanoparticles as efficient catalysts for hydrolytic dehydrogenation of ammonia borane

Biomass-derived porous carbons are generally used as supports for metal nanoparticle (NP) stabilizations, while the strong hydrophilicity of such materials makes the as-prepared catalysts hard to be isolated after reaction, significantly affecting their potential applications. Herein, magnetic N-functionalized carbon (CN) encapsulated Ni composite (Ni@CN) prepared via pyrolysis of bamboo fungus pre-absorbed with nickel nitrate is exploited as a matrix to synthesize Rh/Ni@CN hybrid, which can be used as a magnetically recoverable catalytic material for hydrolytic dehydrogenation of ammonia borane (AB) to generate hydrogen. The Rh/Ni@CN (Rh loading: 0.84 wt%) exhibits an optimal activity (turnover frequency: 351 min⁻¹) for hydrogen evolution from hydrolytic dehydrogenation of AB. Most importantly, this catalyst can be simply isolated by a magnet and reused at least five times with complete conversion of AB to hydrogen. The strong interaction between the two metals and the small size of Rh NPs are responsible for the improved catalytic activity for hydrolytic dehydrogenation of AB. This work provides an eco-friendly and efficient strategy to fabricate excellent catalysts in catalytic applications.     

Efficient hydrogen production from ammonia borane hydrolysis catalyzed by TiO2-supported RuCo catalysts

Hydrolysis of ammonia borane provides a reliable pathway for hydrogen production, while suitable catalysts are indispensable to make the hydrolysis reaction reach a considerable rate. In the present work, a series of TiO₂-supported RuCo catalysts have been fabricated by coprecipitation and subsequent reduction of Ru³⁺ and Co²⁺ on the surface of TiO₂ nanoparticles. Transmission electron microscopy and elemental mapping have verified the good distribution of metal species in the catalysts. The fabricated catalysts have shown excellent performance for catalyzing ammonia borane hydrolysis, especially in alkaline solutions with 0.5 M NaOH. For Ru₁Co₉/TiO₂ in which Ru/Co molar ratio is 1:9, the active energy of catalyzed ammonia borane hydrolysis is 33.25 kJ/mol, and a turnover frequency based on Ru as high as 1408 mol_H2/(mol_Ru·min) is obtained at 25 °C. Moreover, when different types of TiO₂ substrates are used, anatase TiO₂-supported catalysts show better catalytic activity than their counterparts with rutile TiO₂ as substrate or mixture of anatase and rutile TiO₂ as substrate.     

Synergistic catalysis of Pd–Ni(OH)2 hybrid anchored on porous carbon for hydrogen evolution from the dehydrogenation of formic acid

The development of a facile yet efficient strategy to boost the catalytic performance of supported Pd nanoparticles (NPs) toward the dehydrogenation of formic acid (FA) is essential but remains challenging. Here, a novel hybrid nanocatalyst comprising Pd and Ni(OH)₂ supported on porous carbon (PC) is developed. The obtained Pd–Ni(OH)₂/PC nanocatalyst exhibits an excellent catalytic performance for FA dehydrogenation to produce hydrogen. The introduction of Ni(OH)₂ in PC support can significantly promote the catalytic activity of Pd NPs toward FA dehydrogenation. Additionally, the catalytic property of Pd–Ni(OH)₂/PC is correlated with the Pd/Ni ratio. The ₂Pd–₁Ni(OH)₂/PC with the optimum Pd/Ni ratio of 2/1 exhibits the maximum turnover frequency (TOF) of 3409 h⁻¹ at 60 °C for FA dehydrogenation. The highly dispersed ultrafine Pd–Ni(OH)₂ hybrid NPs with numerous accessible active sites and Ni(OH)₂−induced positive synergetic effects with Pd NPs considerably boost the catalytic performance for FA dehydrogenation.     

Nitrogen-phosphorus co-functionalized reduced graphene oxide supported NiCoPd-CeOx nanoparticles as a highly efficient and stable catalyst for formic acid dehydrogenation

Formic acid (HCOOH, FA), a common liquid hydrogen storage material, has attracted tremendous research interest. However, the development of efficient, low-cost and high-stable heterogeneous catalyst for selective dehydrogenation of FA remains a major challenge. In this paper, a simple co-reduction method is proposed to synthesize nitrogen-phosphorus co-functionalized rGO (NPG) supported ultrafine NiCoPd-CeO_x nanoparticles (NPs) with a mean size of 1.2 nm. Remarkably, the as-prepared Ni_0.2Co_0.2Pd_0.6-CeO_x/NPG shows outstanding catalytic activity for FA dehydrogenation, affording a high TOF value of 6506.8 mol H₂ mol Pd^?1 h^?1 at 303 K and a low activation energy of 17.7 kJ mol^?1, which is better than most of the reported heterogeneous catalysts, and can be ascribed to the combined effect of well-dispersed ultrafine NiCoPd-CeO_x NPs, modified Pd electronic structure, and abundant active sites. The reaction mechanism of dehydrogenation of FA is also discussed. Furthermore, the optimized Ni_0.2Co_0.2Pd_0.6-CeO_x/NPG shows excellent stability over 10^th run with 100% conversion and 100% H₂ selectivity, which may provide more possibilities for practical application of FA system on fuel cells.     

Transition metal-catalyzed dehydrogenation of hydrazine borane N2H4BH3via the hydrolysis of BH3 and the decomposition of N2H4

Hydrazine borane N₂H₄BH₃ (denoted HB) is a novel candidate in hydrogen generation by catalytic hydrolysis. The challenge with this material is the dehydrogenation of the N₂H₄ moiety, which occurs after the hydrolysis of the BH₃ group. This challenge requires the utilization of a reactive and selective metal-based catalyst. In this work, we considered various transition metal salts as precursors of in situ forming catalysts by reduction in the presence of HB. According to their reactivity, the metals studied can be classified into 3 groups: (1) Fe- and Re-based catalysts, showing a limited reactivity in the hydrolysis of the BH₃ group; (2) Co-, Ni-, Cu-, Pd-, Pt- and Au-based catalysts, only active in the hydrolysis of BH₃ (3 mol H₂ per mol HB generated); (3) Ru-, Rh, and Ir-based catalysts, being also active in the decomposition of N₂H₄. With the Rh-based catalyst, characterized as agglomerated Rh⁰ nanorods (10 × 4 nm) by XRD, TEM, SAED and XPS, 4.1 mol H₂ + N₂ per mol HB can be produced at 50 °C. Rhodium is thus a possible candidate for synthesizing nanosized particles and bimetallic nanoalloys in order to tune its reactivity and increase its selectivity up to the targeted conversion of 100%. Our main results are reported herein and the behavior of the metals is discussed.     

In situ facile synthesis of bimetallic CoNi catalyst supported on graphene for hydrolytic dehydrogenation of amine borane

Well dispersed magnetically recyclable bimetallic Co_xNi_1−x (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1) nanoparticles (NPs) supported on graphene have been synthesized via a facile in situ one-step procedure, using the mixture of sodium borohydride (NaBH₄) and methylamine borane (MeAB) as the reducing agent under ambient condition. These NPs were composition dependent for catalytic hydrolysis of amine boranes. Among all the CoNi/graphene catalysts tested, the Co_0.9Ni_0.1/graphene NPs exhibit the highest catalytic activity toward hydrolysis of AB with the turnover frequency (TOF) value of 16.4 (mol H₂ min⁻¹ (mol catalyst)⁻¹), being higher than that of most reported non-noble metal-based NPs, and even many noble metal-based NPs. Moreover, the activation energy (E_a) value is 13.49 kJ/mol, which is the second lowest value ever reported for catalytic hydrolytic dehydrogenation of ammonia borane, indicating the superior catalytic performance of the as-synthesized Co_0.9Ni_0.1/graphene catalysts. Additionally, Compared with other reducing agents, such as NaBH₄, AB, MeAB, and the mixture of NaBH₄ and AB, the as-synthesized Co_0.9Ni_0.1/graphene catalysts reduced by the mixture of NaBH₄ and MeAB exert the highest catalytic activity. The Co_0.9Ni_0.1 NPs supported on graphene exhibit higher catalytic activity than catalysts with other conventional supports, such as SiO₂, carbon black, and γ-Al₂O₃. Furthermore, the as-synthesized Co_0.9Ni_0.1/graphene NPs show good recyclability and magnetically reusability for the hydrolytic dehydrogenation of amine boranes, which make the practical reusing application of the catalysts more convenient.     

Strategic synthesis of graphene supported trimetallic Ag-based core–shell nanoparticles toward hydrolytic dehydrogenation of amine boranes

We reported the synthesis and characterization of two trimetallic (Ag@CoFe, and Ag@NiFe) core–shell nanoparticles (NPs), and their catalytic activity toward hydrolytic dehydrogenation of ammonia borane (AB) and methylamine borane (MeAB). The as-synthesized trimetallic core–shell NPs were obtained via a facile one-step in situ procedure using methylamine borane as a reducing agent and graphene as the support under ambient condition. The as-synthesized NPs are well dispersed on graphene, and exhibit higher catalytic activity than the catalysts with other conventional supports, such as the SiO₂, carbon black, and γ-Al₂O₃. Additionally, compared with NaBH₄ and AB, the as-synthesized Ag@CoFe/graphene NPs reduced by MeAB exhibit the highest catalytic activity, with the turnover frequency (TOF) value of 82.9 (mol H₂ min⁻¹ (mol Ag)⁻¹), and the activation energy (E_a) value of 32.79 kJ/mol. Furthermore, the as-prepared NPs exert good durable and magnetically recyclability for the hydrolytic dehydrogenation of AB and MeAB. Moreover, this simple strategic synthesis method can be easily extended to the facile preparation of other graphene supported multi-metal core–shell NPs.     

PdCoNi nanoparticles supported on nitrogen-doped porous carbon nanosheets for room temperature dehydrogenation of formic acid

The development of cost-effective heterogeneous catalysts for the dehydrogenation of formic acid (FA) is the key challenge for the commercialization of FA as a hydrogen-storage medium. Herein, PdCoNi nanoparticles (NPs) with different element ratios supported on N-doped carbon nanosheets (N-CN) were designed, which exhibit excellent catalytic dehydrogenation performance for FA. Compared with PdCoNi NPs loaded on the carbon nanosheets (CN), the introduction of pyrrolic N to CN induces the formation of ultrafine, monodispersed and amorphous Pd_0.6Co_0.2Ni_0.2 NPs with a size of 1.60 nm, which significantly increases the number of active sites and the instant contact between FA and catalysts. The as-prepared Pd_0.6Co_0.2Ni_0.2/N-CN catalyst shows more than 99% conversion and 100% H₂ selectivity at room temperature, with a record-high initial turnover frequency (TOF_initial) of 1249.0 h⁻¹ among non-noble containing Pd-based catalysts, which demonstrates the high potential of Pd_0.6Co_0.2Ni_0.2/N-CN as a practical catalyst for the hydrogen generation from FA.     

TiO2–CdS supported CuNi nanoparticles as a highly efficient catalyst for hydrolysis of ammonia borane under visible-light irradiation

TiO₂–CdS nanotubes (NTs) were used for the first time as a support to load metal nanoparticles (NPs) for the hydrolysis of ammonia borane (AB) which is a new strategy. The TiO₂–CdS NTs support was first synthesized using a hydrothermal method, and then the CuNi NPs were loaded using a liquid-phase reduction method. The synthesized samples were characterized by XRD, SEM-EDS, TEM, XPS, ICP, UV–Vis, and PL analyses. The characterization results show that the CuNi NPs existed in the form of an alloy with a size of ~1.2 nm and uniformly dispersed on the support. Compared with their single metal counterparts, the bimetallic CuNi-supported catalysts showed a higher catalytic activity in the hydrolysis of AB under visible-light irradiation: Cu_0·45Ni_0·55/TiO₂–CdS catalyst had the fastest hydrogen evolution rate with a high conversion frequency (TOF) of 25.9 mol_H2·mol_cat⁻¹ min⁻¹ at 25 °C and low activation energy of 32.8 kJ mol⁻¹. Cu_0.45Ni_0.55/TiO₂–CdS catalyst showed good recycle performance, maintaining 99.3% and 85.6% of the original hydrogen evolution rate even after five and ten recycles, respectively. Strong absorption of visible light, improved electron–hole separation efficiency, and metal synergy between Cu and Ni elements played a crucial role in improving the catalytic hydrolysis performance of AB. The catalyst prepared in this study provides a new strategy for the application of photocatalysts.     

Improved catalytic stability of Pt/TiO2 catalysts for methylcyclohexane dehydrogenation via selenium addition

To improve the catalytic activity of Pt catalysts for methylcyclohexane (MCH) dehydrogenation, which is utilized for hydrogen transportation, the effects of the addition of Se on the performance of Pt/TiO₂ catalysts were investigated. In Se/Pt/TiO₂ catalysts, even a small amount of Se addition (Se/Pt = 0.01) improved the catalyst stability. Se was highly dispersed on the Pt/TiO₂ surface, without volatilizing in a reducing atmosphere at temperatures below 450 °C, and did not form an alloy with Pt. The analysis of adsorption-desorption characteristics revealed that the addition of Se promoted the desorption of products, including the main product, toluene. Moreover, an electron donation effect from Se to Pt was observed by FT-IR measurement after the reduction. The desorption characteristic caused by the electron donation effect suppressed the deterioration of the catalyst and allowed stable catalytic activity toward the MCH dehydrogenation reaction.     

Electrospun nickel doped titanium dioxide nanofibers as an effective photocatalyst for the hydrolytic dehydrogenation of ammonia borane

In this study, Ni-doped titanium dioxide (TiO₂) electrospun nanofibers are introduced as novel material for dehydrogenation of ammonia borane (AB) complex. Hydrolysis experiments with introduced catalytic nanofibers are prevailed to rapidly release hydrogen from AB complex. Typically, Ni nanoparticles (NPs) behave as a catalyst, meanwhile the incorporation of nickel NPs lead to decrease in the electrons/holes recombination rate in TiO₂ which resulted in the increase of active ions in the solution to a rapid evolution of hydrogen gas at room temperature. The utilized physiochemical analyses indicate that the introduced Ni-doped TiO₂ nanofibers have a smooth surface and uniform diameters along their lengths. Under sunlight irradiation, the hydrogen production rate in case of utilizing Ni-doped TiO₂ nanofibers is rapidly increased compared to the pristine TiO₂ nanofibers, the maximum hydrogen equivalent in case of the doped nanofibers is 2.6 while the pristine one is 1.4. Both formulations exhibit almost equal low activity in daylight as the observed hydrogen equivalent is 0.4. Overall, this study proposes cheap, stable and effective material for AB dehydrogenation at room temperature.     

Monodisperse nickel–palladium alloy nanoparticles supported on reduced graphene oxide as highly efficient catalysts for the hydrolytic dehydrogenation of ammonia borane

Addressed herein is the catalysis of reduced graphene oxide-supported monodisperse NiPd alloy nanoparticles (NPs) (rGO-NiPd) in the hydrolytic dehydrogenation of ammonia borane (AB). This is the first example of the use of NiPd alloy NPs as catalyst in the hydrolytic dehydrogenation of AB. Monodisperse NiPd alloy NPs (3.5 nm) were synthesized by co-reduction of nickel(II) acetate and palladium(II) acetylacetonate in oleylamine (OAm) and borane-tert-butylamine complex (BTB) at 100 °C. The current recipe allowed to control the composition of NiPd alloy NPs and to study the composition-controlled catalysis of rGO-NiPd in the hydrolytic dehydrogenation of AB. Among the all compositions tested, the Ni₃₀Pd₇₀ was the most active one with the turnover frequency of 28.7 min⁻¹. The rGO-Ni₃₀Pd₇₀ were also durable catalysts in the hydrolytic dehydrogenation of AB providing 3650 total turnovers in 35 h and reused at six times without deactivation. The detailed reaction kinetics of hydrolytic dehydrogenation of AB revealed that the reaction proceeds first order with respect to the NiPd concentration and zeroth order with respect to the AB concentration. The apparent activation energy of the catalytic dehydrogenation of AB was also calculated to be E_a^app = 45 ± 2 kJ*mol⁻¹.     

Bimetallic Ag-Ni nanoparticles as an effective catalyst for hydrogen generation from hydrolysis of sodium borohydride

Stable Ag-Ni bimetallic NPs was prepared, characterized, and applied for the dehydrogenation of sodium borohydride in aqueous media. The structure morphology and properties of Ag-Ni NPs were characterized by using conventional techniques such as surface field scanning electron microscopy (FESEM), transmission electron microscopy (TEM), scanning electron microscopy (SEM), UV–visible spectroscopy, energy dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy. The Ag-Ni NPs were found to be highly effective catalyst to the hydrogen generation from the hydrolysis of sodium borohydride. The catalytic activity of Ag-Ni was increased with increasing the ratio of Ni (Ag₂₅-Ni₂₅ ˂ Ag₂₅-Ni₅₀ ˂ Ag₂₅-Ni₇₅). The reaction follows first-order kinetics with respect to [NaBH₄]. The apparent activation energy = 16.2 kJ/mol, activation enthalpy = 13.4 kJ/mol, and activation entropy = −135.2 J/K/mol were calculated for the hydrogen generation. The activation energy is much lower than those of the other bimetallic nano catalysts. The excellent catalytic activity, good stability, and low cost make the Ag based Ag-Ni NPs a suitable catalyst for the generation of hydrogen in sodium borohydride hydrolysis. It was found that the Ag₂₅-Ni₇₅ is one of the most reusable and durable catalyst for six consecutive cycles without any significant decrease in their catalytic activity.     

Fabrication of highly dispersed palladium/graphene oxide nanocomposites and their catalytic properties for efficient hydrogenation of p-nitrophenol and hydrogen generation

In this report, graphene oxide (GO) nanosheets decorated with ultrafine Pd nanoparticles (Pd NPs) have been successfully fabricated through a reaction between [Pd₂(μ-CO)₂Cl₄]²⁻ and water in the presence of GO nanosheets without any surfactant or other reductant. The as-synthesized small Pd NPs with average diameter of about 4.4 nm were well-dispersed on the surface of GO nanosheets. The Pd/GO nanocomposites show remarkable catalytic activity toward the hydrogenation of p-nitrophenol at room temperature. The kinetic apparent rate constant (k_app) could reach about 34.3 × 10⁻³ s⁻¹. Furthermore, the as-prepared Pd/GO nanocomposites could also be used as an efficient and stable catalyst for hydrogen production from hydrolytic dehydrogenation of ammonia borane (AB). The catalytic activity is much higher than the conventional Pd/C catalysts.     

In-situ nitrogen and Cr2O3 co-doped MOF-derived porous carbon supported palladium nanoparticles: A highly effective catalyst towards formic acid dehydrogenation

Fast and high selective dehydrogenation of formic acid (FA) is regarded as one of the most promising pathways to obtain the clean energy carrier: hydrogen. In this work, a nitrogen and Cr₂O₃ co-doped hierarchical carbon material has been successfully synthesized by in-situ pyrolysis of NH₂-MIL-101(Cr) in one step, followed by boiling in hot NaOH solution for surface etching. The activated carbon material is used to anchor the ultrafine Pd nanoparticles (2.18 nm) for formic acid dehydrogenation (FAD). As a result, the 5 wt% Pd@Cr₂O₃-NPCB-850 exhibits an excellent catalytic activity towards FAD: the turnover frequency (TOF) value is as high as 11 241 h⁻¹ at 333 K, and the selectivity of H₂ is up to 100%. The excellent catalytic performance is mainly attributed to the existence of N species and Cr₂O₃, which plays an important role of electron transfer and anti-aggregation. Our studies open a new methodology for convenient and fast syntheses of nitrogen and metal oxide co-doped activated carbon material, which also provides potential access for producing more highly effective catalysts for other catalytic reactions.