Cryogenic hydrogen uptake of high surface area porous carbon materials activated by potassium hydroxide

A porous carbon material with specific surface area of 894 m²/g and pore volume of 0.47 cm³/g has been easily synthesized by pyrolysis of a gel containing nickel chloride. Transmission electron microscopy reveals a texture of evenly spreading spherical mesopores and well dispersed micropores. Potassium hydroxide treatment results in a surface area and pore volume of the pristine materials of up to 2930 m²/g and 1.52 cm³/g, respectively. Cryogenic hydrogen uptake capacities were measured and the highest capacity of 6.24 wt% was obtained at 77 K under 2 MPa.     

Synthesis and characterization of layered FePS3 for hydrogen uptake

Iron phosphorus trisulfide FePS₃ is related to the chalcogenides. It is characterized by layered structure. FePS₃ powder was prepared by solid state reaction and heated up to 650 °C using two different heating rates 1 °C/min and 40 °C/min. The results showed that the FePS₃ produced with slow heating rate was highly ordered single crystalline phase while the powder produced with the fast heating rate was poly crystalline phase. The surface morphology and the grain size were influenced by the heating rate used for preparation. The thermal resistance of the highly ordered crystalline phase extended till 680 °C while the less ordered one extended to 660 °C. The products at 900 °C revealed partial decomposition of FePS₃ with subsequent formation of iron sulfide phases poorer with sulfur element. The FePS₃ of single crystalline phase exhibited higher hydrogen sorption capacity at different temperatures than the less ordered crystalline phase. Hydrogen capacity was reduced by cycling as the interlayer gap shrinks.     

Nanoscale CuTe electrocatalyst immobilized at conductor surface for remarkable hydrogen evolution reaction

Hydrogen generation from electrocatalytic water splitting is of supreme significance for resolving energy crisis and environmental concerns. However, developing earth-abundant, efficient, and durable electrocatalyst for high-performance hydrogen evolution and complete water splitting catalysis is a rare instance. We present here the first demonstration of unique copper tellurides nano-structures (CuTe-NS) based electrocatalyst executing HER with high activity and remarkable stability. CuTe-NS based electrocatalysts grown over conductive NiF via drop-casting approach and employed for HER, while achieving a current decade and a current density of 100 mA/cm² just at 0.25 V vs. RHE and 0.27 V vs. RHE, which is comparable to the benchmark Pt/C based HER catalyst. The catalyst demonstrates well-balanced kinetic behavior, low Tafel slope of 36 mV/dec, low charge transfer resistance of 1.71 Ω, high roughness factor, and remarkable stability for more than 60 h of electrolysis. Furthermore, post-catalysis characterizations demonstrate no change in catalyst integrity, morphological, and structural attributes even after many hours of electrolysis which show sustainable behavior of catalyst for long term HER activity. Because of electrochemical and structural stabilities after long term electrolysis experiments, accessible method of preparations, and cost-effectiveness, the catalysis is highly encouraging for real-life applications.     

Optimizing parameters affecting synthetize of CuBTC using response surface methodology and development of AC@CuBTC composite for enhanced hydrogen uptake

CuBTC, a widely studied metal-organic framework, is a promising candidate for industrial applications owing to its easy synthesis procedure and excellent textural properties. In this research CuBTC was synthesized by solvothermal method with the purpose of hydrogen uptake. Response surface methodology (RSM) was employed in order to determine the optimum synthesis condition with the highest hydrogen capacity. Amount of ligand, volume of solvent, synthesis temperature, and synthesis time were chosen as independent variables, while the amount of hydrogen uptake was selected as the response. Subsequently, activated carbon (AC) was incorporated within the optimized CuBTC structure as a “void space filling agent” and adsorption behavior of AC@MOF composite was evaluated from the view point of different AC contents. It was observed that the hydrogen uptake of AC@CuBTC composite was increased compared to bare CuBTC samples. This finding could be attributed to effective utilization of micropore volume of CuBTC structure by AC incorporation.     

Mechanisms of dopants influence on hydrogen uptake in COF-108: A first principles study

Mechanisms of dopants (Li, Na, Mg, and Al) influence on hydrogen uptake in COF-108 were investigated by means of first principles. The binding energy of dopants in COF-108 was estimated from the first principles total energy calculations. All doped systems are shown positive binding energies with the metallic state of the dopant as the reference. The lowest binding energy of 0.518 eV appeared in the Na-doped system while a large amount of energy (2.692 eV) is required for Al to dope into COF-108. Electronic structure analysis shows that dopants Li and Na move the conduction band crossing the Fermi energy level and introduce weakly bonded electrons near the Fermi energy, which may polarize the hydrogen molecules. It is expectable that interaction between hydrogen molecule and the host COF-108 could be enhanced by the polarization of hydrogen molecule. Therefore the hydrogen uptake will be improved in the doped systems. Dopant Mg slightly reduces the band gap between the valence and conduction bands, but is hard to build chemical bonds with the host atoms owing to the less overlaps between the bond peaks of Mg and the COF-108. It hardly affects the electron distributions of the COF-108 and therefore weakly changes the chemical interactions between atoms in COF-108.     

Functionalization of hydrogenated graphene by polylithiated species for efficient hydrogen storage

The hydrogen (H₂) storage capacity of defected graphane (CH) functionalized by polylithiated species CLi₃ and CLi₄ has been investigated by means of first-principles DFT calculations. The stability and electronic structures of these potential H₂ storage materials have also been studied. The binding of these lithium rich species (CLi₃, CLi₄) to the CH sheet has been found to be strong enough to avoid clustering. The nature of bonding in C–Li and C–C has been revealed by Bader charge analysis. It has been found that when both sides of CH sheet are functionalized by polylithiated species, a storage capacity of more than 13 wt% can be achieved with adsorption energies of H₂ in the range of 0.25 eV–0.35 eV, which is suitable for an efficient H₂ storage.     

First-principles identification of the origin for higher activity of surface doped carbon nanohorn: Impact on hydrogen storage

Presence of curvature is considered as a tuning parameter to activate the hydrogen storage capability of carbon nanostructures. Here, we explicate the role of ‘intra-curvature’ in a set of single-walled carbon nanohorns (SWCNHs), to adsorb light metal ad-atoms (M) e.g. Li, Na, Ca and subsequently explore the metal-doped systems for hydrogen storage application using density functional theory. The binding strength of ad-atoms on SWCNHs of different curvature is correlated with the π electron occupancy of the corresponding carbon ring. Higher π electron occupancy causes significantly high binding energy of the metal ad-atoms (M), thereby indicating high stability of those M−C bonds for intra-curvature values more than 11⁰, even at a higher temperature. After full hydrogenation, Li-doped SWCNHs are found to contain a maximum of 7.5 wt % of hydrogen. Overall, our results indicate that Li-doped SWCNHs with intra-curvature values higher than 11⁰, is a potential candidate for hydrogen storage.     

Effects of structural modifications on the hydrogen storage capacity of MOF-5

Here, we describe the preparation of four structurally modified MOF-5s and carried out a systematic study of the effects of the structural modifications on the evolution of the crystal structure, pore characteristics, and H₂ capacities of MOF-5s. The structural modifications were found to significantly influence the pore characteristics, and the specific surface areas of the MOF-5s decreased with the evolution of an ultrafine porosity. These changes were correlated with an increase in the H₂ storage capacity of the MOF-5 (from 1.2 to 2.0 wt% at −196 °C and 1 bar). The structural modifications also enhanced the thermal stability of the MOF-5s (the decomposition temperature increased from 438 °C to 510 °C). These results are particularly useful for the design of favorable MOF-based adsorbents with a high H₂ uptake coupled with a high thermal stability.     

Influence of the phosphorus source on iron phosphide nanoparticle synthesis for hydrogen evolution reaction catalysis

Iron phosphide (FeP) is in the spotlight as a hydrogen evolution reaction (HER) catalyst due to its cost efficiency, good catalytic activity, and stability within a wide pH range. However, there is still a need to synthesize FeP nanoparticles (NPs) with systematic analysis to improve their catalytic activity. Herein, we report FeP NPs synthesized with various phosphorus sources (TOP, trioctylphosphine; TPP, triphenylphosphite; TEAP, tris(diethylamino)phosphine; and TBP, tri-n-butylphosphine) via phosphorization reaction. We clearly demonstrate that the HER activity of the catalyst based on the FeP phase is dependent on the choice of phosphorus source used in the colloidal NP synthesis. Among the samples, FeP NPs synthesized with TPP achieved the highest HER activity with an overpotential of 76 mV at 10 mA cm⁻² in 0.5 M H₂SO₄. Our results reveal a critical aspect of colloidal synthesis to achieve enhanced catalytic activity in the synthesis of transition metal phosphide NPs.     

Theoretical study of hydrogen storage by spillover on porous carbon materials

Hydrogen storage by spillover in porous carbon material (PCM) has achieved great success in experiments. During the past 20 years, a large number of theoretical works have been performed to explore the hydrogen spillover mechanism, look for high-performance hydrogen storage materials and high-efficiency catalysts. In this paper, we summarize and analyze the results of the past researches, and draw the following conclusions: (1) In PCM surface, the stability of chemisorbed H can be reached through phase nucleation process, which can be initiated in the vicinity of surface impurities or defects. (2) To achieve the 2020 U.S. Department of Energy (DOE) target, the PCM material used for hydrogen storage by spillover should have a sp² carbon ratio greater than 0.43 and a surface area less than 3500 m²/g, which gives us an inspiration for exploring hydrogen spillover materials. (3) Due to a high barrier, the hydrogen spillover almost can not be initiated on pure PCM substrate at room temperature. By introducing the defects or impurities (e.g. holes, carbon bridges, oxygen functional groups, boron atoms and fluorine atoms), the spillover barriers can be reduced to a reasonable range. In addition, hydrogen atoms may also migrate in a gas phase. (4) According to our previous results of kinetic Monte Carlo simulations, there is a linear relationship between the reaction temperature and the migration barrier. The optimal barrier for the hydrogen spillover should be in the range of 0.60–0.88 eV. (5) Once the hydrogen atoms are chemically adsorbed on the carbon substrate, it is difficult to diffuse again due to the strong strength of C–H bond. Several theoretical diffusion mechanisms have been proposed. For example, the H atoms in physisorption state can diffuse freely on carbon surfaces with high mobility, using the shuttle gases (e.g. BH⁻₄, H₂O, HF and NH₃) to make the migration thermodynamically possible and decrease the migration barrier, the H atoms diffuse inside the interlayer space of the bi- and tetralayer graphene, and introducing the impurities on the surface to facilitate the hydrogen diffusion. (6) The H desorption through the directly recombination or the reverse spillover is unlikely to occur at normal temperature. The Eley-Rideal reaction may be the only possible mechanism for desorption of the adsorbed H atoms in carbon substrate. Finally, we have made a prospect for further research works on hydrogen storage by spillover.     

Ammonia borane as hydrogen storage materials

Ammonia borane is an appropriate solid hydrogen storage material because of its high hydrogen content of 19.6% wt., high stability under ambient conditions, nontoxicity, and high solubility in common solvents. Hydrolysis of ammonia borane appears to be the most efficient way of releasing hydrogen stored in it. Since ammonia borane is relatively stable against hydrolysis in aqueous solution, its hydrolytic dehydrogenation can be achieved at an appreciable rate only in the presence of suitable catalyst at room temperature. Metal(0) nanoparticles have high initial catalytic activity in releasing H₂ from ammonia borane. Thermodynamically instable metal(0) nanoparticles can kinetically be stabilized against agglomeration either by using ligands in solution or by supporting on the surface of solid materials with large surface area in solid state. Examples of both type of stabilization are presented from our own studies. The results show that metal(0) nanoparticles dispersed in solution or supported on suitable solid materials with large surface area can catalyze the release of H₂ from ammonia borane at room temperature. Dispersion of metal(0) nanoparticles, stabilized in liquid phase by anions or polymers, seems advantageous as providing more active sites compared to the metal nanoparticles supported on a solid surface. However, the supported metal nanoparticles are found to be more stable against agglomeration than the ones dispersed in liquid phase. Therefore, metal nanoparticles supported on solid materials have usually longer lifetime than the ones dispersed in solution. Examples are given from the own literature to show how to improve the catalytic activity and durability of metal nanoparticles by selecting suitable stabilizer or supporting materials for certain metal. For the time being, nanoceria supported rhodium(0) nanoparticles are the most active catalyst providing a turnover frequency of 2010 min^?1 in releasing H₂ from ammonia borane at room temperature.     

Photoproduction of H2 by wildtype Anabaena PCC 7120 and a hydrogen uptake deficient mutant: from laboratory experiments to outdoor culture

We have analyzed the filamentous cyanobacterium Anabaena PCC 7120 (wildtype) containing one nitrogenase, one uptake hydrogenase and one bidirectional hydrogenase and its hydrogen uptake deficient mutant AMC 414 for their H₂ production capacities. Anabaena PCC 7120 and AMC 414 had similar growth rates in turbidostat mode with increased growth rates at higher light intensity. Rates of C₂H₂ reduction were similar for both strains. In contrast to the wildtype, AMC 414 produced H₂ in a PhotoBioReactor (PhBR) using air as the lifting gas. The rate of H₂ production increased with light intensity and was not even saturated at 456 μEm⁻² s⁻¹. H₂ production increased significantly when replacing the air with argon. The maximal H₂ production during outdoor conditions was recorded using AMC 414 with a peak at 14.9 ml H₂ h⁻¹ l⁻¹. Despite the relatively high production, maximal efficiency of solar energy to H₂ conversion was only 0.042%. A molecular method was developed to analyze the relative abundancies of weight and mutant in competition experiments in the PhBR.     

Hydrogen generation via the catalytic hydrolysis of morpholine-borane: A new,efficient and cost-effective hydrogen storage medium

Herein, for the first time, we introduce the morpholine-borane complex (MB) as a new, efficient, cost-effective and commercially available chemical hydrogen storage material for mobile applications. In this regard, hydrogen production from the hydrolysis of MB catalyzed by in situ generated water-soluble polymer stabilized Ag(0) and Pd(0) nanoparticles (NPs) is reported for the first time. In situ generated PSMA-stabilized Ag(0) and Pd(0) NPs showed remarkable activity in hydrogen production from the hydrolysis of MB at room temperature, providing initial TOFs of 16.1 min⁻¹ and 37.3 min⁻¹, respectively. A set of kinetic studies on the catalytic hydrolysis of MB were conducted by changing the catalyst/substrate amount and temperature, and the rate law expression and activation parameters were produced by collecting the kinetic data. The apparent activation energies for the in situ generated Ag(0) and Pd(0) NPs catalyzed MB hydrolysis were calculated to be 71.4 and 32.5 kJ mol⁻¹, respectively.     

Spillover enhanced hydrogen uptake of Pt/Pd doped corncob-derived activated carbon with ultra-high surface area at high pressure

Corncob-derived activated carbon (CAC) was prepared by potassium hydroxide activation. The Pt/Pd-doped CAC samples were prepared by two-step reduction method (ethylene glycol reduction plus hydrogen reduction). The as-obtained samples were characterized by N₂-sorption, TEM and XRD. The results show the texture of CAC is varied after doping Pt/Pd. The Pd particles are easier to grow up than Pt particles on the surface of activated carbon. For containing Pt samples, the pore size distributions are different from original sample and Pd loaded sample. The hydrogen uptake results show excess hydrogen uptake capacity on the Pt/Pd-doped CAC samples are higher than pure CAC at 298 K, which should be attributed to hydrogen spillover effects. The 2.5%Pt and 2.5%Pd hybrid doped CAC sample shows the highest hydrogen uptake capacity (1.65 wt%) at 298 K and 180 bar, The particle size and distribution of Pt/Pd catalysts could play a crucial role on hydrogen uptake by spillover. The total hydrogen storage capacity analysis show that total H₂ storage capacities for all samples are similar, and spillover enhanced H₂ uptakes of metal-doped samples could not well support total H₂ storage capacity. The total pore volume of porous materials also is a key factor to affect total hydrogen storage capacity.     

Impact of surface oxide on hydrogen permeability of chromium membranes

Hydrogen permeation through pure and oxidised bulk chromium membranes was measured by the classical gas technique to get insight into oxide as a hydrogen permeation barrier (HPB). An additional palladium-coated reference chromium membrane was tested to avoid the influence of native Cr oxide. Key parameters for Cr permeability: P₀ = 3.23 × 10^?7 mol H₂/s/m/Pa^0.5 and E_a = 0.68 eV and Cr diffusivity D₀ = 9.0 × 10^?5 m²/s and E_a = 0.59 eV. In the sample preparation stage, a thin ～2 nm thick oxide was formed. Additional oxidation in pure oxygen at 400 °C increased the thickness from 20 to 50 nm. At this temperature, its efficiency as HPB was evaluated by comparing permeation rates to the reference chromium membrane. The highest permeation reduction factor of ～3900 corresponded to only a ～28 nm thick Cr oxide layer. Surface morphology and oxide thickness were investigated by SEM, while the thickness and type of chromium oxide by XPS.     

Transition metal nanoparticle catalysts in releasing hydrogen from the methanolysis of ammonia borane

Ammonia borane (H₃N·BH₃, AB) is one of the promising hydrogen storage materials due to high hydrogen storage capacity (19.6% wt), high stability in solid state as well as in solution and nontoxicity. The methanolysis of AB is an alternative way of releasing H₂ due to many advantages over the hydrolysis such as having high stability against self releasing hydrogen gas. Here we review the reports on using various noble or non-noble metal(0) catalysts for H₂ release from the methanolysis of AB. Ni(0), Pd(0), and Ru(0) nanoparticles (NPs), stabilized as colloidal dispersion in methanol, are highly active and long lived catalysts in the methanolysis of AB. The catalytic activity, lifetime and reusability of transition metal(0) NPs show significant improvement when supported on the surface of solid materials. The supported cobalt, nickel, copper, palladium, and ruthenium based catalysts are quite active in H₂ release from the methanolysis of AB. Rh(0) NPs are highly active catalysts in releasing H₂ from the methanolysis of AB when confined within the void spaces of zeolite or supported on oxide nanopowders such as nanosilica, nanohydroxyapatite, nanoalumina or nanoceria. The oxide supported Rh(0) NPs can provide high activity with turnover frequency values as high as 218 min⁻¹ and long lifetime with total turnover values up to 26,000 in generation of H₂ from the methanolysis of AB at 25 °C. When deposited on carbon the bimetallic AgPd alloy nanoparticles have the highest activity in releasing H₂ through the methanolysis of AB.