Preparation and characterization of activated CMK‐1 with Zn and Ni species applied in hydrogen storage

The aim of this work is to prepare CMK‐1 modified with Zn and Ni in order to improve its capacity in hydrogen storage. The approach that we have followed includes synthesis of nanostructures with the experimental study of its adsorption capacity and storage properties. We have shown that CMK‐1 ordered porous carbon modified with metals is a promising material for hydrogen storage. The incorporation of metals was performed by wetness impregnation. The samples were characterized by X‐ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscope, transmission electron microscopy, X‐ray photoelectron spectroscopy, and Brunauer–Emmett–Teller methods. The CMK‐1 modified with Zn showed the highest H₂ uptake at 77 K and at low and high pressure (1.5 and 4.4 wt.% at 1 and 10 bar, respectively). The introduction of Ni into CMK‐1 does not increase hydrogen storage capacity at low pressure. However, at a higher pressure (10 bars), Ni‐CMK‐1 displays improved results in hydrogen uptake compared with those of CMK‐1 pristine, 2.4 and 2.1 wt.%, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Platinum‐promoted fibrous silica Y zeolite with enhanced mass transfer as a highly selective catalyst for n‐dodecane hydroisomerization

A fibrous silica zeolite Y (HY@KCC‐1) catalyst with a high surface area of 568 m²/g and unique core‐shell morphology was successfully synthesized via a modified KCC‐1 synthesis method. Characterization of the catalysts was achieved with X‐ray powder diffraction (XRD), field emission scanning microscope (FESEM), N₂ adsorption/desorption, and 2,6‐dimethylpyridine adsorbed Fourier‐transform infrared spectroscopy (FTIR). The Pt/HY@KCC‐1 has displayed complete n‐dodecane conversion coupled with an incredibly enhanced isomer yield of 72% at 350°C, nearly two‐fold higher than that of unmodified Pt/HY catalyst. Remarkably, Pt/HY@KCC‐1 had an internal effectiveness factor (η) of unity and negligible internal diffusion limitation, thus suggesting its potential application in hydroisomerization of higher hydrocarbons for enhancing fuel properties.     

Hydrogen adsorption and storage in boron‐substituted and nitrogen‐substituted nano‐carbon materials decorated with alkaline earth metals

Based on ab initio calculations, we have investigated the H₂ adsorption and storage capacity on boron‐substituted and nitrogen‐substituted nano‐carbon materials doped with alkaline earth metal ions (Be²⁺, Mg²⁺, and Ca²⁺) systematically. The calculation results show that the Be²⁺‐decorated, Mg²⁺‐decorated, and Ca²⁺‐decorated carbon‐based materials with B‐substitution and N‐substitution improve the hydrogen storage capacity. H₂ molecules are bound stronger with lighter cations. The adsorption energy of H₂ molecule on the M²⁺‐nano‐carbon complex (M²⁺ = Be²⁺, Mg²⁺, and Ca²⁺) is disproportional to ionic radii of the M²⁺ cations. The interaction between H₂ and M²⁺@nano‐carbon complex is elucidated by Mulliken charge analysis. It is determined that the highest gravimetric density is predicted to be 13.38 and 19.89 wt.% for the B‐substituted and N‐substituted materials, respectively. Copyright © 2015 John Wiley & Sons, Ltd.     

Stability evaluation of ethanol dry reforming on Lanthania‐doped cobalt‐based catalysts for hydrogen‐rich syngas generation

Catalytic stability with time‐on‐stream is an important aspect in ethanol dry reforming (EDR) since catalysts could encounter undesirable deterioration arising from deposited carbon. This work examined the promotional effect of La on 10%Co/Al₂O₃ in terms of activity, stability, and characteristics. Catalysts were characterized by X‐ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Raman, and X‐ray photoelectron spectroscopy (XPS) measurements whilst catalytic EDR performance of La‐promoted and unpromoted 10%Co/Al₂O₃ prepared via wet impregnation technique was investigated at 973 K for 72 h using a stoichiometric feed ratio (C₂H₅OH/CO₂ = 1/1). La promoter substantially enhanced both metal dispersion and metal surface area from 0.11% to 0.64% and 0.08 to 0.43 m² g^?1, respectively. Ethanol and CO₂ conversions appeared to be stable within 50 to 72 h after experiencing an initial activity drop. The conversion of C₂H₅OH and CO₂ for La‐promoted catalyst was about 1.65 and 1.34 times greater than unpromoted counterpart in this order. The carbonaceous deposition was considerably decreased from 55.6% to 36.8% with La promotion due to La₂O₂CO₃ intermediate formation. Additionally, 3%La‐10%Co/Al₂O₃ possessed greater oxygen vacancies acting as active sites for CO₂ adsorption and hence increasing carbon gasification. Even though graphitic and filamentous carbons were formed on used catalyst surface, La‐addition diminished graphite formation and increased the reactiveness of amorphous carbon.     

Pt‐Rh/TiO2/activated carbon as highly active and stable HI decomposition catalyst for hydrogen production in sulfur‐iodine (SI) process

Pt‐TiO₂ loaded on activated carbon was studied as an active and stable catalyst to HI decomposition for H₂ formation in the sulfur‐iodine process. Although the activity of TiO₂‐loaded catalyst was slightly lower HI conversion than that of CeO₂ loaded one, the higher stability against HI decomposition reaction was achieved and almost equilibrium conversion was sustained over ~65 h examined. Moreover, effects of Rh or Ir addition on HI conversion were studied and it was found that Pt‐Rh bimetallic system was highly active and stable to HI decomposition. Scanning transmission electron micrograph observation suggested that the increased HI decomposition activity was assigned to the increased dispersion of Pt particles. High dispersion state of Pt was sustained after HI decomposition at 773 K by addition of Rh. Since the formation of PtI₄ was suggested by X‐ray photoelectron spectroscopy measurement during HI decomposition, increased stability by addition of Rh seems to be assigned to the high chemical stability of Rh against iodine. Almost the equilibrium HI conversion on Pt‐Rh‐TiO₂/M563 was sustained over 300 hours at 673 K.     

Pd‐Ni/Cd loaded PPy/Ti composite electrode: Synthesis,characterization, and application for hydrogen storage

A wide compositional range of Pd‐Ni/Cd on polypyrrole (PPy)‐modified Ti plates (Pd‐Ni/Cd/PPy/Ti) was fabricated via electrochemical deposition. The hydrogen absorption properties of the prepared Pd‐Ni/Cd/PPy/Ti electrodes were evaluated using cyclic voltammetry and chronoamperometry in acidic media. The optimal Pd₃₆‐Ni₇/Cd₅₇/PPy/Ti electrode achieved a hydrogen storage capacity of 331.3 mC cm^?2 mg^?1 and an H/Pd ratio of 0.77. The enhancement of the hydrogen storage was attributed to a synergistic effect between the Pd‐Ni/Cd catalysts. The surface morphology, crystallinity, and chemical composition of the Pd‐Ni/Cd/PPy/Ti electrode were characterized using scanning electron microscope (SEM), X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS), respectively. Hydrogen spillover occurred on the trimetallic catalysts, and secondary hydrogen spillover occurred on the PPy/Ti support. The enhanced hydrogen sorption capacity was due to both the synergistic effect of the trimetallic catalysts and the assistance of PPy, making Pd‐Ni/Cd/PPy/Ti a promising hydrogen storage material.     

One‐pot synthesis of composite NiO/graphitic carbon flakes with contact glow discharge electrolysis for electrochemical supercapacitors

Thanks to their high power density and degree of reversibility, supercapacitors are electrochemical devices that narrow the gap between secondary batteries and traditional dielectric capacitors in the traditional Ragone plot. However, their use is still hindered by their capability to achieve higher energy density. In this work, we present a one‐pot synthesis procedure of composite graphitic carbon flake‐supported NiO for electrochemical energy storage application. We used cathodic contact glow discharge electrolysis by applying 120 Vdc terminal voltage between a thin Pt wire, slightly submerged in an aqueous solution of NiSO₄(H₂O)₆ + Na₂SO₄, and a large surface area carbon graphite anode. Strong active species generated within the micro‐plasma volume locally reduce the nickel precursors to form NiO materials, while at the anodically polarized graphite rod, the forces holding the graphene layers together are weakened by ion/solvent intercalation producing micrometer‐sized graphitic carbon flakes. The morphological characterization is carried out by electron microscopy, energy dispersive X‐ray spectroscopy, powder X‐ray diffraction, and micro‐Raman spectroscopy. Cyclic voltammetry, constant‐current charge/discharge, and electrochemical impedance spectroscopy in 5 mol l^?1 KOH solution are carried out to evaluate the electrochemical energy storage performance of the material. We show that carbon flake‐supported NiO exhibits the dual combination of electric double‐layer capacitance with faradic behavior, giving 495 F g^?1 specific capacitance at 2 A g^?1 current density. Copyright © 2015 John Wiley & Sons, Ltd.     

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.     

Multilayered large‐area WO3 films on sheet and mesh‐type stainless steel substrates for photoelectrochemical hydrogen generation

The objective of this study is to demonstrate the significant improvement in the photoelectrochemical (PEC) hydrogen generation by a photoanode owing to the increased surface area of the substrate. In this work, multilayered tungsten oxide (WO₃) films have been successfully synthesized onto the large‐area sheet (9 × 9cm²) and mesh (1 × 20cm²) ‐type stainless steel (SS) substrates using screen printing and brush painting methods, respectively. All the WO₃ films are porous and nanocrystalline (30–80 nm) in nature with a monoclinic crystal structure as revealed from X‐ray diffraction and scanning electron microscopy studies. The PEC water splitting study is performed under simulated 1 SUN illumination (AM1.5 G) in a typical two‐electrode cell configuration with WO₃ photoanode and Pt wire immersed in 0.5 M H₂SO₄ electrolyte. The photocurrent as well as hydrogen generation rate for WO₃ photoanodes coated on the plane SS sheet substrate is relatively low and showed minimal change with increasing film thickness. On the other hand, the photocurrent as well as the hydrogen generation is enhanced by a 3–4 fold degree for the WO₃ photoanodes coated on SS mesh. We attribute such efficient water splitting to the increment in the filling factor of the WO₃ material due to the large effective surface area of the SS mesh as compared to the SS sheet substrate. Copyright © 2011 John Wiley & Sons, Ltd.     

Investigation on platinum loaded multi-walled carbon nanotubes for hydrogen storage applications

Molecular hydrogen uptake of modified carbon nanotubes is a prospect for efficient hydrogen storage in fuel cell vehicles. In this study, a simple and efficient method to decorate the surface of multi-walled carbon nanotubes (MWNT) with platinum nanoparticles is presented. To load the Pt nanoparticles, hexachloroplatinic acid (H₂PtCl₆·6H₂O) is used as a precursor. Surface morphology of these Pt loaded MWNT is observed using Scanning and Transmission Electron Microscopy. Both samples are also characterized by X-Ray Diffraction. Thermal Gravimetric Analysis results indicate that both as purchased MWNT and Pt loaded MWNT have decomposition temperature higher than 500 °C in air. N₂ adsorption experiments yields a BET area of the sample close to 500 m²/g. This MWNT/Pt sample was reduced in 10% of H₂ in Ar, flowing at 900 °C in a tubular furnace for 1 h before hydrogen adsorption measurements. Hydrogen uptake of MWNT/Pt was measured at 2.5 MPa and 77 K. This hydrogen uptake isotherm is also compared with measurements at ambient temperature.     

Syngas and hydrogen production via stepwise methane reforming over Cu‐ferrite/YSZ

This report investigates the effect of an yttria‐stabilized zirconia (YSZ) supported Cu‐ferrite for the production of syngas and hydrogen via stepwise methane reforming and water splitting reactions. The Cu‐ferrite/YSZ samples were prepared by co‐precipitation and impregnation methods. The samples were characterized by X‐ray diffraction spectroscopy and non‐isothermal hydrogen reduction. To investigate syngas and hydrogen production reactivities, isothermal methane reforming and water splitting reactions were performed at 900 °C and 700 °C, respectively. For Cu‐ferrite/YSZ prepared by impregnation, methane conversion was maintained at high levels of ca. 85% and an H₂/CO ratio close to 2 was observed. A lower methane conversion (>30%) was observed for Cu‐ferrite/YSZ prepared by co‐precipitation. No significant deposited carbon and aggregation of Cu‐ferrite/YSZ (prepared by impregnation) were observed over 10 repeated methane reforming and water splitting reactions. Copyright © 2014 John Wiley & Sons, Ltd.     

Scope of doped mesoporous (<10 nm) surfactant‐modified alumina templated carbons for hydrogen storage applications

Metal (Ni/Pd) and nitrogen codoped mesoporous templated carbons were synthesized using low‐cost surfactant‐modified mesoporous alumina as a hard template via chemical vapor deposition for hydrogen storage application. Initially, high surface area (1508 m²/g) nitrogen‐doped templated carbon was successfully prepared. Pore volume was also significant (1.64 cm³/g). The codoping with metals (Ni or Pd) reduced both the area and pore volume. All the codoped carbons were mesoporous (2‐8 nm). Aggregated morphology was observed for nitrogen‐doped carbon; tubular or noodle shape appeared on codoping with metals. The dispersion of Pd metal within the carbon framework was highest. The 2 wt% Pd codoped carbon showed the highest hydrogen uptake of 5 wt% (?196°C; 25 bar). This may be attributed to its most number of active sites corresponding to the highest metal dispersion and amount of nitrogen present. The cyclic stability of the samples was also good with only 3% to 5% loss in storage capacity up to 10 cycles.     

Photocatalytic hydrogen production from glycerol–water mixture over Pt‐N‐TiO2 nanotube photocatalyst

The effects of several modifications on TiO₂ P25 in producing hydrogen from glycerol–water mixture have been investigated. Prior to further modification, TiO₂ underwent hydrothermal treatment at 130°C for several hours to obtain nanotube shape. TiO₂ nanotubes (TiNT) was then doped with platinum (Pt) and nitrogen (N) by employing photo‐deposition and impregnation method, respectively. SEM and XRD results showed that Pt‐N‐TiNT was successfully obtained as pure anatase crystal structure. The effects of glycerol content to photocatalytic activity of hydrogen production have also been studied, result in 50%v of glycerol as the optimum concentration correspond to the stoichiometric volume ratio of glycerol reforming. The results of photo‐production test showed that TiNT (nanotube) could enhance hydrogen generation by two times compared with unmodified P25 (nanoparticle). Meanwhile, simultaneous modification of TiNT by Pt and N dopants (Pt‐N‐TiNT) lead to activity improvement up to 13 times compared with P25. The output of this study may contribute toward finding an alternative pathway to produce H₂ from renewable resources. Copyright © 2012 John Wiley & Sons, Ltd.     

N‐doped titania powders prepared by different nitrogen sources and their application in quasi‐solid state dye‐sensitized solar cells

Nitrogen‐doped TiO₂ nanocrystalline particles are synthesized by a microwave‐assisted hydrothermal growth method using different amines (Dipropylamine, Diethanolamine and Ammonium hydroxide) as nitrogen sources. Characterization of the nanoparticles was performed with X‐ray diffraction, UV–vis diffuse reflectance spectroscopy, Field Emission Scanning Electron Microscopy and X‐ray Photoelectron Spectroscopy. The prepared N‐doped TiO₂ nanoparticles exhibit pure anatase phase with average diameter of 9 nm and reduced optical energy gap compared to undoped TiO₂. Immobilization of N‐doped and pure TiO₂ nanoparticles on SnO₂:F conductive glass substrates was successfully performed by using doctor‐blade technique and paste of the aforementioned nanoparticles. A series of N‐doped TiO₂ photoelectrodes with varying N dopant source and concentrations were fabricated for quasi‐solid state dye‐sensitized solar cells. The N‐doped solar cells achieve an overall conversion efficiency ranging from 4.0 to 5.7% while undoped TiO₂ showed 3.6%. The basic difference to the electrical performance of the cells is focused to the enhancement in the current density of N‐doped TiO₂‐based cells which was from 11% to 58% compared with undoped TiO₂ cells. Current densities were directly proportional with nitrogen doping level in TiO₂ lattice which differs depending on the amine source nature such as basicity differences, hydrogen bonding abilities and steric inherences. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of different carbon supports for Ni particles for the HER in tetra‐alkylammonium‐sulfonic acid media

Vitreous carbon (VC) and pyrolytic carbon (PC) were covered by nickel particles through sputter deposition, consisting in the Ni/VC and Ni/PC electrodes, respectively. These materials were tested as cathodes in an aqueous solution of tetrafluoroborate of the 3‐triethylammonium‐propane sulfonic acid ionic liquid (TEA‐PS.BF₄) for hydrogen production and characterized by scanning electron microscopy (SEM), chronoamperometry (CA), linear and cyclic voltammetry (LV and CV), and electrochemical impedance spectroscopy (EIS). The mechanism of the hydrogen evolution reaction (HER) was that of Volmer‐Heyrovsky for all the cathodes tested, and the H₂ desorption at the catalytic surface is the determining step. The results indicate that different carbon supports can affect the efficiency of the particulate electrocatalyst deposited on it. The low values of H⁺ adsorption and the H₂ desorption resistances of the modified PC system (0.43 and 0.8 Ω cm², respectively), in relation to the modified VC system (1.13 and 7.9 Ω cm², respectively), attest that Ni particles presence on PC favored the adsorption of H⁺ and H₂ nanobubble desorption. The Ni particles on PC increase exchange current density (80.5 μA cm² for Ni/PC cathode about 38.3 Ω cm² for Ni/VC cathode) and enhance catalytic activity. These results can be attributed to the faster liberation of the active sites due to the interaction between the Ni particles and the PC support. In addition, the TEA‐PS.BF₄ solution can act as a stripper, avoiding the formation of passive oxides in the open circuit and preventing the deactivation of the electrocatalyst.     

Hydrogen storage performance of platinum supported carbon nanohorns: A DFT study of reaction mechanisms,thermodynamics, and kinetics

Platinum (Pt) is one of a robust hydrogen dissociative catalyst. However, the migration of dissociated hydrogens from Pt nanoparticles to carbon supports such as graphene and carbon nanotube are energetically unfavorable reactions. To enhance the hydrogen storage via migration mechanism, carbon nanohorn is applied as a support for Pt nanoparticles (Pt and Pt₄). The H₂ storage performance of Pt and Pt₄ supported on the mono-vacancy carbon nanohorn (vNH) has been investigated by using density functional theory calculations. The Pt and Pt₄ firmly deposit at the vacancy site through the three strong Pt–C bonds with binding energies about ?7.0 eV, which can prevent the metal desorption and migration. The mechanism of H₂ storage starts with H₂ adsorption followed by H₂ spillover reaction. The calculation results reveal that the supported Pt nanoparticles are the active sites for H₂ dissociative adsorption while the high curvature surface of carbon nanohorn is the active area for accommodating the migrated H atoms from the spillover reaction. Remarkably, the hydrogen spillover reactions over Pt– and Pt₄-supported on vNHs in this study are spontaneous at room temperature with highly exothermic reaction energy. The fundamental understanding obtained from this study is beneficial for further design and synthesis of high-performance materials for H₂ storage applications.     

A high‐performance CeO2@Pt‐Beta yolk‐shell catalyst used in low‐temperature ethanol steam reforming for high‐purity hydrogen production

A novel Pt‐based Beta encapsulated CeO₂ yolk‐shell catalyst was successfully synthesized via a RF layer in the synthetic process. The CeO₂@Pt‐Beta catalyst showed high catalytic activity and stability toward the LT‐ESR with respect to the reference Pt‐Beta, CeO₂‐Pt‐Beta, which benefited from the special yolk‐shell structure and the synergistic effect between the CeO₂ movable core and Pt metal. The confinement effect of the yolk‐shell architecture contributed to the high dispersion of Pt nanoparticles as well as to the accumulation of reactant molecules in the enclosed void space, which ensured the reactants reacted with CeO₂ and Pt to achieve a complete reaction.     

Enhancing hydrogen storage on carbon nanotubes via hybrid chemical etching and Pt decoration employing supercritical carbon dioxide fluid

Acidic etching and Pt particle decoration were applied to modify the hydrogen absorption behavior of carbon nanotubes (CNTs). Two different acidic solutions, namely H₂SO₄/HNO₃ and FeSO₄/H₂SO₄/H₂O₂, were used for etching treatment. A novel electroless deposition process, incorporating supercritical CO₂ (sc-CO₂) fluid, was used to decorate finely-dispersed nano-sized Pt particles on CNTs. The hydrogen storage capacities of various modified CNTs were measured by using a high pressure thermal gravimetric microbalance (HPTGA). The experimental results showed that acidic etching could increase the surface defect density and lead to open-up of the caps of CNTs, resulting in an increase in the active adsorption site for physical sorption of H_2. The electroless deposition of nano-Pt particles on CNTs, using conventional electrolyte, could promote chemical sorption of hydrogen via spillover mechanism. By employing sc-CO₂ bath, the Pt particle size became much finer and more uniformly distributed on the surfaces of CNTs, giving rise to a high hydrogen storage capacity. When a hybrid process including sc-CO₂ Pt decoration following acidic etching was applied to modify CNTs, a substantial enhancement of hydrogen storage capacity (about 2.7 wt%) was observed.     

Hydrogen adsorption properties of in-situ synthesized Pt-decorated porous carbons templated from zeolite EMC-2

To increase the interaction between the adsorbed hydrogen and the adsorbent surface to improve the hydrogen storage capacity at ambient temperature, decorating the sorbents with metal nanoparticles, such as Pd, Ni, and Pt has attracted the most attention. In this work, Pt-decorated porous carbons were in-situ synthesized via CVD method using Pt-impregnated zeolite EMC-2 as template and their hydrogen uptake performance up to 20 bar at 77, 87, 298 and 308 K has been investigated with focus on the interaction between the adsorbed H₂ and the carbon matrix. It is found that the in-situ generated Pt-decorated porous carbons exhibit Pt nanoparticles with size of 2–4 nm homogenously dispersed in the porous carbon, accompanied with observable carbon nanowires on the surface. The calculated H₂ adsorption heats at/near 77 K are similar for both the plain carbon (7.8 kJ mol⁻¹) and the Pt-decorated carbon (8.3 kJ mol⁻¹) at H₂ coverage of 0.08 wt.%, suggesting physisorption is dominated in both cases. However, the calculated H₂ adsorption heat at/near 298 K of Pt-decorated carbon is 72 kJ mol⁻¹ at initial H₂ coverage (close to 0), which decreases dramatically to 20.8 kJ mol⁻¹ at H₂ coverage of 0.014 wt.%, levels to 17.9 at 0.073 wt.%, then gradually decreases to 2.6 kJ mol⁻¹ at 0.13 wt.% and closes to that of the plain carbon at H₂ coverage above 0.13 wt.%. These results suggest that the introduction of Pt particles significantly enhances the interaction between the adsorbed H₂ and the Pt-decorated carbon matrix at lower H₂ coverage, resulting in an adsorption process consisting of chemisorption stage, mixed nature of chemisorption and physisorption stage along with the increase of H₂ coverage (up to 0.13 wt.%). However, this enhancement in the interaction is outperformed by the added weight of the Pt and the blockage and/or occupation of some pores by the Pt nanoparticles, which results in lower H₂ uptake than that of the plain carbon.     

High‐pressure hydrogen storage on modified MIL‐101 metal–organic framework

Porous chromium(III) oxoterephthalate MIL‐101 possesses an MTN zeolite‐type framework with tetrahedral micropores (diameter ~0.8 nm) and two types of mesopores (diameter ~3.0 and 2.8 nm, respectively). The hybrid MIL‐101/Pt/C composite materials were produced by a bridge building technique by grinding of ternary mixtures of MIL‐101, glucose, and Pt‐catalyst, followed by a bridge formation via a carbonization of glucose at 160 °C. The hydrogen adsorption properties of porous materials were investigated at pressures up to 1000 bar. Excess adsorption isotherms measured volumetrically at temperatures of 81 and 298 K evidence a remarkable effect of the catalyst on the material behaviors under high hydrogen pressure. There is no saturation at room temperature within the studied pressure range as the excess hydrogen sorption capacity increases gradually with pressure and reaches 1.5 wt.% instead of maximum 0.4 wt.% for the pristine MIL‐101. The maximum total H₂ uptake at 298 K is estimated to be 6.1 wt.% that leads to a shift of the upper limit of the efficiency of the storage system from 25 to 250 bar as compared with the unmodified metal–organic framework. The results obtained demonstrate feasibility of advanced high‐pressure hydrogen storage systems based on hybrid technology. Copyright © 2014 John Wiley & Sons, Ltd.