Effects of reaction conditions on hydrogen production and carbon nanofiber properties generated by methane decomposition in a fixed bed reactor using a NiCuAl catalyst

In this paper, the results obtained in the catalytic decomposition of methane in a fixed bed reactor using a NiCuAl catalyst prepared by the fusion method are presented. The influences of reaction temperature and space velocity on hydrogen concentration in the outlet gases, as well as on the properties of the carbon produced, have been investigated. Reaction temperature and the space velocity both increase the reaction rate of methane decomposition, but also cause an increase in the rate of catalyst deactivation. Under the operating conditions used, the carbon product is mainly deposited as nanofibers with textural properties highly correlated with the degree of crystallinity.     

Synthesis and hydrogen storage capacity of exfoliated turbostratic carbon nanofibers

Turbostratic carbon nanofibers (CNFs) with a rough surface, open pore walls, and a defect structure were continuously produced by the thermal decomposition of alcohol in the presence of an iron catalyst and a sulfur promoter at 1100 °C under a nitrogen atmosphere in a vertical chemical vapor deposition reactor. A graphite exfoliation technique using intercalation and thermal shock was employed to expand the graphene layers of the as-produced turbostratic CNFs. The hydrogen storage capacity of the turbostratic CNF samples was measured using the volumetric method with a pressure of up to 1 MPa at 77 K. The hydrogen storage capacities of the as-produced and exfoliated turbostratic CNFs were 1.5 and 5 wt%, respectively. The defects on the surface and expandable graphitic structure are considered important keys to increasing the hydrogen uptake in turbostratic CNFs.     

Ni–Cu–Zn/MCM-22 catalysts for simultaneous production of hydrogen and multiwall carbon nanotubes via thermo-catalytic decomposition of methane

Pure hydrogen and carbon nanotubes were produced via thermo-catalytic decomposition (TCD) of methane over Ni-loaded MCM-22 catalysts in a vertical fixed-bed reactor. The effect of reaction temperature, gas hourly space velocity (GHSV), Cu/Zn promoter and time on stream on the methane conversion, hydrogen and carbon yields were studied over the synthesized catalysts. The catalytic performance of the 50%Ni–5%Cu–5%Zn/MCM-22 catalyst was found to be highly stable compared to other catalysts. The highest conversion of methane over 50%Ni–5%Cu–5%Zn/MCM-22 catalyst reached 85% with 947% carbon yield. Methane conversion increased on increasing the reaction temperature up to 750 °C and decreased thereafter at higher temperatures. XRD and TEM analysis of the carbon byproduct revealed that graphitic carbon appeared as a major crystalline phase during the reaction. HRTEM results revealed that most of the Ni particles were located on the tip of the carbon nanofibers/nanotubes formed on the spent catalysts. The carbon nanofibres have an average outer diameter of approximately 20–40 nm with an average length of 450–500 nm. Four types of carbon nanofibers were detected and their formation strongly depended on the reaction temperature, time on stream and degree of the interaction between the metallic Ni particle and support. The optimum conditions for CNT production within the experimental ranges were found at a reaction temperature of 750 °C.     

Investigation of hydrogen storage capacity of various carbon materials

Hydrogen storage capacity of various carbon materials, including activated carbon (AC), single-walled carbon nanohorn, single-walled carbon nanotubes, and graphitic carbon nanofibers, was investigated at 303 and 77 K, respectively. The results showed that hydrogen storage capacity of carbon materials was less than 1 wt% at 303 K, and a super activated carbon, Maxsorb, had the highest capacity (0.67 wt%). By lowering adsorption temperature to 77 K, hydrogen storage capacity of carbon materials increased significantly and Maxsorb could store a large amount of hydrogen (5.7 wt%) at a relatively low pressure of 3 MPa. Hydrogen storage capacity of carbon materials was proportional to their specific surface area and the volume of micropores, and the narrow micropores was preferred to adsorption of hydrogen, indicating that all carbon materials adsorbed hydrogen gas through physical adsorption on the surface.     

Defect-rich MoSx/carbon nanofiber arrays on carbon cloth for highly efficient electrocatalytic hydrogen evolution

Engineering MoS₂ catalysts with more active sites and higher conductivity is an effective way to improve its electrochemical activity. Herein, defect-rich amorphous MoS_x/carbon nanofiber (CF) arrays on carbon cloth (CC) support (denoted as MoS_x/CF/CC) was designed and fabricated, which served as an efficient free-standing electrocatalyst for hydrogen evolution reaction (HER) in acid media. This architecture was beneficial to expose more active catalytic sites and improve the electron/ion transport. In addition, abundant defects altered preferred growth direction of MoS_x, resulting in the formation of irregular MoS_x particles at the surface of CF arrays. The as-synthesized MoS_x/CF/CC-2 exhibited excellent stability and superior HER activity, with a small onset overpotential (107 mV) and low Tafel slope (51 mV dec^?1). Such excellent electrochemical performance was attributed to the enriched active sites and shortened charge diffusion distance. This work would pave a new way for rational design and fabrication of defect-rich MoS_x-based composite electrode for renewable energy applications.     

Preparation and application of sodium borohydride composites for portable hydrogen production

Novel composites consisting of cobalt–boron (CoB) catalyst and sodium borohydride (NaBH₄) implantation in polymers (polyethylene glycol (PEG) or sodium alginate) were prepared for portable hydrogen production. The CoB catalyst was synthesized by the reduction of cobalt salt in NaBH₄ solution followed by heat treatment in nitrogen atmosphere. The catalyst was embedded in PEG gel or alginate beads and NaBH₄ was directly added in PEG–dimethylformamide (DMF) gel and adsorbed in alginate beads. It is noted that the composites prepared are stable in dry air and can be easily used for hydrogen production. A rate of hydrogen production of 750 ml min⁻¹ g⁻¹ was reached when simply putting the composites into pure water. The humidified pure hydrogen can be used conveniently for fuel cells.     

Carbon nanofibers as electrocatalyst support for fuel cells: Effect of hydrogen on their properties in CH4 decomposition

The influence of low partial pressure of hydrogen on carbon nanofibers (CNFs) properties has been studied in the synthesis by methane catalytic decomposition, with the purpose of using them in polymer electrolyte fuel cells as electrocatalyst support. Using CNFs in this kind of application presents a good perspective to improve the fuel cell overall performance. CNF growth in the catalytic decomposition of methane and the characteristics which are typically required in a carbonaceous support, are influenced by hydrogen concentration, which has been studied at different temperatures. The textural, morphological and structural characteristics of the obtained CNFs have been determined by nitrogen physisorption, X-ray diffraction, electron microscopy and thermogravimetry. Electrical conductivity of CNFs has been measured compressing the powder and using a two-probe method. It was observed that low values of partial pressure of hydrogen in methane influence positively structural ordering of CNFs, and in turn improve electrical conductivity, with a slight influence on textural properties leading to highly mesoporous carbon.     

Hydrogen generation by water electrolysis using carbon nanotube anode

Anode made of multiwalled carbon nanotubes (MWNT) results in enhancement of exchange current density compared to graphite anode in a conventional alkaline water electrolysis cell. The hydrogen production rate with the nanotubes was measured to be ∼375 lh⁻¹ m⁻² at pH ∼ 14 which was nearly double of that obtained from traditional graphitic carbon electrodes at the same overpotential. This effect appears to be caused by defects on the nanotubes which reduces the energy barrier for the dissociation of OH⁻ into oxygen at the anode.     

Enhancement of photocatalytic hydrogen production by liquid phase plasma irradiation on metal-loaded TiO2/carbon nanofiber photocatalysts

Enhanced hydrogen production by photocatalytic decomposition was assessed using liquid phase plasma over metal-loaded photocatalysts. Effects of irradiation of the liquid phase plasma were evaluated in the photocatalytic hydrogen production of hydrogen. Carbon nanofiber was introduced as photocatalytic support for the Ni-loaded TiO₂ photocatalyst. The influence of addition of organic reagents into water on hydrogen evolution was also evaluated. The photocatalytic decomposition by irradiation of the liquid phase plasma without photocatalyst produced some hydrogen evolution. The rate of hydrogen evolution was improved by the metal loading on the TiO₂ surface. The carbon nanofiber acted as a useful photocatalytic support for the fixation of TiO₂. Hydrogen evolution was enhanced by the Ni loading on the TiO₂ nanocrystallites supported on the carbon nanofiber support. Hydrogen evolution was increased significantly by the addition of organic reagents, which acted as a type of sacrificial reagent promoting photocatalysis.     

Discharging characteristics of CoB nano powders

CoB nano powders, which are considered as prospective anode material for the secondary nickel batteries, were synthesized by the chemical reduction method and their charge/discharge cyclic characteristics were investigated. The effect of heat-treatment on the structure and the discharging behavior of CoB alloy was also investigated. It was observed that the amorphous/nano-crystalline CoB had very limited hydrogen storage capacity and the crystallized CoB had no hydrogen adsorption ability at all. The big portion of boron present in CoB alloy dissolved selectively into 6 M KOH solution in the first discharge process. After selective dissolution of boron even the amorphous/nano-crystalline CoB alloy lost its hydrogen adsorption ability. The initial discharge capacity of CoB alloy increased as the boron content of CoB alloy increased since the oxidation of boron contributed to (created complication in) the initial discharge process of CoB alloy. After initial charge/discharge process all the subsequent charge/discharge processes were controlled totally by the perfectly reversible Co oxidation/reduction reactions which took place more efficiently in the crystallized structures. So this study makes important contribution to the resolution of the disagreement in the literature that CoB cannot be considered as the hydrogen storage alloy.