Tuning catalytic performances of cobalt catalysts for clean hydrogen generation via variation of the type of carbon support and catalyst post-treatment temperature

Multi-walled carbon nanotubes, three types of activated carbons, single wall carbon nanotube and reduced graphene oxides were used to synthesize nano-sized Co catalysts for H₂ preparation via NH₃ decomposition. Catalyst samples were characterized by number of techniques such as N₂ physisorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopes (XPS), Transmission electron microscopy (TEM), CO chemisorption, temperature-programmed reduction (H₂-TPR) and temperature-programmed desorption (N₂-TPD). The catalytic activities of the studied catalysts for H₂ production via NH₃ decomposition were measured in a fixed-bed micro-reactor. Co catalyst supported on multi-wall carbon nanotubes has shown the highest catalytic activity. The Co particles size was significantly affected by the variation of the post-treatment temperature. The Co particles size in the range of 4.7–64.8 nm can be effectively controlled by varying post-treatment temperature between 230 and 700 °C. The maximum TOF of NH₃ decomposition was registered on cobalt catalyst post-treated at 600 °C.     

Graphite carbon nitride loaded nitrogen-doped carbon and cobalt nanoparticles ternary photocatalyst for enhanced solar-driven hydrogen evolution

In this paper, we designed a composite photocatalytic system in which cobalt nanoparticles (Co NPs) are attached to nitrogen-doped carbon (N-d-C) and co-bonded to the surface of the noted photocatalyst graphite carbon nitride (g-C₃N₄), showing an excellent photocatalytic hydrogen production. The bulk g-C₃N₄ was formed in the first thermal treatment in air using melamine as a precursor. Subsequently, the secondary calcination under N₂ led to the synchronous fabrication of N-d-C/Co NPs and their combination with g-C₃N₄ to form a novel ternary photocatalyst (g-C₃N₄/N-d-C/Co NPs). Co NPs exposed on the surface of the nanomaterials endowed much more reaction sites than g-C₃N₄ for photocatalytic hydrogen production. Meanwhile, the embedded N-d-C provided an additional transfer approach for photocarriers. The as-prepared composite nanomaterials own a relatively high specific surface area of 97.45 m² g^?1 with an average pore size of 3.83 nm. As a result, compared with pristine g-C₃N₄ (～25.35 μmol g^?1 h^?1), the photocatalytic performance was increased by over 10 times (～270.05 μmol g^?1 h^?1). Our work gives a novel approach for highly active g–C₃N₄–based photocatalysts in the field of photocatalysis.     

Na-intercalated carbon nanotubes-supported platinum nanoparticles as new highly effective catalysts for preferential CO oxidation in H2-rich stream

Na⁺-intercalated carbon nanotubes (Na-CNTs) were obtained by impregnation of CNTs with sodium acetate followed by annealing at high temperatures under argon. Stable Na-CNTs-supported Pt catalysts (Pt/Na-CNT catalysts) were then prepared for hydrogen purification via preferential CO oxidation in a H₂-rich stream (CO-PROX). Characteristic studies show that the content of Na⁺ species in CNTs is increased with increased annealing temperature and the Pt nanoparticles with an average size of 2–3 nm are uniformly dispersed on the surfaces of Na-CNTs. An optimized Pt/Na-CNT catalyst with 5 wt% Pt loading can completely remove CO from 40 °C to 200 °C. This catalyst also exhibits long-term stability for 1000 h at 100 °C in feed gas containing 1% CO, 1% O₂, 50% H₂, 15% CO₂, and 10% H₂O balanced with N₂. The electron transfer between the Pt nanoparticles and Na⁺ species plays an important role in enhancing the CO-PROX performance of the catalyst.     

Carbon nanostructures as catalyst for improving the hydrogen storage behavior of sodium aluminum hydride

The present paper reports the catalytic effect of carbon nanomaterials, particularly carbon nanotubes (CNTs) and graphitic nanofibres (GNFs) with two different structure morphology, namely planar GNFs (PGNFs) and helical GNFs (HGNFs) as the catalyst for improving the dehydrogenation and rehydrogenation behavior of sodium aluminum hydride (NaAlH₄). It has been observed that HGNFs posses superior catalytic activity than other carbon nanoforms in improving the desorption kinetics and decreasing the desorption temperature of NaAlH₄. Temperature programmed desorption (TPD) reveals that HGNFs admixed NaAlH₄ undergo hydrogen desorption at a much lower temperature than PGNFs and CNTs (SWCNTs and MWCNTs) admixed NaAlH₄. Thus for the heating rate of 2 °C/min, the peak desorption temperature corresponds to initial step decomposition of NaAlH₄ admixed with 2 wt.% HGNFs and 2 wt.% PGNFs has been lowered to 143.6 °C and 152.6 °C, respectively (for pristine NaAlH₄, it is ∼170 °C). In addition to the enhancement in desorption kinetics, the HGNFs admixed NaAlH₄ undergoes fast rehydrogenation at the moderate condition. Microstructural investigation reveals that the HGNFs were present on the surface of NaAlH₄ grains, whereas CNTs were tunneled into the grains of NaAlH₄ suggesting a distinct catalytic behavior of different carbon nanovariants.     

Steam reforming of iso-octane toward hydrogen production over mono- and bi-metallic Cu–Co/CeO2 catalysts: Structure-activity correlations

Τhe feasibility of tailoring the iso-octane steam reforming activity of Cu/CeO₂ catalysts through the use of Co as a second active metal (Cu_20−xCo_x, where x = 0, 5, 10, 15, 20 wt%), is investigated. Characterization studies, involving N₂ adsorption–desorption at −196 °C (BET), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), X-ray Photoelectron Spectroscopy (XPS) and Temperature Programmed Reduction (H₂-TPR), were carried out to reveal the impact of the morphological, structural and surface properties of the catalysts on the reforming performance. The results showed that reforming activity was monotonically increased upon increasing cobalt loading. The Co/CeO₂ catalyst demonstrated the optimum performance with a H₂ yield of 70–80% in the 600–800 °C temperature interval. The Co/CeO₂ catalyst exhibited also excellent stability at temperatures above 700 °C, while Cu-based catalysts rapidly deactivated in long term stability tests. A close correlation between surface/redox properties and steam reforming efficiency was established. The lower reducibility of Co/CeO₂ catalysts, associated with the formation of Co³⁺ species, in Co₃O₄-like phase, can be accounted for the enhanced carbon tolerance of Co-based catalysts. Furthermore, the high concentration of surface oxygen species on Co/CeO₂ catalysts can be considered for their enhanced performance. On the other hand, the Cu-induced easier reducibility of bimetallic catalysts, in conjunction with carbon deposition and active phase sintering can be accounted for their inferior steam reforming performance. Irreversible changes in the redox properties of Cu-based catalysts, taking place under reaction conditions, could be resulted to ceria deactivation thus hindering the redox process to keep on.     

Catalysts evaluation for production of hydrogen gas and carbon nanotubes from the pyrolysis-catalysis of waste tyres

Six different types of catalysts (nickel, iron, and cobalt each supported by γ-Al₂O₃ and activated carbon) that were prepared via impregnation were used to produce hydrogen (H₂) and carbon nanotubes (CNTs) from the pyrolytic product of waste tyres. A two-stage pyrolytic-catalytic reactor was constructed, in which the waste tyre was pyrolyzed in the first pyrolysis reactor, and the resultant pyrolysis vapors underwent the reforming and upgrading step in the downstream catalytic reactor. The results showed that the interaction between the active metal and its support had a remarkable effect on the production of H₂ and CNTs. Compared with the series of γ-Al₂O₃ supported catalysts, all the activated carbon-supported catalysts showed higher H₂ yields and better CNTs quality. For the same catalyst support (γ-Al₂O₃ or activated carbon), the higher yield of H₂ and better quality of CNTs were obtained by the Ni catalysts, followed by the Fe catalysts and the Co catalysts. Among all the catalysts, Ni supported by activated carbon exhibited the best catalytic performance, producing the highest hydrogen yield (59.55 vol.%) and the best CNT quality. Further investigation about the influence of CH₄ and naphthalene as the carbon source on generated CNTs revealed that CH₄ led to longer CNT length and higher graphitization than naphthalene.     

Preparation of non-precious metal catalysts for PEMFC cathode from pyrolyzed vitamin B12

In this study, the effect of non-precious metal catalysts in the form of pyrolyzed Vitamin B12 that is supported by carbon black on oxygen reduction reaction (ORR) is examined. Pyrolysis was carried out at temperatures of 300 °C (py-B12/C-300), 500 °C (py-B12/C-500), 700 °C (py-B12/C-700) and 900 °C (py-B12/C-900) in an N₂-atmosphere. The ring-rotating disk electrode technique revealed that the electron-transfer numbers of py-B12/C-300, py-B12/C-500, py-B12/C-700 and py-B12/C-900 are 3.02, 3.42, 3.90 and 3.57, respectively: py-B12/C-700 exhibits near four-electron transfer. The X-ray absorption spectra demonstrate that during the pyrolysis, as the Co oxidation state of py-B12-700 is changed from Co(III) to Co(II), the Co coordination number changes from 6 to 4, suggesting that the structure is a square-planar Co–N₄ chelate. However, the Co–N₄ chelate is decomposed as the pyrolysis temperature increases to 900 °C, resulting in a loss of ORR activity. The H₂–O₂ PEMFC that uses py-B12/C-700 provides excellent performance, substantially outperforming py-CoTMPP/C.     

Improved hydrogen storage performance of defected carbon nanotubes with Pd spillover catalysts dispersed using supercritical CO2 fluid

Hydrogen storage properties of carbon nanotubes (CNTs) modified by oxidative etching and decoration of Pd spillover catalysts are investigated. A mixed H₂SO₄/H₂O₂ solution containing ferrous ions (Fe²⁺) is useful to open the caps, to shorten the length, and to generate defects on CNTs. The Pd catalysts are deposited on the CNTs with the aid of supercritical carbon dioxide (scCO₂); as a result, a highly dispersed Pd nanoparticles and an intimate connection between Pd and carbon surface can be obtained. Combination of the two approaches can optimize a hydrogen spillover reaction on CNTs, resulting in a superior hydrogen storage capacity of 1.54 wt% (at 25 °C and 6.89 MPa), which corresponds to an enhancement factor of ∼4.5 as compared to that of pristine CNTs.     

Influence of powder composition and manufacturing method on electrical and chromium barrier properties of atmospheric plasma sprayed spinel coatings prepared from MnCo2O4 and Mn2CoO4 + Co powders on Crofer 22 APU interconnectors

Protective coatings based on manganese cobalt oxide spinels are required in solid oxide fuel cells (SOFCs) to prevent the evaporation of volatile Cr(VI)-compounds from the metallic interconnectors and to minimize high temperature corrosion. Atmospheric plasma spraying (APS) was used to manufacture dense manganese cobalt oxide protective coatings on Crofer 22 APU substrates by employing two different spinel powders. The spray powders were MnCo₂O₄ and Mn₂CoO₄ + Co (equivalence for Mn_1.5Co_1.5O₄). The Mn₂CoO₄ + Co powder was prepared by agglomerating the oxide powder with fine metallic cobalt powder. The coated substrates were oxidized at 700 °C in air for 1000 h. During the high temperature oxidation, a four-point on-line measurement technique with a current density of 640 mA/cm² was simultaneously used for area specific resistance (ASR) studies. The coatings were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), an energy dispersive spectrometer (EDS) and Raman spectroscopy.     

Transition metal-decorated activated carbon catalysts for dehydrogenation of NaAlH4

Dehydrogenation of NaAlH₄ can be greatly facilitated by activated carbon catalysts. The catalytic function can be further enhanced by decorating the carbon with Co, Ni, or Cu nanoparticles. The decomposition temperature was lowered by as much as 100 °C using a 3 wt.% Co or Ni-decorated activated carbon, comparable to a Ti-based catalyst, which were the most effective among the metals tested. The catalytic effect is likely due to a combination of hydrogen spillover effect, high contact area between carbon and the hydride, and confinement of the hydride as nano-sized domains in the pores of the carbon matrix. The catalysts were also effective in facilitating rehydrogenation of NaAlH₄ under moderate pressure (75.8 bar H₂) and low temperature (120 °C), when no rehydrogenation would occur without the catalyst. The fact that this new catalyst system is not specific to any hydride offers many potential applications.     

CNT-based catalysts for H2 production by ethanol reforming

Hydrogen production by steam reforming of ethanol (SRE) was studied using steam-to-ethanol ratio of 3:1, between the temperature range of 150–450 °C over metal and metal oxide nanoparticle catalysts (Ni, Co, Pt and Rh) supported on carbon nanotubes (CNTs) and compared to a commercial catalyst (Ni/Al₂O₃). The aim was to find out the suitability of CNTs supports with metal nanoparticles for the SRE reactions at low temperatures. The idea to develop CNT-based catalysts that have high selectivity for H₂ is one of the driving forces for this study. The catalytic performance was evaluated in terms of ethanol conversion, product gas composition, hydrogen yield and selectivity to hydrogen. The Co/CNT and Ni/CNT catalysts were found to have the highest activity and selectivity towards hydrogen formation among the catalysts studied. Almost complete ethanol conversion is achieved over the Ni/CNT catalyst at 400 °C. The highest hydrogen yield of 2.5 is, however, obtained over the Co/CNT catalyst at 450 °C. The formation of CO and CH₄ was very low over the Co/CNT catalyst compared to all the other tested catalysts. The Pt and Rh CNT-based catalysts were found to have low activity and selectivity in the SRE reaction. Hydrogen production via steam reforming of ethanol at low temperatures using especially Co/CNT catalyst has thus potential in the future in e.g. the fuel cell applications.     

Effects of post-treatments on microstructure and hydrogen storage performance of the carbon nano-tubes prepared via a metal dusting process

Preparation of multi-wall carbon nano-tubes (CNTs) is successfully demonstrated via a metal dusting (MD) process, in which a steel coupon and CO–CO₂ mixed gas are the only reactants needed. During the process, fresh Fe–Ni nano-particles are produced spontaneously and continuously from the steel, and consequently catalyze the growth of the CNTs. Post-treatments, including heating in air at 550 °C and etching in boiling nitric acid, are used to purify the as-prepared multi-wall CNTs. The microstructure modification due to the post-treatments are examined with a transmission electron microscopy. The possibility of utilizing the MD-produced CNTs as a hydrogen storage material is also explored in this study.     

Composite electrolytes for fuel cells: Long-term stability under variable atmosphere

Ceria-based composites (50 vol% of the ceramic phase) including one mixture of Li and Na carbonates (1:1 molar ratio), were prepared using either pure ceria (modest conductor) or Gd-doped ceria (excellent oxide–ion conductor) as ceramic matrix. These materials were aged for periods of up to 1000 h at 550 °C, under pure CO₂, in air and in H₂ diluted in N₂, to test their stability and electrical performance. Impedance spectroscopy measurements performed between 300 and 600 °C were complemented by structural and microstructural characterization. The excellent long-term stability in CO₂ drops slightly when moving to air and in a pronounced manner when moving to diluted H₂. In all cases and in all conditions the best performance is observed for pure ceria-based composites. Electrode (Au) and electrolyte degradation were found interrelated.     

Hydrogenation and dehydrogenation of Mg2Co nanoparticles and carbon nanotube composites

This study investigated the hydrogenation and dehydrogenation behavior of Mg₂Co nanoparticles and carbon nanotube (CNT) composites using temperature-programmed deposition, Raman spectroscopy, and X-ray diffraction (XRD). We used the mechanical alloying method to prepare nanosized Mg₂Co particles on CNTs with three loadings of alloys. The introduction of CNTs showed dehydrogenation, hydrogen desorption starting at 370 °C, with the majority of hydrogen being below 500 °C. This can be explained by the fact that Mg₂Co alloy deposited on CNT surface induced the dissociation of hydrogen into two atoms, which were spilt over and then intercalated into the interlayer of CNT. Accordingly, the atomic intercalation enabled the reduction of the hydrogen desorption activation barrier. The spillover mechanism of hydrogen storage can be confirmed by XRD and Raman spectroscopy because of larger interspacing (d_0 0 2) and weaker graphite degree (I_D/I_G) of CNTs after hydrogenation.     

Co and Ni supported on CeO2 as selective bimetallic catalyst for dry reforming of methane

Co/CeO₂ (Co 7.5 wt.%), Ni/CeO₂ (Ni 7.5 wt.%) and Co–Ni/CeO₂ (Co 3.75 wt.%, Ni 3.75 wt.%) catalysts were prepared by surfactant assisted co-precipitation method. Samples were characterized by X-Ray diffraction, BET surface areas measurements, temperature programmed reduction and tested for the dry reforming of methane CH₄ + CO₂ → 2CO + 2H₂ in the temperature range 600–800 °C with a CH₄:CO₂:Ar 20:20:60 vol.% feed mixture and a total flow rate of 50 cm³ min⁻¹ (GHSW = 30,000 mL g⁻¹ h⁻¹). The bimetallic Co–Ni/CeO₂ catalyst showed higher CH₄ conversion in comparison with monometallic systems in the whole temperature range, being 50% at 600 °C and 97% at 800 °C. H₂/CO selectivity decreased in the following order: Co–Ni/CeO₂ > Ni/CeO₂ > Co/CeO₂. Carbon deposition on spent catalysts was analyzed by thermal analysis (TG-DTA). After 20 h under stream at 750 °C, cobalt-containing catalysts, Co/CeO₂ and Co–Ni/CeO₂, showed a stable operation in presence of a deposited amorphous carbon of 6 wt.%, whereas Ni/CeO₂ showed an 8% decrease of catalytic activity due to a massive presence of amorphous and graphitic carbon (25 wt.%).     

Catalytic surface development of novel nickel plate catalyst with combined thermally annealed platinum and alumina coatings for steam methane reforming

Catalytically active surface of small nickel (min 99 wt%) plates for steam methane reforming was enhanced by successive temperature programmed oxidation−reduction (TPO−TPR) pretreatment and combined physical vapor deposition of Pt and Al₂O₃. The effect of annealing time, temperature, order and number of coatings on the catalytic activity was investigated by means of a pulse technique at the reaction temperature of 760 °C. The most active and stable surface phases resulted after the successively deposited layers of Pt, Al₂O₃, and Pt had been annealed for 12 h onto 2-cycle TPO−TPR pretreated nickel plate at the temperature of 700 °C in a circulating atmosphere of N₂. The durability performance of the so-prepared surface phases on a specifically structured plate catalyst element (diameter 43 mm and length 42 mm) was tested in a tubular reactor for some 70 h in temperature range 500−650 °C. Deactivation was mainly caused by carbon surface deposition.     

Improved hydrogen storage performance of Mg(NH2)2/LiH mixture by addition of carbon nanostructured materials

The effect of different carbon nanostructures specifically carbon nanotubes (CNTs) and carbon nanofibers (CNFs) on the improvement of the de/re-hydrogenation characteristics of a Mg(NH₂)₂/LiH mixture have been studied. Amongst CNTs and CNFs, the improvement in the hydrogenation properties for the Mg(NH₂)₂/LiH mixture is higher when CNFs are used as a catalyst. Investigations are also focused on the deployment of two different types of CNF (a) CNF1 (synthesized using a ZrFe₂ catalyst) and (b) CNF2 (synthesized using a LaNi₅ catalyst). The results show that CNF2 is better. The maximum decomposition temperature for the pristine Mg(NH₂)₂/LiH mixture is found to be ∼250 °C, which is reduced to ∼180 and ∼150 °C for the sample mixed with 4 wt% of multi-walled carbon nanotubes (MWCNTs) and CNF2 respectively. The activation energy for the dehydrogenation reaction is found to be 74 and 68 kJ mol⁻¹ for the samples mixed with MWCNT and CNF2 respectively, whereas the activation energy for the dehydrogenation reaction of the pristine Mg(NH₂)₂/LiH mixture is 97 kJ mol⁻¹. The catalytic activity and the de/re-hydrogenation characteristics of the Mg(NH₂)₂/LiH mixture mixed with different carbon nanostructures are described and discussed.     

Copper promoted Co/MgO: A stable and efficient catalyst for glycerol steam reforming

Different types of cobalt-based mixed oxide catalysts (20 wt%Co/MgO, 5 wt%Cu-20 wt% Co/MgO, 20 wt%Co/50%MgO–50%Al₂O₃) were synthesized by the co-precipitation method and applied for hydrogen production from glycerol steam reforming. The catalysts were characterized using X-ray diffraction (XRD), H₂-Temperature-programmed reduction (H₂-TPR), CO₂-Temperature Programmed desorption, CO-Chemisorption, and CHN techniques. The H₂-TPR analysis showed the reducibility of cobalt-oxide (5Cu20CM; 5 wt%Cu-20 wt% Co/MgO) was enhanced by the copper, and reduction profiles of cobalt oxide shifted to a lower temperature (<450 °C). Among the catalysts, 5Cu20CM showed a maximum yield of hydrogen (74.6%) with 100% conversion of glycerol to the gaseous phase. The superior catalytic performance of 5Cu20CM for glycerol conversion was attributed to the smaller particle size (7 nm), higher dispersion of cobalt (35.0%), and the higher surface area (56 m²/g) of cobalt metal. Furthermore, Raman spectroscopy of the spent catalysts confirmed that the copper promoted cobalt-magnesium catalyst suppressed the carbon formation, consequently, 5Cu20CM catalyst showed a stable performance up to 30 h.     

Hydrogen and multiwall carbon nanotubes production by catalytic decomposition of methane: Thermogravimetric analysis and scaling-up of Fe–Mo catalysts

Fe-based catalysts doped with Mo were prepared and tested in the catalytic decomposition of methane (CDM), which aims for the co-production of CO₂-free hydrogen and carbon filaments (CFs). Catalysts performance were tested in a thermobalance operating either at isothermal or temperature programmed mode by monitoring the weight changes with time or temperature, respectively, as a result of CF growth on the metal particles. Maximum performance of Fe–Mo catalysts was found at the temperature range of 700–900 °C. The addition of Mo as dopant resulted in an increase in the rate and amount of deposited carbon, reaching an optimum in the range 1.7–5.1% (mol) of Mo for Fe–Mo/Al₂O₃ catalysts, whereas for Fe–Mo/MgO catalyst an optimum at 5.1% Mo loading was obtained. XRD study revealed the effect of the Mo addition on the Fe₂O₃/Fe crystal domain size in the fresh and reduced catalysts. Tubular carbon nanostructures with high structural order were obtained using Fe–Mo catalysts, mainly as multiwall carbon nanotubes (MWCNTs) and bamboo carbon nanotubes. Fe–Mo catalysts showing best results in thermobalance were tested in a rotary bed reactor leading to high conversions of methane (70%) and formation of MWCNTs (5.3 g/h).     

Dual-production of nickel foam supported carbon nanotubes and hydrogen by methane catalytic decomposition

Uniformly dispersed Ni catalysts supported on SiO₂ wash-coated Ni foams were synthesized by the wet impregnation method and successfully applied for methane catalytic decomposition (MCD) at atmospheric pressure. All the prepared catalysts exhibited high catalytic stability. The effects of reaction temperature, space velocity, Ni loading on the MCD performance and the morphologies of the as-prepared CNTs were investigated. The results show that high reaction temperature, low space velocity, and high Ni loading enhanced the hydrogen concentration in the outlet gases. Additionally, SEM and TEM observations indicate that the size (diameter) distribution of the as-prepared CNTs became broader with increasing reaction temperature and Ni loading, respectively. The uniform nickel-foam-supported CNTs and relatively high concentration of hydrogen were obtained simultaneously at 650 °C and at a weight hourly space velocity of 1 L g⁻¹_cat h⁻¹ by the catalyst with 20 wt% Ni. Raman spectroscopy reveals that the uniform MCNTs had a high degree of amorphization.