High temperature iron-based catalysts for hydrogen and nanostructured carbon production by methane decomposition

The production of hydrogen and filamentous carbon by means of methane decomposition was investigated in a fixed-bed reactor using iron-based catalysts. The effect of the textural promoter and the addition of Mo as a dopant affects the catalysts performance substantially: iron catalyst prepared with Al₂O₃ showed slightly higher catalytic performance as compared to those prepared with MgO; Mo addition was found to improve the catalytic performance of the catalyst prepared with MgO, whereas in the catalyst prepared with Al₂O₃ displayed similar or slightly poorer results. Additionally, the influence of the catalyst reduction temperature, the reaction temperature and the space velocity on the hydrogen yield was thoroughly investigated. The study reveals that iron catalysts allow achieving high methane conversions at operating temperatures higher than 800 °C, yielding simultaneously carbon nanofilaments with interesting properties. Thus, at 900 °C reaction temperature and 1 l g⁻¹_cat h⁻¹ space velocity, ca. 93 vol% hydrogen concentration was obtained, which corresponds to a methane conversion of 87%. Additionally, it was found that at temperatures higher than 700 °C, carbon co-product is deposited mainly as multi walled carbon nanotubes. The textural and structural properties of the carbonaceous structures obtained are also presented.     

Natural Fe-based catalysts for the production of hydrogen and carbon nanomaterials via methane decomposition

Tierga and Ilmenite Fe-based ores are studied for the first time in the catalytic decomposition of methane (CDM) for the production of carbon dioxide-free hydrogen and carbon nanomaterials. Tierga exhibits superior catalytic performance at 800 °C. The effect of the reaction temperature, space velocity and reducing atmosphere in the catalytic decomposition of methane is evaluated using Tierga. The highest stability and activity (70 vol% hydrogen concentration) is obtained at 850 °C using methane as a reducing agent. Reduction with methane causes the fragmentation of the iron active phase and inhibits the formation of iron carbide, improving its activity and stability in the CDM. Hybrid nanomaterials composed of graphite sheets and carbon nanotubes with a high degree of graphitization are obtained. Considering its catalytic activity, the carbon quality, and the low cost of the material, Tierga has a competitive performance against synthetic iron-catalysts for carbon dioxide-free hydrogen and solid carbon generation.     

Comparisons of Pt catalysts supported on active carbon,carbon molecular sieve,carbon nanotubes and graphite for HI decomposition at different temperature

A series of Pt catalysts supported on activated carbon (AC), carbon molecular sieve (CMS), carbon nanotubes (CNT) and graphite (GR) were prepared by the impregnation method. Their catalytic performances in HI decomposition were evaluated in a fixed bed reactor at temperatures ranging from 400 to 550 °C under atmospheric pressure. The different Pt catalysts before and after HI decomposition at different temperature were characterized by BET, XRD and TEM, respectively. The results of the activity evaluation indicated that the activity order of different Pt catalysts changed significantly with the variation of reaction temperature. At 400 °C, different supported Pt catalysts activities decreased in order of Pt/CMS > Pt/AC > Pt/CNT > Pt/GR. At 450 °C, the activities of different Pt catalysts followed the order of Pt/AC ≈ Pt/CNT > Pt/CMS > Pt/GR. At 500 and 550 °C, the Pt/CNT showed the optimum activity and stability during HI decomposition, which could be attributed to the high dispersion of Pt particles and the special microstructure of CNT. The XRD and TEM results illustrated that the Pt particle size or Pt dispersion in different supported Pt catalysts showed different sensitivity to the reaction temperature.     

Morphology and location manipulation of Fe nanoparticles on carbon nanofibers as catalysts for ammonia decomposition to generate hydrogen

Ammonia decomposition over Fe-based catalysts is a typical structure sensitive reaction, and the shape-controlled synthesis of Fe nanoparticles based on catalytic chemical vapor deposition (CCVD) method appears to be an effective method toward enhanced catalytic activity. The objective of this work is to understand effects of the reaction parameters on structural and textural properties of the resultant Fe catalysts and thus catalytic ammonia decomposition performance. The as-obtained catalysts are characterized by multiple techniques (N₂ physisorption, XRD, SEM, TEM, and Raman spectroscopy). Both the morphology and location of Fe nanoparticles are found to strongly depend on the partial pressure of H₂ as well as the growth time of CNFs. The long polyhedron shaped Fe nanoparticles on CNFs exhibit the highest activity among the prepared catalysts, which are relatively higher than the activities of the reported Fe based catalysts. The possible explanation for the good catalytic performance was proposed.     

Morphology dependence of catalytic properties of Ni nanoparticles at the tips of carbon nanofibers for ammonia decomposition to generate hydrogen

Ni nanoparticles at the tips of carbon nanofibers (Ni-CNFs) were synthesized by catalytic chemical vapor deposition (CCVD) method using CH₄ as the carbon source, and then employed as catalysts for the generation of H₂ from ammonia decomposition. The morphology of Ni catalysts is highly sensitive to the ratio of CH₄ to H₂. Especially for the CH₄/H₂ ratio of 4, the as-obtained Ni-CNFs catalyst shows higher H₂ formation rate, which could be due to more accessible facets to the reactants and unique shape effect. Meanwhile, this catalyst also shows good thermal stability, possibly owing to the highly dispersed and spatially isolated Ni nanoparticles by CNFs. Moreover, effect of the surface carbon coverage on the orientation of Ni crystal facets and the matching degree between graphene sheet and Ni crystal facet were investigated by DFT calculations. Finally, a possible formation mechanism of shaped Ni catalysts was discussed by combining experimental and theoretical results.     

Effect of coexistence of H2S on production of hydrogen and solid carbon by methane decomposition using Fe catalyst

Biogas derived from livestock manure and food residue contains CO₂ and H₂S as well as methane. The effect of CO₂ and H₂S coexistence on the production of hydrogen and solid carbon by methane decomposition over iron oxide catalysts was investigated. The catalytic activity for methane decomposition was decreased by the coexistence of H₂S. Moreover, the activity decrease was aggravated by the coexistence of CO₂ as well as H₂S, and higher temperature was required to mitigate the activity decrease by the coexistence of CO₂. By increasing the amount of catalyst, the upstream catalyst was preferentially poisoned, but the downstream catalyst developed catalytic activity thanks to its sacrifice. With 2 g of catalyst, the maximum conversion of pure methane was about 85% at 840 °C, but it was slightly less than 80% in the presence of H₂S or H₂S + CO₂. When the catalyst amount was increased to 4 g, the conversion of pure methane was about 90% at 800 °C, but 84% in the presence of H₂S and 80% in the presence of H₂S + CO₂. The poisoning by H₂S was irreversible at low temperatures but became reversible at higher temperatures. Since H₂S is adsorbed by the deposited carbon, the procedure for further removal of H₂S may be omitted. The coexistence of H₂S also affected the shape of the deposited carbon. Although carbon-based catalysts are known to be effective for methane decomposition in the presence of H₂S, iron oxide catalysts have the advantage of superior methane conversion at low temperatures. By flowing methane with CO₂ and H₂S from the downstream side after the reaction flowing from the upstream side for a certain period of time, the catalytic lifetime was drastically extended and the amount of hydrogen and solid carbon produced was dramatically increased, compared to the case of flowing from upstream all the way.     

Structure and catalytic properties of Ni/MWCNTs and Ni/AC catalysts for hydrogen production via ammonia decomposition

The structure and catalytic properties of nickel catalysts supported on multi-wall carbon nanotubes (MWCNTs) and on three different types of activated carbon (AC) were studied. The surface areas of AC carriers were defining the size of supported nickel particles. Large surface area of AC led to small Ni nanoparticles and high Ni dispersion. Turnover frequency (TOF_NH3) of ammonia decomposition decreased with decreasing of Ni particle size. The highest degree of ammonia conversion was observed on Ni/AC prepared by using of AC support with largest surface area. The catalytic activity of Ni/MWCNTs was much higher than catalytic activity of the studied Ni/AC catalysts. The synergic nickel-support interaction and special electronic conductivity properties of MWCNTs were responsible for high catalytic activity of Ni/MWCNTs catalyst.     

Decomposition of hydrogen iodide via wood-based activated carbon catalysts for hydrogen production

In this study, the catalytic activity of wood-based catalysts produced by different activation methods was evaluated for the decomposition of hydrogen iodide (HI) as part of the sulfur-iodine hydrogen production process. The wood-based activated carbon catalysts showed strong improvement in the HI conversion compared to a blank, especially for carbon catalysts activated using H₃PO₄. Proximate analysis and ultimate analysis, XRD, BET, SEM, Boehm titration, TPD-MS, XPS were carried out to examine the characteristics of the catalysts. High carbon content (C_ad) seemed to favor high catalytic activity, while high ash content (A_ad) reduced catalytic activity of samples likely due to displacement of catalytically active material. Oxygen-containing groups were not directly responsible for catalytic activity. HI conversion increased as the surface area and pore diameter increased. Unsaturated carbon atoms maybe the main active constituent, therefore, low area density of oxygen [O] that was closely related to unsaturated carbon atoms was beneficial to HI conversion.     

Highly dispersed cobalt nanoparticles onto nitrogen-doped carbon nanosheets for efficient hydrogen generation via catalytic hydrolysis of sodium borohydride

Porous carbon nanostructures are promising supports for stabilizing the highly dispersed metal nanoparticles and facilitating the mass transfer during the reaction, which are critical to achieve the high efficiency of hydrogen generation from sodium borohydride dehydrogenation. Herein, the catalytically active porous architectures are simply prepared by using 2-methylimidazole and melamine as reactive sources. The structural and compositional characterizations reveal the coexistence of metallic cobalt and N-doped carbon in porous architectures. Electron microscopy observations indicate that the synthesized products are smartly constructed from the carbon nanosheets with densely dispersed Co nanoparticles. Due to the notable structural features, the prepared Co@NC-600 sample presents the highly efficient activity for catalytic hydrolysis of NaBH₄ with a hydrogen generation rate of 2574 mL min⁻¹ g_cat⁻¹ and an activation energy of 47.6 kJ mol⁻¹. The catalytically active metallic Co and suitable support-effect of N-doped carbon are responsible for catalytic dehydrogenation.     

Green synthesis of porous Ni-silicate catalyst for hydrogen generation via ammonia decomposition

A simple synthetic method without organic template is proposed for the synthesis of Ni-silicate. The resulting Ni-phyllosilicates are reconstructed by hydrothermal treatment to a porous structure with a high surface area (552 m² g⁻¹). Notably, the residual filtrate has a Ni²⁺ ion content of less than 0.1 ppm, and therefore satisfies the effluent standard in Taiwan (<1.0 ppm). As a result, it can be disposed of directly without the need for additional treatment. The effects of the pH value and hydrothermal treatment time on the structure, morphology, and surface area of the Ni-silicate composites have been investigated. When applied to hydrogen production, the mesoporous Ni-silicate shows a high catalytic capability (>99%) toward ammonia decomposition at a temperature of 400°C. Overall, the proposed synthetic method is facile and easily extendable to the production of other metal-silicate materials for hydrogen generation.     

Lowering risk of methanation of carbon support in Ru/carbon catalysts for CO methanation by adding lanthanum

Two series of Ru/C catalysts doped with lanthanum ions are prepared and studied in CO methanation in the H₂-rich gas. The samples are characterized by N₂ physisorption, TG-MS studies, XRD, XPS, TEM/STEM and CO chemisorption. Two graphitized carbons differing in surface area (115 and 80.6 m²/g) are used as supports. The average sizes of ruthenium crystallites deposited on their surfaces are 4.33 and 5.95 nm, respectively. The addition of the proper amount of La to the Ru/carbon catalysts leads to an above 20% increase in the catalytic activity along with stable CH₄ selectivity higher than 99% at all temperatures. Simultaneously, lanthanum acts as the inhibitor of methanation of the carbon support under conditions of high temperature and hydrogen atmosphere. Such positive effects are achieved at a very low concentration of La in the prepared samples, a maximum 0.04 La/Ru (molar ratio). 0.01 mmol La introduced to the Ru/C system leads to 98% CO conversion at 270 °C.     

Influence on hydrogen production of the minor components of natural gas during its decomposition using carbonaceous catalysts

In this work, the catalytic decomposition of the minor hydrocarbons present in natural gas, such as ethane and propane, over a commercial carbon black (BP2000) is studied. The influence of the reaction temperature on the product gas distribution was investigated. Increasing reaction temperatures were found to increase both hydrocarbon conversion and hydrogen selectivity. Carbon produced by ethane and propane was predominantly deposited as long filaments formed by spherical aggregates with diameters on the order of nanometres. Furthermore, the influence of ethane and propane on methane decomposition over BP2000 was also investigated, showing enrichment in hydrogen concentration with the addition of small amounts of these hydrocarbons in the feed. Additionally, the positive catalytic effect of H₂S on methane decomposition over BP2000 is addressed.     

One-step synthesis of Ni/yttrium-doped barium zirconates catalyst for on-site hydrogen production from NH3 decomposition

On-site produced hydrogen from ammonia decomposition can directly fuel solid oxide fuel cells (SOFCs) for power generation. The key issue in ammonia decomposition is to improve the activity and stability of the reaction at low temperatures. In this study, proton-conducting oxides, Ba(Zr,Y) O_3-δ (BZY), were investigated as potential support materials to load Ni metal by a one-step impregnation method. The influence of Ni loading, Ba loading, and synthesis temperature, of Ni/BZY catalysts on the catalytic activity for ammonia decomposition were investigated. The Ni/BZY catalyst with Ba loading of 20 wt%, Ni loading of 30 wt%, and synthesized at 900 °C attained the highest ammonia conversion of 100% at 600 °C. The kinetics analysis revealed that for Ni/BZY catalyst, the hydrogen poisoning effect for ammonia decomposition was significantly suppressed. The reaction order of hydrogen for the optimized Ni/BZY catalyst was estimated as low as ?0.07, which is the lowest to the best of our knowledge, resulting in the improvement in the activity. H₂ temperature programmed reduction and desorption analysis results suggested that a strong interaction between Ni and BZY support as well as the hydrogen storage capability of the proton-conducting support might be responsible for the promotion of ammonia decomposition on Ni/BZY. Based on the experimental data, a mechanism of hydrogen spillover from Ni to BZY support is proposed.     

One-pot synthesis of supported Ni@Al2O3 catalysts with uniform small-sized Ni for hydrogen generation via ammonia decomposition

Nickel based materials are the most potential catalysts for CO_x-free hydrogen production from ammonia decomposition. However, the facile synthesis of supported Ni-based catalysts with small size Ni particles, high porosity and good structural stability is still of great demand. In this work, uniform small-sized Ni particles supported into porous alumina matrix (Ni@Al₂O₃) are synthesized by a simple one-pot method and used for ammonia decomposition. The Ni content is controlled from 5 at.% to 25 at.%. Especailly, the 25Ni@Al₂O₃ catalyst shows the best catalytic performance. With a GHSV of 24,000 cm³g_cat^?1h^?1, 93.9% NH₃ conversion is achieved at 600 °C and nearly full conversion of NH₃ is realized at 650 °C. The hydrogen formation rate of 25NiAl catalyst reaches 3.6 mmol g_cat^?1min^?1 at 400 °C and 7.8 mmol g_cat^?1min^?1 at 450 °C. The enhanced activity observed on 25Ni@Al₂O₃ catalyst can be attributed to the structural characteristic that large amounts of uniform-sized small (7.2 ± 0.9 nm) Ni particles are highly dispersed into porous alumina matrix. The aggregation of active metallic Ni particles during the high temperature reaction can be effectively prevented by the porous alumina matrix due to the strong interaction between them, thus ensuring a good catalytic performance.     

Effect of preparation methods on the catalyst performance of Co/MgLa mixed oxide catalyst for COx-free hydrogen production by ammonia decomposition

This work deals with the effect of catalyst preparation method of the mixed Co, Mg and La oxide catalysts on their structure and catalytic properties for ammonia decomposition. Two methods are used for catalysts preparations impregnation and co-precipitation (in air and in pure O₂ atmosphere), The Mg/La = 2 molar ratio and 5 wt% of cobalt content was maintained same in all catalysts. The catalyst performance was evaluated in the temperature range 300–550 °C at atmospheric pressure. The prepared catalysts were characterized by BET, XRD, TPR, XPS, CO₂-TPD and SEM techniques. No pronounced differences were observed in BET among the catalysts. It was found that the 5CML-OXY (5 wt%Co over MgLa catalyst prepared by co-precipitation method in oxygen atmosphere) has superior activity among the other catalysts. This could be attributed to availability of easily reducible cobalt species determined by TPR studies and enhanced interaction between Mg and La determined by SEM and XPS. The moderate basic site density determined by CO₂-TPD results was also increased in 5CML–OXY catalysts compared with other catalysts. These consequences are might be one of the reasons for enhanced activity of 5CML–OXY catalyst compared to other catalysts. Hence catalyst preparation by co-precipitation in oxygen atmosphere is the best method which might be one of the parameters that influenced on catalytic properties of the cobalt on MgOLa₂O₃ system, for ammonia decomposition.     

High performance of bulk Mo2N and Co3Mo3N catalysts for hydrogen production from ammonia: Role of citric acid to Mo molar ratio in preparation of high surface area nitride catalysts

Hydrogen production from ammonia decomposition was studied using a series of unsupported high surface area molybdenum nitride (Mo₂N) and cobalt promoted molybdenum nitride (3%Co-Mo₂N) catalysts prepared with citric acid (CA) as a chelating agent. To elucidate the influence of citric acid amount in preparation conditions on the structure and catalytic activity, we prepared catalysts with different citric acid to Mo molar ratios i.e. CA/Mo = 1, 2, 3 and 4. The catalytic activity was evaluated in the temperature range of 300–600 °C at atmospheric pressure. The catalytic activity of the tested samples has changed in the following order of CA/Mo atomic ratio of 1 < 2 < 3 > 4. Therefore, the catalyst prepared by using CA/Mo ratio = 3 showed the highest catalytic activity. BET, XRD, XPS, SEM and TEM-EDS techniques were been used to characterize the catalysts. The increased activity of Mo₂N-3:1 and 3%Co-Mo₂N-3:1 catalysts was due to increased surface area, decreased particle size and increased relative proportions of Mo₂N and Co₃Mo₃N phases. The ammonia conversion for 3%Co-Mo₂N catalyst was increased from 75 to 97% at 550 °C with the increase of CA/Mo ratio from 1 to 3. This enrichment of activity in 3%Co-Mo₂N-3:1 catalyst is due to increased dispersion of Co₃Mo₃N microstructure on γ-Mo₂N platelets confirmed by SEM and TEM results. No deactivation was observed for any catalysts investigated in this study for ammonia decomposition.     

Methanation of CO on Ru/graphitized-carbon catalysts: Effects of the preparation method and the carbon support structure

Two kinds of Ru/C catalysts prepared by two different methods and supported on two graphitized carbons differing in their surface area were studied in CO methanation in the H₂-rich gas. The textural parameters of the support materials were characterized by means of N₂ physisorption. XRPD, XPS, TEM and CO- chemisorption studies indicate that the application of wet impregnation leads to more homogeneous composition of the Ru/carbon system and higher Ru dispersion than dry impregnation for both supports. The activity of the Ru/carbon samples in CO methanation in a H₂-rich gas stream depends on the structure and average size of the active phase crystallites. The combination of wet impregnation and the use of graphitized carbon of appropriate structure in the preparation of the Ru/C catalyst lead to a complete conversion of CO at 240 °C.     

Ni/Ce-MCM-41 mesostructured catalysts for simultaneous production of hydrogen and nanocarbon via methane decomposition

For the first time, simultaneous production of hydrogen and nanocarbon via catalytic decomposition of methane over Ni-loaded mesoporous Ce-MCM-41 catalysts was investigated. The catalytic performance of the Ni/Ce-MCM-41 catalysts is very stable and the reaction activity remained almost unchanged during 1400 min steam on time at temperatures 540, 560 and 580 °C, respectively. The methane conversion level over these catalysts reached 60–75% with a 100% selectivity towards hydrogen. TEM observations revealed that most of the Ni particles located on the tip of the carbon nanofibers/nanotubes in the used catalysts, keeping their exposed surface clean during the test and thus remaining active for continuous reaction without obvious deactivation. Two kinds of carbon materials, graphitic carbon (C_g) as major and amorphous carbon (C_A) as minor were produced in the reaction, as confirmed by XRD analysis and TEM observations. Carbon nanofibers/nanotubes had an average diameter of approximately 30–50 nm and tens micrometers in length, depending on the reaction temperature, reaction time and Ni particle diameter. Four types of carbon nanofibers/nanotubes were detected and their formations greatly depend on the reaction temperature, time on steam and degree of the interaction between the metallic Ni and support. The respective mechanisms of the formation of nanocarbons were postulated and discussed.     

Effect of coexistence of siloxane on production of hydrogen and nanocarbon by methane decomposition using Fe catalyst

Biogas derived from sewage sludge contains CO₂, siloxane, and methane. In this study, the effect of coexistence of siloxane on the production of hydrogen and carbon nanofiber by methane decomposition using iron oxide-alumina catalyst was investigated. The catalyst was reduced by heating in a flow of methane. Siloxane addition to methane caused a catalytic activity at lower temperatures, shortened the induction period prior to the activity, and accelerated catalytic deactivation. Thermal decomposition of siloxane can occur at a lower temperature compared to that of methane. Carbon species formed by the siloxane decomposition may have a higher reducibility than methane does. The reactivity may lead to a carbon deposition at a lower temperature. Coexistence of CO₂ and siloxane can prolong a catalytic lifetime because CO₂ may inhibit the carbon deposition on catalyst to some extent.     

Study on the membrane electrode assembly fabrication with carbon supported cobalt triethylenetetramine as cathode catalyst for proton exchange membrane fuel cell

An improved fabrication technique for conventional hot-pressed membrane electrode assemblies (MEAs) with carbon supported cobalt triethylenetetramine (CoTETA/C) as the cathode catalyst is investigated. The V-I results of PEM single cell tests show that addition of glycol to the cathode catalyst ink leads to significantly higher electrochemical performance and power density than the single cell prepared by the traditional method. SEM analysis shows that the MEAs prepared by the conventional hot-pressed method have cracks between the cathode catalyst layer and Nafion membrane, and the contact problem between cathode catalyst layer and Nafion membrane is greatly suppressed by addition of glycol to the cathode catalyst ink. Current density-voltage curve and impedance studies illuminate that the MEAs prepared by adding glycol to the cathode catalyst ink have a higher electrochemical surface area, lower cell ohmic resistance, and lower charge transfer resistance. The effects of CoTETA/C loading, Nafion content, and Pt loading are also studied. By optimizing the preparation parameters of the MEA, the as-fabricated cell with a Pt loading of 0.15 mg cm⁻² delivers a maximum power density of 181.1 mW cm⁻², and a power density of 126.2 mW cm⁻² at a voltage of 0.4 V.