Synthetical catalysis of nickel and graphene on enhanced hydrogen storage properties of magnesium

Reduced graphene-oxide-supported nickel (Ni@rGO) nanocomposite catalysts were synthesized, and incorporated into magnesium (Mg) hydrogen storage materials with the aim of improving the hydrogen storage properties of these materials. The experimental results revealed that the catalytic effect of the Ni@rGO nanocomposite on Mg was more effective than that of single nickel (Ni) nanoparticles or graphene. When heated at 100 °C, the Mg–Ni and Mg–Ni@rGO composites absorbed 4.70 wt% and 5.48 wt% of H₂, respectively, whereas the pure Mg and Mg@rGO composite absorbed almost no hydrogen. The addition of the Ni@rGO composite as a catalyst yielded significant improvement in the hydrogen storage property of the Mg hydrogen storage materials. The apparent activation energy of the pure Mg sample (i.e., 163.9 kJ mol⁻¹) decreased to 139.7 kJ mol⁻¹ and 123.4 kJ mol⁻¹, respectively, when the sample was modified with single rGO or Ni nanoparticles. Under the catalytic action of the Ni@rGO nanocomposites, the value decreased further to 103.5 kJ mol⁻¹. The excellent hydrogen storage properties of the Mg–Ni@rGO composite were attributed to the catalytic effects of the highly surface-active Ni nanoparticles and the unique structure of the composite nanosheets.     

Synergistic catalytic effects of ZIF-67 and transition metals (Ni,Cu, Pd,and Nb) on hydrogen storage properties of magnesium

MgTM/ZIF-67 nanocomposites were prepared by the deposition-reduction method using ZIF-67, MgCl₂, and TMCl_x (TM = Ni, Cu, Pd, Nb) as raw materials. The dehydrogenation activation energies of MgTM/ZIF-67 (TM = Ni, Cu, Pd, Nb) nanocomposites were calculated to be 115.4 kJ mol⁻¹ H₂, 115.7 kJ mol⁻¹ H₂, 113.6 kJ mol⁻¹ H₂, and 75.8 kJ mol⁻¹ H₂, respectively; hence, the MgNb/ZIF-67 nanocomposite manifested the best comprehensive hydrogen storage performance. The hydrogen storage capacity of the MgNb/ZIF-67 nanocomposite was hardly attenuated after the 100th hydrogen absorption-desorption cycle. The dehydrogenated enthalpies of MgH₂ and CoMg₂H₅ in MgNb/ZIF-67 hydride were calculated to be 72.4 kJ mol⁻¹ H₂ and 81.0 kJ mol⁻¹ H₂, respectively, which were lower than those of additive-free MgH₂ and Mg/ZIF-67. The improved hydrogen storage properties of MgNb/ZIF-67 can be ascribed to the CoMg₂–Mg(Nb) core-shell structure and the catalytic effects of NbH and niobium oxide nanocrystals.     

Magnetic dendritic KCC-1 nanosphere-supported cobalt composite as a separable catalyst for hydrogen generation from NaBH4 hydrolysis

The introduction of magnetism into a catalyst can greatly optimize its separation performance. In the present work, a kind of magnetically separable catalysts for promoting NaBH₄ hydrolysis have been fabricated by anchoring cobalt nanoparticles on magnetic dendritic KCC-1 nanospheres composed of magnetic Fe₃O₄ core and fibrous shell. The fabricated catalysts were characterized with various characterization methods, including absorption spectroscopy (AAS), scanning electron microscopy (SEM), high-resolution transmission electronic microscopy (HRTEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM), and Fourier transform infrared (FT-IR), etc. This kind of catalysts exhibit high catalytic activity for promoting the hydrolysis of NaBH₄ under alkaline conditions, giving a hydrogen generation rate and activation energy of 3.83 L min⁻¹ g_Co⁻¹ (30 °C) and 53.63 kJ mol⁻¹, respectively. After used for 5 cycles, the catalyst showed 36.5% catalytic activity reserved. Most importantly, the magnetism of the catalyst made it easily separated and recycled from the solution after the reaction completed. The development of this kind of catalysts could provide a promising option for catalyzing NaBH₄ hydrolysis for portable hydrogen production from.     

A study on hydrogen generation from NaBH4 solution using Co-loaded resin catalysts

Hydrogen production via chemical processes has gained great attention in recent years. In this study, Co-based complex catalyst obtained by adsorption of Co metal to Amberlite IRC-748 resin and Diaion CR11 were tested for hydrogen production from alkaline NaBH₄ via hydrolysis process. Their catalytic activity and microstructure were investigated. Process parameters affecting the catalytic activity, such as NaOH concentration, Co percentage and catalyst amount, as well as NaBH₄ concentration and temperature were investigated. Furthermore, characteristics of these catalysts were carried out via SEM, XRD and FT-IR analysis. Hydrogen production rates equal to 211 and 221 ml min⁻¹ g_cat⁻¹ could be obtained with Amberlite IRC-748 resin and Diaion CR11 Co based complex catalysts, respectively. The activation energies of the catalytic hydrolysis reaction of NaBH₄ were calculated as 46.9 and 59.42 kJ mol⁻¹ for Amberlite IRC-748 resin and Diaion CR11 based catalysts respectively kJ mol⁻¹ from the system consisting of 3% Co, 10 wt% NaBH₄ and 7 wt% NaOH as well as 50 mg catalyst dosage. It can be concluded that Co-based resins as catalysts for hydrogen production is an effective alternative to other catalysts having higher rate.     

Hydrogen generation from alkaline NaBH4 solution using nanostructured Co–Ni–P catalysts

In the present study, nanostructured Co–Ni–P catalysts have been successfully prepared on Cu sheet by electroless plating method. The morphologies of Co–Ni–P catalysts are composed of football-like, granular, mockstrawberry-like and shuttle-like shapes by tuning the depositional pH value. The as-deposited mockstrawberry-like Co–Ni–P catalyst exhibits an enhanced catalytic activity in the hydrolysis of NaBH₄ solution. The hydrogen generation rate and activation energy are 2172.4 mL min⁻¹ g⁻¹ and 53.5 kJ mol⁻¹, respectively. It can be inferred that the activity of catalysts is the result of the synergistic effects of the surface roughness, the particle size and microscopic architectures. Furthermore, the stability of mockstrawberry-like Co–Ni–P catalyst has been discussed, and the hydrogen generation rate remains about 81.4% of the initial value after 5 cycles.     

Study on catalytic effect and mechanism of MOF (MOF = ZIF-8, ZIF-67, MOF-74) on hydrogen storage properties of magnesium

Using a deposition-reduction method, Mg/MOF nanocomposites were prepared as composites of Mg and metal-organic framework materials (MOFs = ZIF-8, ZIF-67 and MOF-74). The addition of MOFs can enhance the hydrogen storage properties of Mg. For example, within 5000 s, 0.6 wt%, 1.2 wt%, 2.7 wt%, 3.7 wt% of hydrogen were released from Mg, Mg/MOF-74, Mg/ZIF-8, Mg/ZIF-67, respectively. Activation energy values of 198.9 kJ mol⁻¹ H₂, 161.7 kJ mol⁻¹ H₂, 192.1 kJ mol⁻¹ H₂ were determined for the Mg/ZIF-8, Mg/ZIF-67, Mg/MOF-74 hydrides, which are 6 kJ mol⁻¹ H₂, 43.2 kJ mol⁻¹ H₂, and 12.8 kJ mol⁻¹ H₂ lower than that of Mg hydride, respectively. Moreover, the cyclic stability characterizing Mg hydride was significantly improved when adding ZIF-67. The hydrogen storage capacity of the Mg/ZIF-67 nanocomposite remained unchanged, even after 100 cycles of hydrogenation/dehydrogenation. This excellent cyclic stability may have resulted from the core-shell structure of the Mg/ZIF-67 nanocomposite.     

Theoretical prediction and experimental study on catalytic mechanism of incorporated Ni for hydrogen absorption of Mg

Transition metals, including Ni, show good catalytic activity in the hydrogen storage reaction of Mg. In the present paper, first-principles calculation is performed to predict and analyze the hydriding reaction of Ni-incorporated Mg and experimental study is used to verify the accuracy of the forecast. Theoretical studies show that the hydriding reaction of Ni-incorporated Mg is a diffusion-controlled process. With Ni incorporation, the energy barrier of H₂ dissociation is significantly decreased and the diffusion becomes the limiting step. Experimental studies confirm the results of theoretical studies. Besides, the material with Ni incorporation shows excellent activation performance and rapid absorption rates, leading to a high hydrogen content of 4.1 wt% in 60 s under 240 °C 3.0 MPa H₂ and a low activation energy of 56.1 kJ mol⁻¹ versus 0.4 wt% and 73.5 kJ mol⁻¹ for the material without Ni incorporation. Atomic Ni only plays a role of catalyst.     

Effects of KNbO3 catalyst on hydrogen sorption kinetics of MgH2

The influences of Nb-containing oxides and ternary compound in hydrogen sorption performance were investigated. As faster desorption kinetic and lower activation energy were reported by addition of a ternary compound catalyst such as K₂NiF₆, the influence of KNbO₃ on hydrogen storage properties of MgH₂ has been investigated for the first time. The MgH₂ - KNbO₃ composite desorbed 3.9 wt% of hydrogen within 10 min, while MgH₂ and MgH₂-Nb₂O₅ composites desorbed 0.66 wt% and 3.2 wt% respectively under similar condition. For MgH₂ with other Nb-contained catalysts such as Nb, NbO and Nb₂O₃, the desorption rate was almost the same as the one registered for as-milled MgH₂. The analysis of differential scanning calorimetry (DSC) showed that MgH₂-KNbO₃ composite started to release hydrogen at ∼335 °C which is 50 °C lower compared to as-milled MgH₂ without any additives. The activation energy for the hydrogen desorption was estimated to be about 104 ± 6.8 kJ mol⁻¹ for this material, while for the as-milled MgH₂ was about 165 ± 2.0 kJ mol⁻¹. It is believed that Nb-ternary oxide catalyst (KNbO₃) showed a good catalytic effect and enhance the sorption kinetics of MgH₂.     

Co−O−P composite nanocatalysts for hydrogen generation from the hydrolysis of alkaline sodium borohydride solution

In recent years, catalytic hydrolysis of sodium borohydride is considered to be a promising approach for hydrogen generation towards fuel cell devices, and highly efficient and noble-metal-free catalysts have attracted increasing attention. In our present work, Co₃O₄ nanocubes are synthesized by solvothermal method, and then vapor-phase phosphorization treatment is carried out for the preparation of novel Co−O−P composite nanocatalysts composed of multiple active centers including Co, CoO, and Co₂P. For catalyst characterization, field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS), X-ray diffraction (XRD) and X-ray photoelectric spectroscopy (XPS) are conducted. Optimal conditions for catalyst preparation and application were investigated in detail. At room temperature (25 °C), maximum hydrogen generation rate (HGR) is measured to be 4.85 L min⁻¹ g⁻¹ using a 4 wt% NaBH₄ − 8 wt% NaOH solution, which is much higher than that of conventional catalysts with single component reported in literature. It is found that HGR remarkably increases with the increasing of reaction temperature, and apparent activation energy for catalytic hydrolysis of NaBH₄ is calculated to be 63 kJ mol⁻¹. After reusing for five times, the Co−O−P composite nanocatalysts still retains 78% of the initial activity.     

Ruthenium nanoparticles supported in the network of HES-p(AMPS) IPN hydrogel as efficient catalyst for hydrogen production from the hydrolysis of ethylenediamine bisborane

In this study, Ru(0) nanoparticles supported in 2-hydroxyethyl starch-p-(2-Acrylamido-2-methyl-1-propanesulfonic acid) interpenetrating polymeric network (HES-p(AMPS) IPN) were synthesized as hydrogel networks containing hydroxyethyl starch, which is a natural polymer with oxygen donor atoms. The structure and morphology of the prepared HES-p(AMPS) IPN hydrogel and Ru@HES-p(AMPS) IPN catalyst were characterized using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscope (SEM), X-ray diffraction (XRD), and transmission electron microscope (TEM). Ru@HES-p(AMPS) IPN was used as catalyst for hydrogen production from the hydrolysis of ethylenediamine bisborane (EDAB). The activation parameters for the hydrolysis reaction of EDAB catalyzed by Ru@HES-p(AMPS) IPN were calculated as E_a = 38.92 kJ mol⁻¹, ΔH^# = 36.28 kJ mol⁻¹, and ΔS^# = −111.85 J mol⁻¹ K⁻¹, respectively. The TOF for the Ru@HES-p(AMPS) IPN catalyst was 2.253 mol H₂ (mol Ru(0) min)⁻¹. It was determined that Ru@HES-p(AMPS) IPN, a reusable catalyst, still had 81.5% catalytic activity after the 5th use.     

Insight into the role of solvents in enhancing hydrogen production: Ru-Co nanoparticles catalyzed sodium borohydride dehydrogenation

Ru-Co nanoparticles prepared in nano-size by combustion derived of citric acid used sol-gel technique followed by calcination process at 450 °C. The external and internal properties of nano-sized catalyst were characterized by XRD, XPS, SEM, TEM, ICP-OES, and N₂ sorption techniques. The characterization results proved that nano-sized catalyst was mixture of cubic Co₃O₄ (18 nm) and tetragonal RuO₂ (40 nm) crystals with mesoporous structure (12.64 m²g^-1). Insight into the role of solvents for enhancing hydrogen production from Ru-Co nanoparticles catalyzed sodium borohydride (NaBH₄, SBH) was systematically studied by altering the dehydrogenation medium with water or methanol. The reaction kinetic performance of nano-sized catalyst was evaluated by performing both hydrogen generation reactions at various reaction temperatures, initial SBH concentration, and catalyst dosage to evaluate the hydrogen generation activity. Ru-Co nanoparticles exhibited exclusive catalytic performance for hydrogen generation by hydrolysis and methanolysis of SBH. The apparent activation energies (E_a) for the catalytic hydrolysis and methanolysis of SBH over Ru-Co nanoparticles were determined to be 20.02 kJ mol⁻¹ and 54.38 kJ mol⁻¹, respectively. Furthermore, Ru-Co nanoparticles also performed satisfied stability for both hydrolysis and methanolysis reactions. Beside both hydrogen generation was achived with fully conversion of SBH, Ru-Co nanoparticles promised good recyclability for at least 5 cycle for methanolysis of SBH.     

Efficient generation of hydrogen from biomass without carbon monoxide at room temperature – Formaldehyde to hydrogen catalyzed by Ag nanocrystals

In this paper, we present a new route for hydrogen generation from biomass at room temperature without any carbon monoxide over nano-metal-catalysts. It has been found that the Ag nanocrystals are highly efficient and stable catalysts for the CO-free hydrogen production from formaldehyde (HCHO), a model compound of biomass, at room temperature and at atmospheric pressure. By optimizing the structure and component of catalysts, reaction parameters such as temperature, catalyst amounts, oxygen, formaldehyde concentrations, and NaOH concentrations, the hydrogen generation rate has been maintained for hours without any decay. Furthermore, the apparent activation energy of the Ag catalyzed hydrogen production reaction is determined to be 11.8 kJ mol⁻¹, which was much lower than that of the literature results (65 kJ mol⁻¹) without catalyst. Because of its high hydrogen generation rate, hydrogen generation efficiency, lower activation energy, and the low cost, we speculate that this novel Ag catalyst based hydrogen generation reaction should be a promising candidate for providing hydrogen in PEMFCs at room temperature.     

Coupling ultralow-content ruthenium with nickel hydroxide via corrosion engineering for highly efficient hydrogen generation from ammonia borane

Efficient and controllable release of hydrogen from solid hydrogen storage materials is a promising way to produce hydrogen safely and on-demand. The development of economical, highly active, easily recyclable catalysts is critical for practical applications, which remains a great challenging. Herein, the easily controllable and cost-effective corrosion strategy is ingeniously developed to simply prepare ultralow-content ruthenium coupled with nickel hydroxide on nickel foam (Ru–Ni–NF). After experiencing the spontaneous oxidation-reduction reactions between the reactive NF and Ru³⁺, ultrafine Ru nanoparticles decorated nickel hydroxide nanosheets are in situ intimately grown on porous NF networks. The optimal Ru–Ni–NF catalyst exhibits the excellent performance for catalytic hydrolysis of ammonia borane with a high turnover frequency (TOF) of 539.6 mol_H2 mol_Ru^?1 min^?1 at 298 K and a low apparent activation energy of 36.4 kJ mol^?1, due to the synergistic effect between Ru nanoparticles and nickel hydroxide nanosheets. Furthermore, the Ru–Ni–NF catalyst possesses easy separation and outstanding durability, which is superior to powdered catalysts. This study provides a facile and economical strategy for the preparation of ultralow-content noble metal supported metal foam-type catalysts for dehydrogenation of ammonia borane.     

Surface modification of graphitic carbon nitride nanoparticles with B,O and S doping/carbon vacancy for efficient dehydrogenation of sodium borohydride in methanol

Herein, the surface properties of graphitic carbon nitride (GCN) with sulphur(S), boron (B) and oxygen (O) dopants were improved. The heteroatom-doped metal-free GCN exhibited both rich surface functional groups and a carbon defect structure. These metal-free catalysts were used to obtain hydrogen (H₂) from the sodium borohydride (SB) methanolysis for the first time. Compared to GCN, S, B, and O doped GCN catalyst obtained showed a 2.2-fold improvement in H₂ production. HGR value obtained with B, O and S doped GCN (10 mg) via SB of 2.5% was 9166 ml min ⁻¹g⁻¹. XPS, SEM-EDX, TEM, FTIR, and XRD analyses were used for the structural properties of catalysts. The activation energy (Ea) for B, O and S doped GCN was 28.89 kJ mol⁻¹.     

Low-cost CuFeCo@MIL-101 as an efficient catalyst for catalytic hydrolysis of ammonia borane

Trimetallic nanoparticles of non-noble Cu–Fe–Co with different molar ratios were successfully immobilized in the metal-organic frameworks (MIL-101) via an easy impregnation–reduction process. XRD, TEM, XPS, ICP-MS and BET methods were used to characterize the catalyst. Comparing to their bimetallic counterparts, Cu₆Fe_0.8Co_3.2@MIL-101 demonstrates the best catalytic performance for dehydrogenation of ammonia borane by hydrolysis at 298 K Cu₆Fe_0.8Co_3.2@MIL-101 shows a total turnover frequency (TOF) value of 23.2 mol_H2 mol_catalyst⁻¹ min⁻¹ and an activation energy value of 37.1 kJ mol⁻¹. The enhancement of catalytic activity was attributed to a synergistic effect among copper, cobalt and iron nanoparticles supported on MIL-101. In addition, the catalyst still exhibits good stability and magnetic recyclability after seven cycles. The low-cost catalyst has good prospect for application in the field of hydrogen storage.     

Graphene modified Co–B catalysts for rapid hydrogen production from NaBH4 hydrolysis

Graphene oxide (GO) modified Co–B catalysts for NaBH₄ hydrolysis have been synthesized by the chemical reduction in this work. The structural features and catalytic performance of as-prepared samples have been investigated and discussed as a function of amounts of GO. According to structure characterization, the catalysts still retain the amorphous structure of Co–B alloy with the addition of GO, while GO exists as reduced GO (r-GO). The textural analysis and morphology observation indicate that the appropriate amount of GO in Co–B catalyst results in the obvious increase of specific surface area and uniform clustered morphology, which contributes to improve active surface area for catalytic reactions. The results of surface species characterization show that the electron density at active Co sites increases due to an electron transfer from B to Co facilitated by r-GO. It has been found that 50 mg GO modified Co–B catalyst exhibits especially high activity with a hydrogen generation rate of 14.34 L min⁻¹·g_catalyst⁻¹ and much lower activation energy of 26.2 kJ mol⁻¹ for hydrolysis reaction of NaBH₄. Meanwhile, the reusability evaluations show that the catalyst preserves high stability which can still maintain 81.5% of its initial activity after 5 catalytic cycles.     

Remarkable isosteric heat of hydrogen adsorption on Cu(I)-exchanged SSZ-39

Hydrogen storage capacity on Cu(I)-exchanged SSZ-39 (AEI), -SSZ-13 (CHA) and Ultra stable-Y (US–Y, FAU) at temperatures between 279 K and 304 K are investigated. The gravimetric hydrogen storage capacity values reaching 83 μmol H₂ g⁻¹ (at 279 K and 1 bar) are found to be comparable with the highest adsorption capacity values reported on metal-organic frameworks. The volumetric hydrogen storage capacity values; on the other hand, are found to be more than three times of those reported on metal-organic frameworks (0.57 g/L on Cu(I)-SSZ-39 at 1 bar and 296 K vs. ca. 0.18 g/L on Co₂(m-dobdc) at 1 bar and 298 K (Kapelewski MT, Runčevski T, Tarver JD, Jiang HZH, Hurst KE, Parilla PA et al. Record High Hydrogen Storage Capacity in the Metal-Organic Framework Ni₂(m-dobdc) at Near-Ambient Temperatures. Chem Mater 2018; 30:8179–89)). The isosteric heat of adsorption values are calculated to be between 80 kJ mol⁻¹ and 49 kJ mol⁻¹ on Cu(I)-SSZ-39 and between 22 kJ mol⁻¹ and 15 kJ mol⁻¹ on Cu(I)-US-Y indicating H₂ adsorption mainly at Cu(I) cations located at the eight-membered rings on Cu(I)-SSZ-39 and at six-membered rings on Cu(I)-US-Y. Hydrogen adsorption experiments performed at 77 K showed higher adsorption capacity values for Cu(I)-SSZ-39 at 1 bar, but Cu(I)-US-Y showed potential for hydrogen storage at higher pressure values.     

Milling induced surface modification of V-based catalyst to improve sorption kinetics of KSiH3: An XPS investigation

Hydrogen as an energy carrier has shown promises for future energy infrastructure. Due to its light weight and explosive nature, hydrogen need to be stored in safe and efficient way. The storage in solid state materials has been proposed as the safest method, which can store hydrogen through chemical bonding. Among several studied materials so far, KSiH₃ is one of the leading contender with a total hydrogen capacity of 4.3 wt %, which is more than what is offered by its rivals such as BCC hydrides or AB₅ type hydrides. However, the high activation energy slows down the hydrogen charging/discharging rate and allow the working only at higher temperatures (～200 °C). The kinetics of hydrogen absorption and desorption intensely improved by the addition of a catalyst. In this work, vanadium based catalysts are added to KSiH₃ system to modify the surface and to enhance the kinetics of this system. Specially, V₂O₅ addition, as leading candidate among the studied catalyst, decreased the activation energy to 83 kJmol^-1 from 142 kJ/mol for pristine KSi. KSiH₃ system with catalyst V₂O₅ started desorbing at 100 °C and could achieve highest weight loss 3.7 wt % which is very close to theoretical value. No disproportionation phenomenon is detected which indicated that the reaction between KSiH₃ and KSi is flawlessly reversible with a hydrogen storage capacity of 3.7 wt % H₂. The XPS investigation suggested a partial reduction of +5 oxidation state (corresponding to V₂O₅) to metallic state, which is proposed as the possible cause of this improvement.     

Electrocatalytic hydrogen evolution on metallic and bimetallic Pd–Co alloy nanoparticles

Increasing world energy demands and crises led to alternative energy production methods, such as fuel cells using hydrogen gas which is the half electrochemical reaction of water splitting process. Herein, we synthesize polyvinylpyrrolidone coated Pd, Co and Pd_xCo_1-x (x: 0.5, 0.12, 0.23, 0.49, 0.55, 0.62) metallic and bimetallic nanoparticles (NPs) via polyol process alternative to Pt-based catalysts for hydrogen evolution reaction (HER). Detailed structural analyses of Pd, Co and Pd_xCo_1-x NPs revealed that fcc-Pd, fcc/hcp-Co and fcc-PdCo NPs crystal structures, and the lattice parameters were calculated as 3.5358 Å for Co NPs and 3.9777 Å for Pd NPs. The average size confirmed below 9 nm via TEM imaging and XPS data confirmed the formation of a bimetallic PdCo structure. Although Pd catalyst is mostly responsible for HER process, Pd₆₂Co₃₈ catalysts reduced the onset potential to about 197 mV and provided greater current density. Although E_a values were slightly higher against the Pt/C (20 wt %) benchmark which is reported as 16 kJ mol⁻¹, PdCo NPs provided considerably reduced activation energy (E_a) values compared to Pd/C catalyst of 31 kJ mol⁻¹. The best onset potential was recorded for Pd₆₂Co₃₈ catalysts for HER activity which is 16 mV higher compared to commercially available Pt/C catalyst.     

Effect of alkaline earth oxides on nickel catalysts supported over γ-alumina for butanol steam reforming: Coke formation and deactivation process

Nickel catalysts were synthesized by the wet impregnation of three different supports: γ-Al₂O₃ and alumina promoted with either 10 wt % of MgO or 10 wt% of CaO. The catalysts were evaluated in butanol steam reforming at 500 °C, atmospheric pressure, GHSV of 500,000 h⁻¹ and 10% v/v butanol in the feed. Both promoters decreased catalyst acidity and increased basicity. The catalyst promoted with MgO exhibited the lowest acidity (1.1 μmolNH₃ m⁻²), whereas that promoted with CaO, the highest basicity (870.7 μmolCO₂ m⁻²). The promotion with MgO led to the highest hydrogen yield (66%) and stability, associated with its highest nickel dispersion (3.4%), lowest acidity and lowest coke formation normalized by carbon converted (3.0 mmol L mol⁻¹). The catalyst promoted with CaO presented the most severe deactivation, associated with its lowest dispersion (1.0%) and the highest amount of encapsulated coke (3.5 mmol L mol⁻¹).