Slow and fast pyrolysis of Douglas-fir lignin: Importance of liquid-intermediate formation on the distribution of products

The formation of liquid intermediates and the distribution of products were studied under slow and fast pyrolysis conditions. Results indicate that monomers are formed from lignin oligomeric products during secondary reactions, rather than directly from the native lignin. Lignin from Douglas-fir (Pseudotsuga menziesii) wood was extracted using the milled wood enzyme lignin isolation method. Slow pyrolysis using a microscope with hot-stage captured the liquid formation (>150 °C), shrinking, swelling (foaming), and evaporation behavior of lignin intermediates. The activation energy (E_a) for 5–80% conversions was 213 kJ mol⁻¹, and the pre-exponential factor (log A) was 24.34. Fast pyrolysis tests in a wire mesh reactor were conducted (300–650 °C). The formation of the liquid intermediate was visualized with a fast speed camera (250 Hz), showing the existence of three well defined steps: formation of lignin liquid intermediates, foaming and liquid intermediate swelling, and evaporation and droplet shrinking. GC/MS and UV-Fluorescence of the mesh reactor condensate revealed lignin oligomer formation but no mono-phenols were seen. An increase in pyrolytic lignin yield was observed as temperature increased. The molar mass determined by ESI-MS was not affected by pyrolysis temperature. SEM of the char showed a smooth surface with holes, evidence of a liquid intermediate with foaming; bursting from these foams could be responsible for the removal of lignin oligomers. Py-GC/MS studies showed the highest yield of guaiacol compounds at 450–550 °C.     

Deactivation and in-situ regeneration of Dy-doped Ni/SiO2 catalyst in CO2 reforming of methanol

The self-regeneration of Ni-based catalysts has been considered as a promising approach to maintain not only a continuous but also economical process. However, the effect of catalyst nature, operating temperature, amount and types of carbon deposits on the effectiveness of the in-situ regeneration is still not well-investigated. Therefore, in this work, the self-regeneration ability of the undoped and Dy-doped Ni/SiO₂ catalysts, which were prepared by the same impregnation method, were examined in the dry reforming of methanol. The physicochemical properties of the fresh and spent catalysts were analyzed by various techniques such as X-ray diffraction (XRD), hydrogen temperature-programmed reduction (H₂-TPR), oxygen temperature-programmed desorption (O₂-TPD), transmission electron microscopy (TEM), N₂-BET isothermal adsorption. The nature and chemical reactivity of coke deposits formed during dry reforming at various temperatures (550, 600, and 650 °C) and the regeneration possibility of used catalysts through CO₂ gasification at these temperatures were investigated by the in-situ temperature-programmed gasification by CO₂ (TPCO₂). The Dy additive significantly improves the dispersion of the nickel active sites of Ni/SiO₂ catalyst, as demonstrated by the decreased Ni crystal size as well as the increased specific surface area and reduction degree of the catalyst. Furthermore, Dy promotion increases the quantity of oxygen vacancies and the nature of oxygen species, thereby improving the catalyst activity and stability. Specifically, methanol conversion dropped from 93% to 96%–61% and 31% for undoped Ni/SiO₂ at 600 °C and 650 °C, respectively and from about 99% to 87% (at 600 °C) and 52% (at 650 °C) for Dy-doped catalyst.     

Synthesis and regeneration of mesoporous Ni–Cu/Al2O4 catalyst in sub-kilogram-scale for methanol steam reforming reaction

A green template-free method is proposed for the synthesis of mesoporous Ni–Cu/Al₂O₄ catalyst in sub-kilogram scale. In the convenient synthetic method, an intermediate is formed via electrostatic forces and hydrogen bonding interactions between the aluminate ions and the metal ions and/or metal hydroxides under suitable pH conditions. The desired Ni–Cu/Al₂O₄ composites, with Ni/Cu molar ratios of 10%, 20% and 30% of Cu at Cu/Al molar ratio of 10.0%, respectively, are then obtained from calcination. The nitrogen adsorption-desorption isotherms show that the Ni–Cu/Al₂O₄ composites have specific surface areas of 136–170 m²g^-1. The Ni–Cu/Al₂O₄ products are used as catalyst materials in the methanol steam reforming (MSR) of hydrogen and are shown to have a high conversion efficiency (>99%), a low methane concentration, good stability, and a high hydrogen yield (H₂/methanol molar ratio ≈ 3.0) at low reaction temperatures in the range of 200–300 °C. In addition, the coke formation on the catalyst surface is less than 1.0 wt% even after a reaction time of 30 h. Notably, the Ni–Cu/Al₂O₄ catalyst can be regenerated by calcination at 800 °C and retains a high methanol conversion efficiency of close to >99% when reused in MSR.     

Biogas reforming for hydrogen-rich syngas production over a Ni–K/Al2O3 catalyst using a temperature-controlled plasma reactor

Plasma-enhanced catalytic biogas reforming for hydrogen-rich syngas production over a Ni–K/Al₂O₃ catalyst was investigated using a tabular dielectric barrier discharge non-thermal plasma reactor. To better understand the plasma catalysis synergy at elevated temperatures, we compared different reaction modes: plasma catalysis, plasma alone, and catalysis alone in a reaction temperature range of 160–400 °C. The combination of Ni–K/Al₂O₃ and plasma produced synergistic effects. Notably, the plasma-catalytic synergy was temperature-dependent and varied at different reaction temperatures. Using plasma catalysis, the maximum conversion of CH₄ and CO₂ (31.6% and 22.8%, respectively) was attained over Ni–K/Al₂O₃ at 160 °C, while increasing the reaction temperature to 340 °C noticeably enhanced the H₂/CO ratio to 2.71. Moreover, compared to plasma-catalytic biogas reforming at 160 °C, increasing the reaction temperature to 400 °C suppressed biogas conversion with dramatically reduced coke formation on the Ni–K/Al₂O₃ surface from 6.81 wt% to 3.37 wt%.     

Hydrogen-rich syngas production by catalytic cracking of tar in wastewater under supercritical condition

This paper presents the results from experimental study of syngas production by catalytic cracking of tar in wastewater under supercritical condition. Ni/Al₂O₃ catalysts were prepared via the ultrasonic assisted incipient wetness impregnation on activated alumina, and calcined at 600 °C for 4 h. All catalysts showed mesoporous structure with specific surface area in a range of 146.6–215.3 m²/g. The effect of Ni loading (5–30 wt%), reaction temperature (400–500 °C), and tar concentration (0.5–7 wt%) were systematically investigated. The overall reaction efficiency and the gas yields, especially for H₂, were significantly enhanced with an addition of Ni/Al₂O₃ catalysts. With 20%Ni/Al₂O₃, the H₂ yield increased by 146% compared to the non-catalytic experiment. It is noteworthy that the reaction at 450 °C with the addition of 20%Ni/Al₂O₃ had a comparable efficiency to the reaction without catalyst at 500 °C. The maximum H₂ yield of 46.8 mol/kg_tar was achieved with 20%Ni/Al₂O₃ at 500 °C and 0.5 wt% tar concentration. The catalytic performance of the catalysts gradually decreased as the reuse cycle increased, and could be recovered to 88% of the fresh catalyst after regeneration. 20%Ni/Al₂O₃ has a potential to improve H₂ production, as well as a good reusability. Thus, it is considered a promising catalyst for energy conversion of tar in wastewater.     

Highly dispersed Fe-decorated Ni nanoparticles prepared by atomic layer deposition for dry reforming of methane

Dry reforming of methane (DRM) is a sustainable chemical process that can simultaneously transform methane and carbon dioxide, which are generally considered greenhouse gases, into syngas with H₂/CO ratio close to 1. The deposition of carbon on the active sites during long-period DRM tests will lead to severe deactivation of Ni-based catalysts. Thus, in this work, we proposed a series of uniformly dispersed Fe-decorated Ni/Al₂O₃ catalysts via atomic layer deposition (ALD) to solve this key issue. Modification with trace amounts of Fe (0.3–0.6%) had multiple effects on facilitating the CH₄ dissociation on Ni⁰, improving the low-temperature catalytic activity, moderating the carbon species and accelerating coke oxidation. The sample denoted as 0.3%Fe/Ni/Al₂O₃ exhibited almost no activity loss in the 72 h test at 650 °C. The Fe-decorated Ni/Al₂O₃ structure achieved a balance between the enhancement of CH₄ cracking and the elimination of coke. Furthermore, this advanced ALD approach of preparing uniform secondary metal nanoparticle-decorated catalysts provided guidance to other bimetallic systems, such as Pt/Ni, Mn/Ni, and Cu/Ni.     

Comprehensive experimental study on supercritical water gasification of oilfield sludge: Effect of operation parameters,and catalysts on the products

Supercritical water gasification (SCWG) was adopted to treat oilfield sludge and produce syngas. The effect of temperature (400–450 °C), reaction time (30–90 min) and catalyst addition on syngas production and residual products during SCWG of oilfield sludge was studied. When increasing SCWG temperature from 400 to 450 °C with reaction time of 60 min, the H₂ yield and the selectivity of H₂ increased significantly from 0.53 mol/kg and 75.53% to 0.98 mol/kg and 78.09%, respectively. It is noteworthy that when the reaction time was too long, CO₂ and CO were converted to CH₄ with the consumption of H₂ via methanation reaction. The addition of Ni/Al₂O₃ catalyst can substantially promote the production of high-quality syngas from SCWG of oilfield sludge. The H₂ yield and its selectivity at 450 °C and 60 min were as high as 1.37 mol/kg and 84.05% with 10Ni/Al catalyst. Moreover, the catalysts with bimetal loading (Fe–Ni, Rb–Ni or Ce–Ni) were found to be beneficial for improving gasification efficiency, H₂ yield, and the degradation of organic compounds. Among them, 5 wt% Rb on 10Ni/Al catalyst performed the best catalytic activity for SCWG at 450 °C and 60 min, which had the highest H₂ yield of 1.67 mol/kg and selectivity of 86.09%. More than 90% of total organic carbon in sludge was decomposed after the SCWG with all the catalysts. These findings indicated that catalytic SCWG is a promising alternative for efficiently dealing with oilfield sludge.     

Ni/La2O3 catalysts for dry reforming of methane: Effect of La2O3 synthesis conditions on the structural properties and catalytic performances

10 wt%Ni/La₂O₃ catalysts for dry reforming of methane (DRM) were synthesized by wetness impregnation of lanthana supports prepared using sol-gel citric method with and without NH₃ addition (Ni–La CA-NH₃ and Ni–La CA, respectively). The support preparation conditions affect the nature, phase composition, and distribution of Ni phases (LaNiO₃, NiO and La₃Ni₂O₆). The gradient temperature DRM tests (400–800 °C) reveal higher catalytic activity of Ni–La CA (at 650 °C, X(CO₂) = 65.7%, X(CH₄) = 54.6%, H₂/CO = 0.71). The Ni–La CA-NH₃ shows higher stability (at 650 °C and 24 h, X(CO₂): 73.7% => 76.4%, X(CH₄): 64.7% => 64.6%, H₂/CO: 0.77 => 0.72). For both catalysts, La₂O₂CO₃ phase is formed after long run tests at 650 °C 24 h, with the greater TGA weight loss and stronger deactivation being observed for Ni–La CA. The H₂-reduced Ni La CA-NH₃ features ultrasmall (1–2 nm) Ni NPs strongly interacting with the support. Catalyst nature affects the amount of carbon coke formed.     

Study on solid waste pyrolysis coke catalyst for catalytic cracking of coal tar

Low value solid waste pyrolysis coke was used as a catalyst to catalytically crack gas-phase tar to improve tar yield and gas production. Pyrolysis coke with different pyrolysis final temperature and pyrolysis time were prepared, the effect of tar cracking products was studied, and the optimal pyrolysis coke were screened. The pyrolysis coke catalyst was characterized by BET, FTIR, SEM. The results show that the optimal preparation final temperature of pyrolysis coke is 750 °C, and the optimal preparation pyrolysis time is 2 h. Compared with the pyrolysis of raw coal, the tar cracking rate increased by 9.3%, after added the pyrolysis coke catalyst, the gas increased by 23.2%, and the light component increased to 36.6%. And the OH, C–N and C–O–C functional groups present on coke are the factors that affect the catalytic cracking.     

Oxidative catalytic steam gasification of sugarcane bagasse for hydrogen rich syngas production

Reactive Flash Volatilization (RFV) is an emerging thermochemical method to produce tar free hydrogen rich syngas from waste biomass at relatively lower temperature (<900 °C) in a single stage catalytic reactor within a millisecond residence time. Here, we show catalytic RFV of bagasse using Ru, Rh, Pd, or Re promoted Ni/Al₂O₃ catalysts under steam rich and oxygen deficient environment. The optimum reaction conditions were found to be 800 °C, steam to carbon ratio = 1.7 and carbon to oxygen ratio = 0.6. Rh–Ni/Al₂O₃ performed the best, resulting in highest hydrogen concentration in the synthesis gas at 54.8%, with a corresponding yield of 106.4 g-H₂/kg bagasse. A carbon conversion efficiency of 99.96% was achieved using Rh–Ni, followed by Ru–Ni, Pd–Ni, Re–Ni and mono metallic Ni catalyst in that order. Alkali and Alkaline Earth Metal species present in the bagasse ash and char, that deposited on the catalyst, was found to enhance its activity and stability. The hydrogen yield from bagasse was higher than previously reported woody biomass and comparable to the microalgae.     

Methanol steam reforming over highly efficient CuO–Al2O3 nanocatalysts synthesized by the solid-state mechanochemical method

CH₃OH steam reforming is an attractive way to produce hydrogen with high efficiency. In this study, CuO.xAl₂O₃ (x = 1, 2, 3, and 4) were fabricated based on the solid-state route, and the calcined samples were employed in methanol steam reforming at atmospheric pressure and in the temperature range of 200–450 °C. The results revealed that all samples have a high BET area (173–275 m² g⁻¹), and their crystallinity was reduced by increasing the alumina content in the catalyst formulation. The catalytic activity tests showed that the CH₃OH conversion and H₂ selectivity decreased by rising the Al₂O₃·CuO molar ratio. The methanol conversion enhanced from 13% to 85% by increasing the reaction temperature from 200 °C to 450 °C over the CuO·Al₂O₃ catalyst, due to the higher reducibility of this catalyst at lower temperatures compared to other prepared samples. The influence of calcination temperature (300–500 °C), GHSV (28,000–48000 ml h⁻¹. g⁻¹_cat), feed ratio (C:W = 1:1 to 1:9), and reduction temperature (250–450 °C) was also determined on the yield of the chosen sample. The results revealed that the maximum methanol conversion decreased from 90 to 79% by raising the calcination temperature from 300 to 500 °C due to the reduction of surface area and sintering of species at high calcination temperatures.     

Improvement in the hydrogenation-dehydrogenation performance of a Mg–Al alloy by graphene supported Ni

Mg-based materials are very promising candidates for hydrogen storage. In this paper, the graphene supported Ni was introduced to the Mg₉₀Al₁₀ system by hydrogenation synthesis (HS) and mechanical milling (MM). The 80 wt%Ni@Gn catalyst was synthesized by a facile chemical reduction method. The microstructures of the catalyst and composite show that Ni nanoparticles are well supported on the surface of graphene and they are dispersed uniformly on the surface of MgH₂ particles. After heating to 450 °C and holding at 340 °C for 2 h subsequently under 2.0 MPa hydrogen pressure, all the samples are almost completely hydrogenated. According to the temperature programmed desorption test, the Mg₉₀Al₁₀-8(80 wt%Ni@Gn) composite could desorb 5.85 wt% H₂ which comes up to 96% of the theoretical hydrogen storage capacity. Moreover, it shows the optimal hydriding/dehydriding performance, absorbing 5.11 wt% hydrogen within 400 s at 523 K, and desorbing 5.81 wt% hydrogen within 1800 s at 573 K.     

Steam reforming of acetic acid for hydrogenproduction: Catalytic performances of Ni and Co supported on Ce0·75Zr0·25O2 catalysts

The catalytic steam reforming of acetic acid over both Ni/ and Co/Ce_0·75Zr_0·25O₂ (CZO) catalysts in the temperature range of 450–650 °C and steam-to-carbon molar ratios of 3–9 was studied. It was found that the complete acetic acid conversion was achieved for all the conditions investigated. Nevertheless, the C–C bond cleavage conversion was attained less than the acetic acid conversion at a given condition due to carbon deposition on the catalyst. However, hydrogen yield was obtained in the same trend as C–C bond cleavage conversion as well. The results revealed that the CZO as an active support prefers to promote the ketonization reaction to the C-C bond cleavage reaction at a lower temperature, and vice versa at a higher temperature. The Ni/CZO catalyst exhibits higher C–C bond cleavage conversion than the Co/CZO catalyst particularly at 650 °C whereas the Co/CZO catalyst is more active for ketonization reaction at low temperatures. However, as an increase in reaction temperature, the Co/CZO catalyst promotes ketonization reaction more pronouncedly toward aldol-condensation reaction thus giving rise to the carbon deposition. The results deduced from the effect of space velocity on the activity and product distribution suggested that the steam reforming of acetic acid over Ni/CZO catalyst is dominated by decomposition of acetic acid, while that of Co/CZO catalyst by ketonization reaction.     

Hydrogen production from acetic acid steam reforming over nickel-based catalyst synthesized via MOF process

In our earlier work, we have reported that Ni supported on γ-Al₂O₃–La₂O₃–CeO₂ (ALC) catalyst prepared via metal organic framework (MOF) was more active for acetic acid steam reforming (AASR) [1]. Here we report detailed study on the performance of this catalyst for AASR. Effects of operating conditions such as temperatures (400–650 °C), steam to carbon molar ratio (S/C) and feed flow rate (1.5–5.5 mL/h) were evaluated and optimized. Results showed an excellent activity for AASR at the molar ratio S/C = 6.5, feed flow rate = 2.5 mL/h and, at 600 °C with almost total conversion and more than 90% of H₂ yield. The ordered porous structure of embedded nickel supported catalyst promotes excellent steam reforming activity and water gas shift reaction even at low temperatures, which leads to the good stable behaviour up to 36 h of TOS. The coke formation was also significantly suppressed by ALC support. Catalyst regenerated by passing oxygen at 500 °C and followed by reduction in hydrogen also show a good activity. Catalysts were characterized by DT-TGA, XRD, TEM, H₂-TPR and N₂-adsorption-desorption to understand the micro structure and coke deposition behaviour.     

Three-dimensional porous Mn–Ni/Al2O3 microspheres for enhanced low temperature CO hydrogenation to produce methane

CO methanation has attracted much attention because it transforms CO in syngas and coke oven gas into CH₄. Here, porous Al₂O₃ microspheres were successfully used as catalyst supports meanwhile the Mn was used as a promoter of Ni/Al₂O₃ catalysts. The as-obtained Ni/Al₂O₃ and Mn–Ni/Al₂O₃ samples display a micro-spherical morphology with a center diameter near 10 μm. Versus the Ni/Al₂O₃ catalyst, the 10Mn–Ni/Al₂O₃ catalyst exhibits a high specific surface area of 92.5 m²/g with an average pore size of 7.0 nm. The 10Mn–Ni/Al₂O₃ catalyst has the best performance along with can achieve a CO conversion of 100% and a CH₄ selectivity of 90.7% at 300 °C. Even at 130 °C, the 10Mn–Ni/Al₂O₃ catalyst shows a CO conversion of 44.0% and a CH₄ selectivity of 84.1%. The higher low-temperature catalytic activity may be since the catalyst surface contains more CO adsorption sites and thus has a stronger adsorption performance for CO. Density functional theory (DFT) calculations confirm that the Mn additive enhances the adsorption of CO, especially for the 10Mn–Ni/Al₂O₃ catalyst with the strongest adsorption energy.     

Effect of pre-treatment and calcination temperature on Al2O3-ZrO2 supported Ni-Co catalysts for dry reforming of methane

In this paper, the effect of pre-treatment and calcination temperature on a series of 5%Co/Al₂O₃-ZrO₂, 5%Ni/Al₂O₃-ZrO₂ and 2.5%Co-2.5%Ni/Al₂O₃-ZrO₂ catalysts for dry reforming of methane was investigated. Main focus of our research was to improve the catalyst stability by proper pre-treatment and reaction conditions. The first approach aimed at the catalyst pre-treatment by using bimetallic systems and the second strategy at the in situ suppression of coke. The catalytic activity of bimetallic system was indeed higher compared to the monometallic in the temperature range of 500–800 °C (space velocity 18000 ml h⁻¹·g_cat⁻¹, CH₄/CO₂ = 1). The bimetallic catalyst calcined at 800 °C showed highest CH₄ conversion without deactivation and gave a H₂/CO ratio of 91% and 0.96, respectively, and good stability with less coke deposition over 28 h at 800 °C reaction temperature. This improvement is assigned to the synergism between Co and Ni, their high dispersion according to interaction with support. It has been shown in our work that pretreatment temperatures and atmospheres have strong impact on stability of the catalyst. TEM, XRD and TPO investigations confirmed that the slight catalyst deactivation was related to the formation of multiwall carbon nanotubes with hollow inner tube structure. The addition of small amounts of steam or oxygen during DRM improved both the catalyst activity and stability as the bimetallic catalyst lost around 9.4% conversion in DRM, 5.4% in presence of water and only 3.2% in presence of O₂.     

Nanoporous nickel oxide catalyst with uniform Ni dispersion for enhanced hydrogen production from organic waste

In this report, we propose magnetically separable porous nickel oxide nanostructure with uniform Ni distribution having the large surface area and atomically dispersed Si sites for enhanced hydrogen production from organic waste. The catalyst showed ten times higher production rate from volatiles during carbonization of organic waste and coal than that in the absence of the catalyst. The reduced Ni/NiO catalyst yielded two times higher hydrogen production compared to the traditional Ni/Al₂O₃ catalyst. The highest yield of hydrogen over reduced Ni/NiO was 32 g/kg_feed at 600 °C in fixed bed reactor via pyrolysis-reforming of bagasse. The Ni/NiO showed far more efficient recyclability compared to traditional Ni/Al₂O₃. The economic aspect of the Ni/NiO catalyst was compared with the Ni/Al₂O₃ catalyst based on H₂ yield. TGA and TPO analysis confirmed the presence of amorphous coke.     

From wood wastes to hydrogen – Preparation and catalytic steam reforming of crude bio-ethanol obtained from fir wood

Fir wood wastes were used to produce crude bio-ethanol by two methods: simultaneous saccharification and fermentation (SSF) and acid hydrolysis followed by the fermentation of the acid hydrolyzate. The main components of crude bio-ethanol are ethanol and acetic acid. In addition, low concentrations of a wide range of alcohols, acids, esters, ethers and aldehydes are also present. Ethanol concentration is higher in the SSF process than in the acid hydrolysis: 43.69 g/L compared to 37.53 g/L, respectively. Opposite to ethanol concentration, the acetic acid concentration is higher in the acid hydrolysis process: 16.36 g/L compared to 10.24 g/L, respectively. The crude bio-ethanol was used to produce hydrogen by catalytic steam reforming. The tested catalysts were the common Ni/Al₂O₃ and two rare earth oxides promoted Ni catalysts: Ni/La₂O₃–Al₂O₃ and Ni/CeO₂–Al₂O₃ prepared by successive wet impregnation. The characterization techniques revealed that the addition of rare earth oxides improves the Ni dispersion and the reducibility of the promoted catalysts. The best feed rate which assures the optimal ratio between conversion and catalyst deactivation is 0.8 mL/min bio-ethanol. The addition of extra oxide (La₂O₃ and CeO₂) to the support improves the ethanol conversion especially at 250 °C, but no significant effect on the acetic acid conversion was observed. At 250 °C the ethanol conversion is almost 90% for Ni/La₂O₃–Al₂O₃ and Ni/CeO₂–Al₂O₃, but the acetic acid conversion is below 30% for all catalysts. At 350 °C both ethanol and acetic acid present maximum conversion. At this temperature the best hydrogen production is obtained for Ni/La₂O₃–Al₂O₃ due to better ethanol conversion and better selectivity for hydrogen formation. At 350 °C the promoted catalysts are stable for 4 h time on stream, different degrees of deactivation being obtained at lower temperatures.     

LiFePO4/carbon cathode materials prepared by ultrasonic spray pyrolysis

Small crystallites LiFePO₄ powder with conducting carbon coating can be synthesized by ultrasonic spray pyrolysis. Cheaper trivalent iron ion is used as the precursor. The pure olivine phase can be prepared with the duplex process of spray pyrolysis (synthesized at 450, 550 or 650 °C) and subsequent heat-treatment (at 650 °C for 4 h). The results indicate that the pyrolysis temperature of 450 °C is appropriate for best results. The carbon coating on the LiFePO₄ surface is critical to the electrochemical performance of LiFePO₄ cathode materials of the lithium secondary battery, since the carbon coating does not only increase the electronic conductivity via carbon on the surface of particles, but also enhance the ion mobility of lithium ion due to prohibiting the grain growth during post-heat-treatment. The carbon of 15 wt.% evenly distributed on the final LiFePO₄ powders can get the highest initial discharge capacity of 150 mA h g⁻¹ at C/10 and 50 °C.     

Zirconia supported nickel catalysts for glycerol steam reforming: Effect of zirconia structure on the catalytic performance

The effect of the zirconia structure in Ni/ZrO₂ catalysts on the glycerol steam reforming (GSR) reaction was studied. A tetragonal zirconia support was synthesized via a hydrolysis technique and loaded with 5 wt% Ni via a wet-impregnation method. Similarly, a commercial monoclinic zirconia support was also impregnated with 5 wt% Ni. Following calcination at 600 °C, physico-chemical properties of the prepared catalysts were investigated by X-Ray Diffraction (XRD), H₂-Temperature Programmed Reduction (H₂-TPR) and CO₂-Temperature Programmed Desorption (CO₂-TPD) techniques. The catalysts were then tested in the GSR reaction in the 400–700 °C range with a steam to glycerol molar ratio of 9:1 and a flow rate of 0.025 mL/min. The monoclinic catalyst exhibited a better performance giving higher hydrogen yields and glycerol conversions. This was attributed to an improved reducibility of Ni in this catalyst. Stability tests at 600 °C revealed the deactivation of the tetragonal catalyst during 6 h as a result of the formation of encapsulating coke which blocked active Ni metal sites. The monoclinic catalyst, exhibiting the formation of only filamentous coke, remained relatively stable for 24 h.