Search Results (23)

Dry reforming of methane (DRM) is a promising way to convert methane and carbon dioxide into syngas, which can be further utilized to synthesize value-added chemicals. One of the main challenges for the DRM process is finding catalysts that are highly active and stable. This study explores the potential use of Ni-based catalysts modified by Ga. Different Ni-Ga/(Mg, Al)O_x catalysts, with various Ga/Ni molar ratios (0, 0.1, 0.3, 0.5, and 1), were synthesized by the co-precipitation method. The catalysts were tested for the DRM reaction to evaluate their activity and stability. The Ni/(Mg, Al)O_x and its Ga-modified Ni-Ga/(Mg, Al)O_x were characterized by N₂ adsorption–desorption, Fourier Transform Infrared Spectroscopy (FTIR), H₂-temperature-programmed reduction (TPR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and Raman techniques. The test of catalytic activity, at 700 °C, 1 atm, GHSV of 42,000 mL/h/g, and a CH₄: CO₂ ratio of 1, revealed that Ga incorporation effectively enhanced the catalyst stability. Particularly, the Ni-Ga/(Mg, Al)O_x catalyst with Ga/Ni ratio of 0.3 exhibited the best catalytic performance, with CH₄ and CO₂ conversions of 66% and 74%, respectively, and an H₂/CO ratio of 0.92. Furthermore, the CH₄ and CO₂ conversions increased from 34% and 46%, respectively, when testing at 600 °C, to 94% and 96% when the catalytic activity was operated at 850 °C. The best catalyst’s 20 h stream performance demonstrated its great stability. DFT analysis revealed an alteration in the electronic properties of nickel upon Ga incorporation, the d-band center of the Ga modified catalyst (Ga/Ni ratio of 0.3) shifted closer to the Fermi level, and a charge transfer from Ga to Ni atoms was observed. This research provides valuable insights into the development of Ga-modified catalysts and emphasizes their potential for efficient conversion of greenhouse gases into syngas. Full article

Current global challenges associated with energy security and climate emergency, caused by the combustion of fossil fuels (e.g., jet fuel and diesel), necessitate the accelerated development and deployment of sustainable fuels derived from renewable biomass-based chemical feedstocks. This study focuses on the production of long-chain (straight and branched) ketones by direct α-alkylation of short chain ketones using both homogenous and solid base catalysts in water. Thus, produced long-chain ketones are fuel precursors and can subsequently be hydrogenated to long-chain alkanes suitable for blending in aviation and liquid transportation fuels. Herein, we report a thorough investigation of the catalytic activity of Pd in combination with, (i) homogenous and solid base additives; (ii) screening of different supports using NaOH as a base additive, and (iii) a comparative study of the Ni and Pd metals supported on layered double oxides (LDOs) in α-alkylation of 2-butanone with 1-propanol as an exemplar process. Among these systems, 5%Pd/BaSO₄ with NaOH as a base showed the best results, giving 94% 2-butanone conversion and 84% selectivity to alkylated ketones. These results demonstrated that both metal and base sites are necessary for the selective conversion of 2-butanone to alkylated ketones. Additionally, amongst the solid base additives, Pd/C with 5% Ba/hydrotalcite showed the best result with 51% 2-butanone conversion and 36% selectivity to the alkylated ketones. Further, the screening of heterogenous acid-base catalysts 2.5%Ni/Ba_1.2Mg₃Al₁ exhibited an adequate catalytic activity (21%) and ketone selectivity (47%). Full article

Hydrotalcite-derived mixed metal oxides containing Co and Ni and containing these metals supported on MgO and Al₂O₃ were prepared and tested as catalysts for the decomposition of ammonia to hydrogen and nitrogen. The obtained samples were characterised in terms of chemical composition (ICP-OES), structure (XRD), textural parameters (low-temperature N₂ adsorption–desorption, SEM), form and aggregation of transition-metal species (UV-Vis DRS), reducibility (H₂-TPR) and surface acidity (NH₃-TPD). The catalytic efficiency of the tested systems strongly depends on the support used. Generally, the alumina-based catalyst operated at lower temperatures compared to transition metals deposited on MgO. For both series of catalysts, a synergistic effect of the co-existence of cobalt and nickel on the catalytic efficiency was observed. The best catalytic results were obtained for hydrotalcite-derived catalysts; however, in the case of these catalysts, an increase in the Al/Mg ratio resulted in a further increase in catalytic activity in the decomposition of ammonia. Full article

Semi-hydrogenation of acetylene to ethylene over metal oxide-supported Au nanoparticles is an interesting topic. Here, a hydrotalcite-based MMgAlO_x (M=Cu, Ni, and Co) composite oxide was exploited by introducing different Cu, Ni, and Co dopants with unique properties, and then used as support to obtain Au/MMgAlO_x catalysts via a modified deposition–precipitation method. XRD, BET, ICP-OES, TEM, Raman, XPS, and TPD were employed to investigate their physic-chemical properties and catalytic performances for the semi-hydrogenation of acetylene to ethylene. Generally, the catalytic activity of the Cu-modified Au/CuMgAlO_x catalyst was higher than that of the other modified catalysts. The TOR for Au/CuMgAlO_x was 0.0598 h⁻¹, which was 30 times higher than that of Au/MgAl₂O₄. The SEM and XRD results showed no significant difference in structure or morphology after introducing the dopants. These dopants had an unfavorable effect on the Au particle size, as confirmed by the TEM studies. Accordingly, the effects on catalytic performance of the M dopant of the obtained Au/MMgAlO_x catalyst were improved. Results of Raman, NH₃-TPD, and CO₂-TPD confirmed that the Au/CuMgAlO_x catalyst had more basic sites, which is beneficial for less coking on the catalyst surface after the reaction. XPS analysis showed that gold nanoparticles exhibited a partially oxidized state at the edges and surfaces of CuMgAlO_x. Besides an increased proportion of basic sites on Au/CuMgAlO_x catalysts, the charge transfer from nanogold to the Cu-doped matrix support probably played a positive role in the selective hydrogenation of acetylene. The stability and deactivation of Au/CuMgAlO_x catalysts were also discussed and a possible reaction mechanism was proposed. Full article

Catalytic conversion of biomass-derived ethanol into n-butanol through Guerbet coupling reaction has become one of the key reactions in biomass valorization, thus attracting significant attention recently. Herein, a series of supported Cu catalysts derived from Ni-based hydrotalcite (HT) were prepared and performed in the continuous catalytic conversion of ethanol into butanol. Among the prepared catalysts, Cu/NiAlO_x shows the best performance in terms of butanol selectivity and catalyst stability, with a sustained ethanol conversion of ~35% and butanol selectivity of 25% in a time-on-stream (TOS) of 110 h at 280 °C. While for the Cu/NiFeO_x and Cu/NiCoO_x, obvious catalyst deactivation and/or low butanol selectivity were obtained. Extensive characterization studies of the fresh and spent catalysts, i.e., X-ray diffraction (XRD), Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Hydrogen temperature-programmed reduction (H₂-TPR), reveal that the catalysts’ deactivation is mainly caused by the support deconstruction during catalysis, which is highly dependent on the reducibility. Additionally, an appropriate acid–base property is pivotal for enhancing the product selectivity, which is beneficial for the key process of aldol-condensation to produce butanol. Full article

Catalysts derived from Ni/Al/Mg/Ce hydrotalcite were prepared via a co-precipitation method, varying the Ce/Al atomic ratio. All of the catalytic systems thus prepared were tested for CO₂ methanation under dark and photocatalytic conditions (visible and ultraviolet) under continuous flow with the light intensity set to 2.4 W cm⁻². The substitution of Al by Ce formed a solid solution, generating oxygen vacancies and Ce³⁺/Ce⁴⁺ ions that helped shift the dissociation of CO₂ towards the production of CH₄, thus enhancing the activity of methanation, especially at lower temperatures (<523 K) and with visible light at temperatures where other catalysts were inactive. Additionally, for comparison purposes, Ni/Al₂O₃-based catalysts prepared via wetness impregnation were synthesized with different Ni loadings. Analytical techniques were used for the characterization of the systems. The best results in terms of activity were as follows: Hydrotalcite with Ce promoter > Hydrotalcite without Ce promoter > 25Ni/Al₂O₃ > 13Ni/Al₂O₃. Hydrotalcite, with a Ce/Al atomic ratio of 0.22 and a Ni content of 23 wt%, produced 7.74 mmol CH₄ min⁻¹·g_cat at 473 K under visible light. Moreover, this catalyst exhibited stable photocatalytic activity during a 24 h reaction time with a CO₂ conversion rate of 65% and CH₄ selectivity of >98% at 523 K. This photocatalytic Sabatier enhancement achieved activity at lower temperatures than those reported in previous publications. Full article

Ce-promoted NiMgAl mixed-oxide (NiCex-C, x = 0, 1, 5, 10) catalysts were prepared from the quaternary hydrotalcite precursors for CO₂ hydrogenation to methane. By engineering the Ce contents, NiCe5-C showed its prior catalytic performance in low-temperature CO₂ hydrogenation, being about three times higher than that of the Ce-free NiCe0-C catalyst (turnover frequency of NiCe5-C and NiCe0-C: 11.9 h⁻¹ vs. 3.9 h⁻¹ @ 225 °C). With extensive characterization, it was found that Ce dopants promoted the reduction of NiO by adjusting the interaction between Ni and Mg(Ce)AlOx support. The highest ratio of surface Ni⁰/(Ni²⁺ + Ni⁰) was obtained over NiCe5-C. Meanwhile, the surface basicity was tailored with Ce dopants. The strongest medium-strength basicity and highest capacity of CO₂ adsorption was achieved on NiCe5-C with 5 wt.% Ce content. The TOF tests indicated a good correlation with medium-strength basicity over the NiCex-C samples. The results showed that the high medium-strength and Ce-promoted surface Ni⁰ species endows the enhanced low-temperature catalytic performance in CO₂ hydrogenation to methane. Full article

Hydrotalcite, first found in natural ores, has important applications in supercapacitors. NiCoAl-LDH, as a hydrotalcite-like compound with good crystallinity, is commonly synthesized by a hydrothermal method. Al${}^{3+}$ plays an important role in the crystallization of hydrotalcite and can provide stable trivalent cations, which is conducive to the formation of hydrotalcite. However, aluminum and its hydroxides are unstable in a strong alkaline electrolyte; therefore, a secondary alkali treatment is proposed in this work to produce cation vacancies. The hydrophilicity of the NiCoAl-OH surface with cation vacancy has been greatly improved, which is conducive to the wetting and infiltration of electrolyte in water-based supercapacitors. At the same time, cation vacancies generate a large number of defects as active sites for energy storage. As a result, the specific capacity of the NiCoAl-OH electrode after 10,000 cycles can be maintained at 94.1%, which is much better than the NiCoAl-LDH material of 74%. Full article

Ni(Mg)Al-layered hydroxides with molar ratios of (Ni + Mg)/Al = 2, 3, 4 and Ni/(Ni + Mg) = 0.1, 0.3, 0.5, 0.7 were synthesized by mechanochemical activation. It has been proven that the phase composition of the samples was presented by a single hydrotalcite phase up to Ni/(Ni + Mg) = 0.5. For the first time, catalysts based on Ni(Mg)Al-layered hydroxides prepared by a mechanochemical route have been studied in the reaction of furfural hydrogenation. The correlation between furfural conversion, the selectivity of the products, and the composition of the catalysts was established. The effect of phase composition, surface morphology, and microstructure on the activity of the catalysts was shown by XRD, SEM, and TEM. It was found that catalysts with Ni/(Ni + Mg) = 0.5 have the highest furfural conversion. Herewith, the product selectivity can be regulated by the (Ni + Mg)/Al ratio. Full article

In this article, the catalysts of hydrotalcite-derived Ni_1.5Co_0.5AlO nanosheet-supported highly dispersed Pt nanoparticles (Pt_n/Ni_1.5Co_0.5AlO, where n% is the weigh percentage of the Pt element in the catalysts) were elaborately fabricated by the gas-bubble-assisted membrane--reduction method. The specific porous structure formed by the stack of hydrotalcite-derived Ni_1.5Co_0.5AlO nanosheets can increase the transfer mass efficiency of the reactants (O₂, NO, and soot) and the strong Pt–Ni_1.5Co_0.5AlO interaction can weaken the Ni/Co-O bond for promoting the mobility of lattice oxygen and the formation of surface-oxygen vacancies. The Pt_n/Ni_1.5Co_0.5AlO catalysts exhibited excellent catalytic activity and stability during diesel soot combustion under the loose contact mode between soot particles and catalysts. Among all the catalysts, the Pt₂/Ni_1.5Co_0.5AlO catalyst showed the highest catalytic activities for soot combustion (T₅₀ = 350 °C, TOF = 6.63 × 10⁻³ s⁻¹). Based on the characterization results, the catalytic mechanism for soot combustion is proposed: the synergistic effect of Pt and dual Ni/Co cations in the Pt/Ni_1.5Co_0.5AlO catalysts can promote the vital step of catalyzing NO oxidation to NO₂ in the NO-assisted soot oxidation mechanism. This insight into the synergistic effect of Pt and dual Ni/Co cations for soot combustion provides new strategies for reducing the amounts of noble metals in high-efficient catalysts. Full article

Development of ceramic pigments with controlled particle sizes below 1 µm is essential for the preparation of ceramic inks used in inkjet digital decoration that is currently being applied in the ceramics sector. A black ceramic pigment based on NiCoCrFe composition has been prepared using thermal decomposition of hydrotalcite-like compounds. The stoichiometry ratio between different cations was studied to obtain the blackest pigment, giving Ni_0,5Co_0,5CrFeO₄ the better cation ratio, also the thermal treatment, comparing traditional firing in an electric furnace with microwave treatment. Samples have been characterized by X-ray diffraction, Scanning Electron Microscopy and Lab colour measurement. Microwave treatment showed the best way to obtain a pigment with spinel-type structure and a homogeneous size distribution near to 150 nm, with a high intensity and colorimetric data, reducing drastically the temperature and energy consumption to obtain a black ceramic pigment suitable to be utilized in digital ceramic inks. Full article

Within the Waste2Fuel project, innovative, high-performance, and cost-effective fuel production methods from municipal solid wastes (MSWs) are sought for application as energy carriers or direct drop-in fuels/chemicals in the near-future low-carbon power generation systems and internal combustion engines. Among the studied energy vectors, C₁-C₂ alcohols and ethers are mainly addressed. This study presents a potential bio-derived ethanol oxidative coupling in the gas phase in multicomponent systems derived from hydrotalcite-containing precursors. The reaction of alcohol coupling to ethers has great importance due to their uses in different fields. The samples have been synthesized by the co-precipitation method via layered double hydroxide (LDH) material synthesis, with a controlled pH, where the M(II)/M(III) ≈ 0.35. The chemical composition and topology of the sample surface play essential roles in catalyst activity and product distribution. The multiple redox couples Ni²⁺/Ni³⁺, Cr²⁺/Cr³⁺, Mn²⁺/Mn³⁺, and the oxygen-vacant sites were considered as the main active sites. The introduction of Cr (Cr³⁺/Cr⁴⁺) and Mn (Mn³⁺/Mn⁴⁺) into the crystal lattice could enhance the number of oxygen vacancies and affect the acid/base properties of derived mixed oxides, which are considered as crucial parameters for process selectivity towards bio-DEE and bio-butanol, preventing long CH chain formation and coke deposition at the same time. Full article

This work focused on the synthesis of a catalyst based on layered double hydroxides with a molar cation concentration Ni/Cu/Fe/Mg/Al of 30/5/5/40/20 and its performance in the steam reforming of toluene as a model compound of biomass tar. Its performance at different temperatures (500, 600, 700, 800, and 900 °C) and steam/carbon molar ratios (S/C ratios) (1, 2, 4, 6, 8) was studied. The contact time used was 0.32 g h mol⁻¹. The catalyst obtained allowed us to reach 98–99.87% gas conversion of toluene with a low carbon deposition on catalyst surface (1.4 wt %) at 800 °C and S/C = 4. In addition, conversions in the range of 600–700 °C were higher than 80% and 90%, respectively, and the type of carbon deposited on the catalyst was found to be filamentous, which did not significantly reduce the performance of the catalyst. Full article

Lignocellulosic materials are promising alternatives to non-renewable fossil sources when producing aromatic compounds. Lignins from Populus salicaceae. Pinus radiata and Pinus pinaster from industrial wastes and biorefinery effluents were isolated and characterized. Lignin was depolymerized using homogenous (NaOH) and heterogeneous (Ni-, Cu- or Ni-Cu-hydrotalcites) base catalysis and catalytic hydrogenolysis using Ru/C. When homogeneous base catalyzed depolymerization (BCD) and Ru/C hydrogenolysis were combined on poplar lignin, the aromatics amount was ca. 11 wt.%. Monomer distributions changed depending on the feedstock and the reaction conditions. Aqueous NaOH produced cleavage of the alkyl side chain that was preserved when using modified hydrotalcite catalysts or Ru/C-catalyzed hydrogenolysis in ethanol. Depolymerization using hydrotalcite catalysts in ethanol produced monomers bearing carbonyl groups on the alkyl side chain. The analysis of the reaction mixtures was done by size exclusion chromatography (SEC) and diffusion ordered nuclear magnetic resonance spectroscopy (DOSY NMR). ³¹P NMR and heteronuclear single quantum coherence spectroscopy (HSQC) were also used in this study. The content in poly-(hydroxy)-aromatic ethers in the reaction mixtures decreased upon thermal treatments in ethanol. It was concluded that thermo-solvolysis is key in lignin depolymerization, and that the synergistic effect of Ni and Cu provided monomers with oxidized alkyl side chains. Full article

In the last decades, environmental crises and increasing energy demand have motivated researchers to investigate the practical techniques for the production of clean fuels through renewable energy resources. It is essential to develop technologies to utilize glycerol as a byproduct derived from biodiesel. Glycerol is known as a sustainable and clean source of energy, which can be an alternative resource for the production of value-added chemicals and hydrogen. The hydrogen production via steam reforming (SR) of glycerol using Ni-based catalysts is one of the promising approaches for the entry of the hydrogen economy. The purpose of this review paper is to highlight the recent trends in hydrogen production over Ni-based catalysts using the SR of glycerol. The intrinsic ability of Ni to disperse easily over variable supports makes it a more viable active phase for the SR catalysts. The optimal reaction conditions have been indicated as 650–900 °C, 1 bar, and 15 wt% Ni in catalysts for high glycerol conversion. In this review paper, the effects of various supports, different promoters (K, Ca, Sr, Ce, La, Cr, Fe), and process conditions on the catalytic performance have been summarized and discussed to provide a better comparison for the future works. It was found that Ce, Mg, and La have a significant effect on catalytic performance as promoters. Moreover, SR of glycerol over hydrotalcite and perovskite-based catalysts have been reviewed as they suggest high catalytic performance in SR of glycerol with improved thermal stability and coke resistance. More specifically, the Ni/LaNi_0.9Cu_0.1O₃ synthesized using perovskite-type supports has shown high glycerol conversion and sufficient hydrogen selectivity at low temperatures. On the other hand, hydrotalcite-like catalysts have shown higher catalytic stability due to high thermal stability and low coke formation. It is vital to notice that the primary concern is developing a high-performance catalyst to utilize crude glycerol efficiently. Full article