Search Results (42)

A series of silica-supported, nitrogen-doped carbon-encapsulated cobalt–nickel alloy catalysts (Co_xNi_y@NC/SiO₂) was successfully synthesized and systematically evaluated for the liquid-phase hydrogenation of 1-nitronaphthalene to 1-naphthylamine. Physicochemical characterization confirmed that the incorporation of nickel promotes the formation of Co–Ni alloys and modulates the electronic structure of the catalysts. The catalytic performance was found to be highly sensitive to the Co/Ni ratio, with Co₂Ni₁@NC/SiO₂ exhibiting the most outstanding activity. Under optimized reaction conditions (90 °C, 0.6 MPa H₂, 5.5 h), both the conversion of 1-nitronaphthalene and the selectivity toward 1-naphthylamine reached approximately 99%. The catalyst also demonstrated excellent stability and recyclability, attributed to the protective nitrogen-doped carbon shell and the synergistic interaction between the Co–Ni alloy and M–N_x active sites. This work provides a new strategy for designing efficient and robust non-noble-metal catalysts for hydrogenation reactions. Full article

In recent years CO₂ reforming of methane has attracted great interest as it produces high CO/H₂ ratio syngas suitable for the synthesis of higher hydrocarbons and oxygenated derivatives since it is a way for disposing and recycling two greenhouse gases with high environmental impact, CH₄ and CO₂, and because it is regarded as a potential route to store and transmit energy due to its strong endothermic effect. Along with noble metals, all the group VIII metals except for osmium have been studied for catalytic CO₂ reforming of methane. It was found that the catalytic activity of Ni, though lower than those of Ru and Rh, was higher than the catalytic activities of Pt and Pd. Although noble metals have been proven to be insensitive to coke, the high cost and restricted availability limit their use in this process. It is therefore valuable to develop stable Ni-based catalysts. In this contribution, we show how their activity and coking resistivity are greatly related to the size and dispersion of Ni particles. Well-dispersed Ni nanoparticles were achieved by multistep impregnation on a mesoporous silica support, namely SBA-15, obtained through a sol-gel method, using acetate as a nickel precursor and keeping the Ni loading between 5% and 11%. Significant catalytic activity was obtained at temperatures as low as 450 °C, a temperature well below their deactivation temperature, i.e., 700 °C. For the pre-reduced samples, a CO₂ conversion higher than 99% was obtained at approximately 680 °C. As such, their deactivation by sintering and coke formation was prevented. To the best of our knowledge, no Ni-based catalysts with complete CO₂ conversion at temperatures lower than 800 °C have been reported so far. Full article

The fabrication of highly loaded and uniformly dispersed metal oxide nanoparticles (NPs) is much desired but still remains a great challenge. Herein, the NiO NPs exclusively confined in mesoporous silica SBA-15 were obtained by using nickel nitrate hydrate as a precursor through a facile solvent-free preparation method, which comprised manual grinding of Ni(NO₃)₂·6H₂O with SBA-15 and subsequent air calcination. Characterization results from X-ray diffraction (XRD) and transmission electron microscope (TEM) revealed that aggregation-free NiO nanoparticles with sizes of 3–5 nm were obtained at loading as high as 20 wt.% (weight%). Further increasing the NiO loading to 30 wt.% led to partial agglomeration of discrete nanoparticles to rod-like particles, while no external particles were observed. By comparing the sample derived from nickel acetate with exclusively external NiO particles, it was established that the pore confinement provided NiO nanoparticles with high thermal stability. Lastly, the catalytic performance of the prepared sample was evaluated in the model reaction of ammonia decomposition to CO_x-free H₂, and the stable NH₃ conversion of 93.7% was achieved at the weight hourly space velocity (WHSV) value of 30,000 mL·g⁻¹·h⁻¹ and at high temperature of 650 °C for 60 h, demonstrating the great potential of the solvent-free method in preparing thermally stable and robust supported catalysts. Full article

This study investigates the effects of samarium (Sm) promotion on the catalytic activity of 5 weight percent Ni catalysts for partial oxidation of methane (POM)-based hydrogen production supported on a Si-Al mixed oxide (10SiO₂+90Al₂O₃) system. Several 5% Ni-based catalysts supported on silica–alumina was used to test the POM at 600 °C. Sm additions ranged from 0 to 2 wt.%. Impregnation was used to create these catalysts, which were then calcined at 500 °C and examined using BET, H₂-TPR, XRD, FTIR, TEM, Raman spectroscopy, and TGA methods. Methane conversion (57.85%) and hydrogen yield (56.89%) were greatly increased with an ideal Sm loading of 1 wt.%, indicating increased catalytic activity and stability. According to catalytic tests, 1 wt.% Sm produced high CH₄ conversion and H₂ production, as well as enhanced stability and resistance to carbon deposition. Nitrogen physisorption demonstrated a progressive decrease in pore volume and surface area with the addition of Sm, while maintaining mesoporosity. At moderate Sm loadings, H₂-TPR and XRD analyses showed changes in crystallinity and increased NiO reducibility. Sm incorporation into the support and its impact on the ordering of carbon species were indicated by FTIR and Raman spectra. The optimal conditions to maximize H₂ yield were successfully identified through optimization of the best catalyst, and there was good agreement between the theoretical predictions (87.563%) and actual results (88.39%). This displays how successfully the optimization approach achieves the intended outcome. Overall, this study demonstrates that the performance and durability of Ni-based catalysts for generating syngas through POM are greatly enhanced by the addition of a moderate amount of Sm, particularly 1 wt.%. Full article

The pore structure of a hydrotreating catalyst plays a pivotal role in hydrodemetallization (HDM) reactions. To effectively construct a meso-macroporous catalyst, we employed a CTAB-guided in situ TEOS hydrolysis approach to prepare silica-coated γ-Al₂O₃@SiO₂ composite supports. The silica shell incorporation significantly enhances specific surface area and reduces the metal–support interactions, thereby improving the dispersion of NiMo active components and boosting the deposition of metal impurity. Hence, the NiMo/Al₂O₃@SiO₂ catalyst (2.8 wt.% NiO, 4.3 wt.% MoO₃) exhibits much higher HDM activity than that of NiMo/Al₂O₃. This is evidenced by markedly higher demetallization rate constant (1.38 h⁻¹) and turnover frequency (0.56 h⁻¹) of the NiMo/Al₂O₃@SiO₂. The NiMo/Al₂O₃@SiO₂ catalyst further demonstrates excellent recyclability during sequential HDM reactions. This superior catalytic behavior stems from the hierarchical meso-macroporous structure, which simultaneously facilitates the deposition of metal impurities and mitigates deactivation by pore blockage. Full article

Catalytic CO₂ methanation represents a promising process route for converting carbon dioxide into methane, a valuable energy carrier. This study investigates the performance of Ni-based catalysts on mixed silica and MgO support materials for CO₂ methanation. Silica was derived from rice husk (SiO₂(RH)), representing a sustainable, cost-effective source for catalyst support, and MgO was used as a reference and to enhance the catalytic activity of the Ni-based catalysts through admixture with SiO₂(RH). The results were compared to CO₂ methanation over Ni-based catalysts on reduced iron ore from natural siderite (siderite_reduced), providing another abundant source for catalyst support. The experiments were conducted in a tubular reactor with a feed gas composition of H₂:CO₂:N₂ = 56:14:30, feed gas flow rates ranging from 4.01 to 14.66 m³·kg⁻¹·h⁻¹ (STP), and reaction temperatures of 548–648 K. The highest CO₂ conversion with the Ni/SiO₂(RH) catalyst was 39.01% at a methane selectivity of 92.64%. The use of mixed silica and MgO supports (SiO₂(RH)/MgO) for nickel revealed a beneficial effect, enhancing CO₂ conversion and methane formation. In this case, methane selectivities consistently exceeded 91.57%. Superior methane selectivity and CO₂ conversion were obtained with Ni/MgO catalysts and Ni/SiO₂(RH)/MgO catalysts with high MgO fractions, highlighting the fundamental effect of MgO in the catalyst support for CO₂ methanation. Full article

Understanding the catalytic behavior of heterogeneous systems for the copolymerization of ethylene with polar monomers is essential for developing advanced functional polyolefins. In this study, we conducted a quantum chemical investigation of the SiO₂-supported Ni–allyl–α-imine ketone catalyst (Ni-OH@SiO₂) to uncover the factors governing monomer insertion, selectivity, and reactivity. Using DFT calculations and energy decomposition analysis (ALMO-EDA), we evaluated the coordination and insertion of six industrially relevant polar monomers, comparing their behavior to ethylene homopolymerization. Our results show that special polar monomers (SPMs) with aliphatic spacers, such as vinyltrimethoxysilane (vTMS) and 5-hexenyl acetate (AMA), exhibit favorable insertion profiles due to enhanced electrostatic and orbital interactions with minimal steric hindrance. In contrast, fundamental polar monomers (FPMs), including methyl acrylate (MA) and vinyl chloride (vCl), show higher activation barriers and increased Pauli repulsion due to strong electron-withdrawing effects and conjugation with the vinyl group. AMA displayed the lowest activation barrier (7.4 kcal/mol) and highest insertion thermodynamic stability (−17.6 kcal/mol). These findings provide molecular-level insight into insertion mechanisms and comonomer selectivity in Ni–allyl catalysts supported on silica, extending experimental understanding. This work establishes key structure–reactivity relationships and offers design principles for developing efficient Ni-based heterogeneous catalysts for polar monomer copolymerization. Full article

Rising greenhouse gas concentrations are causing climatic change that threatens ecosystem sustainability. This study investigated the impact of silica incorporation into alumina-supported nickel catalysts for the partial oxidation of methane (POM), a crucial process for syngas production. The investigation also focuses on the impact of using different calcination temperatures. The catalysts were synthesized using the impregnation method and structurally characterized with BET, TPR, FTIR, UV, XRD, TGA, Raman, and TEM analysis techniques. These characterization techniques revealed that increasing the silica content reduced the surface area and weakened the interaction between nickel and the support. The calcination temperature significantly influenced catalyst properties, affecting pore structure, nickel reducibility, and the formation of nickel aluminates and silicates. Activity tests of synthesized catalysts were performed in a packed-bed reactor at 600 °C with a 24 mL/min gas flow rate. The catalyst composition of 5Ni/10Si + 90Al demonstrated the highest activity, achieving optimal performance at lower calcination temperatures. This catalyst generates a greater concentration of active sites, primarily due to nickel oxide (NiO), which creates these sites through both mild and strong interactions. The degree of graphitization is notably lowest for the 5Ni/10Si + 90Al composition. This catalyst achieved an impressive hydrogen yield of approximately 54%, with an H₂/CO ratio of 3.4 over a streaming period of up to 240 min. When the silica loading exceeds 10 wt.%, the interaction between the metal and the support weakens, resulting in a significant decrease in surface area and, subsequently, lower catalytic activity. The 5Ni/10Si + 90Al catalyst, which was prepared with calcination temperatures above 500 °C, has very few active sites during the Partial Oxidation of Methane (POM) reaction at a reaction temperature of 600 °C. This catalyst also exhibits a high degree of crystallinity, which leads to reduced exposure of the active sites. As a result, incorporating higher weight percentages of silica into the 5Ni/xSi + (100 − x) Al catalysts results in decreased activity. When the silica loading exceeds 10 wt.%, the interaction between the metal and the support weakens, resulting in a significant decrease in surface area and, subsequently, lower catalytic activity. The 5Ni/10Si + 90Al catalyst, which was prepared with calcination temperatures above 500 °C, has very few active sites during the POM reaction at a reaction temperature of 600 °C. This catalyst also exhibits a high degree of crystallinity, which leads to reduced exposure of the active sites. As a result, incorporating higher wt.% of silica into the 5Ni/xSi + (100 − x) Al catalysts results in decreased activity. These findings highlight the complex interplay between silica content, calcination temperature, and catalyst properties, significantly influencing catalytic performance in POM. Full article

In this study, bimetallic NiCo nanoparticles (NPs) were encapsulated within the mesopores of carboxylic acid functionalized mesoporous silica (CMS) through the chemical reduction approach. Both NaBH₄ and NH₃BH₃ were used as reducing agents to reduce the metal ions simultaneously. The resulting composite was used as a catalyst for hydrolysis of ammonia borane (NH₃BH₃, AB) to produce H₂. The bimetallic NiCo NPs supported on carboxylic group functionalized mesoporous silica, referred to as Ni_xCo_100−x@CMS, exhibited significantly higher catalytic activity for AB hydrolysis compared to their monometallic counterparts. The remarkable activity of Ni_xCo_100−x@CMS could be ascribed to the synergistic contributions of Ni and Co, redox reaction during the hydrolysis, and the fine-tuned electronic structure. The catalytic performance of the Ni_xCo_100−x@CMS nanocatalyst was observed to be dependent on the composition of Ni and Co. Among all the compositions investigated, Ni₄₀Co₆₀@CMS demonstrated the highest catalytic activity, with a turn over frequency (TOF) of 18.95 mol_H2min⁻¹mol_catalyst⁻¹ and H₂ production rate of 8.0 L min⁻¹g⁻¹. The activity of Ni₄₀Co₆₀@CMS was approximately three times greater than that of Ni@CMS and about two times that of Co@CMS. The superior activity of Ni₄₀Co₆₀@CMS was attributed to its finely-tuned electronic structure, resulting from the electron transfer of Ni to Co. Furthermore, the nanocatalyst exhibited excellent durability, as the carboxylate group in the support provided a strong metal–support interaction, securely anchoring the NPs within the mesopores, preventing both agglomeration and leakage. Full article

Nickel catalysts promoted with Mo and supported on silica were studied for renewable diesel production from triglyceride biomass, through the selective deoxygenation process. The catalysts were prepared by wet co-impregnation of the SiO₂ with different Ni/(Ni + Mo) atomic ratios (0/0.84/0.91/0.95/0.98/1) and a total metal content equal to 50%. They were characterized by XRD, XPS, N₂ physisorption, H₂-TPR, and NH₃-TPD. Evaluation of the catalysts for the transformation of sunflower oil to renewable (green) diesel took place in a high-pressure semi-batch reactor, under solvent-free conditions. A very small addition of Mo, namely the synergistic Ni/(Ni + Mo) atomic ratio equal to 0.95, proved to be the optimum one for a significant enhancement of the catalytic performance of the metallic Ni/SiO₂ catalyst, achieving 98 wt.% renewable diesel production. This promoting action of Mo has been attributed to the significant increase of the metallic Ni active phase surface area, the suitable regulation of surface acidity, the acceleration of the hydro-deoxygenation pathway (HDO), the creation of surface oxygen vacancies, and the diminution of coke formation provoked by Mo addition. Full article

Among the countless routes for renewable hydrogen (H₂) production, Biogas Dry Reforming (DR) has been highlighted as one of the most promising for the circular bio-economy sector. However, DR requires high operating temperatures (700 °C–900 °C), and, for greater efficiency, a thermally stable catalyst is necessary, being, above all, resistant to coke formation, sintering, and sulfur poisoning. Mesoporous metallic catalysts, such as nickel (Ni) supported on silica, stand out due to their high catalytic activity concerning such characteristics. In this regard, the presented work evaluated the influences of the nickel addition stage during the synthesis of mesoporous catalyst type Si-MCM-41. Two different catalysts were prepared: catalyst A (Ni/Si-MCM-41_A), synthesized through the in situ addition of the precursor salt of nickel (Ni(Ni(NO₃)₂·6H₂O) before the addition of TEOS (Tetraethyl orthosilicate) and after the addition of the directing agent; and catalyst B (Ni/Si-MCM-41_B), resulting from the addition of the precursor salt after the TEOS, following the conventional methodology, by wet impregnation in situ. The results evidenced that the metal addition stage has a direct influence on the mesoporous structure. However, no significant influence was observed on the efficiency concerning BDR, and the conversions into H₂ were 97% and 96% for the Ni/SiMCM-41_A and Ni/Si-MCM-41_B catalysts, respectively. Full article

Global energy demand escalates the interest in effective and durable catalytic systems for the dry reforming of methane (DRM), a process that converts CO₂/CH₄ into H₂/CO syngas. Porous silica-supported nickel (Ni) catalysts are recognized as a promising candidate due to robust DRM activity associated with the confinement of Ni particles in the mesopores that reduces the catalyst deactivation by carbon byproduct deposits and sintering of active Ni sites. However, the small-sized pore configurations in the mesoporous catalysts hinders the fast mass transfer of reactants and products. A unique combination of the hierarchical nanostructure with macro–mesoporous features of the support is adopted to enhance the catalytic performance via the dual effect of the efficient mass transfer and minimized sintering issue. This study delves into the influence of SiO₂ geometry and pore structure on the catalytic performance of Ni-based catalysts. Three types of porous silica supports were synthesized through various methods: (a) hydrothermal-assisted sol–gel for dendritic mesoporous silica (DMS), (b) spray-pyrolysis-assisted sol–gel for spray evaporation-induced self-assembly (EISA) silica, and (c) oven-assisted sol–gel for oven EISA silica. Among the prepared catalysts the hierarchical external nanostructured Ni/DMS showed the superior CH₄ and CO₂ conversion rates (76.6% and 82.1%), even at high space velocities (GHSV = 360 L∙g⁻¹·h⁻¹). The distinctive macro–mesoporous geometry effectively prevents the sintering of Ni particles and promotes the smooth diffusion of the reactants and products, thus improving catalytic stability over extended reaction periods (24 h). This research highlights the significant impact of macro–mesoporosity revealed in DMS support catalysts on the physicochemical properties of Ni/DMS and their crucial role in enhancing DRM reaction efficiency. Full article

The recent unusual weather changes occurring in different parts of the world are caused by global warming, a consequence of the release of extreme amounts of greenhouse gases into the atmosphere. Carbon dioxide (CO₂) is one of these greenhouse gasses, which can be captured and reused to generate fuel through the methanation process. Nickel- and silica-based catalysts have been recognized as promising catalysts due to their efficiency, availability, and low prices. However, these catalysts suffer from metal sintering at high temperatures. Researchers have achieved remarkable improvements through altering conventional synthesis methods, supports, metal loading amounts, and promoters. The modified routes have enhanced stability and activity while the supports offer large surface areas, dispersion, and strong metal–support interactions. Nickel loading affects the formed structure and catalytic activity, whereas doping causes CO₂ conversion at low temperatures and forms basic sites. This review aims to discuss the CO₂ methanation process over Ni- and SiO₂-based catalysts, in particular the silica-supported Ni metal in previously reported research works and point out directions for potential future work. Full article

Copper and iron-based bimetallic nickel catalysts supported on Mesostructured Silica Nanoparticles (MSNs) with compositions of 50% Ni–5% Cu/MSN and 50% Ni–5% Fe/MSN were prepared using an impregnation method, and they were compared with a monometallic 50% Ni–MSN catalyst for their activity and stability in methane decomposition reaction. The influence of promoters, such as Cu and Fe, at different reaction temperatures (700 °C, 800 °C and 900 °C) was investigated. The results revealed that the Cu and Fe-promoted catalysts significantly increased the hydrogen yield in methane decomposition compared with the unpromoted catalyst. This could be attributed to the formation of Ni–Cu and Ni–Fe bimetallic alloys in the catalysts, respectively, and this favored the stability of the catalysts. With increasing reaction temperature, the hydrogen yield also increased. However, the hydrogen yield and the lifetime of the nickel catalyst were enhanced upon the addition of iron compared to copper at all the reaction temperatures. The analysis conducted over the spent catalysts validated the formation of multi-walled carbon nanotubes with a bamboo-like internal channel over the catalysts along with a high crystallinity and graphitization degree of the carbon produced. Full article

Citric acid, one of the representative chelate compounds, has been widely used as an additive to achieve the highly dispersed metal-supported catalysts. This study aimed to investigate the effect of citric acid concentration on the preparation of the highly dispersed Ni catalysts on mesoporous silica (SBA-15) for the dry reforming of methane. A series of Ni/SBA-15 catalysts with citric acid were prepared using the acid-assisted incipient wetness impregnation method, and the Ni/SBA-15 catalyst as a reference was synthesized via the impregnation method. First of all, the citric acid addition during the catalyst synthesis step regardless of its concentration resulted in highly dispersed Ni particles of ~4–7 nm in size in Ni/SBA-15 catalysts, which had a superior and stable catalytic performance in the dry reforming of methane (93% of CO₂ conversion and 86% of CH₄ conversion). In addition, the amount of coke formation was much lower in a series of Ni/SBA-15 catalysts with citric acid (~2–5 mg_coke g_cat⁻¹ h⁻¹) compared to pristine Ni/SBA-15 catalysts (~22 mg_coke g_cat⁻¹ h⁻¹). However, when the concentration of citric acid became higher, the more free NiO species that formed on the SBA-15 support, leading to large Ni particles after the stability test. The addition of citric acid is a very clear strategy for making highly dispersed catalysts, but its concentration needs to be carefully controlled. Full article