Search Results (112)

The catalytic removal of toluene, a representative aromatic volatile organic compound (VOC), requires efficient and stable catalysts. This study systematically investigated the effect of B-site doping with transition metals (Fe, Cu, and Ni) on the catalytic performance of LaMnO₃ perovskite for toluene oxidation. The LaMn_0.5X_0.5O₃ catalysts were synthesized via a sol–gel method and evaluated. The LaMn_0.5Ni_0.5O₃ catalysts exhibited the optimal catalytic performance, achieving toluene conversion temperatures of 243 °C at 50% conversion (T₅₀) and 296 °C at 90% conversion (T₉₀). Comprehensive characterization revealed that Ni doping effectively refined the catalyst’s microstructure (grain size decreased to 19.21 nm), increased the concentration of surface-active oxygen species (142.7%), elevated the Mn⁴⁺/Mn³⁺ ratio to 0.65, and enhanced lattice oxygen mobility. These modifications collectively contributed to its outstanding catalytic activity. The findings demonstrate that targeted B-site doping, particularly with Ni, is a promising strategy for engineering efficient perovskite catalysts for VOC abatement. Full article

Three-dimensionally ordered macroporous (3DOM) La₂O₃-supported Ni catalysts exhibit outstanding performance for methane dry reforming (DRM). The 5Ni/La₂O₃-3DOM catalyst achieves 79% CH₄ and 84% CO₂ conversions at 800 °C under the reaction conditions of atmospheric pressure, CH₄:CO₂ molar ratio of 1:1, and gas hourly space velocity (GHSV) = 36,000 mL·gcat⁻¹·h⁻¹, outperforming its counterparts (5Ni/La₂O₃-PP prepared by means of co-precipitation and 5Ni/La₂O₃-GNC prepared by means of glycine–nitrate combustion) by 15–20%. Long-term stability tests at 700 °C (same CH₄:CO₂ ratio and GHSV as above) show that the 5Ni/La₂O₃-3DOM catalyst maintains CH₄ and CO₂ conversions at approximately 80% and 85%, respectively, with zero deactivation over 50 h. Meanwhile, its carbon deposition rate plummets to 1.1 mg·g⁻¹·h⁻¹, which is 75% lower than that of the precipitation-derived 5Ni/La₂O₃-PP catalyst. This excellent performance stems from the synergy of nano-confined Ni particles (11.2 nm in crystallite size after reduction) and abundant surface oxygen species (38 μmol·g⁻¹), establishing 3DOM La₂O₃ as a superior anti-coking support platform for scalable H₂ production via DRM. Full article

Developing cost-effective, sustainable, and high-performance air electrode catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) remains a significant challenge in the advancement of rechargeable zinc–air batteries (ZABs). Herein, we successfully construct a vacancy-rich heterogeneous perovskite La_0.85Y_0.15Ni_0.7Fe_0.3O₃ (LYNF) hybridized with Co₃O₄ spinel nanoparticles using a simple chemical bath-assisted method. The Co₃O₄ composite LYNF material is systematically evaluated as the bifunctional catalyst for ZABs in the proportion of 25 wt%, 50w t%, and 75 wt% (denoted as LYNF-xCo₃O₄, x = 0.25, 0.5, 0.75). The results confirm an intimate coupling between the perovskite and spinel phases, along with a significant increase in oxygen vacancy concentration. Among the composites, LYNF-0.5Co₃O₄ exhibits the best performance, achieving an ORR onset potential of 0.813 V vs. RHE at −0.1 mA cm⁻² and a lower OER overpotential of 441 mV at 10 mA cm⁻². When applied as the air electrode catalyst in ZABs, LYNF-0.5Co₃O₄ displays the highest discharge voltage and a peak power density of 115 mW cm⁻², representing a 20% improvement over pristine LYNF. The enhanced performance of the LYNF-0.5Co₃O₄ composite is attributed to the accumulation of Co₃O₄ nanoparticles within the LYNF matrix, which introduces numerous electrochemically active sites and facilitates the charge and mass transport during the catalytic process in ZABs. Full article

One viable technical approach for achieving hydrogen-blended combustion in marine ammonia-fueled engines is to utilize online ammonia decomposition to produce hydrogen, which is then introduced into the engine for combustion. This work carried out ammonia decomposition experiments using various catalysts, examining the effects of temperature and space velocity on Ru/Ce_0.33Zr_0.58La_0.03Nd_0.03Pr_0.03O_2.09 and Ni/Ce_0.36Zr_0.64O₂ catalysts. Based on the experimental data obtained, the kinetic parameters of ammonia decomposition were fitted using four different models: mass action law, first-order reaction, Langmuir, and Temkin–Pyzhev kinetics across two catalysts, with the subsequent mechanistic analysis of catalytic reaction processes within the reactor. The results revealed that the NH₃ conversion rate of the Ru/Ce_0.33Zr_0.58La_0.03Nd_0.03Pr_0.03O_2.09 catalyst was superior to that of the Ni/Ce_0.36Zr_0.64O₂ catalyst, with temperature activity windows of 250–450 °C and 400–600 °C, respectively. Within the range of 2000–32,000 mL·g⁻¹·h⁻¹), an increase in space velocity led to a decrease in NH₃ conversion rate by approximately half. All four models were able to predict NH₃ conversion rates for the different catalysts with reasonable accuracy. The activation energies for Ru/Ce_0.33Zr_0.58La_0.03Nd_0.03Pr_0.03O_2.09 and Ni/Ce_0.36Zr_0.64O₂ catalysts were found to be 37.7 kJ·mol⁻¹ and 66 kJ·mol⁻¹, respectively. Targeting hydrogen requirements of 10–40% vol for ammonia engines, the corresponding catalytic temperatures for Ru/Ce_0.33Zr_0.58La_0.03Nd_0.03Pr_0.03O_2.09 and Ni/Ce_0.36Zr_0.64O₂ were above 267 °C and 500 °C, respectively. Full article

2-Methyltetrahydrofuran (2-MTHF), a hydrogenated derivative of levulinic acid (LA), is a biomass-derived platform compound with diverse and significant applications as a biofuel, gasoline additive, green solvent, and pharmaceutical synthesis intermediate. This study investigates the preparation of a Cu₁Ni₂/Al₂O₃ catalyst through the calcination–reduction of CuNiAl hydrotalcite as a precursor, which was subsequently utilized in the hydrogenation of LA to produce 2-MTHF. The calcination–reduction process applied to CuNiAl hydrotalcite results in a lattice confinement effect. This method not only disperses the active metal sites but also alters the bonding patterns of the active metals, thereby enhancing the activity and stability of the Cu₁Ni₂/Al₂O₃ catalyst. The results indicate that complete conversion of LA and a 2-MTHF yield of 87.6% can be achieved under optimal conditions of 190 °C, 5 MPa hydrogen, and a reaction time of 5 h, demonstrating an efficient one-step conversion process. Additionally, the catalyst’s recyclability was assessed through multiple reuse tests, with a loss of activity of only 9.2% after six cycle experiments, suggesting its feasibility and reliability for industrial applications. Full article

γ-Valerolactone (GVL) is a promising bio-based platform molecule with significant potential for energy applications. The production of GVL via biomass-based levulinic acid (LA) is an important reaction. To enhance the conversion and selectivity of non-precious-metal catalysts in the LA-to-GVL process and to better understand the key factors influencing this conversion, we conducted a series of experiments. In this study, supported Cu-Ni bimetallic catalysts (Cu-Ni₂/Al₂O₃) were prepared using layered double hydroxides (LDHs) as a precursor. Compared with Cu-Ni catalysts synthesized via the conventional impregnation method, the Cu-Ni₂/Al₂O₃ catalysts exhibit higher catalytic activity and stability. The results demonstrated that efficient conversion was achieved with isopropanol as the hydrogen donor solvent, a reaction temperature of 180 °C, and a reaction time of 1 h. The yield of GVL reached nearly 90%, with a decrease of approximately only 6% after six consecutive cycles. The Cu-Ni₂/Al₂O₃ catalyst proved to be effective for converting biomass-derived LA to GVL, offering a route that not only reduces production costs and environmental impact but also enables efficient biomass-to-energy conversion. Full article

The auto-thermal reforming (ATR) of acetic acid is an effective hydrogen production method, but it suffers from catalyst deactivation by coking. Sm-promoted layered La₂NiO₄ perovskite catalysts were synthesized via the sol–gel method and its catalytic performance in the ATR of HAc was further evaluated. The characterization results demonstrate that the incorporation of Sm into the lattice of La₂NiO₄ perovskite led to the formation of Ni-La-Sm-O species, inducing crystal defects in the perovskite structure which could promote the gasification of coking precursors. Additionally, Sm regulated the reduction characteristics of La₂NiO₄, resulting in the formation of highly dispersed nickel nanoparticles upon the hydrogen reduction, which increased the number of active sites available for acetic acid conversion. Consequently, a stable reactivity without obvious coking was obtained over a Ni_0.42La_0.7Sm_0.36O_2.01±δ catalyst within the ATR of Hac. The hydrogen yield reached 2.53 mol-H₂/mol-HAc along with the complete conversion of acetic acid. Full article

Developing more effective gold–support synergy is essential for enhancing the catalytic performance of supported gold nanoparticles (AuNPs) in the gas-phase oxidation of ethanol to acetaldehyde (AC) at lower temperatures. This study demonstrates a significantly improved Au–support synergy achieved by copper doping in LaMO₃ (M = Mn, Fe, Co, Ni) perovskites. Among the various Au/LaMCuO₃ catalysts, Au/LaMnCuO₃ exhibited exceptional catalytic activity, achieving an AC yield of up to 91% and the highest space-time yield of 764 g_AC g_Au⁻¹ h⁻¹ at 225 °C. Notably, this catalyst showed excellent hydrothermal stability, maintaining performance for at least 100 h without significant deactivation when fed with 50% aqueous ethanol. Comprehensive characterization reveals that Cu doping facilitates the formation of surface oxygen vacancies on the Au/LaMCuO₃ catalysts and enhances Au–support interactions. The LaMnCuO₃ perovskite stabilizes the crucial Cu⁺ species, resulting in a stable Au-Mn-Cu synergy within the Au/LaMnCuO₃ catalyst, which facilitates the activation of O₂ and ethanol at lower temperatures. The optimization of the reaction conditions further improves AC productivity. Kinetic studies indicate that the cleavages of both the O-H bond and the α-C-H bond of ethanol are the rate-controlling steps. Full article

Metallic Pd/Ni gauzes, located downstream of the Pt/Rh ammonia oxidation catalyst nets in the Ostwald process, is the current technology for capturing volatile gas phase platinum and rhodium species lost from the Pt/Rh combustion catalyst through evaporation. In this screening study, we explore four oxide families, ABO₃ perovskites, (ABO₃)_n(AO) Ruddlesden–Popper (RP) phases, AO rock salt, and A₂O₃ sesquioxide type oxides, as alternative materials for platinum capture. It was found that all the tested nickelates, LaNiO₃, NdNiO₃, La₂NiO₄, and La₄Ni₃O₁₀, captured platinum well and formed A₂NiPtO₆. In contrast, La_0.85Sr_0.15FeO₃, LaFeO₃, and LaCoO₃ did not capture platinum. CaO, SrO, and Nd₂O₃ formed low-dimensional platinates such as Ca_xPt₃O₄, Sr₄PtO₆, and a newly discovered neodymium platinate, Nd_10.67Pt₄O₂₄. Gd₂O₃ did not capture platinum in bench-scale experiments in dry air, but did, however, seem to capture platinum under pilot plant conditions, likely due to the co-capture of Co lost from the N₂O abatement catalyst. The catalytic activity of both oxides and platinum-containing products were studied, toward NO_x and N₂O decomposition. None of the oxides showed significant activity toward NO_x decomposition, and all showed activity toward N₂O decomposition, but to different extents. An overall assessment of the screened oxides with respect to potential use in industrial Ostwald conditions is provided. All tested oxides except CaO and SrO withstood industrial conditions. From our assessments, the nickelates and A₂O₃ (A = Nd, Gd) stand out as superior oxides for platinum capture. Full article

Perovskites exhibit catalytic properties on the oxygen evolution reaction (OER) in water electrolysis. Elemental doping by specific preparation methods is a good strategy to obtain highly catalytical active perovskite catalysts. In this work, La_0.5Sr_0.5Co_1−xNi_xO_3−δ perovskite materials doped with different ratios of nickel were successfully synthesized by the sol-gel method. The electrochemical measurement results show that for OER in 1 M KOH solution, La_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ prepared by the sol-gel method requires only a low overpotential of 213 mV to reach 10 mA cm⁻², which is significantly lower than that of La_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ prepared by the hydrothermal method for the increasing about 45.24% (389 mV at 10 mA cm⁻²). In addition, La_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ by the sol-gel method can be kept stable in an alkaline medium tested for 30 h without degradation. This indicates that the prepared La_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ has better OER performance. The X-ray diffraction (XRD) results show that SrCO₃ is the main phase formed, which is a disadvantage of this method. The performance improvement may be affected by the carbonate phase. The scanning electron microscopy (SEM) results show that layer structured La_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ by the sol-gel method has more surface pores with a pore diameter of about 0.362 μm than spherical granular structured La_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ by the hydrothermal method. X-ray photoelectronic spectroscopy (XPS) results reveal that the crystal lattice of La_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ by nickel doping is lengthened, and the electronic configuration of Co is also changed by the sol-gel preparation process. The improved electrocatalytic performance of La_0.5Sr_0.5Co_0.8Ni_0.2O_3−δ may be attributed to the pore structure formed providing more active sites during the sol-gel process and the improved oxygen mobility with Ni doping by the sol-gel method. The doping strategy using the sol-gel method provides valuable insights for optimizing perovskite catalytic properties. Full article

In hydrogen processes, managing CO emissions and removal by catalytic oxidation is crucial during H₂ production, storage/transportation, and use, ensuring the efficiency and safety of hydrogen systems and contributing to more sustainable energy solutions. Perovskite-structured transition metal oxide catalysts have been widely studied in various energy and environmental applications due to their extensive compositional modifications and electronic adjustments, facilitating catalytic behavior. Here, Ce-based perovskite catalysts with dual active metal doping at varying Co and Ni ratios are investigated to understand their structural and redox properties in CO oxidation. The reaction mechanism involves CO adsorption, oxygen activation, and redox cycling, confirming catalytic turnover. In situ DRIFTS analysis reveals real-time surface transformations with catalytic activity, which vary with Co and Ni doping ratio. Relatively, CO adsorption on Co³⁺ dominates the low-temperature activity, whereas Ni contributes to the efficiency at elevated temperatures. LCCNTxy (La_0.7Ce_0.1Co_xNi_yTi_0.6O₃) with x = 0.3 and y = 0.1 exhibits the highest performance, achieving T₁₀ above 40 °C and the fastest T₉₀ at 230 °C. This study highlights the compositional tuning in dual-doped perovskites and complementary roles of Co and Ni in CO oxidation for developing efficient industrial catalysts. Full article

Hydrogen production from ethanol steam reforming (ESR) was performed using the synthesized LaNi_xCu_1−xO_3−λ perovskite-type catalysts in a continuous two-stage fixed-bed reactor from 450 to 700 °C under atmospheric pressure. The elemental analysis (EA), XRD, SEM, BET, and TGA-DTG technologies were used to characterize the structures and properties of the synthesized catalysts. The thermodynamic equilibrium model, based on the minimization of Gibbs free energy using a non-stoichiometric methodology, was carried out and compared with experimental data. The results demonstrated that the catalytic activity of the perovskite-type catalysts for ESR can be improved after modification with a certain amount of copper (about 0.67 mmol/g) and decreased further with an increase in copper content (about 3.41 mmol/g). The most active catalyst was found to be LaNi_0.9Cu_0.1O_3−λ, with an ethanol conversion value of 96.0% and hydrogen selectivity of 71.3%. The perovskite-type catalysts with an appropriate amount of Cu promoter improved coking resistance and presented excellent stability with no loss of activity over 101 h at 700 °C. Based on the power-law kinetic model with the first reaction order, the activation energy and the frequency factor for ethanol steam reforming by perovskite-type catalysts were calculated. Our studies indicated the enhanced effects of Ni and Cu on the small Ni-Cu bimetallic particles in the water gas shift (WGS) reaction, which could also contribute to the activity and stability of the LaNi_xCu_1−xO_3−λ perovskite-type catalysts in hydrogen production. Full article

CH₄ has become the most attractive fuel for solid oxide fuel cells due to its wide availability, narrow explosion limit range, low price, and easy storage. Thus, we present the concept of on-cell reforming via SOFC power generation, in which CH₄ and CO₂ can be converted into H₂ and the formed H₂ is electrochemically oxidized on a Ni-BZCYYb anode. We modified the porosity and specific surface area of a perovskite reforming catalyst via an optimized electrostatic spinning method, and the prepared LCMN nanofibers, which displayed an ideal LaMnO₃-type perovskite structure with a high specific surface area, were imposed on a conventional Ni-BZCYYb anode for on-cell CH₄ reforming. Compared to LCMN nanoparticles used as on-cell reforming catalysts, the NF-SOFC showed lower ohmic and polarization resistances, indicating that the porous nanofibers could reduce the resistances of fuel gas transport and charge transport in the anode. Accordingly, the NF-SOFC displayed a maximum power density (MPD) of 781 mW cm⁻² and a stable discharge voltage of around 0.62 V for 72 h without coking in the Ni-BZCYYb anode. The present LCMN NF materials and on-cell reforming system demonstrated stability and potential for highly efficient power generation with hydrocarbon fuels. Full article

The hydroprocessing of gasoline on modified alumina catalysts makes it possible to obtain high-octane products. The implementation and development of the process have largely become possible due to the development of modified alumina catalysts that do not contain noble metals and exhibit special catalytic properties. This article discusses topical issues of petrochemistry, namely the creation of catalysts with improved characteristics for the production of high-octane gasoline with low sulfur content. New catalytic systems based on alumina and other carriers modified with transition metals, lanthanum and phosphorus were synthesized. By physico-chemical methods of analysis TPD of ammonia, TEM and XRD, we studied the acid–base and structural characteristics of the developed catalysts. The activity of the developed catalysts in the studied process of hydrotreating gasoline fractions depends on the structure and condition of the active centers. The process of hydrotreating straight-run gasoline in the presence of synthesized catalysts was carried out on a laboratory flow unit. It was shown that, during the hydrotreating of straight-run gasoline on the NiO-MoO₃-La-P-HZSM-HY-Al₂O₃ catalyst, the octane number in the final product increased to 88.6, and the sulfur content decreased from 0.0088 to 0.001%. It was found that the minimum sulfur content in the gasoline hydrotreating product of 0.0005% was achieved on the catalyst CoO-WO₃-La-P-HZSM-HY-Al₂O₃, which is significantly lower than for other studied catalytic systems. The obtained results of the sulfur content in the hydrotreating products fully comply with the Euro-5 standard. Thus, the efficiency of hydrotreating the gasoline fractions studied in this work was mainly determined by the nature of the carriers and modifiers used for the synthesis of catalysts and the technological parameters of the process. The synthesized catalysts showed high activity and selectivity, resulting in high-octane gasoline with a low sulfur content that meets international quality standards. Full article

The effect of high concentrations of H₂S in sour natural gas on the catalytic dry reforming of methane (DRM) process has seldom been studied previously in the literature. Herein, several types of catalysts, including MgO, NiO/MgO, and LaNiO₃ in different states, were prepared for conducting DRM at 800 °C and 0.1 MPa in a feed of 20 vol% CO₂ and 20 vol% CH₄, and their catalytic performance under conditions of the absence and presence of H₂S was compared. A promotion effect of increasing H₂S concentration on both the conversions of CO₂ and CH₄ and the molar yields of CO and H₂ was observed on all the catalysts and was particularly remarkable on the MgO and the pristine NiO/MgO. For NiO/MgO, the addition of 15 vol% H₂S increased the conversion of CH₄ from 6.92% to 26.86% and CO₂ from 9.15% to 42.10%. While there was a significant decline in the catalytic activity of the reduced NiO/MgO and LaNiO₃ catalysts after adding H₂S, moderate reactant conversions were still sustained. The results of process analysis and catalyst structure characterization suggest that H₂S participation can contribute to the increment in CO₂ and CH₄ conversion, and active S-adsorbed species may play the key role of catalysis in reactions involving H₂S. Full article