Temperature-programmed Reduction Research Articles

On the Application of an In Situ Catalyst Characterization System (ICCS) and a Mass Spectrometer Detector as Powerful Techniques for the Characterization of Catalysts

The in situ characterization of catalysts provides important information on the catalyst and the understanding of its catalytic performance and selectivity for a specific reaction. Temperature programmed analyses (TPX) techniques for catalyst characterization reveal the role of the support on the stabilization and dispersion of the active sites. However, these can be altered at high temperatures since sintering of active species can occur as well as possible carbon deposition which hinders the active species and deactivates the catalyst. The in situ characterization of the spent catalyst, however, may expose the causes of catalyst deactivation. For example, a simple temperature programmed oxidation (TPO) analysis on the spent catalyst may produce CO and CO2 via a reaction with O2 at high temperatures and this is a strong indication that deactivation may be due to the deposition of carbon. Other TPX techniques such as temperature programmed reduction (TPR) and pulse chemisorption are also valuable techniques when they are applied in situ to the fresh catalyst and then to the catalyst upon deactivation. In this work, two Ni supported catalysts were considered as examples to elucidate the importance of these techniques in the characterization study of catalysts applied to the reaction of hydrogenation of CO2.

Ruthenium Catalysts Supported on Hydrothermally Treated Carbon from Rice Husk: The Effect of Reduction Temperature on the Hydrogenation Reaction of Levulinic Acid to γ-Valerolactone

Ru catalysts supported on activated carbon obtained by hydrothermal treatment of rice husk were evaluated in the hydrogenation reaction of levulinic acid to γ-valerolactone. The hydrothermally treated carbon was characterized by nitrogen physisorption, elemental analysis, and thermogravimetric analysis, and the catalysts were characterized by FTIR spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed reduction, and temperature-programmed desorption of pyridine (acidic properties). Prior to the reaction, the catalysts were reduced at different temperatures in the range of 100–350 °C to evaluate the effect of the reduction temperature on the performance in the hydrogenation of levulinic acid. The reaction was carried out in a batch reactor at 70 °C and 1.5 MPa. The results of conversion and selectivity to γ-valerolactone showed that the catalyst with the best performance was the sample reduced at 200 °C. After 2 h of reaction, a γ-valerolactone yield of 74% was achieved. This catalyst presented the lowest acidity value, and the ruthenium-containing phase consisted mainly of RuO2, with a small portion of Ru0. The solid catalyst can be recovered and successfully reused for three runs with the GVL yield at 56%.

Conductometric room temperature NOx sensor based on metal-organic framework-derived Fe2O3/Co3O4 nanocomposite

In this work, Fe2O3/Co3O4 heterostructures were prepared via the ion-exchange between Co-MOFs template and Fe3+. At room temperature (25 °C), gas-sensing measurements revealed the Fe2O3/Co3O4 composites showed high response (Ra/Rg =2.54, 97.0 ppm), excellent selectivity and low detection limit (0.97 ppm) to NOx. The special oxygen temperature-programmed desorption (O2-TPD) and hydrogen temperature-programmed reduction (H2-TPR) curves indicated addition of Fe not only damaged the structure, but also increased the active sites of composites. Mott-Schottky (MS) plots testing and Electrochemical Impedance Spectroscopy (EIS) analysis were used to further quantitatively analyze the effect of Fe content on carrier density (Nd) and charge transfer resistance (Rct). The enhanced sensing mechanism of Fe2O3/Co3O4 composites were attributed to the as-formed heterojunctions that offered numerous diffusion channels and the additional modulation of resistance. By employing a facile MOFs hybrid-assisted method to design heterojunction composites, this work comprehensively analyzed the influence of heterogeneous structure on gas sensitivity, providing insights into the understanding of heterojunction gas sensor materials.

Kinetic modeling of NH3-selective catalytic reduction (SCR) over a mildly hydrothermally aged commercial Cu-SSZ-13 catalyst

Cu-SSZ-13 is often studied as a selective catalytic reduction (SCR) of NOx catalyst for diesel after-treatment systems. Mild hydrothermal aging (HTA) is commonly known to cause changes in catalyst performance. In this study, a kinetic model of SCR over a Cu-SSZ-13 catalyst that includes mild HTA and its impact on the SCR reaction was developed. The migration of Cu species during HTA, and how this change in Cu distribution affects low-temperature and high-temperature NH3 oxidation and SCR reaction mechanisms, were considered. Flow reactor test results were used for parameter estimation and verification. Different characterization techniques, including H2 temperature-programmed reduction (H2-TPR), NO + NH3-TPR, NH3 temperature-programmed desorption (NH3-TPD), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), were used to characterize and quantify catalyst site densities. The model can simulate the migration of Cu species and the NOx reduction performance changes during mild hydrothermal aging as a function of aging temperature and time.

Hydrogen production from sorption enhanced steam reforming of ethanol using bifunctional Ni and Ca-based catalysts doped with Mg and Al

This work evaluated the performance of nickel-based catalysts supported on CaO and CaO–MgO–Al2O3 in the sorption enhanced steam reforming of ethanol (SESRE) aiming the production of high purity H2. The catalysts were prepared by sol-gel method and characterized by different methods: Temperature programmed reduction (TPR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM) with chemical element mapping, N2 physisorption and CO2 capture capacity determined by thermogravimetric analysis (TGA). XRD analysis showed that the predominant phases were CaO, MgO, CaCO3, Ca(OH)2 and NiO in the calcined samples and Ni0 in the reduced and passivated samples. TPR profiles indicated that all catalysts presented a high degree of reduction (Ni/CaMgAl-68 > Ni/CaMgAl-79 > Ni/Ca), although Ni/CaMgAl-X samples presented high reduction temperatures indicating the formation of NiAl2O4. The addition of MgO and Al2O3 to CaO was very beneficial since the deactivation coefficients, calculated by the TGA data modeling, decreased by a factor of 3.8 for Ni/CaMgAl-79 and by a factor of 4.3 for Ni/CaMgAl-68 when compared to the Ni/Ca catalyst. The catalytic tests in the SESRE showed that Ni/CaMgAl-79 catalyst had the best performance since it had the longest high purity hydrogen production time. In the pre-breakthrough period, the H2 mole fractions were close to 90% for all samples during all reaction cycles. After the reaction-regeneration cycles, the average crystallite size of CaO estimated by XRD increased around 38, 6 and 35% for Ni/Ca, Ni/CaMgAl-79 and Ni/CaMgAl-68, respectively. Thus, adding a dopant to the sorbent material proved to be an effective strategy to obtain a more stable catalyst capable to produce hydrogen of high purity.

Designing a Bifunctional Pt/Cu-SSZ-13 Catalyst for Ammonia-Selective Catalytic Oxidation with Superior Selectivity

Ammonia-selective catalytic oxidation (NH3-SCO) is an effective technology to solve the problem of ammonia leakage from diesel vehicles, while ammonia oxidation catalysts (AOC) still suffer from insufficient low-temperature activity and poor nitrogen selectivity. Herein, we prepared a bifunctional Pt/Cu-SSZ-13 catalyst containing an SCO component (Pt) and a selective catalytic reduction (SCR) component (Cu). This bifunctional catalyst exhibited excellent catalytic performance during NH3 oxidation under practical conditions containing water vapor, achieving >85% N2 selectivity over the whole temperature range. Catalysts were systematically characterized by Brunauer–Emmett–Teller, X-ray diffraction, inductively coupled plasma optical emission spectrometry, X-ray photoelectron spectroscopy, H2 temperature-programmed reduction, NH3 temperature-programmed desorption, high-angle annular dark-field scanning transmission electron microscopy, and X-ray absorption fine structure analysis. The results showed that metallic Pt nanoparticles were mainly present on the exterior surface of the Pt/Cu-SSZ-13 zeolite catalyst, while dispersed Cu2+ cations were present in the interior of the zeolite. Based on operando diffuse reflectance infrared Fourier transform spectroscopy with mass spectrometry experiments, it was confirmed that on Pt/SSZ-13, over-oxidation of NH3 produced large amounts of N2O and NOx at low and high temperatures, respectively, resulting in a poor N2 selectivity. With Cu present, in contrast, the byproduct (NO) would further react with adsorbed NH3 on Cu Lewis acid sites to produce N2 by a tandem SCR reaction, thus contributing to the superior N2 selectivity of the Pt/Cu-SSZ-13 bifunctional catalyst.

Preparation of highly dispersed silicon spheres supported cobalt-based catalysts and their catalytic performance for Fischer-Tropsch synthesis

A series of silicon spheres supported cobalt catalysts were prepared by incipient wetness impregnation followed by decomposition under treatment of glow discharge plasma with different intensities. The catalysts were characterized by X-ray powder diffraction, N2 physical adsorption-desorption, H2 temperature-programmed reduction, transmission electron microscope and Fourier-Transform Infrared spectroscopy. The Fischer-Tropsch synthesis performance were tested on a fixed bed reactor. The influence of plasma treatment on cobalt dispersion, reducibility and cobalt-support interaction were analyzed and discussed. The results showed that the plasma-treated catalysts had better catalytic performance than the calcined sample. The Co/SP-P650W catalyst showed the highest reaction activity due to the proper cobalt dispersion and higher cobalt reducibility.

Recognizing zeolite topologies for Cu2+ localizations with effective activities for selective catalytic reduction of nitrogen oxide

Cu-loaded zeolites are widely investigated in selective catalytic reduction of nitrogen oxide, but effects of zeolite topologies on formed active species and the changing tendency remain unexplored. In this work, catalytic turnover frequencies (TOF) of Cu loaded ZSM-5, Beta, MOR, and SSZ-13 were first determined. The topology-localized Cu species in these zeolites were analyzed by temperature-programmed reduction of H2. Then Multiple Linear Regression distinguished TOF contributions (kj, s−1·mol−1) of the Cu species. Density functional theory calculated NH3 dehydrogenation energy of the Cu species. As a result, topologies with more node atoms showed bigger kj and lower dehydrogenation energies simultaneously. The best topology in each zeolite was 10-membered ring (ZSM-5), 6-membered ring facing a 12-membered ring (Beta), 8-membered ring (MOR), and cha cage (SSZ-13). Moreover, cha cage-localized Cu2+ exhibited the largest kj and the lowest dehydrogenation energy among all the Cu species. This work reveals topology-catalysis relationships in the zeolite, which benefits zeolite design for enhanced catalytic performances.

Comparative Study of Commercial Silica and Sol-Gel-Derived Porous Silica from Cornhusk for Low-Temperature Catalytic Methane Combustion.

The synthesis and characterization of sol-gel-derived cornhusk support for low-temperature catalytic methane combustion (LTCMC) were investigated in this study. The prepared cornhusk support was impregnated with palladium and cerium oxide (Pd/CeO2) via the classical incipient wetness method. The resulting catalyst was characterized using various techniques, including X-ray diffraction (XRD), N2 physisorption (BET), transmission electron microscopy (TEM), and hydrogen temperature-programmed reduction (H2-TPR). The catalytic performance of the Pd/CeO2/CHSiO2 catalyst was evaluated for methane combustion in the temperature range of 150-600 °C using a temperature-controlled catalytic flow reactor, and its performance was compared with a commercial catalyst. The results showed that the Pd/CeO2 dispersed on SiO2 from the cornhusk ash support (Pd/CeO2/CHSiO2) catalyst exhibited excellent catalytic activity for methane combustion, with a conversion of 50% at 394 °C compared with 593 °C for the commercial silica catalyst (Pd/CeO2/commercial). Moreover, the Pd/CeO2/CHSiO2 catalyst displayed better catalytic stability after 10 h on stream, with a 7% marginal loss in catalytic activity compared with 11% recorded for the Pd/CeO2/commercial catalyst. The N2 physisorption and H2-TPR results indicated that the cornhusk SiO2 support possessed a higher surface area and strong reducibility than the synthesized commercial catalyst, contributing to the enhanced catalytic activity of the Pd/CeO2/SiO2 catalyst. Overall, the SiO2 generated from cornhusk ash exhibited promising potential as a low-cost and environmentally friendly support for LTCMC catalysts.

Quantitative, Spectro-kinetic Analysis of Oxygen in Electron-Beam Sensitive, Multimetallic Oxide Nanostructures.

The oxygen stoichiometry of hollandite, KxMnO2-δ, nanorods has been accurately determined from a quantitative analysis of scanning-transmission electron microscopy (STEM) X-Ray Energy Dispersive Spectroscopy (XEDS) experiments carried out in chrono-spectroscopy mode. A methodology combining 3D reconstructions of high-angle annular dark field electron tomography experiments, using compressed-sensing algorithms, and quantification through the so-called ζ-factors method of XEDS spectra recorded on a high-sensitivity detector has been devised to determine the time evolution of the oxygen content of nanostructures of electron-beam sensitive oxides. Kinetic modeling of O-stoichiometry data provided K0.13MnO1.98 as overall composition for nanorods of the hollandite. The quantitative agreement, within a 1% mol error, observed with results obtained by macroscopic techniques (temperature-programmed reduction and neutron diffraction) validate the proposed methodology for the quantitative analysis, at the nanoscale, of light elements, as it is the case of oxygen, in the presence of heavy ones (K, Mn) in the highly compromised case of nanostructured materials which are prone to electron-beam reduction. Moreover, quantitative comparison of oxygen evolution data measured at macroscopic and nanoscopic levels allowed us to rationalize beam damage effects in structural terms and clarify the exact nature of the different steps involved in the reduction of these oxides with hydrogen.

Effect of CaO, Al2O3, and MgO Supports of Ni Catalysts on the Formation of Graphite-like Carbon Species during the Boudouard Reaction and Methane Cracking.

The investigation of the course of the Boudouard reaction and methane cracking was performed over nickel catalysts based on oxides of calcium, aluminum, and magnesium. The catalytic samples were synthesized by the impregnation method. The physicochemical characteristics of the catalysts were determined using atomic adsorption spectroscopy (AAS), Brunauer-Emmett-Teller method analysis (BET), temperature-programmed desorption of ammonia and carbon dioxide (NH3- and CO2-TPD), and temperature-programmed reduction (TPR). Qualitative and quantitative identification of formed carbon deposits after the processes were carried out using total organic carbon analysis (TOC), temperature-programmed oxidation (TPO), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The selected temperatures for the Boudouard reaction and methane cracking (450 and 700 °C, respectively) were found to be optimal for the successful formation of graphite-like carbon species over these catalysts. It was revealed that the activity of catalytic systems during each reaction is directly related to the number of weakly interacted nickel particles with catalyst support. Results of the given research provide insight into the mechanism of carbon deposit formation and the role of the catalyst support in this process, as well as the mechanism of the Boudouard reaction.

Synthesis and Characterization of Supported Mixed MoW Carbide Catalysts.

For mixed MoW carbide catalysts, the relationship between synthesis conditions, evolution of (mixed) phases, extent of mixing, and catalytic performance of supported Mo/W carbides remains unclear. In this study, we prepared a series of carbon nanofiber-supported mixed Mo/W-carbide catalysts with varying Mo and W compositions using either temperature-programmed reduction (TPR) or carbothermal reduction (CR). Regardless of the synthesis method, all bimetallic catalysts (Mo:W bulk ratios of 1:3, 1:1, and 3:1) were mixed at the nanoscale, although the Mo/W ratio in individual nanoparticles varied from the expected bulk values. Moreover, the crystal structures of the produced phases and nanoparticle sizes differed depending on the synthesis method. When using the TPR method, a cubic carbide (MeC1-x ) phase with 3-4 nm nanoparticles was obtained, while a hexagonal phase (Me2C) with 4-5 nm nanoparticles was found when using the CR method. The TPR-synthesized carbides exhibited higher activity for the hydrodeoxygenation of fatty acids, tentatively attributed to a combination of crystal structure and particle size.

ZnO-ZnFe2O4 Catalyst for Hydrogen Production from Methanol Steam Reforming

In this study, ZnFe2O4 and ZnO-ZnFe2O4 catalysts were prepared using the glycine–nitrate process (GNP). The prepared ZnFe2O4 and ZnO-ZnFe2O4 catalyst powders were characterized using a scanning electron microscope, transmission electron microscope, XRD diffraction studies, and selected area diffraction pattern studies. In addition, the specific surface area was measured using a Brunauer–Emmett–Teller specific surface area analysis. The hydrogen reduction in different temperature ranges was analyzed using the H2 temperature-programmed reduction technique. The specific surface area of the ZnFe2O4 was 5.66 m2/g, and the specific surface area of the ZnO-ZnFe2O4 was 8.20 m2/g at a G/N ratio of 1.5 and at a G/N ratio of 1.7, respectively. The specific surface area of the ZnFe2O4 was 6.03 m2/g, and the specific surface area of the ZnO-ZnFe2O4 was 11.67 m2/g. The ZnFe2O4 and ZnO-ZnFe2O4 were found to have the best catalytic effect at 500 °C. In particular, the highest H2 generation rate of the ZnO-ZnFe2O4 (GN = 1.7) at 500 °C was 7745 mL STP min−1 g-cat−1. Moreover, the ZnO-ZnFe2 O4 catalyst demonstrated good H2 selectivity and stability during the process of steam reforming methanol. Therefore, the ZnO-ZnFe2O4 catalyst powder exhibited high catalytic activity due to the good dispersibility of the ZnO, which increased the specific surface area of the catalyst. In the future, the catalyst can be applied to the steam reforming of methanol for industrial purposes.

Effect of B-Site Element on the Structure and Catalytic Performance for Toluene of the 3DOM CeBO3 Catalyst.

A series of 3DOM cerium-based perovskite catalysts with different B-site elements were prepared by the colloidal crystal template method and excess impregnation method with Cr, Ni, and Mn as the B-site elements. The physical and chemical properties of the catalysts were investigated by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H2-TPR), and oxygen temperature-programmed desorption (O2-TPD) characterization techniques. The results showed that the catalyst with Mn as the B-site element had a high-quality macropore structure (pore size 200-250 nm), large specific surface area (45.26 m2/g), and abundant surface adsorbed oxygen content (Oads/Olatt = 0.46). The addition of manganese enhanced the low-temperature reducibility, and the main reduction peak was below 400 °C. The O2-TPD results showed that 3DOM CeMnO3 expressed the highest adsorption oxygen content. The 3DOM CeMnO3 possessed the best catalytic performance with T50% = 102 °C and T90% = 203 °C during the catalytic oxidation of toluene. Intermediate product study hinted that toluene was first converted into benzoic acid and benzaldehyde and then further degraded into small molecules. The catalyst with the best activity also exhibited good stability, and toluene degradation rate remained above 85% at 200°C for more than 20 h of continuous experiments.

LaMnxCo1‐xO3 (x=0, 0.25) Perovskites: Novel Nano Catalysts for Removal of Thiophene compounds in Fuels by Catalytic and Ultrasound‐assisted Oxidative Desulfurization

AbstractLaMnxCo1‐xO3 (x=0, 0.25) perovskites were developed as novel nanocatalysts for the desulfurization of thiophenes compounds by catalytic oxidative desulfurization (CODS) and ultrasound‐assisted oxidative desulfurization (UAOD). The perovskites were synthesized by the sol‐gel auto‐combustion method and characterized by X‐ray diffraction (XRD), temperature programmed reduction (TPR), Scanning electron microscopy (SEM) and BET surface area. The experiments were designed by the Box‐Behnken method of response surface methodology. The catalytic experiments were designed by response surface methodology (RSM). LaMn0.25Co0.75O3 despite having a lower surface area rather than LaCoO3 exhibited superior activity due to easy reducibility and high surface electron density approved by TPR. Pareto analysis indicated that the DBT concentration had the most effect on the CODS process. Ultrasound waves enhanced the activity of the catalysts via the formation of hot spots as an accelerating and de‐agglomerating agent in the UAOD process, leading the LaMn0.25Co0.75O3 to be reusable at least for 5 cycles. A mechanism for DBT oxidation was proposed by the formation of DBT sulfone. Due to steric hindrance and the electron density of the sulfur atoms in thiophene derivatives, the following order resulted in their desulfurization rate: DBT>4‐MDBT>BT. The study indicated that perovskites could be novel and promising nanocatalysts for the desulfurization of fuels.

Glycerol valorization using Colombian olivine as a catalyst

The biodiesel industry currently generates large amounts of crude glycerol that are not marketed, thus accumulating, and causing environmental problems. This study evaluates the catalytic potential of Colombian olivine, using glycerol steam reforming to assess valorization alternatives for this by-product. The analyzed olivine was thermally treated at 1200 °C and reduced at 900 °C, then producing nanometer-sized Fe compounds. The catalyst was characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area, scanning electron microscopy (SEM), temperature-programmed reduction (TPR), and transmission electron microscopy (TEM). Calcined olivine increased glycerol conversion at 600 °C from 43% (without catalyst) to 96% with the formation of liquid-phase products such as aldehydes and carboxylic acids. In addition, syngas with H2/CO ratios of 1.1 and 1.5 was generated at reaction temperatures of 700 °C and 800 °C, respectively, with low CH4 content. Finally, it was established that olivine from Medellín, under the conditions used for glycerol steam reforming, is a viable and interesting alternative to valorize glycerol into gas- or liquid-phase products.

Hydrogen production from waste-derived synthesis gas over Ni(x)Fe(3-x)-CeO2 catalyst: optimization of Ni/Fe ratio

In this study, the effect of the Ni/Fe molar ratio on the Ni(x)Fe(3-x)-CeO2 catalyst was investigated for the high-temperature water-gas shift reaction, which produces hydrogen from waste-derived synthesis gas. The catalysts were synthesized via a co-precipitation method, using different Ni/Fe molar ratios (0.5:2.5, 1.0:2.0, 1.5:1.5, 2.0:1.0, and 2.5:0.5). The physicochemical properties of these catalysts were analyzed by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction using hydrogen (H2-TPR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and H2-O2 pulse analyses to determine their reaction performance. The Ni1.0Fe2.0-CeO2 catalyst exhibited the highest activity (Xco = 88%, T = 500 °C) without any side reactions at a high gas hourly space velocity of 41,823 mL·g−1 h−1, compared to the other catalysts tested, owing to its high oxygen vacancies and oxygen storage capacity (OSC). In addition, when the Ni/Fe molar ratio was higher than 1, a side reaction (methanation) occurred. Therefore, it was concluded that the Ni1.0Fe2.0-CeO2 catalyst is optimal for hydrogen production via the high-temperature water-gas shift reaction from waste-derived synthesis gas.

The study of CO2 reforming of methane over Ce/Sm-promoted NiCaAl catalysts

In this work, we synthesized Ce and Sm-promoted NiCaAl layered catalysts via co-precipitation and freeze-drying strategies for alleviating some problems, such as coke deposition and agglomeration of active sites, in dry reforming of methane. Employing such promoters leads to rising O2 vacancies on the catalyst's surface, resulting from adsorbing CO2 gas under the reaction. X-ray diffraction (XRD) analysis confirmed the formation of a hydrotalcite network. High-resolution transmission electron microscopy (HR-TEM) and field emission scanning electron microscopy (FE-SEM) images also indicated a wealth of nanocatalysts, well distributed on the surface and within a porous scaffold structure. The temperature-programmed reduction (H2-TPR) proved that cerium (H2 consumption = 1.2 mmol.g-1) could weaken the interactions between nickel and Ca/Al, leading to better reducibility than samarium (H2 consumption = 1.35 mmol.g-1). Moreover, the temperature-programmed deposition (CO2-TPD) showed the Ce-promoted catalyst possesses more basic sites (0.41 mmol.g-1) on its surface than the Sm-enhanced one (0.25 mmol.g-1). Consequently, the Ce-enhanced catalyst with a smaller crystallite size (8.9 nm), higher dispersion of Ni (10.8%), better reducibility, and more basic sites, which caused the highest methane conversion (82%), and H2/CO ratio (0.9) at 700 °C without any coke deposition after 5 h of time on stream.

Hydrogen Production from Biogas: Development of an Efficient Nickel Catalyst by the Exsolution Approach

Hydrogen production from biogas over alumina-supported Ce1−xNixO2−x catalysts was studied in a temperature range of 600–850 °C with an initial gas composition of CH4/CO2/H2O of 1/0.8/0.4. To achieve a high and stable hydrogen yield, highly dispersed Ni catalysts were prepared through the exsolution approach. A solid solution of Ce1−xNixO2−x was firstly formed on the surface of Al2O3 and then activated in H2/Ar at 800 °C. The genesis and properties of the Ce1−xNixO2−x/Al2O3 catalysts were established using X-ray fluorescence analysis, thermal analysis, N2 adsorption, ex situ and in situ X-ray diffraction, Raman spectroscopy, electron microscopy, EDX analysis, and temperature-programmed hydrogen reduction. The performance of Ce1−xNixO2−x/Al2O3 catalysts in biogas conversion was tuned by regulation of the dispersion and reducibility of the active component through variation of content (5–20 wt.%) and composition (x = 0.2, 0.5, 0.8) of Ce1−xNixO2−x as well as the mode of its loading (co-impregnation (CI), citrate sol–gel method (SG)). For the 20 wt.% Ce1−xNixO2−x/Al2O3 catalyst, the rate of the coke formation decreased by a factor of 10 as x increased from 0.2 to 0.8. The optimal catalyst composition (20 wt.% Ce0.2Ni0.8O1.8/80 wt.% Al2O3) and preparation mode (citrate sol–gel method) were determined. At 850 °C, the 20 wt.% Ce0.2Ni0.8O1.8/Al2O3-SG catalyst provides 100% hydrogen yield at full CH4 conversion and 85% CO2 utilization.

Nanocrystalline Sulfided NiMoW Catalyst Supported on Mesoporous Aluminas for the Hydrodesulfurization of 4,6-Dimethyldibenzothiophene

Tri-metallic NiMoW catalysts prepared by impregnating mesoporous aluminas (pore sizes of ~9 nm and surface areas of ~225 m2/g) obtained by sol-gel (NiMoW/Al) and hydrothermal (NiMoW/AlHYDT) processes were investigated in the hydrodesulfurization (HDS) of thiophene and 4,6-dimethyldibenzothiophene (4,6-DMDBT) at H2 pressures of 1 MPa and 5.0 MPa, respectively. The supports and catalysts were characterized by N2 physisorption, X-ray diffraction (XRD), scanning electron microscopy (SEM), ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), temperature-programmed reduction (TPR), X-ray photoelectron spectroscopy (XPS), and high-resolution transmission electron microscopy (HRTEM). The NiMoW/AlHYDT catalyst, which was the most active in both test HDS reactions, was characterized by a pore size of 7.5 nm, whereas the pore size of the catalyst on sol-gel alumina (NiMoW/Al) was only 4.8 nm. Moreover, the NiMoW/AlHYDT catalyst exhibited reduction peaks shifted to a lower temperature during TPR, indicating weaker metal support interactions, a higher degree of Mo (79%) and W (48%) sulfidation, and an optimal layer slab length distribution of Mo(W)S2 nanocrystals preferentially between 2–4 nm with an average layer stacking of 1.7 compared to the NiMoW/Al counterpart.