Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.     

Hyperpolarized 129Xe NMR and N2 sorption cross-investigations of the crystallization of Al-SBA-15 amorphous walls into ZSM-5 type materials

The present work deals with the study of the parameters which govern the partial conversion of the amorphous walls of Al-SBA-15 supports into ZSM-5 type deposits under alkaline aqueous conditions. The influence of the mode of insertion of aluminium into Al-SBA-15 as well as of the quantities of ammonium fluoride and ZSM-5 template (TPABr) has been investigated. XRD and nitrogen sorption data indicate that the mesopore network is very fragile under the conditions required for the crystallization of ZSM-5. A compromise was found by using a TPABr/Al molar ratio lower than 1, thus affording materials containing both mesopores and zeolite-type micropores. The combined use of hyperpolarized (HP) ¹²⁹Xe NMR and α-plot studies gave evidence for the ZSM-5 nature of the micropores as well as some indications in favour of the interconnection of the different pore networks. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Hydrothermal synthesis and characterization of dioctahedral smectites: A montmorillonites series

The aim of this study is to synthesize and finely characterize montmorillonite samples, dioctahedral smectites without tetrahedral charges (structural formulae Na_x(Al_(2 − x)Mg_x)Si₄O₁₀(OH)₂), to allow their use as reference samples in clay science. The montmorillonites synthesis under hydrothermal conditions at different pressures and with various layer charge deficit has been attempted. The temperature was fixed at 320 °C, the pressure parameter values were 20 MPa, 80 MPa, 120 MPa and 200 MPa. The Mg content varied from 0.25 to 0.60 per half unit cell. The reaction products have been characterized with multi-technique analyses (ICP-AES, EMP, CEC, XRD, FTIR, NMR and TGA).Montmorillonite phase was only produced at 120 and 200 MPa.At 20 and 80 MPa, the results suggest that a 0.33 and 0.16-tetrahedral charge deficit exist in the formed samples. Moreover, the octahedral occupancies are higher than two (2.15 and 2.07 at 20 and 80 MPa respectively). In these experimental conditions, the synthetic smectites are mixtures between montmorillonite, beidellite and saponite.At 120 MPa and for a Mg content of 0.25 or higher than 0.33, the synthetic products were also mixtures of smectites. Tetrahedral charge deficits of 0.11, 0.11 and 0.15 were found for Mg contents of 0.25, 0.50 and 0.60 respectively. The octahedral occupancy was also higher than 2.00.A montmorillonite phase with only octahedral charges and an octahedral occupancy near 2.00 was synthesized for a Mg content of 0.33 and at pressures equal to or higher than 120 MPa. This low charge reference smectite shows a very low amount of accessory minerals and an octahedral charge deficit only created by the presence of magnesium in the structure. This montmorillonite can be compared structurally to the most studied natural one: the montmorillonite SWy-2 from Wyoming.     

Observation of [Al(OH) n (H2O)6-n ] n (MoO4) in hydrotreating catalyst precursors by solid-state27 Al NMR

A previously unobserved octahedral²⁷Al MAS NMR resonance has been detected in rehydrated calcined Mo/Al₂O₃ hydrotreating catalyst precursors. This resonance is attributed to the presence of hydrated forms of aluminum molybdate such as [Al(OH) _n (H₂O)_6-n ] _n (MoO₄) (n = 1 or 2). The cross-polarization relaxation parameters, obtained from variable contact time experiments, yielded information on the relative sizes of the [Al(OH) _n (H₂O)_6-n ] _n (MoO₄) domains in the catalysts with different molybdenum loadings. Analysis of the²⁷A1 MAS NMR spectra of P-Mo(8)/Al₂O₃ and P-Mo(12)/Al₂O₃ (wt%P = 0.0–12.0) shows that a function of the phosphate in the 12 wt% Mo catalyst is to prevent the re-hydration of the molybdate phases on the calcined catalysts.     

Infrared Study of Benzene Hydrogenation on Pt/SiO2 Catalyst by Co-adsorption of CO and Benzene

FT-IR spectra of the co-adsorption of benzene and CO have been performed to identify the preferred adsorption sites of hydrogen and benzene on a Pt/SiO₂ catalyst for hydrogenation of benzene. Results of CO adsorbed on atop sites on Pt/SiO₂ includes: an α peak at 2091 cm⁻¹, a β peak at 2080 cm⁻¹ and a γ peak at 2067 cm⁻¹ indicating three kinds of adsorption sites for dissociative hydrogen on Pt/SiO₂. The site of lowest CO stretching frequency offers stronger adsorbates–metal interaction for benzene and hydrogen. Hydrogen binding on the site of lowest CO stretching frequency before benzene adsorption significantly enhances the reaction rate of benzene hydrogenation.     

Surface-enhanced IR spectroscopy investigation on the electro-oxidation of CO adlayer at a polycrystalline Pt film electrode in Cl-containing HClO4

The electro-oxidation of CO adlayer on Pt electrode in Cl⁻-containing 0.1 M HClO₄ has been investigated with in situ attenuated-total-reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS). Two potentials were selected for predosing CO on the Pt electrode: one is in the H-UPD region, i.e., 0.1 V (vs. RHE) and the other is in the double-layer region, i.e., 0.45 V (vs. RHE). The broadening of the prewave and the main peak for the CO oxidation is observed, in addition to the positively shifted oxidation potentials. The spectroelectrochemical data suggest the specific adsorption of Cl⁻ starts at a potential as negative as 0.1 V which may compete with the adsorption of OH at CO-unoccupied sites (including but not limited to defect sites) and/or hinder the diffusion of CO to OH adsorption sites on Pt electrode, slowing down the CO oxidation. This competitive Cl⁻ adsorption at lower potentials disrupts the interfacial free H₂O structure on the top of CO adlayer, signaled by a reduced OH stretching band intensity.     

Characterisation by TPR, XRD and NOx Storage Capacity Measurements of the Ageing by Thermal Treatment and SO2 Poisoning of a Pt/Ba/Al NOx-Trap Model Catalyst

The deactivation of a Pt/Ba/Al₂O₃ NO _x -trap model catalyst submitted to SO₂ treatment and/or thermal ageing at 800 °C was studied by H₂ temperature programmed reduction (TPR), X-ray diffraction (XRD) and NO _x storage capacity measurements.The X-ray diffractogram of the fresh sample exhibits peaks characteristic for barium carbonate. Thermal ageing leads to the decomposition of barium carbonate and to the formation of BaAl₂O₄. The TPR profile of the sulphated sample shows the presence of (i) surface aluminium sulphates, (ii) surface barium sulphates, (iii) bulk barium sulphates. The exposure to SO₂ after ageing leads to a small decrease of the surface barium-based sulphates, expected mainly as aluminate barium sulphates. This evolution can be attributed to a sintering of the storage material. TPR experiments also show that thermal treatment at 800 °C after the exposure to SO₂ involves the decomposition of aluminium surface sulphates to give mainly bulk barium sulphates, also pointed out by XRD. Thus, the thermal treatment at 800 °C leads to a stabilization of the sulphates.These results are in accordance with the NO _x storage capacity measurements. On non-sulphated catalysts, the treatment at 800 °C induces to a decrease of the NO _x storage capacity, showing that barium aluminate presents a lower NO _x storage capacity than barium carbonate. Sulphation strongly decreases the NO _x storage capacity of catalysts, whatever the initial thermal treatment, showing that barium sulphates inhibit the NO₂ adsorption. Moreover, the platinum activity for the NO to NO₂ oxidation is lowered by thermal treatments.     

Changes upon heating of the distribution of Al,P and Si atoms in the SAPO-37 molecular sieve

A drastic change in the environment of Si atoms in SAPO-37 after heating at 1173 K is seen in the²⁹Si MAS NMR spectrum. This suggests a modification of the location of Si, Al and P atoms. Three main phases would coexist in large amounts in the faujasite structure, the SAPO-37 originating phase, pure SiO₄ islands and an aluminosilicate phase comparable to Si-Al faujasite.     

Effect of the preparation method on the surface coverage of Mo/Al2O3 catalysts

Two series of Mo/Al₂O₃ catalysts were prepared by equilibrium adsorption and incipient wetness impregnation methods. The effect of preparation method on the surface coverages of the calcined catalysts was investigated by the combined use of CO₂ chemisorption, low temperature CO adsorption and ion scattering spectroscopy (ISS). For a given Mo loading, the CO₂ and CO adsorption results showed little difference between the two preparation methods. As previously noted, the CO₂ chemisorption method overestimated the Mo surface coverage. In contrast to the adsorption methods, the ISS technique gave different Mo surface coverage values for a given Mo content of the two series of catalysts. This apparent discrepancy was attributed to different repartition of the Mo phase between the internal and external surfaces which can only be detected by ISS. This interpretation is supported by the observed agreement between the coverage values measured from ISS and low temperature CO adsorption for presumably uniform catalysts obtained by the equilibrium adsorption method.     

Ship-in-Bottle synthesis of Pt9-Pt15 carbonyl clusters inside NaY and NaX zeolites,in-situ FTIR and EXAFS characterization and the catalytic behaviors in13CO exchange reaction and NO reduction by CO

[Pt₉(CO)₁₈]^2–/NaY (orange-brown, 2056 and 1798 cm^–1), [Pt₁₂(CO)₂₄]^2–/NaY (dark-green, 2080 and 1824 cm^–1 and [Pt₁₅(CO)₃₀]^2–/NaX (yellow-green, 2100 and 1865 cm^–1) were stoichiometrically synthesized by the reductive carbonylation of [Pt(NH₃)₄]²⁺/NaY, Pt²⁺/NaY and Pt²⁺/NaX, respectively. The IR bands characteristic of their linear carbonyls shift to higher frequencies whereas the bridging CO bands to lower frequencies, compared with those on the external zeolites and in solution. In-situ FTIR studies suggested that the subcarbonyl species such as PtO(CO) and Pt₃(CO)₃(₂ –CO)₃ are formed as the proposed intermediates towards [Pt₁₂(CO)₂₄]^2–/NaY in the reductive carbonylation of Pt²⁺/NaY.¹³CO exchange reaction preceded with the different intrazeolite Pt carbonyl species in the following order of activity at 298–343 K: Pt₃(CO)₃(₂ –CO)₃/NaY PtO(CO)/NaY>[Pt₉(CO)₁₈]^2–/NaY >[Pt₁₂(CO)₂₄]^2–/NaY. Pt-L₃-edge EXAFS measurment for these synthesized samples demonstrated that they are consistent with the Pt carbonyl clusters having trigonal prismatic Pt₉ and Pt₁₂ frameworks infered to a series of the Chini complexes such as [NEt₄]₂[Pt₃(CO)₆] _n ( _n = 3–5). The intrazeolite Pt₉ and Pt₁₂ carbonyl clusters exhibited higher cataytic activity in NO reduction by CO towards N₂ and N₂O at 473 K, compared with those on the conventional Pt/Al₂O₃ catalysts. The mechanism of intrazeolite Pt₉-Pt₁₅ carbonyl cluster formation are discussed in terms of the intrazeolite basicity and acidity.On leave from National Laboratory for Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 129 Street, China.     

Determination of Cis- and Trans-18:1 fatty acid isomers in hydrogenated vegetable oils by high-resolution carbon nuclear magnetic resonance

Carbon nuclear magnetic resonance (¹³C NMR) methods for determining the composition of cis-/trans- and positional isomers in hydrogenated vegetable oils were developed to reduce analytical time. By selecting appropriate olefinic carbon peaks and by measuring individual peak areas subsequent to the identification of isomeric peaks on the NMR spectrum, compositional results of the isomers coincided well with those obtained by conventional gas chromatography (GC). Therefore, it is highly beneficial to choose the ¹³C NMR method when analysis time is limited. Though the proposed ¹³C NMR method is promising, further development is needed. For the time being, combination with the traditional GC method is still encouraged for precise compositional analysis of cis-/trans- and positional isomers.     

An NMR Comparison of the Whole Lignin from Milled Wood,MWL, and REL Dissolved by the DMSO/NMI Procedure

Abstract

Lignins isolated from pine milled wood, milled wood lignin (MWL), and residual enzyme lignin (REL) were compared using modified thioacidolysis, modified DFRC, gel permeation chromatography (GPC), two‐dimensional Heteronuclear Multiple Quantum Coherence (HMQC) NMR, and quantitative ¹³C NMR. Dissolution of the lignin for solution‐state NMR was accomplished by utilizing the recently reported DMSO/N‐methylimidazole/acetic anhydride solvent system. Contrary to previous reports, comparison of the lignin preparations by thioacidolysis indicated that REL was more structurally similar to the lignin in the milled wood and Wiley wood meal than MWL. Total monomer yields indicated that the MWL was lower in β‐aryl ether content than the other preparations, and this was verified by quantitative ¹³C NMR. NMR analysis indicated that the inter‐unit linkages present in all the lignin preparations are consistent with the present knowledge about lignin biosynthesis. The contribution of minor end group structures in the MWL are further decreased in the milled wood, indicating that they are preferentially isolated as low molecular weight material, possibly generated during the milling process. All other structural moieties were similar in all preparations. GPC data indicated that the milled wood and REL both contain a portion of lignin with a molecular weight of 55,000 g/mol. Data indicate that the inefficiency of the DFRC method may be related to molecular mobility or accessibility in higher molecular weight portions of the lignin polymer.     

The Sites of Molecular and Dissociative Hydrogen Adsorption in High-Silica Zeolites Modified with Zinc Ions. III DRIFT Study of H2 Adsorption by the Zeolites with Different Zinc Content and Si/Al Ratios in the Framework

study of dihydrogen adsorbed at 77K by the zinc-modified hydrogen forms of mordenite and ZSM-5 zeolites with the different Si/Al ratios in the framework indicated the existence of several adsorption sites connected with the modifying zinc ions. The fraction of the sites of the strongest perturbation of adsorbed molecular hydrogen with the H–H stretching frequency of ca. 3930–3950 cm^-1 is the highest at the highest Si/Al ratios of 41 or 80. These sites dissociatively adsorb hydrogen at moderately elevated temperatures. Adsorption of hydrogen with the higher H–H stretching frequency of about 3970–4000 cm^-1 predominates at the lower Si/Al ratios. It does not result in the dissociation of adsorbed molecules. It was concluded that the most active sites are most probably connected with the zinc ions, which compensate two distantly separated negatively charged [AlO₄]^- tetrahedra localized in the adjacent five- or six-membered rings on the walls of the large channels of the pentasil's framework. The sites of the weaker perturbation of adsorbed hydrogen are most probably connected with Zn⁺² ions at the conventional exchangeable cationic positions with two aluminum atoms in the same five- or six-membered ring.     

Influence of the Type of Reducing Agent (H2, CO, C3H6 and C3H8) on the Reduction of Stored NOX in a Pt/BaO/Al2O3 Model Catalyst

In this investigation, a comparative study for a NO _X storage catalytic system was performed focusing on the parameters that affect the reduction by using different reductants (H₂, CO, C₃H₆ and C₃H₈) and different temperatures (350, 250 and 150 °C), for a Pt/BaO/Al₂O₃ catalyst. Transient experiments show that H₂ and CO are highly efficient reductants compared to C₃H₆ which is somewhat less efficient. H₂ shows a significant reduction effect at relatively low temperature (150 °C) but with a low storage capacity. We find that C₃H₈does not show any NO _X reduction ability for NO _X stored in Pt/BaO/Al₂O₃ at any of the temperatures. The formation of ammonia and nitrous oxide is also discussed.     

NO● Represses the Oxygenation of Arachidonoyl PE by 15LOX/PEBP1: Mechanism and Role in Ferroptosis

We recently discovered an anti-ferroptotic mechanism inherent to M1 macrophages whereby high levels of NO^● suppressed ferroptosis via inhibition of hydroperoxy-eicosatetraenoyl-phosphatidylethanolamine (HpETE-PE) production by 15-lipoxygenase (15LOX) complexed with PE-binding protein 1 (PEBP1). However, the mechanism of NO^● interference with 15LOX/PEBP1 activity remained unclear. Here, we use a biochemical model of recombinant 15LOX-2 complexed with PEBP1, LC-MS redox lipidomics, and structure-based modeling and simulations to uncover the mechanism through which NO^● suppresses ETE-PE oxidation. Our study reveals that O₂ and NO^● use the same entry pores and channels connecting to 15LOX-2 catalytic site, resulting in a competition for the catalytic site. We identified residues that direct O₂ and NO^● to the catalytic site, as well as those stabilizing the esterified ETE-PE phospholipid tail. The functional significance of these residues is supported by in silico saturation mutagenesis. We detected nitrosylated PE species in a biochemical system consisting of 15LOX-2/PEBP1 and NO^● donor and in RAW264.7 M2 macrophages treated with ferroptosis-inducer RSL3 in the presence of NO^●, in further support of the ability of NO^● to diffuse to, and react at, the 15LOX-2 catalytic site. The results provide first insights into the molecular mechanism of repression of the ferroptotic Hp-ETE-PE production by NO^●.     

NO Reduction with CO in the Presence of O2 over Cu/Al2O3 (3) – Structural Analysis of Active Species by Means of XAFS and UV/VIS/NIR Spectroscopy

The local structure around Cu supported on Al₂O₃ was determined by UV/VIS/NIR and XAFS spectroscopic techniques. The relationship between catalytic performance for NO–CO–O₂ reaction and the state of supported Cu species is discussed. A new method for estimating the fraction of aggregated to isolated Cu species is proposed.     

Influence of the Oxidation State of Rhodium in Three-Way Catalysts on Their Catalytic Performances: An in situ FTIR and Catalytic Study

Simultaneous IR spectroscopic and catalytic measurements have been performed in order to investigate the nature of adsorbed species involved in the formation of N₂O on Rh/Al₂O₃ in the course of the CO + NO reaction. Only nitrosyl species have been isolated that could be involved in the formation of N₂ and N₂O in accordance with previous kinetic investigations [Granger et al. J. Catal. 175(1998) 194]. Sequential and simultaneous NO and CO exposures lead to the observation of different nitrosyl species that could act as intermediates in the formation of N₂ and N₂O. Correlations between the appearance/disappearance of Rh(NO) ⁺ species and an extra formation of N₂O have been established.     

Corrosion inhibitors : Part II: Quantum chemical studies on the corrosion inhibitions of steel in acidic medium by some triazole, oxadiazole and thiadiazole derivatives

The corrosion inhibition efficiencies of some triazole, oxadiazole and thiadiazole derivatives for steel in presence of acidic medium have been studied by using AM1, PM3, MINDO/3 and MNDO semi-empirical SCF molecular orbital methods. Geometric structures, total negative charge on the molecule (TNC), highest occupied molecular energy level (E_HOMO), lowest unoccupied molecular energy level (E_LUMO), core-core repulsion (CCR), dipole moment (μ) and linear solvation energy terms, molecular volume (V_i) and dipolar-polarization (π^*), were correlated to corrosion inhibition efficiency. Four equations were proposed to calculate corrosion inhibition efficiency. The agreement with the experimental data was found to be satisfactory; the standard deviations between the calculated and experimental results ranged between ±0.03 and ±4.18. The inhibition efficiency was closely related to orbital energies (E_HOMO and E_LUMO) and μ. The correlation between quantum parameters and experimental inhibition efficiency has been validated by single point calculations for the semi-empirical AM1 structures using B3LYP/6-31G^** as a higher level of theory. The proposed equations were applied to predict the corrosion inhibition efficiency of some related structures to select molecules of possible activity from a presumable library of compounds.