ESR study of species formed by reaction of O,adsorbed on magnesium oxide with O2, CO and ethylene

When N₂O reacts with irradiated MgO, an ESR signal due to O⁻ is found. This species is highly reactive and when molecular oxygen, carbon monoxide and ethylene are adsorbed at 77°K on O⁻, new signals are found due to the formation of O₃⁻, CO₂⁻ and C₂H₄O⁻ radicals.     

Formation of superoxide ions upon oxygen adsorption on magnesium-doped magnesium oxide: An EPR investigation

Oxygen adsorption on the surface of MgO, previously submitted to magnesium metal vapour, gives rise to the formation of at least five distinct species of adsorbed superoxide (O₂⁻) characterized by different g_zz values. Besides species previously observed on MgO, where O₂⁻ is generated by other methods, two new species are observed, having g_zz = 2.091 and g_zz = 2.064 respectively. The latter species is tightly bound to the surface and is assigned to O₂⁻ adsorbed on top of an array of five Mg²⁺ ions exposed because of the presence of an anion vacancy. The former is assigned to O₂⁻ weakly adsorbed on top of a five-coordinated Mg²⁺ ion at the (100) planar face of the oxide. This species differs from the other species present at the surface in that it is mobile and, as the temperature is raised from 77 to 298 K, exhibits rotation around the axis perpendicular to the surface. Spectra obtained by employing ¹⁷O-enriched O₂ indicate that both superoxide species are symmetrically adsorbed on the surface.     

Non equivalency of oxygen nuclei in 17O−2 adsorbed on oxides

Oxygen enriched with ¹⁷O has been used to investigate the nature of oxygen species adsorbed on oxides. The variations in the hyperfine constants of O^?₂, small (<3%) for MgO and ZnO, are due to different adsorption sites. They become large (>15%) for supported molybdenum due to the different spin densities on the two nuclei showing that O^?₂ probably adsorbed at an angle to the surface.     

EPR studies of isotopic exchange involving adsorbed oxygen species on MgO

In the EPR spectra of ¹⁷O₂^? adsorbed on MgO, the hyperfine lines due to ¹⁷O(I = $\text{5}\text{2}$) have been used to monitor the isotopic exchange with gas phase oxygen. The predicted behaviour of the different possible mechanisms (place exchange and/or isotopic exchange) is compared with the experimental results which show that, on MgO at room temperature, isotopic exchange occurs via an intermediate species which is tentatively identified as O₄^?.     

Study on carbon dioxide reduction with water over metal oxide photocatalysts

Various metal oxides with 0.1 wt% Ag loaded as a cocatalyst were prepared by an impregnation method and examined their photocatalytic activity for CO₂ reduction with water. Among all the prepared Ag-loaded metal oxides, Ga₂O₃, ZrO₂, Y₂O₃, MgO, and La₂O₃ showed activities for CO and H₂ productions under ultraviolet light irradiation. Thus, metal oxides involving metal cations with closed shell electronic structures such as d⁰, d¹⁰, and s⁰ had the potential for CO₂ reduction with water. In situ Fourier transform infrared measurement revealed that the photocatalytic activity and selectivity for CO production are controlled by the amount and chemical states of CO₂ adsorbed on the catalyst surface and by the surface basicity, as summarized as follows: Ag/ZrO₂ enhanced H₂ production rather than CO production due to very little CO₂ adsorption. Ag/Ga₂O₃ exhibited the highest activity for CO production, because adsorbed monodentate bicarbonate was effectively converted to bidentate formate being the reaction intermediates for CO production owing to its weak surface basicity. Ag/La₂O₃, Ag/Y₂O₃, and Ag/MgO having both weak and strong basic sites adsorbed larger amount of carbonate species including their ions and suppressed H₂ production. However, the adsorbed carbonate species were hardly converted to the bidentate formate.     

The oxidation of carbon monoxide on a catalyst with a spinel structure containing Mg ferrite

The oxidation of carbon monoxide on xMgO · yFe₂O₃ catalysts was studied over the temperature range 440–660 K. The catalysts contained 5, 40, and 75 at % Fe and the spinel MgFe₂O₄ and MgO phases. Complete CO conversion on compact and deposited (on γ-Al₂O₃) catalysts containing 75 at. % Fe occurred at 650–660 K. The kinetics of interaction of CO with adsorbed oxygen was studied on catalysts with 5 and 40 at % Fe below and above the Curie point (T _c = 593 ± 10 K). The differences in the reaction orders with respect to gaseous CO and adsorbed oxygen below and above T _c were explained as follows. In the ferromagnetic state of the active MgFe₂O₄ phase, oxidation involved adsorbed oxygen localized at oxygen vacancies in the environment of Fe³⁺ ions, whereas, in the paramagnetic state, superexchange interactions were absent in spinel structure fragments.     

The state of metals in the Pt/Al2O3 and (Pt-Cu)/Al2O3 catalysts as indicated by IR spectroscopy with isotope dilution of 12C16O with 13C18O molecules

Adsorption of ¹³C¹⁸O+¹²C¹⁶O mixtures on the Pt(2.9%)/γ-Al₂O₃, (Pt(2.6%)+Cu(2.7%))/γ-Al₂O₃, and (Pt(2.6%)+Cu(5.1%))/γ-Al₂O₃ catalysts was studied by FTIR spectroscopy. On the metallic Pt surface at coverages close to saturation, CO is adsorbed both strongly and weakly to form linear species for which the vibrational frequencies of the isolated ¹³C¹⁸O molecules adsorbed on Pt are ∼1940 and ∼1970 cm⁻¹, respectively. The redistribution of intensities of the high-and low-frequency absorption bands in the spectra of adsorbed ¹³C¹⁸O indicates that these linear forms are present on the adjacent metal sites. The weak adsorption is responsible for the fast isotope exchange between the gaseous CO and CO molecules adsorbed on metal. The Pt-Cu alloys, in which the electronic state of the surface Pt atoms characteristic of monometallic Pt remains unchanged, are formed on the surface of the reduced Pt-Cu bimetallic catalysts. The decrease in the vibrational frequencies of the isolated C=O bonds in the isolated Pt-CO complexes suggests that the CO molecules adsorbed on the Cu atoms affect the electronic properties of Pt. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 831–836, May, 2007.     

Interaction of chromocene with MgO and reactivity of the adsorbed species towards CO: An IR study

The interaction of chromocene with partially and totally dehydroxylated MgO and the reactivity of the adsorbed species towards CO have been studied by IR spectroscopy. Cp₂Cr is weakly adsorbed on residual surface MgOH groups, forming hydrogen bonded species and, on the extended (100) faces, forming clustered (Cp₂Cr)_n species. A stronger interaction is observed with the highly unsaturated ions located on the edges and corners of the MgO microcrystals. Upon dosage of CO at room temperature, Cp₂CrCO complexes are formed which are stabilized by interaction with the Mg²⁺ and O²⁻ ions of the surface. The occurrence of an activated process leading to [Cp₂Cr]⁺ and [CpCr(CO)₃]⁻ charged reaction products is also observed.     

碱性条件下Ru/C催化5-羟甲基糠醛选择氧化反应

以活性炭负载金属钌(Ru/C)为催化剂,在碱性水溶液中研究了5-羟甲基糠醛(HMF)选择氧化反应.与MgO,Ca(OH)₂和NaOH相比,加入具有合适碱强度的镁铝水滑石有利于生成5-甲酰基-2-呋喃甲酸(FFCA)或2,5-呋喃二甲酸(FDCA).X射线光电子能谱实验表明金属态的钌是活性催化中心.同位素示踪结果则表明水而非氧气提供了5-甲酰基-2-呋喃甲酸及2,5-呋喃二甲酸等羧酸产物的氧源.根据这些结果,并结合HMF和2,5-呋喃二甲醛氧化的动力学研究,我们提出HMF选择性氧化制备FFCA遵循Langmuir-Hinshelwood反应机理.其中,HMF在金属Ru表面饱和解离吸附,在解离吸附的氧原子的协助下发生β-脱氢生成2,5-呋喃二甲醛(DFF)吸附物种.该DFF物种进一步发生水合与氧化形成FFCA产物.     

Size effects in the CO-oxidation over supported Pd particles

Low pressure CO oxidation was studied over small supported Pd particles by means of static secondary ion mass spectrometry (SSIMS). The SSIMS spectra of adsorbed layers on Pd particles with diameters below ～7nm contained, besides other species, Pd _n X⁺ ions (X=C, O, CO;n=1–3). In experiments with Pd films, Pd _n C⁺ species were much less abundant or even absent from the mass spectra. We conclude that CO decomposed in appreciable amounts only on Pd particles. No significant influence of the support material (mica, MgO,α-Al₂O₃) was seen and posthumous TEM analysis revealed well defined particle morphologies with largely (111) and (100) facets. At total pressures below 10^?4 Pa, the relative carbidic intensities Pd _n C⁺/Pd _n ⁺ , which were taken as proportional to the carbon surface concentrations, first increased with increasing temperatures and then decreased after they passed a maximum at T=400–440 K. The smaller the particle size, the more intense were the maxima. For T ?440 K, carbon was removed from the surface via reaction with oxygen. Strong hysteresis effects in the C_ad and CO_ad concentrations occurred during temperature variation measurements. The Pd _n C⁺/Pd _n ⁺ ratios displayed maxima during heating but not during cooling. While the Pd _n CO⁺/Pd _n ⁺ ratios were always high at 300 K and always low at T>550 K, they were more intense in the medium temperature range when subjecting the samples to heating. These hysteresis effects are discussed in terms of asymmetric adsorption and reaction behaviour of CO/O₂ mixtures, involving inhibition of CO₂ formation by adsorbed carbon and carbon monoxide.     

Synthesis of high surface area nanometer magnesia by solid-state chemical reaction

Nanometer MgO samples with high surface area, small crystal size and mesoporous texture were synthesized by thermal decomposition of MgC₂O₄ · 2H₂O prepared from solid-state chemical reaction between H₂C₂O₄ · 2H₂O and Mg (CH₃COO)₂ · 4H₂O. Steam produced during the decomposition process accelerated the sintering of MgO, and MgO with surface area as high as 412 m² · g⁻¹ was obtained through calcining its precursor in flowing dry nitrogen at 520°C for 4 h. The samples were characterized by X-ray diffraction, N₂ adsorption, transmission electron microscopy, thermogravimetry, and differential thermal analysis. The as-prepared MgO was composed of nanocrystals with a size of about 4–5 nm and formed a wormhole-like porous structure. The MgO also had good thermal stability, and its surface areas remained at 357 and 153 m²·g⁻¹ after calcination at 600 and 800°C for 2 h, respectively. Compared with the MgO sample prepared by the precipitation method, MgO prepared by solid-state chemical reaction has uniform pore size distribution, surface area, and crystal size. The solid-state chemical method has the advantages of low cost, low pollution, and high yield, therefore it appears to be a promising method in the industrial manufacture of nanometer MgO. Translated from Chinese Journal of Catalysis, 2006, 27(9): 793–798 (in Chinese)     

Porous Magnesium Oxide by Twin Polymerization: From Hybrid Materials to Catalysis

Twin monomers [Mg(2-OCH₂-^cC₆H₄O)][L]_0.8 ( 2 , L=diglyme) and [Mg(2-OCH₂-^cC₆H₄O)][L]_0.66 ( 3 , L=tmeda) form by their thermal polymerization interpenetrating organic-inorganic hybrid materials in a straightforward manner. Carbonization (Ar) followed by calcination gave porous MgO ( 2 : surface area 200 m² g⁻¹, 3 : 400 m² g⁻¹), which showed in catalytic studies towards Meerwein-Ponndorf-Verley reductions excellent yields and complete conversions for cyclohexanone and benzaldehyde. However, with crotonaldehyde a mixture of C₄–C₈ compounds was obtained. When MgO was exposed to air then primarily crotyl alcohol was formed. The range of applications could be easily extended by twin polymerization of 3 in presence of [Cu(O₂CCH₂O(CH₂CH₂O)₂Me)₂] ( 4 ) or [Ag(O₂CCH₂-^cC₄H₃S)(PPh₃)] ( 5 ), resulting in the formation of nanoparticle-decorated porous CuO@MgO or Ag@MgO materials, which showed high catalytic reactivity towards the reduction of methylene blue.     

CH bond activation in the presence or absence of oxygen or nitrous oxide

The reaction of C₂H₆with lattice oxygen, O^2- (in the absence of gaseous oxygen), or “adsorbedℍ oxygen (in the presence of gaseous oxygen) over NiMoO₄ catalysts has been performed and compared to C₃H₈ activation. The results obtained indicate that adsorbed oxygen exhibits a higher reactivity to C₂H₆, while lattice oxygen is more reactive relative to C₃H₈. Kinetic studies of these two reactions in presence of molecular oxygen have indeed shown that the ethane oxidative dehydrogenation (ODH) is dependent on the oxygen partial pressure, whilst on the contrary propane ODH is not. In order to confirm the presence of “adsorbed” oxygen for ethane activation, ODH tests have been performed with N₂O. On increasing temperature, the O^- adsorbed species enhances the mild oxidation of ethane. The activation energy of ethane consumption E_C2H6, relative to propane (E_C3H8 = 133 kJ/mol) is 145 kJ/mol. A possible mechanism is proposed for the oxidative dehydrogenation of ethane. This revised version was published online in August 2006 with corrections to the Cover Date.     

Photooxidation of Methane over TiO2

Fourier‐transform infrared spectroscopy has been employed to investigate the adsorption and photo‐oxidation of CH₄ over powdered TiO₂. The interaction between the CH₄ and TiO₂ surface is weak. It is found that no CH₄ molecules are adsorbed on the surface at 35 °C in a vacuum. Under UV irradiation, CH₄ decomposes to form CO_(a), CO_2(g), H20_(a), and HCOO_(a) in the presence of O₂. The photoreaction rate is retarded and only small amounts of CO_(a) and HCOO_(a) are formed in the absence of O₂. It is observed that the oxygen atoms of O₂ are incorporated into these photoproducts as ¹⁸O₂ is used. The major ¹⁸O‐containing products are C¹⁸O_(a), C¹⁸O_2(g), H₂ ¹⁸O_(a), HC¹⁶O¹⁸O_(a), and HC¹⁸O¹⁸O_(a) after 180 min UV irradiation. However, the extent of ¹⁸O incorporating into the adsorbed formate is dependent on UV irradiation time. In the early stage of UV irradiation HC¹⁶O¹⁶O_(a) is the major formate form indicating the involvement of TiO₂ lattice oxygens for its formation, but HC¹⁸O¹⁸O_(a) becomes the major one after 180 min indicating the involvement of ¹⁸O₂. Formate on TiO₂ further photodecomposes to CO_2(g), but not to CO_(a). CO_(a) formation is directly from CH₄ photodecomposition with the participation of TiO₂ lattice oxygens and O₂.     

Formation of Superoxo Species by Interaction of O2 with Na Atoms Deposited on MgO Powders: A Combined Continuous‐Wave EPR (CW‐EPR), Hyperfine Sublevel Correlation (HYSCORE) and DFT Study

The formation of O₂^? radical anions by contact of O₂ molecules with a Na pre‐covered MgO surface is studied by a combined EPR and quantum chemical approach. Na atoms deposited on polycrystalline MgO samples are brought into contact with O₂. The typical EPR signal of isolated Na atoms disappears when the reaction with O₂ takes place and new paramagnetic species are observed, which are attributed to different surface‐stabilised O₂^? radicals. Hyperfine sublevel correlation (HYSCORE) spectroscopy allows the superhyperfine interaction tensor of O₂^?Na⁺ species to be determined, demonstrating the direct coordination of the O₂^? adsorbate to surface Na⁺ cations. DFT calculations enable the structural details of the formed species to be determined. Matrix‐isolated alkali superoxides are used as a standard to enable comparison of the formed species, revealing important and unexpected contributions of the MgO matrix in determining the electronic structure of the surface‐stabilised Na⁺? O₂^? complexes.     

层状K/Mg-Fe-Al催化剂的制备及其CO加氢性能研究

采用共沉淀法制备了系列不同Mg/Fe/Al配比MgFeAl-HTLcs前驱体,经焙烧、浸渍K改性、二次焙烧后用于CO加氢反应。采用N2吸附-脱附、SEM、TG、XRD、H2-TPR、XPS等手段对催化剂进行了表征。结果表明,共沉淀法制备的不同配比MgFeAl-HTLcs类水滑石前躯体均具有典型层状结构;焙烧后生成MgO、Fe2O3以及少量MgFeAlO4物相,三组元间相互作用增强,反应后以MgCO3和Fe3O4物相为主,同时出现较弱的Fe5C2相;K改性后发生结构重构,热稳定性增强,且随Al含量增加,比表面积显著单调下降;与K/Mg-Fe相比,K/Mg-Fe-Al样品中Fe2O3到Fe3O4的还原受到抑制;二次焙烧后,反应前表面相对富Fe,反应后表面富K。在CO加氢反应中,K/Mg-Fe-Al系列催化剂均表现出较高的反应活性以及烯烃选择性,随Fe/Al配比相对增加,C5+含量呈降低趋势,O/P值增加;与K/1.5Mg-0.67Fe相比,K/1.5Mg-0.67Fe-0.33Al催化剂C5+含量由22.17%降至10.90%,C=2-4含量由40.98%提高至47.28%。     

Lithium Promotes Acetylide Formation on MgO During Methane Coupling Under Non-Oxidative Conditions

A prototypical material for the oxidative coupling of methane (OCM) is Li/MgO, for which Li is known to be essential as a dopant to obtain high C₂ selectivities. Herein, Li/MgO is demonstrated to be an effective catalyst for non-oxidative coupling of methane (NOCM). Moreover, the presence of Li is shown to favor the formation of magnesium acetylide (MgC₂), while pure MgO promotes coke formation as evidenced by solid-state ¹³C NMR, thus indicating that Li promotes C−C bond formation. Metadynamic simulations of the carbon mobility in MgC₂ and Li₂C₂ at the density functional theory (DFT) level show that carbon easily diffuses as a C₂ unit at 1000 °C. These insights suggest that the enhanced C₂ selectivity for Li-doped MgO is related to the formation of Li and Mg acetylides.     

Studies on Redispersion and Stability of Platinum in Pt/MgO System during Oxygen Treatment at High Temperatures

Transmission Electron Microscopy and X-ray Diffraction showed that high temperature oxygen treatment results in redispersion of Pt/MgO system. Two catalysts in this study were prepared by impregnation using H₂PtCl₆ or Pt(C₅H₇O₂)₂ as the precursors and two MgO supports of different purity. Pt/MgO system indicated a high stability in oxygen at temperature ranging from 550 to 700°C.     

Does the valence state of an ion affect its diffusivity? Part I: Oxygen activity dependence of the diffusion of iron in alumina-doped MgO

To investigate whether a change in the valence state of tracer ions affects their diffusivity or not, the iron tracer diffusion in Al₂O₃-doped MgO, in which 0.5% of the cations were Al³⁺ ions, has been studied experimentally. Samples were prepared from high purity aluminum and magnesium nitrates using a chemical solution method and from powders of high purity Al₂O₃ and MgO. Because the concentration of the Al³⁺ dopant ions present in the samples was much larger than that of all other impurities, the concentration of the majority point defects, cation vacancies, was determined by the Al³⁺ concentration. Therefore, when changing the oxygen activity, the diffusivity of iron tracer ions can only be altered by changes in their valence state. Measurements of iron tracer diffusion coefficients were performed as a function of the oxygen activity at 1100 and 1200 °C. The experimental results indicate that the mean diffusivity of iron ions in Al₂O₃-doped MgO increases with increasing oxygen activity at both temperatures, suggesting that Fe³⁺ ions diffuse in Al₂O₃-doped MgO faster than Fe²⁺ ions.     

Sites for Methane Activation on Lithium‐Doped Magnesium Oxide Surfaces

Density functional calculations yield energy barriers for H abstraction by oxygen radical sites in Li‐doped MgO that are much smaller (12±6 kJ mol^?1) than the barriers inferred from different experimental studies (80–160 kJ mol^?1). This raises further doubts that the Li⁺O^.? site is the active site as postulated by Lunsford. From temperature‐programmed oxidative coupling reactions of methane (OCM), we conclude that the same sites are responsible for the activation of CH₄ on both Li‐doped MgO and pure MgO catalysts. For a MgO catalyst prepared by sol–gel synthesis, the activity proved to be very different in the initial phase of the OCM reaction and in the steady state. This was accompanied by substantial morphological changes and restructuring of the terminations as transmission electron microscopy revealed. Further calculations on cluster models showed that CH₄ binds heterolytically on Mg²⁺O^2? sites at steps and corners, and that the homolytic release of methyl radicals into the gas phase will happen only in the presence of O₂.