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The calormetically measured heats of adsorption of Cu, Ag, and Pb on MgO(100), previously measured in our group, are correlated with bulk properties of the metals and their sticking probabilities and film morphologies. The low-coverage heats of adsorption (when the metals are mainly in two-dimensional (2D) islands) are used to estimate metal-MgO(100) bond energies within a pairwise bond additivity model. These values correlate well with the observed initial sticking probabilities and saturation island densities of the metals. This supports a transient mobile precursor model for adsorption. The values also correlate with their bulk sublimation energies, which suggests that covalent metal-Mg bonding dominates the interaction at low coverage, probably due to very strong bonding at defects. The heats of adsorption integrated up to multilayer coverages provide the metal-MgO(100) adhesion energies and metal-MgO(100) bond energies for metals in 3D films. These values correlate with the sum of magnitudes of the metal's bulk sublimation energy plus the heat of formation of the bulk oxide of the metal per mole of metal atoms. This suggests that local chemical bonds, both metal-oxygen and covalent metal-Mg, dominate the interfacial bonding for 3D films.
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PMID:Metal adsorption and adhesion energies on MgO(100). 1214 27

CaMgSiOs6 : Eu samples were synthesized by a normal solid state reaction using CaCO3, MgO, SiO2 and Eu2O3 as starting materials. The properties of structure, VUV excitation and luminescence under VUV excitation were studied. CaMgSi2O6 : Eu belongs to the monoclinic space group, and the crystal structure does not change as the crystal lattice is doped with Eu ions. The emission spectra of CaMgSi2O6 : Eu3+ have revealed an intense and sharp (611 nm) red color emission from Eu3+ ((5)D0-->(7)F2) transition under 147 nm VUV excitation. The correlative data shows that the concentration quenching occurs when the Eu3+ mole concentration ranges from 0.02 to 0.10 mol. The emission spectra of CaMgSi2O6 : Eu2+ have revealed an intense and sharp (452 nm) blue color emission from Eu2+ (5d-->4f) transition under 172 nm VUV excitation. It can be seen that the intensity of the emission peak increases with increasing H3BO3 concentration.
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PMID:[VUV spectral properties of CaMgSi2O6 : Eu]. 1765 18

A new and sensitive differential drop solution calorimetric technique was developed for very small samples. A single experiment using one 5.18-milligram sample of perovskite, synthesized at 25 gigapascals and 1873 Kelvin, gave 110.1 +/- 4.1 kilojoules per mole for the enthalpy of the ilmenite-pervoskite transition in MgSiO(3). The thermodynamics of the reaction of MgSiO(3) (ilmenite) to MgSiO(3) (perovskite) and of Mg(2)SiO(4) (spinel) to MgSiO(3) (pervoskite) and MgO (periclase) were assessed. Despite uncertainties in heat capacity and molar volume at high pressure and temperature, both reactions clearly have negative pressure-temperature slopes, -0.005 +/- 0.002 and -0.004 +/- 0.002 gigapascals per Kelvin, respectively. The latter may be insufficiently negative to preclude whole-mantle convection.
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PMID:Negative Pressure-Temperature Slopes for Reactions Formign MgSiO3 Perovskite from Calorimetry. 1783 41

The catalysed oxidation of CO using mass-selected Pd(13) clusters supported on thin MgO films was modelled using a microkinetic simulation of the reaction. The model of the system includes reverse spill-over calculations which were intrinsically incorporated into the formulation of the kinetics. The spill-over model is based on a capture-zone approach including a co-dependence on the variables of the kinetic equations. The experimental values were determined using dual pulsed-molecular beam measurements and recorded at a range of temperatures. The experiment allowed the turn-over frequency and reaction probability to be determined as a function of mole fraction. Comparison of the kinetic model with the experimental data gives excellent agreement and strongly highlights the importance of substrate effects. In particular, the origin of the low temperature catalysis of the Pd clusters is elucidated. The model allows the mole fraction and temperature dependent values such as the sticking coefficients for these clusters to be predicted.
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PMID:Microkinetic simulations of the oxidation of CO on Pd based nanocatalysis: a model including co-dependent support interactions. 1881 41

The catalytic advanced oxidation process (CAOP) of O(3)/MgO/H(2)O(2) was integrated with a sequencing batch reactor (SBR) system to completely treat concentrated formaldehyde wastewater, demonstrating that this combination is an effective method for treating such wastewaters. The influence of several operational variables--including pH, MgO powder dosage, and the concentrations of H(2)O(2) and O(3)--was investigated for the O(3)/MgO/H(2)O(2) degradation of a 7000 mg/L formaldehyde wastewater. The optimum conditions were found to be a pH of 8, 5 g/L dose of MgO powder, 0.09 mole/L concentration of H(2)O(2), and 0.153 g/L min dose of O(3). The formaldehyde and COD concentrations were reduced 79% and 65.6%, respectively, in the CAOP for 120 min of reaction time under the optimum condition stated above. The remaining concentrations of formaldehyde and COD were 1500 mg/L and 3200 mg/L, respectively, in the effluent. The degradation of formaldehyde in CAOP was determined to be a first-order reaction with a constant of 0.015/min, and radical oxidation was the predominant degradation mechanism. This effluent was post-treated in SBR system for a total cycle time of 24h. The SBR completely removed the formaldehyde and removed 98% of the COD, reducing the COD concentration to lower than 60 mg/L. Therefore, the integrated O(3)/MgO/H(2)O(2) and SBR process is demonstrated as a promising technology for the complete treatment of wastewater with high concentrations of toxic and inhibitory compounds such as formaldehyde.
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PMID:The removal of formaldehyde from concentrated synthetic wastewater using O3/MgO/H2O2 process integrated with the biological treatment. 1961 92

A series of glasses xMgO-(1-x)SiO(2) with compositions from enstatite MgSiO(3) (x=0.5) to forsterite Mg(2)SiO(4) (x=0.667) in mole fraction intervals of x approximately 0.02 have been prepared by containerless levitation techniques and CO(2) laser heating. Polarized and depolarized Raman spectra measured at ambient conditions for all these glasses show systematic and smooth band intensity changes with composition. Analysis of the Raman band contours in terms of vibrations due to different oxygen bridged SiO(4) tetrahedra (Q(i), species analysis) undoubtedly shows that bridging oxygens are present in all glasses studied even in the limit of the forsterite composition where bridged Si(2)O(7) (6-) ionic dimers are formed. Furthermore the relative amounts of the Q(i) species change smoothly with composition while at high MgO content "free" oxygens are present presumably forming Mg-O-Mg bridges, which contribute to the glass stability at these compositions. Raman spectra measurements at different temperature below T(g) show small alterations in the Q(i) species in the MgSiO(3) region while no changes were observed in the Mg(2)SiO(4) region. The Boson peak frequency is practically invariant on both composition and temperature and this is in contrast to the systematics followed by most silicate glasses. It is suggested that at compositions near the forsterite ioniclike glasses are formed arising from a very fragile liquid.
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PMID:Glass formation and structure in the MgSiO(3)-Mg(2)SiO(4) pseudobinary system: From degraded networks to ioniclike glasses. 1977 35

The energies of silver (Ag) atoms in Ag nanoparticles supported on different cerium and magnesium oxide surfaces, determined from previous calorimetric measurements of metal adsorption energies, were analyzed with respect to particle size. Their stability was found to increase with particle size below 5000 atoms per particle. Silver nanoparticles of any given size below 1000 atoms had much higher stability (30 to 70 kilojoules per mole of silver atoms) on reduced CeO2(111) than on MgO(100). This effect is the result of the very large adhesion energy (approximately 2.3 joules per square meter) of Ag nanoparticles to reduced CeO2(111), which we found to be a result of strong bonding to both defects and CeO2(111) terraces, apparently localized by lattice strain. These results explain the unusual sinter resistance of late transition metal catalysts when supported on ceria.
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PMID:Ceria maintains smaller metal catalyst particles by strong metal-support bonding. 2072 31

Many catalysts consist of metal nanoparticles anchored to the surfaces of oxide supports. These are key elements in technologies for the clean production and use of fuels and chemicals. We show here that the chemical reactivity of the surface metal atoms on these nanoparticles is closely related to their chemical potential: the higher their chemical potential, the more strongly they bond to small adsorbates. Controlling their chemical potential by tuning the structural details of the material can thus be used to tune their reactivity. As their chemical potential increases, this also makes the metal surface less noble, effectively pushing its behavior upwards and to the left in the periodic table. Also, when the metal atoms are in a nanoparticle with higher chemical potential, they experience a larger thermodynamic driving force to sinter. Calorimetric measurements of metal vapor adsorption energies onto clean oxide surfaces in ultrahigh vacuum show that the chemical potential increases with decreasing particle size below 6 nm, and, for a given size, decreases with the adhesion energy between the metal and its support, Eadh. The structural factors that control the metal/oxide adhesion energy are thus also keys for tuning catalytic performance. For a given oxide, Eadh increases with (deltaHsub,M--deltaHf,MOx)/OmegaM2/3 for the metal, where deltaHsub,M is its heat of sublimation, deltaHf,MOx is the standard heat of formation of that metal's most stable oxide (per mole of metal), and OmegaM is the atomic volume of the bulk solid metal. The value deltaHsub,M--deltaHf,MOx equals the heat of formation of that metal's oxide from a gaseous metal atom plus O2(g), so it reflects the strength of the chemical bonds which that metal atom can make to oxygen, and OmegaM2/3 simply normalizes this energy to the area per metal atom, since Eadh is the adhesion energy per unit area. For a given metal, Eadh to different clean oxide surfaces increases as: MgO(100) approximately TiO2(110) < or = alpha-Al2O3(0001) < CeO2-x(111) < or = Fe3O4(111). Oxygen vacancies also increase Eadh, but surface hydroxyl groups appear to decrease Eadh, even though they increase the initial heat of metal adsorption.
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PMID:Anchored metal nanoparticles: effects of support and size on their energy, sintering resistance and reactivity. 2401 80

Struvite crystallization (SCP) is combined with a nitrification inhibitor (dicyandiamide, DCD) to mitigate the NH3 and N2O emission during composting. The MgO and H3PO4 were added at a rate of 15% (mole/mole) of initial nitrogen, and the DCD was added at rates of 0%, 2.5%, 5.0%, 7.5% and 10% (w/w) of initial nitrogen respectively. Results showed that the combination use of SCP and DCD was phytotoxin free. The SCP could significantly reduce NH3 losses by 45-53%, but not the DCD. The DCD significantly inhibits nitrification when the content was higher than 50mgkg(-1), and that could reduce the N2O emission by 76.1-77.6%. The DCD degraded fast during the thermophilic phase, as the nitrification will be inhibited by the high temperature and high free ammonia content in this stage, the DCD was suggested to be applied in the maturing periods by 2.5% of initial nitrogen.
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PMID:Combined use of nitrification inhibitor and struvite crystallization to reduce the NH3 and N2O emissions during composting. 2686 57

Two new mesoporous magnesium silicate gel adsorbents, MgO x 2SiO2 and MgO x 6SiO2, have been successfully prepared by hydrothermal method. The synthetic factors including reaction pH, temperature, time and calcination temperature were studied. The aiming products were characterized by N2 adsorption/desorption isotherms, FT-IR spectroscopy and Scanning Electron Microscopy (SEM). The adsorption behaviors for cobalt ions were also systematically investigated. The results show that the reaction pH was the decisive factor for Si/Mg mole ratios. The special surface areas are 534.29 m2 x g(-1) for MgO x 2SiO2 and 181.61 m2 x g(-1) for MgO x 6SiO2, respectively. The maximum adsorption capacities of MgO x 2SiO2 and MgO x 6SiO2 for cobalt ions are 135.5 and 52.5 mg x g(-1). Furthermore, the experimental data are well described by pseudo-second order adsorption and Langmuir isotherm models. The experiment would afford one excellent adsorbent for solving the wastewater pollution and also providing metal cobalt for modern industry including new energy car.
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PMID:Preparation and Characterization of Mesoporous Magnesium Silicate Gels and Application for Cobalt(II) Removal. 2742 37


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