Construction of embedded-atom-method interatomic potentials for alkaline metals (Li,Na,and K) by lattice inversion

The lattice-inversion embedded-atom-method interatomic potential developed previously by us is extended to alkaline metals including Li,Na,and K.It is found that considering interatomic interactions between neighboring atoms of an appropriate distance is a matter of great significance in constructing accurate embedded-atom-method interatomic potentials,especially for the prediction of surface energy.The lattice-inversion embedded-atom-method interatomic potentials for Li,Na,and K are successfully constructed by taking the fourth-neighbor atoms into consideration.These angular-independent potentials markedly promote the accuracy of predicted surface energies,which agree well with experimental results.In addition,the predicted structural stability,elastic constants,formation and migration energies of vacancy,and activation energy of vacancy diffusion are in good agreement with available experimental data and first-principles calculations,and the equilibrium condition is satisfied.

Solvent Extraction of Alkaline Earth Metals with Alkylphosphorus Acids

Solvent extraction equilibria of four main alkaline earth metals(magnesium, calcium, strontium and barium) with di (2-ethylhexyl)phosphoric acid (DEHPA), 2-ethylhexyl phosphonic acidmono-(2-ethylhexyl) esters, di (2, 4, 4-tri-methylpentyl) phosphinicacid and IR spectra of the extracts have been studied. Theselectivity order is dependent on the e/r value and hydration energyof the metal ions. The minor shift of the P→O in IR absorption ofthe alkaline earth metal extracts indicates that the interactionbetween the metal ions and P→O is much weaker for alkaline earthmetals than for transitional metals.

Some New Results from the Electron Theory on the Elastical of Alkahoe Earth Metals and Rare Earth Elements

With the introduction of Poisson's ratio in the expression of Young's modulus,nearly all the theoretical values of the various elastic moduli for the alkaline earth metals and rare earth elements can be greatly refined, with the single exception of the theoreticalvalue of Young's modulus for Pr which is slightly increased This points to the validityof the new theory, that the bulk modulus is independent of the Poisson's ratio, and further that the valency electron structures of solids as determined by Yu's theory are correct.

Alkaline leaching of metal melting industry wastes and separation of zinc and lead in the leach solution

In this work, a thorough examinations on the extractability of zinc and lead present in the steelmaking dusts using alkaline leaching process and the effectiveness of the zinc and lead separation in the resultant leaching solutions using sulfide precipitation method were made. It was found that only about 53% of zinc and over 70% of the lead could be leached out of the dusts, while the other 47% of zinc and 30% of lead were left in the leaching residues. The zinc and lead in the resultant leaching solution can be effectively and selectively separated. When the weight ratio of sodium sulfide (M.W. = 222-240) to Pb was kept at 1.8, the lead in the solution could be precipitated out quantitatively while all the zinc was remained in the solution. The zinc left in the solution can be further recovered by the addition of extra sodium sulfide with a weight ratio of sodium sulfide to the zinc over 2.6. The resultant filtrate can be recycled to the leaching of dust in the next leaching process.

Syntheses of Alkaline Earth and Lanthanide Cryptates with Pyridine-Based Group

New alkaline earth metal cryptates [ML]（NO3）2 ·2H2O （M=Ca^2＋, Sr^2＋, Ba^2＋; L = 1, 4,12,15,18, 26, 31, 39, 42, 43, 44-undecaazapentacyclo- [ 13.13.13.1^6,10 .1^20,24 .1^33,37 ]-tetratetraconta -4, 6, 8, 10（44）, 11, 18, 20, 22, 24（43）, 25, 31, 33, 35, 37（42）, 38-pentadecaene） were synthesized by [2 ＋ 3 ] template condensation of tris（2-aminoethyl） amine with 2, 6-diformylpyridine, and then by transmetallation reactions of the calcium cryptate [CaL] （NO3）2·2H2O with corresponding lanthanide ions; three lanthanide cryptates [ LnL] （NO）3·3H2O （Ln = Eu, Gd, Tb） were synthesized and characterized by physical methods. The crystal structure of the terbium cryptate [TbL] （NO）3·3H2O was studied by X-ray analysis. The central atom was coordinated by three pyridyl and six imino nitrogen atoms and exhibited a distorted tricapped trigonal prismatic coordination geometry.

Microcalorimetric study on host-guest complexation of naphtho-15-crown-5 with four ions of alkaline earth metal

Thermodynamic parameters of complexation of naphto- 15-crown-5 with four alkaline earth ions in aqueous media was determined using titration microcalorimetry at 298.15 K. The stability of the complexes, thermal effect and entropy effect of the complexation is discussed on the basis of the guest ions structure and the solvent effect. The stability constants tendency to vary with ion radius was interpreted. Complex of naphtha-15-crown-5 with calcium ion is very stable due to the synergism of static electric interaction and size selectivity between the host and the guest.

Electrocatalytic Activity of Ni/C Electrodes Prepared by Metal Vapor Synthesis For Hydrogen Evolution in Alkaline Solution

The metal vapor synthesis (MVS) methed was used to prepare activatedcarbon supported nickel electrode. The electrocatalytic activity of the electrode forhydrogen evolution reaction(HGR) in alkaline solution was studied. Cathodicpolarization curves showed the electrocatalytic activity of Ni/C electrode prepared byMVS method was higher than that of the one prepared by conventional method.

Syntheses and Characterization of Two New Alkaline Earth Metal-organic Topological Frameworks with 3-Amino-1H-1,2,4-triazole-5-carboxylate

Two new alkaline earth metal coordination polymers constructed from the deriva-tive of 1,2,4-triazole are presented herein,namely,{[Sr（AmTAZAc）2（H2O）]}（1） and {[Ba（AmTAZAc）2（H2O）]}（2）（AmTAZAc = 3-amino-1H-1,2,4-triazole-5-carboxylate）,which have been synthesized by using the layering method and structurally characterized by elemental analysis,IR,and single-crystal X-ray diffraction.Complexes 1 and 2 are isostructural,and both crystallize in the orthorhombic system,space group Fdd2.X-ray structural analysis shows that 1 or 2 has an intriguing 3-D infinite network of（318.438.510） topology based on a 2-D sheet structure of（4,4） net.The result shows that noncovalent interactions play an important role in strengthening the whole structures of the compounds.

Effect of BaNH,CaNH,Mg3N2 on the activity of Co in NH3 decomposition catalysis

Development of active and non-noble metal-based catalyst for H2 production via NH3 decomposition is crucial for the implementation of NH3 as a H2 carrier.Co-based catalysts have received increasing attention because of its high intrinsic activity and moderate cost.In this work,we examined the effect of BaNH,CaNH and Mg3 N2 on the catalytic activity of Co in the NH3 decomposition reaction.The H2 formation rate ranks the order as Co-BaNH>Co-CaNH>Co-Mg3 N2≈Co/CNTs within a reaction temperature range of 300-550℃.It is worth pointing out that the H2 formation rate of Co-BaNH at 500℃reaches20 mmolH2 gcat-1 min-1,which is comparable to those of the active Ru/Al2 O3(ca.17 mmolH2 gcat-1 min1)and Ru/AC(21 mmolH2 gcat-1 min-1)catalysts under the similar reaction conditions.In-depth research shows that Co-BaNH exhibits an obviously higher intrinsic activity and much lower Ea(46.2 kJ mol-1)than other Co-based catalysts,suggesting that BaNH may play a different role from CaNH,Mg3 N2 and CNTs during the catalytic process.Combined results of XRD,Ar-TPD and XAS show that a[Co-N-Ba]-like intermediate species is likely formed at the interface of Co metal and BaNH,which may lead to a more energy-efficient reaction pathway than that of neat Co metal for NH3 decomposition.

Carbon dioxide adsorption behaviors of aluminum-pillared montmorillonite-supported alkaline earth metals

The Al-pillared montmorillonite-supported alkaline earth metal 5M/Al-PILC(PILC = pillared clay, M = Mg, Ca, Sr, and Ba) and x Mg/Al-PILC( x = 1, 3, 5, and 7 wt.%) samples were prepared using an impregnation method. Physical properties of the materials were determined by means of X-ray diffraction(XRD) and N2 adsorption-desorption, and their CO2 adsorption behaviors were investigated using the thermogravimetric analyzer(TG), CO2 temperatureprogrammed desorption(CO2-TPD), and in situ diffuse reflectance infrared transform spectroscopy(in situ-DRIFTS) techniques. It is shown that 5 Mg/Al-PILC possessed the highest CO2 adsorption capacity(2.559 mmol/g). The characterization results indicate that Alpillaring increased the specific surface area of montmorillonite, which was beneficial for the adsorption of CO2. The CO2 adsorption process on the sample was mainly chemical adsorption, and alkalinity was the main factor influencing its adsorption capacity. The alkalinity of the sample was enhanced by loading an appropriate amount of alkaline earth metal, and the adsorbed CO2 was present in the form of bicarbonate and carbonate. In addition, the 5Mg/Al-PILC sample exhibited an excellent regeneration efficiency. We believe that the outcome of this research would provide a good option for developing highly effective CO2 adsorption materials.

Crystal Structures,Characterizations and Fluorescence Properties of Two 3D Ca(Ⅱ)/Sr(Ⅱ)Coordination Polymers Based on 2-Sulfoterephthalate

Two alkaline earth metal coordination polymers [M（2-Hstp）（H2O）] （M = Ca2＋ （1） and Sr2＋ （2）, 2-H3stp = 2-sulfoterephthalate） were synthesized under hydrothermal conditions by the precursor [Mn（2-Hstp）2（4,4？-Hbpy）2] and alkaline earth metal salts. The two alkaline earth complexes are not isomorphic. Complex 1 crystallizes in the monoclinic space group P21/m, while 2 in the monoclinic space group P21/c, despite of their similar formulas. In 1, the Ca2＋ ion lies in a seven-coordinated pentagon bipyramidal configuration, coordinated with five 2-Hstp2- anions and one water molecule. However, the Sr2＋ ion in 2 is coordinated by nine oxygen atoms to form a single-capped square antiprism polyhedron. Both 1 and 2 exhibit π-π＊ emission of the 2-sulfotere- phthalate ligand.

Direct Fluorescence Sensing of Metal Ions in Aqueous Solution Using Intramolecular Charge Transfer Emission from Aggregates of Pentaerythrityl Tetra(p-dimethylaminobenzoate)

Pentaerythrityl tetra(p-dimethylaminobenzoate) (PTDMAB) was synthesized and shown to emit in water-rich aqueous dioxane solutions the intramolecular charge transfer fluorescence that was sensitive to the presence of metal ions.

Photostimulated Luminescence and F-centers of Sr_3Ca_2(PO_4)_3X:Eu^(2+)(X=F,Cl,Br)

This paper reports the F-centers and photostimulated luminescence of Eu^(2+)-activated Sr_3Ca_2(PO_4)_3X crystals.The influence of various halide ions on the F-centers and their energy level is discussed.The mechanism for the photostimulated luminescence and valence change of Eu ion in that process have been investigated.

Study on sulfur migration in activated carbon adsorption-desorption cycle: Effect of alkali/alkaline earth metals

Activated carbon(AC)has been widely used in the removal of SO_(2) from flue gas owing to its well-developed pore structure and abundant functional groups.Herein,the effect of alkali/alkaline earth metals on sulfur migration was investigated based on the dynamic adsorption and temperature programmed desorption experiment.The adsorption and desorption properties of six types of AC(three commercial and three laboratory-made)were carried out on a fixed-bed experimental device,and the physical and chemical properties of samples were determined by X-ray fluorescence,X-ray diffraction,scanning electron microscopy/energy dispersive X-ray,and X-ray photoelectron spectroscopy analysis.The experimental results showed that the adsorbed SO_(2) cannot be completely desorbed by increasing the regeneration temperature(350-850℃),while the SO_(2) fixed in the AC combines with the Ca-based minerals in the ash to form a stable sulfate.For different samples,higher ash content,higher CaO content in the ash and a more developed pore structure lead to a higher SO_(2) fixation rate.Moreover,the multiple adsorption-desorption cycles experiment showed that the effect of SO_(2) fixation is mainly reflected in the first cycle,after which the adsorption and desorption amount are approximately the same.This study elucidates the effect of alkali/alkaline earth metals on the adsorption-desorption cycle of AC,which provides a deeper understanding of sulfur migration in the AC flue gas desulfurization process.

Role of carbon matrix heteroatoms at synthesis of carbons for catalysis and energy applications

The conceptual ideas about the positive effects of N- and O-heteroatoms on the reactivity of carbons in gasification processes, their catalytic activity in electron transfer reactions, as well as the performance of the electrode double-layer supercapacitors due to their electron-donating influence on the 7r-conjugated system of graphene layers have been developed. This influence decreases both work function and band gap of carbons, and also significantly affects their electron-donating properties. As a result of our investigations based on quantum chemical calculations of model graphene clusters with N- and O-heteroatoms in different positions, prognostic data have been obtained. These data have been confirmed by our experimental results of catalytic activity of corresponding carbons in H202 decomposition reaction, their reactivity in gasification processes, and also their performance as electrodes in supercapacitors.

Theoretical Studies on Dihedral Angle-Bending Isomers of M2Pt2^0/- Clusters

The structures and electronic properties of the gaseous M2Pt20/-clusters(M represents the alkaline earth metal)were investigated using the density functional theory(B3LYP and PBE0)and wave function theory(SCS-MP2,CCSD and CCSD(T)).The results indicate that the D2 hisomers with the planar structures are more stable than the C2v isomers with smaller dihedral angles and shorter Pt-Pt bond lengths.The mutual competition of M(s,p)-Pt(5d)interaction and Pt-Pt covalent bonding contributes to the different stabilizations of the two kinds of isomers.The M(s,p)-Pt(5d)interaction favors the planar isomers with D2 hsymmetry,while the Pt-Pt covalent bonding leads to the C2 visomers with bending structures.Two different crossing points are determined in the potential energy curves of Be2Pt2 with the singlet and triplet states.But there is just one crossing point in potential energy curves of Ra2Pt2 and Ca2Pt2-because of flatter potential energy curves of Ra2Pt2 with the triplet state or Ca2Pt2-with quartet state.The results reveal a unique example of dihedral angle-bending isomers with the smallest number of atoms and may help the understanding of the bonding properties of other potential angle-bending isomers.

Two New Alkaline Metal Borates with Supramolecular Framework Constructed from 1D{B5}/{B6}Helical Chains

Two new alkaline metal borates containing 1D{B5}/{B6}oxoboron helical chains,namely Na0.5[B5O8(OH)2]0.5[B5O6(OH)2]0.5·0.5H3O(1)and NaKCs[B6O9(OH)3](2)were synthesized under solvothermal conditions.Compound 1 contains the interesting alternative left-and right-handed helical{[B5O8(OH)2][B5O6(OH)2]}2-({B5}-1 and{B5}-2)1D chains and compound 2 possesses the similar[B6O11(OH)3]7-({B6})chains.Their 1D chains are further assembled into 2D layers and 3D supramolecular frameworks through O-H…O hydrogen bonds.In addition,the UV cutoff edge of compounds 1 and 2 is both below 190 nm.

Low-temperature(NO + O_(2)) adsorption performance of alkaline earth metal-doped C-FDU-15

To improve the removal capacity of NO + O_(2) effectively, the alkaline earth metal-doped order mesoporous carbon(A-C-FDU-15(0.001)(A = Mg, Ca, Sr and Ba)) and Mg-C-FDU-15( x)( x = 0.001-0.003) samples were prepared, and their physicochemical and NO + O_(2) adsorption properties were determined by means of various techniques. The results show that the sequence in(NO + O_(2)) adsorption performance was as follows: Mg-C-FDU-15(0.001)(93.2 mg/g) > Ca-C-FDU-15(0.001)(82.2 mg/g) > Sr-C-FDU-15(0.001)(76.1 mg/g) > Ba-C-FDU-15(0.001)(72.9 mg/g) > C-FDU-15(67.1 mg/g). Among all of the A-C-FDU-15(0.001) samples, Mg-C-FDU-15(0.001) possessed the highest(NO + O_(2)) adsorption capacity(106.2 mg/g). The species of alkaline earth metals and basic sites were important factors determining the adsorption of NO + O_(2) on the A-C-FDU-15( x) samples, and(NO + O_(2)) adsorption on the samples was mainly chemical adsorption. Combined with the results of(NO + O_(2))-temperatureprogrammed desorption((NO + O_(2))-TPD) and in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS) characterization, we deduced that there were two main pathways of(NO + O_(2)) adsorption: one was first the conversion of NO and O_(2) to NO_(2) and then part of NO_(2) was converted to NO_(2)^(-) and NO_(3)^(-);and the other was the direct oxidation of NO to NO-2 and NO_(3)^(-).

Effect of semi-continuous water washing on the combustion behaviors of agricultural organic solid waste

Combustion of agricultural organic solid waste(AOSW)was an ideal solution for their resource utilization in view of their massive annual production and great potential for reduction of fossil fuel utilization.However,high alkali and alkaline earth metals(AAEMs)content in the feedstock can arose severe fouling and slagging issues and thus prohibiting its vast utilization.In this study,a semi-continuous water washing method was proposed to preliminarily remove AAEMs from agricultural organic solid waste and its effects on the combustion behaviors of washed solid product were investigated.Results showed that the combustion index S were improved to 2.63×10-6,over 68%of the total ashes were removed from the cotton stalk,and 96.3%,89.0%and 74.7%of K,Na and Mg were effectively removed,respectively.Moreover,the softening temperature of low temperature ash from the washed sample was as high as 1450◦C,538◦C higher than the low temperature ash from the original sample;the base acid ratio and fouling index were improved from high slagging and fouling risk(1.7 and 90.8)of the original organic solid waste to low and medium risk(0.4 and 3.5),respectively.All these results signified the contributing effect of proposed semi-continuous water washing method on the combustion of agricultural organic solid waste.In a word,this study provided a promising method for fouling and slagging inhibition during the agricultural organic solid waste combustion.

9-Benzylidene-9H-fluorene Derivatives Linked to Monoaza- 15-crown-5： Synthesis and Metal Ion Sensing

Two kinds of novel styryl chemosensory 2-FMNC and 3-FMNC, were designed and synthesized by an apporiate introduction of 9-benzylidene-9H-fluorene group as fluorophore with the aim at avoiding photoisomerisation. These 9-benzylidene-9H-fluorene derivatives showed the similar selectivity and sensitivity upon addition of metal ions. The sensitivity of FMNC to alkaline earth metal ions was Ba2＋〉 Sr2＋〉Ca2＋≈Mg2＋.