Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an ef...Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.展开更多
Zeolite synthesis was studied using two silica rich filtration residues (FR 1 and FR 2) as Si-source and sodium aluminate in a direct synthesis at 60°C at strong alkaline conditions (8 M - 16 M NaOH). In addition...Zeolite synthesis was studied using two silica rich filtration residues (FR 1 and FR 2) as Si-source and sodium aluminate in a direct synthesis at 60°C at strong alkaline conditions (8 M - 16 M NaOH). In addition to these one-pot syntheses, a two-step process was investigated. Here, an alkaline digestion of FR at 60°C was followed by gel precipitation with sodium aluminate and gel crystallization under usual conditions of 80°C - 90°C. The results show that the substitution of chemical reagent sodium silicate by a waste material like FR as Si-source is possible but requires fine tuning of the reaction conditions as zeolite crystallization is a process under kinetic control. The solubility behaviour and impurities of the inserted filtration residues strongly influenced the course of reaction. Thus zeolites like hydrosodalite or intermediate zeolite between cancrinite and sodalite, or zeolite NaA or Z-21 in cocrystallization with hydrosodalite could be observed in the one pot syntheses already in a short time interval between 1 - 4 h depending on the alkalinity. The two step process yield to zeolites NaA and NaX in very good quality. The reaction process of FR in both reaction methods was characterized by chemical analyses, X-ray powder diffraction, Fourier transform infrared spectroscopy as well as scanning electron microscopy. Surface area and water content of selected products were further characterized by the BET-method and by thermogravimetry. Summing up the results, we can show that zeolite formation from filtration residues is possible by several reaction procedures as model cases for a re-use of industrial waste materials. Beside the importance for environmental protection, the reactions are of interest for zeolite chemistry as the re-use of FR is possible under economically conditions of low energy consumption at 60°C and short reaction periods.展开更多
基金Project supported by the Natural Science Foundation of Anhui Province(Grant No.1908085MA12)the National Natural Science Foundation of China(Grant No.21703222)。
文摘Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.
基金the Deutsche Forschungsgemeinschaft for funding this research project.
文摘Zeolite synthesis was studied using two silica rich filtration residues (FR 1 and FR 2) as Si-source and sodium aluminate in a direct synthesis at 60°C at strong alkaline conditions (8 M - 16 M NaOH). In addition to these one-pot syntheses, a two-step process was investigated. Here, an alkaline digestion of FR at 60°C was followed by gel precipitation with sodium aluminate and gel crystallization under usual conditions of 80°C - 90°C. The results show that the substitution of chemical reagent sodium silicate by a waste material like FR as Si-source is possible but requires fine tuning of the reaction conditions as zeolite crystallization is a process under kinetic control. The solubility behaviour and impurities of the inserted filtration residues strongly influenced the course of reaction. Thus zeolites like hydrosodalite or intermediate zeolite between cancrinite and sodalite, or zeolite NaA or Z-21 in cocrystallization with hydrosodalite could be observed in the one pot syntheses already in a short time interval between 1 - 4 h depending on the alkalinity. The two step process yield to zeolites NaA and NaX in very good quality. The reaction process of FR in both reaction methods was characterized by chemical analyses, X-ray powder diffraction, Fourier transform infrared spectroscopy as well as scanning electron microscopy. Surface area and water content of selected products were further characterized by the BET-method and by thermogravimetry. Summing up the results, we can show that zeolite formation from filtration residues is possible by several reaction procedures as model cases for a re-use of industrial waste materials. Beside the importance for environmental protection, the reactions are of interest for zeolite chemistry as the re-use of FR is possible under economically conditions of low energy consumption at 60°C and short reaction periods.
