Information on the binding of organic ligands to metal （hydr）oxide surfaces is useful for understanding the adsorption behaviour of natural organic matter on metal （hydr）oxide. In this study, benzoate and salicyla...Information on the binding of organic ligands to metal （hydr）oxide surfaces is useful for understanding the adsorption behaviour of natural organic matter on metal （hydr）oxide. In this study, benzoate and salicylate were employed as the model organic ligands and aluminum hydroxide as the metal hydroxide. The attenuated total reflectance Fourier transform infrared （ATR-FTIR） spectra revealed that the ligands benzoate and salicylate do coordinate directly with the surface of hydrous aluminum hydroxide, thereby forming innersphere surface complexes. It is concluded that when the initial pH is acidic or neutral, monodentate and bridging complexes are to be formed between benzoate and aluminum hydroxide while bridging complexes predominate when the initial pH is alkalic. Monodentate and bridging complexes can be formed at pH 5 while precipitate and bridging complexes are formed at pH 7 when salicylate anions are adsorbed on aluminum hydroxide. The X-ray photoelectron （XP） spectra demonstrated the variation of C 1 s binding energy in the salicyate and phenolic groups before and after adsorption. It implied that the benzoate ligands are adsorbed through the complexation between carboxylate moieties and the aluminum hydroxide surface, while both carboxylate group and phenolic group are involved in the complexation reaction when salicylate is adsorbed onto aluminum hydroxide. The information offered by the XPS confirmed the findings obtained with ATR-FTIR.展开更多
A method was proposed to determine boron trifluoride in boron trifluoride complex using fluoride ion selective electrode(ISE). Hydroxide was chosen to mask aluminum for the determination of 0.01—0.1 mol/L of fluoride...A method was proposed to determine boron trifluoride in boron trifluoride complex using fluoride ion selective electrode(ISE). Hydroxide was chosen to mask aluminum for the determination of 0.01—0.1 mol/L of fluoride. The simulation indicated that the permissible aluminum masked at a certain p H value was limited and hardly related to F-concentration and boric acid. It is better to control p H value below 11.5 and the aluminum concentration within 0.025 mol/L to minimize the interference of hydroxide to the fluoride ISE. The decomposition conditions of boron trifluoride by aluminum chloride were investigated. It is found that the F-detection ratio will approach 1.0 if the Al/F molar ratio is 0.3—0.7 and aluminum concentration is no more than 0.02 mol/L when heated at 80 ℃ for 10 min. In one word, hydroxide is quite fit to mask aluminum for samples which contain high content of fluoride and aluminum and the BF3 content can be successfully determined by this method.展开更多
Four Cu2＋ complexes of salicylidene-amino acid Schiff base with 1,10-phenanthroline （Phen） or 2,2＇- bipyridine （Bipy） were successfully intercalated in interlayer galleries of Mg/AI-NO3-1ayered double hydroxide ...Four Cu2＋ complexes of salicylidene-amino acid Schiff base with 1,10-phenanthroline （Phen） or 2,2＇- bipyridine （Bipy） were successfully intercalated in interlayer galleries of Mg/AI-NO3-1ayered double hydroxide （LDH） by the swelling-restored method. The hybrids were characterized by elemental analysis, X-ray diffraction, FT-IR spectra, UV-vis DRS, TG-DTA and SEM observation. Good protection of the complexes by LDH in neutral and weak acidic solutions was revealed by UV spectra, cyclic voltammograms and luminescence spectra.展开更多
Heterometallic copper(Ⅱ)-lanthanide(Ⅲ) complexes have been made with a variety of exclusively O-donor ligands including betaines (zwitterionic carboxylates) and chloroac-etate,which are dinuclear CuLn,tetranuclear C...Heterometallic copper(Ⅱ)-lanthanide(Ⅲ) complexes have been made with a variety of exclusively O-donor ligands including betaines (zwitterionic carboxylates) and chloroac-etate,which are dinuclear CuLn,tetranuclear Cu2Ln2,pen-tanuclear Cu2Ln2,and octadecanuclear Cu12Ln6 complexes.Hie results show that subtle changes in both the carboxylates and acidity of the reaction solution can cause drastic changes in the structures of the products.Magnetic studies exhibit that shielding of the Ln3+ 4f electrons by the outer shell electrons is very effective to preclude significant coupling interaction between the Ln3+ 4f electrons and Cu2+ 3d electrons in either a mono-atomic hydroxide-bridged,or a carboxylate-bridged system.展开更多
文摘Information on the binding of organic ligands to metal （hydr）oxide surfaces is useful for understanding the adsorption behaviour of natural organic matter on metal （hydr）oxide. In this study, benzoate and salicylate were employed as the model organic ligands and aluminum hydroxide as the metal hydroxide. The attenuated total reflectance Fourier transform infrared （ATR-FTIR） spectra revealed that the ligands benzoate and salicylate do coordinate directly with the surface of hydrous aluminum hydroxide, thereby forming innersphere surface complexes. It is concluded that when the initial pH is acidic or neutral, monodentate and bridging complexes are to be formed between benzoate and aluminum hydroxide while bridging complexes predominate when the initial pH is alkalic. Monodentate and bridging complexes can be formed at pH 5 while precipitate and bridging complexes are formed at pH 7 when salicylate anions are adsorbed on aluminum hydroxide. The X-ray photoelectron （XP） spectra demonstrated the variation of C 1 s binding energy in the salicyate and phenolic groups before and after adsorption. It implied that the benzoate ligands are adsorbed through the complexation between carboxylate moieties and the aluminum hydroxide surface, while both carboxylate group and phenolic group are involved in the complexation reaction when salicylate is adsorbed onto aluminum hydroxide. The information offered by the XPS confirmed the findings obtained with ATR-FTIR.
基金Supported by the Independent Innovation Fund of Tianjin University(No.1307)
文摘A method was proposed to determine boron trifluoride in boron trifluoride complex using fluoride ion selective electrode(ISE). Hydroxide was chosen to mask aluminum for the determination of 0.01—0.1 mol/L of fluoride. The simulation indicated that the permissible aluminum masked at a certain p H value was limited and hardly related to F-concentration and boric acid. It is better to control p H value below 11.5 and the aluminum concentration within 0.025 mol/L to minimize the interference of hydroxide to the fluoride ISE. The decomposition conditions of boron trifluoride by aluminum chloride were investigated. It is found that the F-detection ratio will approach 1.0 if the Al/F molar ratio is 0.3—0.7 and aluminum concentration is no more than 0.02 mol/L when heated at 80 ℃ for 10 min. In one word, hydroxide is quite fit to mask aluminum for samples which contain high content of fluoride and aluminum and the BF3 content can be successfully determined by this method.
基金supported by Beijing Municipal Natural Science Foundation(No.2112022)Key Laboratory of Radiopharmaceuticals of Ministry of Education(College of Chemistry, Beijing Normal University) and Analytical and Testing Center of Beijing Normal University
文摘Four Cu2＋ complexes of salicylidene-amino acid Schiff base with 1,10-phenanthroline （Phen） or 2,2＇- bipyridine （Bipy） were successfully intercalated in interlayer galleries of Mg/AI-NO3-1ayered double hydroxide （LDH） by the swelling-restored method. The hybrids were characterized by elemental analysis, X-ray diffraction, FT-IR spectra, UV-vis DRS, TG-DTA and SEM observation. Good protection of the complexes by LDH in neutral and weak acidic solutions was revealed by UV spectra, cyclic voltammograms and luminescence spectra.
基金Project supported by Guangdong Natural Science Foundationthe National Natural Science Foundation of China (No. 29625102)
文摘Heterometallic copper(Ⅱ)-lanthanide(Ⅲ) complexes have been made with a variety of exclusively O-donor ligands including betaines (zwitterionic carboxylates) and chloroac-etate,which are dinuclear CuLn,tetranuclear Cu2Ln2,pen-tanuclear Cu2Ln2,and octadecanuclear Cu12Ln6 complexes.Hie results show that subtle changes in both the carboxylates and acidity of the reaction solution can cause drastic changes in the structures of the products.Magnetic studies exhibit that shielding of the Ln3+ 4f electrons by the outer shell electrons is very effective to preclude significant coupling interaction between the Ln3+ 4f electrons and Cu2+ 3d electrons in either a mono-atomic hydroxide-bridged,or a carboxylate-bridged system.
