Trivalent chromium(Cr(Ⅲ))can form stable soluble complexes with organic components,altering its adsorption properties in the water-soil environment.This increases the risk of Cr(Ⅲ)migrating to deeper soils and trans...Trivalent chromium(Cr(Ⅲ))can form stable soluble complexes with organic components,altering its adsorption properties in the water-soil environment.This increases the risk of Cr(Ⅲ)migrating to deeper soils and transforming into toxic Cr(VI)due to the presence of manganese oxides in sediments.In this study,Citric Acid(CA)was selected as a representative organic ligand to prepare and characterize Cr(III)-CA complexes.The characteristics,mechanisms and environmental factors influencing the adsorption of Cr(Ⅲ)-CA on porous media(silts and fine sands)were investigated in the study.The results show that Cr(Ⅲ)coordinates with CA at a 1:1 molar ratio,forming stable and soluble Cr(Ⅲ)-CA complexes.Compared to Cr(III)ions,the equilibrium adsorption capacity of Cr(Ⅲ)-CA is an order of magnitude lower in silts and fine sands.The adsorption of Cr(Ⅲ)-CA in silts and fine sands is dominated by chemical adsorption of monolayers,following the pseudo-second-order kinetic equation and the Langmuir isotherm adsorption model.Varying contents of clay minerals and iron-aluminum oxides prove to be the main causes of differences in adsorption capacity of Cr(Ⅲ)-CA in silts and fine sands.Changes in solution pH affect the adsorption rate and capacity of Cr(Ⅲ)-CA by altering its ionic form.The adsorption process is irreversible and only minimally influenced by ionic strength,suggesting that inner-sphere complexation serves as the dominant Cr(Ⅲ)-CA adsorption mechanism.展开更多
A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized un...A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized under solvothermal conditions,and structurally characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.It crystallizes in orthorhombic system,space group Pnma with a = 16.1102（9）,b = 33.5805（19）,c = 16.8593（10） ？,β = 97.344（11）°,V = 9120.7（9） ？-3,Z = 4,F（000） = 5184,the final R = 0.0530 and w R = 0.1306.In complex 1,the Tm（Ⅲ） ions adopt two types of coordination fashions.Complex 1 shows onedimensional（1-D） Tm-Zn heteronuclear zigzag chains,and these chains are further linked by H3 mimda ligands into Tm-Zn heteronuclear 2-D lattice-like arrays.The 2-D heteronuclear units were connected through [Zn6（mimda）6] rings to give rise to the Tm-Zn heteronuclear cages.Finally,H3 mimda ligands connected the cages into a 3-D heterometallic framework by the combination of [TmO7]n and Tm-Zn heteronuclear cages.In addition,the thermal stability and luminescent property have been investigated.展开更多
A new quaternary mixed anion complex of gadolinium(Ⅲ), [Gd(CH 3CH 2COO) 2(N O 3)(phen)] 2, was synthesized and structurally characterized. The ESR spectr um of the complex with effective g values of 5.314, 2 47...A new quaternary mixed anion complex of gadolinium(Ⅲ), [Gd(CH 3CH 2COO) 2(N O 3)(phen)] 2, was synthesized and structurally characterized. The ESR spectr um of the complex with effective g values of 5.314, 2 473 and 1.880 in poly crys talline powder at room temperature is quite different from the U spectrum. The c oordination number of Gd 3+ is nine with a monocapped square antiprism geom etry. And the stacking effect was observed in the complex. The crystal of the co mplex belongs to triclinic with space group P 1, a=0.9626(4) n m, b=0.9732(4) nm, c=1.1758(5) nm, α=102.45(1)°, β=108.16(1) °, γ=96.68(2)°, V=1.0018(7) nm3, Z=2, D c=1.80 g·cm -3 , μ(MoKα)=33.63 mm -1, F(000)=530, GOF=1.80, R=0.023 and R w=0.027.展开更多
Co（Ⅱ）-salen was encapsulated in MIL- 100（Cr） metal organic framework by ＂ship in a bottle＂ to synthesize a new electrocatalyst, Cosalen@MIL- 100（Cr）. The material was characterized by XRD, FT-IR, UV-Vis and N...Co（Ⅱ）-salen was encapsulated in MIL- 100（Cr） metal organic framework by ＂ship in a bottle＂ to synthesize a new electrocatalyst, Cosalen@MIL- 100（Cr）. The material was characterized by XRD, FT-IR, UV-Vis and N2-adsorption. The Cosalen@MIL-100（Cr） modified glassy carbon electrode exhibits a well-defined reduction peak at the potential of -0.21 V toward the oxygen reduction reaction （ORR） by cyclic voltam- metry （CV） in pH = 6.84 phosphate buffer. Almost 400 mV positive shift of potential at Cosalen@MIL-100（Cr） modified electrode for ORR compared with that at bare glassy carbon, indicates that Cosalen@MIL-100（Cr） possesses excellent electrocatalytic activity. The transferred number of electrons for ORR was determined by chronocoulometry. The result suggests that the introduction of Co（II）-salen complex into MOF increases the electrocatalytic activity via a four-electron reduction pathway. Furthermore, this electrocatalyst exhibits good stability and reproducibility.展开更多
Hexavalent chromium[Cr(VI)]bioreduction produces soluble Cr(Ⅲ)-organic complexes.The Cr(Ⅲ)-organic complexes are relatively stable once they are formed,and no data about their toxicity were reported.Therefore,this s...Hexavalent chromium[Cr(VI)]bioreduction produces soluble Cr(Ⅲ)-organic complexes.The Cr(Ⅲ)-organic complexes are relatively stable once they are formed,and no data about their toxicity were reported.Therefore,this study aims to investigate the bioavailability and toxicity of the soluble Cr(Ⅲ)-organic complexes.Saccharomyces cerevisiae L^(-1)wild type yeast strain was chosen as the model organism and Cr(Ⅲ)-citrate was selected as the representative compound of the Cr(Ⅲ)-organic complexes.The short-term chronic aquatic toxicity tests of the Cr(Ⅲ)-citrate was explored by measuring growth inhibition,direct viable cell count,dry biomass,biosorption,and the amount of CO_(2)production.Cr(Ⅲ)-citrate exerted a toxicity of 51 mg/L with an EC_(50),which was calculated from the percent growth inhibition.These toxicity data would be helpful to define the toxic potential of the organo-chromium-Ⅲcompounds in the environment.展开更多
基金financially supported jointly by Natural Science Foundation of Fujian Province of China(NO.2023J01227)Natural Science Foundation of Hebei Province(NO.D2020504003)Key Laboratory of Groundwater Remediation of Hebei Province and China Geological Survey(NO.SK202303).
文摘Trivalent chromium(Cr(Ⅲ))can form stable soluble complexes with organic components,altering its adsorption properties in the water-soil environment.This increases the risk of Cr(Ⅲ)migrating to deeper soils and transforming into toxic Cr(VI)due to the presence of manganese oxides in sediments.In this study,Citric Acid(CA)was selected as a representative organic ligand to prepare and characterize Cr(III)-CA complexes.The characteristics,mechanisms and environmental factors influencing the adsorption of Cr(Ⅲ)-CA on porous media(silts and fine sands)were investigated in the study.The results show that Cr(Ⅲ)coordinates with CA at a 1:1 molar ratio,forming stable and soluble Cr(Ⅲ)-CA complexes.Compared to Cr(III)ions,the equilibrium adsorption capacity of Cr(Ⅲ)-CA is an order of magnitude lower in silts and fine sands.The adsorption of Cr(Ⅲ)-CA in silts and fine sands is dominated by chemical adsorption of monolayers,following the pseudo-second-order kinetic equation and the Langmuir isotherm adsorption model.Varying contents of clay minerals and iron-aluminum oxides prove to be the main causes of differences in adsorption capacity of Cr(Ⅲ)-CA in silts and fine sands.Changes in solution pH affect the adsorption rate and capacity of Cr(Ⅲ)-CA by altering its ionic form.The adsorption process is irreversible and only minimally influenced by ionic strength,suggesting that inner-sphere complexation serves as the dominant Cr(Ⅲ)-CA adsorption mechanism.
基金Supported by the Foundation for Science&Technology Innovation Talents in Henan Province(Nos.14HASTIT014,and 16410010012)Natural Science Foundation of China(Nos.21671114)the Foundation of Education Committee of Henan province,China(No.14B150033)
文摘A d-f heteronuclear metal-organic framework（MOF）,{[Tm3Zn6（bipy2）2（mimda）7（H2O）3]·（H2O）5}n（1,H3 mimda = 2-methyl-1-H-imidazole-4,5-dicarboxylic acid,and bipy = 4,4？-bipyridine）,has been synthesized under solvothermal conditions,and structurally characterized by elemental analysis,IR spectra and X-ray single-crystal diffraction.It crystallizes in orthorhombic system,space group Pnma with a = 16.1102（9）,b = 33.5805（19）,c = 16.8593（10） ？,β = 97.344（11）°,V = 9120.7（9） ？-3,Z = 4,F（000） = 5184,the final R = 0.0530 and w R = 0.1306.In complex 1,the Tm（Ⅲ） ions adopt two types of coordination fashions.Complex 1 shows onedimensional（1-D） Tm-Zn heteronuclear zigzag chains,and these chains are further linked by H3 mimda ligands into Tm-Zn heteronuclear 2-D lattice-like arrays.The 2-D heteronuclear units were connected through [Zn6（mimda）6] rings to give rise to the Tm-Zn heteronuclear cages.Finally,H3 mimda ligands connected the cages into a 3-D heterometallic framework by the combination of [TmO7]n and Tm-Zn heteronuclear cages.In addition,the thermal stability and luminescent property have been investigated.
文摘A new quaternary mixed anion complex of gadolinium(Ⅲ), [Gd(CH 3CH 2COO) 2(N O 3)(phen)] 2, was synthesized and structurally characterized. The ESR spectr um of the complex with effective g values of 5.314, 2 473 and 1.880 in poly crys talline powder at room temperature is quite different from the U spectrum. The c oordination number of Gd 3+ is nine with a monocapped square antiprism geom etry. And the stacking effect was observed in the complex. The crystal of the co mplex belongs to triclinic with space group P 1, a=0.9626(4) n m, b=0.9732(4) nm, c=1.1758(5) nm, α=102.45(1)°, β=108.16(1) °, γ=96.68(2)°, V=1.0018(7) nm3, Z=2, D c=1.80 g·cm -3 , μ(MoKα)=33.63 mm -1, F(000)=530, GOF=1.80, R=0.023 and R w=0.027.
基金supported by the Program for New Century Excellent Talents in University(NCET-04-0270)the National Basic Research Program of China(2011CB201301)
文摘Co（Ⅱ）-salen was encapsulated in MIL- 100（Cr） metal organic framework by ＂ship in a bottle＂ to synthesize a new electrocatalyst, Cosalen@MIL- 100（Cr）. The material was characterized by XRD, FT-IR, UV-Vis and N2-adsorption. The Cosalen@MIL-100（Cr） modified glassy carbon electrode exhibits a well-defined reduction peak at the potential of -0.21 V toward the oxygen reduction reaction （ORR） by cyclic voltam- metry （CV） in pH = 6.84 phosphate buffer. Almost 400 mV positive shift of potential at Cosalen@MIL-100（Cr） modified electrode for ORR compared with that at bare glassy carbon, indicates that Cosalen@MIL-100（Cr） possesses excellent electrocatalytic activity. The transferred number of electrons for ORR was determined by chronocoulometry. The result suggests that the introduction of Co（II）-salen complex into MOF increases the electrocatalytic activity via a four-electron reduction pathway. Furthermore, this electrocatalyst exhibits good stability and reproducibility.
基金the National High Technology Research and Development Program of China(863 Program)(Grant No.2007AA06Z337)。
文摘Hexavalent chromium[Cr(VI)]bioreduction produces soluble Cr(Ⅲ)-organic complexes.The Cr(Ⅲ)-organic complexes are relatively stable once they are formed,and no data about their toxicity were reported.Therefore,this study aims to investigate the bioavailability and toxicity of the soluble Cr(Ⅲ)-organic complexes.Saccharomyces cerevisiae L^(-1)wild type yeast strain was chosen as the model organism and Cr(Ⅲ)-citrate was selected as the representative compound of the Cr(Ⅲ)-organic complexes.The short-term chronic aquatic toxicity tests of the Cr(Ⅲ)-citrate was explored by measuring growth inhibition,direct viable cell count,dry biomass,biosorption,and the amount of CO_(2)production.Cr(Ⅲ)-citrate exerted a toxicity of 51 mg/L with an EC_(50),which was calculated from the percent growth inhibition.These toxicity data would be helpful to define the toxic potential of the organo-chromium-Ⅲcompounds in the environment.
