Photo-assisted electrochemical technique provides a promising approach towards carcinogen chromium(Ⅵ)detection,which requires reasonable catalyst design.Herein,an unusual hexa-nuclear cadmium cluster functionalized r...Photo-assisted electrochemical technique provides a promising approach towards carcinogen chromium(Ⅵ)detection,which requires reasonable catalyst design.Herein,an unusual hexa-nuclear cadmium cluster functionalized reductive phosphomolybdate hybrid as photo-electrochemical sensor was designed and synthesized with formula of{[Cd(H_(2)O)_(2)]_(2)[Cd(btmbp)]_(2)}{Cd(P_(4)Mo_(6)O_(31)H_(7))_(2)}·20H_(2)O(1)(btmbp=4,4′-bis((^(1)H-1,2,4-triazol-1-yl)methyl)biphenyl),in which the photoactive hexa-nuclear{Cd_(6)}clusters cooperated with reductive phosphomolybdate[P_(4)Mo_(6)O_(31)]^(12)−endow the material with wide light absorption and remarkable redox activity,thus achieving efficient photo-assisted electrochemical Cr(Ⅵ)detection performance.Under visible-light assistance,the detection limit(LOD)and sensitivity of Cr(Ⅵ)is 4.17 nmol/L(0.225 ppb)and 226.32μA L/μmol,which is apparently superior to the performance without photo-assistance(6.25 nmol/L and 106.95μA L/μmol)and far satisfies the demands of world health organization(WHO)for potable water(50 ppb).Moreover,compound 1 showed prominent Cr(Ⅵ)detection performance in practical water samples together with remarkable anti-interference capacity and good electrochemical durability.This work provides an important guidance for designing efficient polyoxometalate-based crystalline sensors for Cr(Ⅵ)detection.展开更多
A new sandwiched polyoxometalate [HK11Cd4Cl2（PW9034）2]·18H2O （1）, incor- porating a unique hybrid tetranuclear cadmium cluster （abbreviated to {Cd4}） with two trivacant polyanions [B-α-PW9O34]9-, has been ...A new sandwiched polyoxometalate [HK11Cd4Cl2（PW9034）2]·18H2O （1）, incor- porating a unique hybrid tetranuclear cadmium cluster （abbreviated to {Cd4}） with two trivacant polyanions [B-α-PW9O34]9-, has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, UV-vis, and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, space group C2/c, a = 19.2997（4）, b = 13.8014（3）, c = 31.9819（8） A, β = 102.764（2）°, V= 8308.3（3） A3, Z = 4, P2O86Cl2K11Cd4W18H37, Mr = 5735.13, Dc = 4.584 mg-mm-3, F（000） = 10084, μ = 26.579 mm-1, the final R = 0.0378 and wR = 0.0989 for 6558 observed reflections （I〉 2σ（I））. X-ray crystallographic study shows that the molecular structure of 1 contains four cadmium atoms. Two CdO6 distorted octahedra and two CdOsC1 distorted octahedra combine with each other in turn via edge-sharing, resulting in a regular rhomb-like cluster sandwiched between two {B-a-PW9034} units. Further, the sandwich-type polyoxoanions were connected by K＋ ions to form a complicated 3-D open-framework through connecting with each terminal O atom of the [Cd4C12（PW9O34）2]12- polyoxoanions. In addition, compound 1 exhibits photoluminescence property at room temperature and the band gap can be assessed at 3.25 eV.展开更多
A novel 2-D {[Cd4（tpt）2（Cl）4（2,4-pdc）2]·4H2O}n （1） has been synthesized from the hydrothermal reaction of 3,5,6-tris（2-pyridyl）-1,3,5-triazine （tpt）, hydrated CdCI2, and 2,4-dicarboxylic acid （2,4-H2...A novel 2-D {[Cd4（tpt）2（Cl）4（2,4-pdc）2]·4H2O}n （1） has been synthesized from the hydrothermal reaction of 3,5,6-tris（2-pyridyl）-1,3,5-triazine （tpt）, hydrated CdCI2, and 2,4-dicarboxylic acid （2,4-H2pdc）. Compound 1 crystallizes in triclinic, P1^- space group with a = 8.9434（5）, b = 9.5486（7）, c = 17.5772 （8） A, a = 75.014 （5）, β= 83.778（5）, γ = 68.304（6）°, V = 1347.14（14） A^3, C50H38Cd4C14N14O12, Mr = 1618.32, Dc = 1.990 g/cm^3, S = 0.95,μ（MoKa） = 1.83 mm^-1, F（000） = 788, Z = 1, R = 0.039 and wR = 0.080. The structure consists of tetranuclear [Cd4（tpt）2（Cl）4]^4＋ cores as the secondary building unit, which is further connected by the ligand pdc2 to give a 2-D extended structure. Tpt entities are located on both sides of each 2-D framework and act as ＇side arms＇ to form a corrugated layer and the adjacent layers are arranged in a tongue-and-groove interdigitating fashion. 1 was characterized by IR, TGA, PX1RD, and elemental analysis. The solid state luminescent properties were also investigated at room temperature.展开更多
In this paper a new cadmium(Ⅱ) complex,[Cd(H2PTA)(H2O)3].3H2O,has been synthesized and characterized by elemental analysis,IR,and X-ray diffraction single crystal structure ananlysis. It belongs to triclinic system,w...In this paper a new cadmium(Ⅱ) complex,[Cd(H2PTA)(H2O)3].3H2O,has been synthesized and characterized by elemental analysis,IR,and X-ray diffraction single crystal structure ananlysis. It belongs to triclinic system,with space group P1,a=0.947 84(19) nm,b=0.990 8(2) nm,c=0.994 3(2) nm,α=114.06(3)°,β=98.56(3)°,γ=111.29(3)°,V=0.744 5(3) nm3,Z=2. This complex is a binuclear unit,and then the binuclear molecules are alternatively assembled into 3D supramolecular network by hydrogen-bond in which there exists a (H2O)4 water cluster. CCDC:724104.展开更多
High performance Dynamic Light Scattering (DLS) has been used to determine the hydrodynamic di-ameters of CdSe nanocrystals as well as CdSe cluster molecules in a size range of 1 to 10 nm (Eichh鰂er et al., 2001). The...High performance Dynamic Light Scattering (DLS) has been used to determine the hydrodynamic di-ameters of CdSe nanocrystals as well as CdSe cluster molecules in a size range of 1 to 10 nm (Eichh鰂er et al., 2001). The method enables the determination of their particle size, including their ligand shells, in solution. The results are consistent with the blue shift of the absorption bands, as well as Transmission Electron Microscope (TEM) experiments. The sizes of the cluster molecules were estimated from space filling models constructed from the results of a single crystal X-ray structure determination. DLS gave comparable results for the size of both types of compound, indicating that it is potentially an important additional measurement technique to TEM, which uses harsh measurement conditions, and to powder X-ray diffraction, which is difficult to interpret below 5 nm.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21871076.21901060)Natural Science Foundation of Hebei Province(Nos.B2016205051,B2020205008 and B2019205074)+2 种基金Science and Technology Project of Hebei Education Department(No.BJ2020037)Project funded by China Postdoctoral Science Foundation(No.2021TQ0095)the Science Foundation of Hebei Normal University(No.L2019B15).
文摘Photo-assisted electrochemical technique provides a promising approach towards carcinogen chromium(Ⅵ)detection,which requires reasonable catalyst design.Herein,an unusual hexa-nuclear cadmium cluster functionalized reductive phosphomolybdate hybrid as photo-electrochemical sensor was designed and synthesized with formula of{[Cd(H_(2)O)_(2)]_(2)[Cd(btmbp)]_(2)}{Cd(P_(4)Mo_(6)O_(31)H_(7))_(2)}·20H_(2)O(1)(btmbp=4,4′-bis((^(1)H-1,2,4-triazol-1-yl)methyl)biphenyl),in which the photoactive hexa-nuclear{Cd_(6)}clusters cooperated with reductive phosphomolybdate[P_(4)Mo_(6)O_(31)]^(12)−endow the material with wide light absorption and remarkable redox activity,thus achieving efficient photo-assisted electrochemical Cr(Ⅵ)detection performance.Under visible-light assistance,the detection limit(LOD)and sensitivity of Cr(Ⅵ)is 4.17 nmol/L(0.225 ppb)and 226.32μA L/μmol,which is apparently superior to the performance without photo-assistance(6.25 nmol/L and 106.95μA L/μmol)and far satisfies the demands of world health organization(WHO)for potable water(50 ppb).Moreover,compound 1 showed prominent Cr(Ⅵ)detection performance in practical water samples together with remarkable anti-interference capacity and good electrochemical durability.This work provides an important guidance for designing efficient polyoxometalate-based crystalline sensors for Cr(Ⅵ)detection.
基金Supported by theNNSFC(No.51108122)Open Project of State Key Laboratory of Urban Water Resource and Environment,Harbin Institute of Technology(No.QA201025)+1 种基金Fundamental Research Funds for the Central Universities(No.HIT.NSRIF.2010053)Science and Technology Innovation Talents Special Foundation of Harbin(2010RFQXG035 and 2007RFXXG018)
文摘A new sandwiched polyoxometalate [HK11Cd4Cl2（PW9034）2]·18H2O （1）, incor- porating a unique hybrid tetranuclear cadmium cluster （abbreviated to {Cd4}） with two trivacant polyanions [B-α-PW9O34]9-, has been hydrothermally synthesized and structurally characterized by elemental analyses, IR spectroscopy, UV-vis, and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, space group C2/c, a = 19.2997（4）, b = 13.8014（3）, c = 31.9819（8） A, β = 102.764（2）°, V= 8308.3（3） A3, Z = 4, P2O86Cl2K11Cd4W18H37, Mr = 5735.13, Dc = 4.584 mg-mm-3, F（000） = 10084, μ = 26.579 mm-1, the final R = 0.0378 and wR = 0.0989 for 6558 observed reflections （I〉 2σ（I））. X-ray crystallographic study shows that the molecular structure of 1 contains four cadmium atoms. Two CdO6 distorted octahedra and two CdOsC1 distorted octahedra combine with each other in turn via edge-sharing, resulting in a regular rhomb-like cluster sandwiched between two {B-a-PW9034} units. Further, the sandwich-type polyoxoanions were connected by K＋ ions to form a complicated 3-D open-framework through connecting with each terminal O atom of the [Cd4C12（PW9O34）2]12- polyoxoanions. In addition, compound 1 exhibits photoluminescence property at room temperature and the band gap can be assessed at 3.25 eV.
基金supported by the financial support of National Natural Science Foundation of China(21201023)the scientific research fund of Hubei Provincial Education Department(D20131202)
文摘A novel 2-D {[Cd4（tpt）2（Cl）4（2,4-pdc）2]·4H2O}n （1） has been synthesized from the hydrothermal reaction of 3,5,6-tris（2-pyridyl）-1,3,5-triazine （tpt）, hydrated CdCI2, and 2,4-dicarboxylic acid （2,4-H2pdc）. Compound 1 crystallizes in triclinic, P1^- space group with a = 8.9434（5）, b = 9.5486（7）, c = 17.5772 （8） A, a = 75.014 （5）, β= 83.778（5）, γ = 68.304（6）°, V = 1347.14（14） A^3, C50H38Cd4C14N14O12, Mr = 1618.32, Dc = 1.990 g/cm^3, S = 0.95,μ（MoKa） = 1.83 mm^-1, F（000） = 788, Z = 1, R = 0.039 and wR = 0.080. The structure consists of tetranuclear [Cd4（tpt）2（Cl）4]^4＋ cores as the secondary building unit, which is further connected by the ligand pdc2 to give a 2-D extended structure. Tpt entities are located on both sides of each 2-D framework and act as ＇side arms＇ to form a corrugated layer and the adjacent layers are arranged in a tongue-and-groove interdigitating fashion. 1 was characterized by IR, TGA, PX1RD, and elemental analysis. The solid state luminescent properties were also investigated at room temperature.
文摘In this paper a new cadmium(Ⅱ) complex,[Cd(H2PTA)(H2O)3].3H2O,has been synthesized and characterized by elemental analysis,IR,and X-ray diffraction single crystal structure ananlysis. It belongs to triclinic system,with space group P1,a=0.947 84(19) nm,b=0.990 8(2) nm,c=0.994 3(2) nm,α=114.06(3)°,β=98.56(3)°,γ=111.29(3)°,V=0.744 5(3) nm3,Z=2. This complex is a binuclear unit,and then the binuclear molecules are alternatively assembled into 3D supramolecular network by hydrogen-bond in which there exists a (H2O)4 water cluster. CCDC:724104.
文摘High performance Dynamic Light Scattering (DLS) has been used to determine the hydrodynamic di-ameters of CdSe nanocrystals as well as CdSe cluster molecules in a size range of 1 to 10 nm (Eichh鰂er et al., 2001). The method enables the determination of their particle size, including their ligand shells, in solution. The results are consistent with the blue shift of the absorption bands, as well as Transmission Electron Microscope (TEM) experiments. The sizes of the cluster molecules were estimated from space filling models constructed from the results of a single crystal X-ray structure determination. DLS gave comparable results for the size of both types of compound, indicating that it is potentially an important additional measurement technique to TEM, which uses harsh measurement conditions, and to powder X-ray diffraction, which is difficult to interpret below 5 nm.
