A new member of mixed-metal Ba2Bi2M-Ⅱ（PO4）4 monophosphate, namely Ba2Bi2Co（PO4）4, was synthesized by solid state method and characterized by X-ray single-crystal diffraction and powder diffraction for the first t...A new member of mixed-metal Ba2Bi2M-Ⅱ（PO4）4 monophosphate, namely Ba2Bi2Co（PO4）4, was synthesized by solid state method and characterized by X-ray single-crystal diffraction and powder diffraction for the first time. It crystallizes in the orthorhombic system with space group Pnma（No. 62） and features a 3D architecture built up of adjacent zig-zag linear structures of [CoP4O（16）]∞ along [100], and further connected by [Bi2O（11）] dimers to form a 3D framework, where the Ba2＋ are located in the free space. The stereochemical activity of the Bi3＋ lone pair has also been discussed. The result of magnetic property measurement confirms the antiferromagnetic property of Ba2Bi2Co（PO4）4.展开更多
The mixed-metal cluster Yb4O4（OiPr）16Na12 has been synthesized and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. The crystal belongs to the cubic system, space group P23 wi...The mixed-metal cluster Yb4O4（OiPr）16Na12 has been synthesized and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. The crystal belongs to the cubic system, space group P23 with a = b = c = 13.9788（3）A, V = 2731.55（10）A3, Z = 1, Dc = 1.202 g/cm3, Mr = 1977.42,/J = 3.480 mm-1, F（000） = 972, the final R = 0.0288 and wR = 0.1511 for 1677 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that Yb4O4（Oipr）16Na12 is centrosym- metric and the structure contains four ytterbium metals and twelve sodium metals, and each ytterbium atom is coordinated by six oxygen atoms. In addition, an ancillary computational analysis of the optimized molecular unit was provided. The large energy gap （3,31 eV） between HOMO and LUMO indicates that the structure framework is particularly stable.展开更多
The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane,...The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.展开更多
Two mixed metal complexes [Cr2Fe(μ3-O) (μ-O2CC2H5)6Py3]Cl (A)and [CrFe2 (μ3-O) (μ-O2CC2H5 )6Py3] Cl (B) have been prepared in non-aqueous sol-vents. Crystal (A) is monoclinic, space group C2/c, with a= 13. 782(3),...Two mixed metal complexes [Cr2Fe(μ3-O) (μ-O2CC2H5)6Py3]Cl (A)and [CrFe2 (μ3-O) (μ-O2CC2H5 )6Py3] Cl (B) have been prepared in non-aqueous sol-vents. Crystal (A) is monoclinic, space group C2/c, with a= 13. 782(3), b= 18. 381(4), c= 16. 643(2) A, β= 92. 84(5)°, V=4211. 1 (4) A3, Z=4, Mr= 887. 03, Dc= 1. 40 g/cm3, μ= 5. 0 cm-1, F(000) = 1836 and R(Rw) = 0. 057(0. 062) for 2134 unique reflections with I> 3δ(I). Crystal (B) is also monoclinic, space group C2/c ,with a= 13. 793(4), b= 18. 401 (6), c= 16. 657(5) A’, β= 93. 18(3)°, V=4221. 3(5) A3, Z= 4, Mr=890. 88, Dc= 1. 40 g/cm3, μ= 10. 5 cm-1, F(000) = 1844 and R(Rw) = 0. 067 (0. 069) for 2131 unique reflections with I>3δ(I). Both (A) and (B)have been characterized by IR spectra. Besides, the relations between the structuresand IR are discussed.展开更多
The heterotrinuclear cluster compound [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub>-（ H<sub>2<...The heterotrinuclear cluster compound [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub>-（ H<sub>2</sub>O）<sub>3</sub>] ZnBr4·4H<sub>2</sub>O was prepared by the redox reaction of Mo （CO）<sub>6</sub> with Na<sub>2</sub>W<sub>O</sub>4 in propionic anhydride. The crystal is monoclinic of space group P2/c with a =16. 334（4） , b= 9. 657（5） , c=19. 889（9） ,β= 139. 79 （5）°,V= 2026 （2） ￣3 , Z=2 , D<sub>c</sub>=2. 30 g/cm￣3 μ（MoKa） =106. 6 cm￣（-1） ,F（000）=1176 ,final R=0. 065 and R<sub>ω</sub>=0. 072 for 1964 reflections with I≥3σ（I）. In the structure of cation [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub> （H<sub>2</sub>O）<sub>3</sub>]￣（2+） molybdenum and tungsten atoms are statistically disordered. Three metal atoms form an equilateral triangle with the distance of M-M being 2. 735.展开更多
Ammonia is the feedstock chemical for most fertilizers and the alternative of renewable energy carriers.Environmentally benign electrochemical nitrogen reduction reaction (NRR) under mild conditions has been recognize...Ammonia is the feedstock chemical for most fertilizers and the alternative of renewable energy carriers.Environmentally benign electrochemical nitrogen reduction reaction (NRR) under mild conditions has been recognized as one of the most attractive strategies for N_(2) fixation.Herein,inspired by Mobased nitrogenase,W/Mo-doping electrocatalysts were developed with mixed-metal polyoxometalate H_(3)PW_6Mo_6O_(40) as the precursor for high performance electrocatalytic NRR.Trace amount of Pt was transplanted on the surface of W/Mo@rGO via in situ electroplating treatment to further improve the NRR performance.The resulting Pt-W/Mo@rGO-6 achieves excellent performance for NRR with a high NH_(3)yield of 79.2μg h^(-1)mg_(cat)^(-1) due to the multicomponent synergistic effect in the composite catalyst.The Pt-W/Mo@rGO-6 represents the first example of highly efficient NRR electraocatalyst derived from mixed-metal polyoxometalate,which exhibits outstanding stability confirmed by the constant catalytic performance over 24 h chronoamperometric test.This finding opens a new avenue to construct highly efficient NRR electrocatalyst by employing mixed metal polyoxometalate as the precursor under ambient conditions.展开更多
Coordination polymers(CPs)have great potential to be used in electrocatalysis owing to their designable compositions and structures.It is highly challenging to apply CPs as electrocatalysts for oxygen evolution reacti...Coordination polymers(CPs)have great potential to be used in electrocatalysis owing to their designable compositions and structures.It is highly challenging to apply CPs as electrocatalysts for oxygen evolution reaction(OER)on account of insufficient catalytic efficiency and relatively poor stability of current electrocatalysts.Herein,through a mixed-metal strategy,one-dimensional Co_(x)Ni_(1-x)-HIPA with dual active sites was synthesized and studied for OER electrocatalysts.By changing the metal ratio of CoxNi1-x-HIPA,the OER performance was well regulated.The optimized Co_(1/2)Ni_(1/2)-HIPA exhibited minimum reaction activation energy,and represented an overpotential of 367 m V to reach 10 mA/cm^(2) at 25℃.Moreover,an overpotential of 314 m V at 10 m A/cm^(2) was obtained from Co_(1/2)Ni_(1/2)-HIPA at 55℃.This mixed-metal strategy provides a feasible way for adjusting the electronic states of the electrocatalysts to improve the electrocatalytic OER performance.展开更多
In this research, for the first time, a series of Co(Ⅱ) doped copper terephthalate(Co X-Cu BDC,where X is doping percentage) were successfully synthesized via solvothermal method and were tested for dye removal appli...In this research, for the first time, a series of Co(Ⅱ) doped copper terephthalate(Co X-Cu BDC,where X is doping percentage) were successfully synthesized via solvothermal method and were tested for dye removal application. The physical properties of Co X-CuBDC were studied by several techniques including X-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), energy-dispersive spectroscopy(EDS), thermogravimetric analysis(TGA)and Brunauer–Emmett–Teller(BET) surface area analysis. The incorporation of Co(Ⅱ) dopant leads to isomorphic substitution of Cu(II) in the CuBDC framework with the maximum doping percentage of 22. Doping and parent MOFs which are non-porous were used for removal of Methylene Blue(MB) from aqueous solution. Adsorption capacity of Co22-CuBDC and CuBDC are 52 and 58 mg/g, respectively, both of which are higher than the adsorption capacity recorded from several high porosity MOFs. Adsorption kinetic studies indicate that adsorption process follows pseudo-second order model while the adsorption mechanism is dominated by electrostatic attraction. Overall, even though these materials show non-porous characteristic,it can be used effectively in wastewater treatment application.展开更多
基金Supported by the National Natural Science Foundation of China(No.21101156)the State Key Laboratory of Structural Chemistry(No.20150016)+1 种基金Outstanding youth of colleges and universities of Department of Education,Fujian Province Natural Science Foundation for Youths(No.2016J05109)Fujian Education Department(No.JK2015056)
文摘A new member of mixed-metal Ba2Bi2M-Ⅱ（PO4）4 monophosphate, namely Ba2Bi2Co（PO4）4, was synthesized by solid state method and characterized by X-ray single-crystal diffraction and powder diffraction for the first time. It crystallizes in the orthorhombic system with space group Pnma（No. 62） and features a 3D architecture built up of adjacent zig-zag linear structures of [CoP4O（16）]∞ along [100], and further connected by [Bi2O（11）] dimers to form a 3D framework, where the Ba2＋ are located in the free space. The stereochemical activity of the Bi3＋ lone pair has also been discussed. The result of magnetic property measurement confirms the antiferromagnetic property of Ba2Bi2Co（PO4）4.
基金Supported by the National Natural Science Foundation of China(No.20902001 and 21102001)the Natural Science Foundation of Anhui Province(No.090416220)the 211 Project of Anhui University
文摘The mixed-metal cluster Yb4O4（OiPr）16Na12 has been synthesized and structurally determined by IR, elemental analysis, and single-crystal X-ray diffraction. The crystal belongs to the cubic system, space group P23 with a = b = c = 13.9788（3）A, V = 2731.55（10）A3, Z = 1, Dc = 1.202 g/cm3, Mr = 1977.42,/J = 3.480 mm-1, F（000） = 972, the final R = 0.0288 and wR = 0.1511 for 1677 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that Yb4O4（Oipr）16Na12 is centrosym- metric and the structure contains four ytterbium metals and twelve sodium metals, and each ytterbium atom is coordinated by six oxygen atoms. In addition, an ancillary computational analysis of the optimized molecular unit was provided. The large energy gap （3,31 eV） between HOMO and LUMO indicates that the structure framework is particularly stable.
文摘The complexes [Pt2L2（μ-dppm）]（ClO4）2 （1） and {[Pt2L2（μ-dppm）Li（CH3CN）2]（ClO4）3}n （2）, where HL is 6-[4-（diethoxyphosphorylmethyl）phenyl]-2,2′-bipyridinyl and dppm is bis（diphenylphosphino）methane, have been synthesized and characterized. In complex 1 the platinum（Ⅱ） center adopts a distorted square planar coordination geometry. The polymer 2 exhibits a ＂stairstep＂ configuration with one-dimensional Pt（Ⅱ）N^N^CPO- Li（Ⅰ）-OPC^N^ NPt（Ⅱ） mixed-metal units which are linked through dppm. Both complexes have metal-metal interaction with Pt- Pt distances of 3.325（2） and 3.1432（9） A, respectively, and display strong metal-metal-to-ligand charge-transfer （MMLCT） triplet state emission. The density-functional-theory calculation was used to interpret the absorption spectra of the complexes.
文摘Two mixed metal complexes [Cr2Fe(μ3-O) (μ-O2CC2H5)6Py3]Cl (A)and [CrFe2 (μ3-O) (μ-O2CC2H5 )6Py3] Cl (B) have been prepared in non-aqueous sol-vents. Crystal (A) is monoclinic, space group C2/c, with a= 13. 782(3), b= 18. 381(4), c= 16. 643(2) A, β= 92. 84(5)°, V=4211. 1 (4) A3, Z=4, Mr= 887. 03, Dc= 1. 40 g/cm3, μ= 5. 0 cm-1, F(000) = 1836 and R(Rw) = 0. 057(0. 062) for 2134 unique reflections with I> 3δ(I). Crystal (B) is also monoclinic, space group C2/c ,with a= 13. 793(4), b= 18. 401 (6), c= 16. 657(5) A’, β= 93. 18(3)°, V=4221. 3(5) A3, Z= 4, Mr=890. 88, Dc= 1. 40 g/cm3, μ= 10. 5 cm-1, F(000) = 1844 and R(Rw) = 0. 067 (0. 069) for 2131 unique reflections with I>3δ(I). Both (A) and (B)have been characterized by IR spectra. Besides, the relations between the structuresand IR are discussed.
文摘The heterotrinuclear cluster compound [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub>-（ H<sub>2</sub>O）<sub>3</sub>] ZnBr4·4H<sub>2</sub>O was prepared by the redox reaction of Mo （CO）<sub>6</sub> with Na<sub>2</sub>W<sub>O</sub>4 in propionic anhydride. The crystal is monoclinic of space group P2/c with a =16. 334（4） , b= 9. 657（5） , c=19. 889（9） ,β= 139. 79 （5）°,V= 2026 （2） ￣3 , Z=2 , D<sub>c</sub>=2. 30 g/cm￣3 μ（MoKa） =106. 6 cm￣（-1） ,F（000）=1176 ,final R=0. 065 and R<sub>ω</sub>=0. 072 for 1964 reflections with I≥3σ（I）. In the structure of cation [MoW<sub>2</sub>O<sub>2</sub> （O<sub>2</sub>CC<sub>2</sub>H<sub>5</sub> ）<sub>6</sub> （H<sub>2</sub>O）<sub>3</sub>]￣（2+） molybdenum and tungsten atoms are statistically disordered. Three metal atoms form an equilateral triangle with the distance of M-M being 2. 735.
基金supported by the National Natural Science Foundation of China(Nos.92161103,U21A20286,22071180)Natural Science Foundation of Tianjin City of China(No.18JCJQJC47700)。
文摘Ammonia is the feedstock chemical for most fertilizers and the alternative of renewable energy carriers.Environmentally benign electrochemical nitrogen reduction reaction (NRR) under mild conditions has been recognized as one of the most attractive strategies for N_(2) fixation.Herein,inspired by Mobased nitrogenase,W/Mo-doping electrocatalysts were developed with mixed-metal polyoxometalate H_(3)PW_6Mo_6O_(40) as the precursor for high performance electrocatalytic NRR.Trace amount of Pt was transplanted on the surface of W/Mo@rGO via in situ electroplating treatment to further improve the NRR performance.The resulting Pt-W/Mo@rGO-6 achieves excellent performance for NRR with a high NH_(3)yield of 79.2μg h^(-1)mg_(cat)^(-1) due to the multicomponent synergistic effect in the composite catalyst.The Pt-W/Mo@rGO-6 represents the first example of highly efficient NRR electraocatalyst derived from mixed-metal polyoxometalate,which exhibits outstanding stability confirmed by the constant catalytic performance over 24 h chronoamperometric test.This finding opens a new avenue to construct highly efficient NRR electrocatalyst by employing mixed metal polyoxometalate as the precursor under ambient conditions.
基金the National Natural Science Foundation of China(Nos.21622105 and 21931004)the Natural Science Foundation of Tianjin(No.18JCJQJC47200)the Ministry of Education of China(No.B12015)。
文摘Coordination polymers(CPs)have great potential to be used in electrocatalysis owing to their designable compositions and structures.It is highly challenging to apply CPs as electrocatalysts for oxygen evolution reaction(OER)on account of insufficient catalytic efficiency and relatively poor stability of current electrocatalysts.Herein,through a mixed-metal strategy,one-dimensional Co_(x)Ni_(1-x)-HIPA with dual active sites was synthesized and studied for OER electrocatalysts.By changing the metal ratio of CoxNi1-x-HIPA,the OER performance was well regulated.The optimized Co_(1/2)Ni_(1/2)-HIPA exhibited minimum reaction activation energy,and represented an overpotential of 367 m V to reach 10 mA/cm^(2) at 25℃.Moreover,an overpotential of 314 m V at 10 m A/cm^(2) was obtained from Co_(1/2)Ni_(1/2)-HIPA at 55℃.This mixed-metal strategy provides a feasible way for adjusting the electronic states of the electrocatalysts to improve the electrocatalytic OER performance.
基金funded by the new researcher in science and technology supporting fund of Thailand(No.SCH-NR2014-172)
文摘In this research, for the first time, a series of Co(Ⅱ) doped copper terephthalate(Co X-Cu BDC,where X is doping percentage) were successfully synthesized via solvothermal method and were tested for dye removal application. The physical properties of Co X-CuBDC were studied by several techniques including X-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), energy-dispersive spectroscopy(EDS), thermogravimetric analysis(TGA)and Brunauer–Emmett–Teller(BET) surface area analysis. The incorporation of Co(Ⅱ) dopant leads to isomorphic substitution of Cu(II) in the CuBDC framework with the maximum doping percentage of 22. Doping and parent MOFs which are non-porous were used for removal of Methylene Blue(MB) from aqueous solution. Adsorption capacity of Co22-CuBDC and CuBDC are 52 and 58 mg/g, respectively, both of which are higher than the adsorption capacity recorded from several high porosity MOFs. Adsorption kinetic studies indicate that adsorption process follows pseudo-second order model while the adsorption mechanism is dominated by electrostatic attraction. Overall, even though these materials show non-porous characteristic,it can be used effectively in wastewater treatment application.
