A novel cobalt（Ⅱ） coordination polymer, [Co（tdc）（bpmp）（H2O）]n（1）, was hydrothermally synthesized using 2,5-thiophenedicarboxylate（tdc） and bis（4-pyridylmethyl）piperazine（bpmp） ligand as the organic li...A novel cobalt（Ⅱ） coordination polymer, [Co（tdc）（bpmp）（H2O）]n（1）, was hydrothermally synthesized using 2,5-thiophenedicarboxylate（tdc） and bis（4-pyridylmethyl）piperazine（bpmp） ligand as the organic linkers. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the monoclinic Cc space group, with a = 18.836（2）, b = 5.9540（7）, c = 20.414（2） A, β = 97.4300（10）°, V = 2270.1（5） A3, Z = 4, Mr = 515.44, Dc = 1.508 Mg/m^3, μ = 0.890 mm-1, F（000） = 1068, the final R = 0.0263 and w R = 0.0665 for 3714 observed reflections with I 2σ（I）. In compound 1, the Co（Ⅱ） ions are connected by tdc2- anions to form a 1D double chain, and such chains are further linked by bpmp ligands to form a three-dimensional（3D） structure. Topologically, the structure of 1 represents a uninodal 3D dia（6^6） topology. What＇s more, powder X-ray diffraction patterns and photocatalytic property for 1 have also been investigated.展开更多
采用Co_(3)O_(4)吸附脱除模拟柴油中的喹啉、吡啶或苯胺,考察了最佳吸附温度、吸附时间等条件,同时进行了吸附热力学和动力学研究;基于第一性原理对Co_(3)O_(4)晶胞进行相分析,对3种氮化物进行最高占据分子轨道(HOMO)-最低未占据分子轨...采用Co_(3)O_(4)吸附脱除模拟柴油中的喹啉、吡啶或苯胺,考察了最佳吸附温度、吸附时间等条件,同时进行了吸附热力学和动力学研究;基于第一性原理对Co_(3)O_(4)晶胞进行相分析,对3种氮化物进行最高占据分子轨道(HOMO)-最低未占据分子轨道(LUMO)分析,计算了吸附构型的吸附能和最稳定吸附构型的Mulliken电荷转移与电子密度。结果表明:在15 mL模拟柴油中加入0.6 g Co_(3)O_(4),苯胺、吡啶、喹啉的最佳吸附温度分别为20、20和30℃,最佳吸附时间分别为30、30、40 min,吸附容量由大到小顺序均为苯胺>吡啶>喹啉。热力学与动力学分析表明,喹啉、吡啶、苯胺的吸附均更符合多分子层吸附的Freundlich模型和准二级动力学方程。HOMO-LUMO分析结果表明,Co_(3)O_(4)为电子接受体,3种氮化物为电子给予体,Co_(3)O_(4)对喹啉、吡啶的配位吸附结构最稳定,对苯胺的π络合吸附最稳定。电荷转移计算表明,苯胺、吡啶、喹啉向Co_(3)O_(4)团簇转移的电荷数分别为0.423、0.394、0.368,说明Co_(3)O_(4)吸附3种氮化物的吸附能力大小为苯胺>吡啶>喹啉;电子密度图结果表明,最稳定吸附结构中Co_(3)O_(4)与3种氮化物均形成了化学键。展开更多
By using ＂pillaring＂ strategy, a new Co（Ⅱ）-MOF, [Co_2（abtc）（bimb）_2]·2H_2O（1, H_4abtc = 3,3？,5,5？-azobenzenetetracarboxylic acid, bimb = 4,4？-bis（imidazole-1-ylmethyl）biphenyl）, has been solvother...By using ＂pillaring＂ strategy, a new Co（Ⅱ）-MOF, [Co_2（abtc）（bimb）_2]·2H_2O（1, H_4abtc = 3,3？,5,5？-azobenzenetetracarboxylic acid, bimb = 4,4？-bis（imidazole-1-ylmethyl）biphenyl）, has been solvothermally synthesized and structurally characterized. The structural determination revealed that 1 features a 3D pillar-layered framework with（4,8）-connected {4^4.6^2}{4^8.6^（20）} topology based on dinuclear Co（Ⅱ）-SBUs. The magnetic investigation shows that the dominant antiferromagnetic coupling is observed in compound 1.展开更多
基金supported by the Natural Science Foundation of Henan Province(132300410326)
文摘A novel cobalt（Ⅱ） coordination polymer, [Co（tdc）（bpmp）（H2O）]n（1）, was hydrothermally synthesized using 2,5-thiophenedicarboxylate（tdc） and bis（4-pyridylmethyl）piperazine（bpmp） ligand as the organic linkers. X-ray single-crystal diffraction determination reveals that 1 crystallizes in the monoclinic Cc space group, with a = 18.836（2）, b = 5.9540（7）, c = 20.414（2） A, β = 97.4300（10）°, V = 2270.1（5） A3, Z = 4, Mr = 515.44, Dc = 1.508 Mg/m^3, μ = 0.890 mm-1, F（000） = 1068, the final R = 0.0263 and w R = 0.0665 for 3714 observed reflections with I 2σ（I）. In compound 1, the Co（Ⅱ） ions are connected by tdc2- anions to form a 1D double chain, and such chains are further linked by bpmp ligands to form a three-dimensional（3D） structure. Topologically, the structure of 1 represents a uninodal 3D dia（6^6） topology. What＇s more, powder X-ray diffraction patterns and photocatalytic property for 1 have also been investigated.
文摘采用Co_(3)O_(4)吸附脱除模拟柴油中的喹啉、吡啶或苯胺,考察了最佳吸附温度、吸附时间等条件,同时进行了吸附热力学和动力学研究;基于第一性原理对Co_(3)O_(4)晶胞进行相分析,对3种氮化物进行最高占据分子轨道(HOMO)-最低未占据分子轨道(LUMO)分析,计算了吸附构型的吸附能和最稳定吸附构型的Mulliken电荷转移与电子密度。结果表明:在15 mL模拟柴油中加入0.6 g Co_(3)O_(4),苯胺、吡啶、喹啉的最佳吸附温度分别为20、20和30℃,最佳吸附时间分别为30、30、40 min,吸附容量由大到小顺序均为苯胺>吡啶>喹啉。热力学与动力学分析表明,喹啉、吡啶、苯胺的吸附均更符合多分子层吸附的Freundlich模型和准二级动力学方程。HOMO-LUMO分析结果表明,Co_(3)O_(4)为电子接受体,3种氮化物为电子给予体,Co_(3)O_(4)对喹啉、吡啶的配位吸附结构最稳定,对苯胺的π络合吸附最稳定。电荷转移计算表明,苯胺、吡啶、喹啉向Co_(3)O_(4)团簇转移的电荷数分别为0.423、0.394、0.368,说明Co_(3)O_(4)吸附3种氮化物的吸附能力大小为苯胺>吡啶>喹啉;电子密度图结果表明,最稳定吸附结构中Co_(3)O_(4)与3种氮化物均形成了化学键。
基金Supported by the National Natural Science Foundation of China(Nos.21201109,21373122 and 21301106)
文摘By using ＂pillaring＂ strategy, a new Co（Ⅱ）-MOF, [Co_2（abtc）（bimb）_2]·2H_2O（1, H_4abtc = 3,3？,5,5？-azobenzenetetracarboxylic acid, bimb = 4,4？-bis（imidazole-1-ylmethyl）biphenyl）, has been solvothermally synthesized and structurally characterized. The structural determination revealed that 1 features a 3D pillar-layered framework with（4,8）-connected {4^4.6^2}{4^8.6^（20）} topology based on dinuclear Co（Ⅱ）-SBUs. The magnetic investigation shows that the dominant antiferromagnetic coupling is observed in compound 1.
