CN103709182A - Transition metal compounds based on semi-rigid, synthetic method and applications - Google Patents
Transition metal compounds based on semi-rigid, synthetic method and applications Download PDFInfo
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- CN103709182A CN103709182A CN201310650212.XA CN201310650212A CN103709182A CN 103709182 A CN103709182 A CN 103709182A CN 201310650212 A CN201310650212 A CN 201310650212A CN 103709182 A CN103709182 A CN 103709182A
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- mip
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- dioctyl phthalate
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Abstract
Provided are a The molecular formulas are as follows: [Cu(3-bpah)(5-MIP)].2H20; [Ni(3-bpah)(5-MIP)].H20; [Co(3-bpah)(5-MIP)].H20; [Cu(4-bpah)(5-MIP)(H20)]; [Ni(4-bpah)(5-MIP)(H20)].H2O; [Co(4-bpah)(5-MIP)]. Transition metal chlorides, semi-rigid bispyridine bisamide ligands and 5-methyl isophthalic acid are added into deionized water, after pH adjustment, the above mixture is reacted under hydrothermal conditions, and products are obtained. The transition metal compounds are advantageous in that the transition metal compounds have a simple synthetic method, have strong affinity to organic pollutants of methylene blue, methyl orange and rhodamine B, and have good catalytic degradation effects.
Description
Technical field
The invention belongs to photocatalyst material and synthetic method field, particularly a kind of transition metal complex and synthetic method and application based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate.
Background technology
Transition metal functional complexes based on building containing oxygen organic carboxyl acid part and nitrogenous organic heterocyclic part mixed ligand is a kind of hybrid material of inorganic-organic functionalization, has that structure is rich and varied, catalytic performance good, the feature of applied range.Although utilize so far hydrothermal technique to synthesize that properties is excellent, the transition metal complex material of novel structure, but because transition metal ion not only can exert an influence to the properity of this type of hybrid material, and the change of Nitrogen-Containing Heterocyclic Ligand kind is also the important factor that determines functional complexes final structure and performance, the intrinsic structural performance of Nitrogen-Containing Heterocyclic Ligand can restrict the synthetic of this class functional complexes, as the quantity of the snappiness of part, part length, hapto etc.; Therefore, effectively design, the synthetic complex material with specific function are still more difficult.
At present, be used for constructing the shared ratio maximum of part that contains pyridine groups in the nitrogen heterocyclic ring organic ligand of transition metal functional complexes, but pyridine functional groups only plays the effect with transition-metal coordination, the title complex that causes its formation is hydrophobic nature, therefore poor to the affinity of water miscible organic pollutant, catalyzed degradation effect is poor.In addition, known functional title complex normally has good degradation capability to a certain specific organic pollutant in waste water as photocatalyst, the Some Organic Pollutants of catalysis simultaneously, and catalytic capability has limitation.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of, transition metal complex based on semi-rigid pair pyridine bisamide part and oreinol dioctyl phthalate and synthetic method and application that catalyzed degradation effective strong to multiple water soluble contaminants affinity.
Technical solution of the present invention is:
A transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, the molecular formula of this title complex is as follows:
[Cu(3-bpah)(5-MIP)]·2H
2O；
[Ni(3-bpah)(5-MIP)]·H
2O；
[Co(3-bpah)(5-MIP)]·H
2O；
[Cu(4-bpah)(5-MIP)(H
2O)]；
[Ni(4-bpah)(5-MIP)(H
2O)]·H
2O；
[Co(4-bpah)(5-MIP)]；
Wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 4-bpah is
n,
n'-bis-(Isonicotinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate.
onethe synthetic method of planting the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, its concrete steps are:
By Cu
2+or Ni
2+or Co
2+muriate, the semi-rigid pair of pyridine bisamide part, oreinol dioctyl phthalate, add deionized water, at room temperature stir 20min～60min and form suspended mixture, the mol ratio of described semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate is 1:1～1:2, described semi-rigid pair of pyridine bisamide part and Cu
2+, Ni
2+, Co
2+muriatic mol ratio be 1:1～1:3, with NaOH solution, adjusting pH is 6.0～7.5, pour in autoclave and be warming up to 110 ℃～130 ℃, under hydrothermal condition, be incubated 48h～96h, cool to room temperature and obtain bulk crystals, with deionized water and ethanol, alternately clean 2 times～5 times, under room temperature, naturally dry, obtain the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate.
Semi-rigid pair of described pyridine bisamide part is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene or
n,
n'-bis-(Isonicotinamide)-1,2-hexanaphthene.
Described Cu
2+, Ni
2+, Co
2+the mol ratio of muriate, the semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate be 2:1:1.5.
Described Cu
2+, Ni
2+, Co
2+muriate be respectively CuCl
22H
2o, NiCl
26H
2o, CoC l
26H
2o.
During intensification, temperature rise rate is 5 ℃/h～15 ℃/h; During cooling, rate of temperature fall is 2.5 ℃/h～10 ℃/h.
The add-on of described deionized water is 30%～70% of autoclave volume.
The concentration of described NaOH solution is 0.1mol/L～1.0mol/L.
A kind of transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate is as the application in photocatalyst material.
A kind of transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate is as the application in the photocatalyst material of methylenum coeruleum organic pollutant, tropeolin-D organic pollutant and rhodamine B organic pollutant.
The present invention with
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene or
n,
n'-bis-(Isonicotinamide)-1,2-cyclohexane give is neutral organic ligand, usings oreinol dioctyl phthalate as anion ligand, semirigid by changing
n,
n'-bis-(pyridine carboxamide)-1, in 2-hexanaphthene part, the difference of pyridine nitrogen position is adjusted the structure of title complex; In two pyridine ligands, introduce the length that can increase organic ligand and the snappiness of bisamide group, can participate in by changing flexibly part configuration the coordination of transition metal ion, thereby adjust the structure of title complex; The introducing of the amide group in this type of part not only can make title complex form higher-dimension supramolecular structure by hydrogen bond action, and can increase the wetting ability of title complex, thereby makes title complex have good catalytic performance; 6 transition metal complexes respectively with one dimension, 2 and 3 dimensional organization have been synthesized.Wherein, [Cu (3-bpah) (5-MIP)] 2H
2o is two dimension (4,4) trellis; [Ni (3-bpah) (5-MIP)] H
2o and [Co (3-bpah) (5-MIP)] H
2o is isostructural compounds, and they are 3-dimensional metal-organic backbone, shown a kind of (2,3,5) of three nodes-connected (4
268
410
212) (4
26) (8) topological framework; [Cu (4-bpah) is (H (5-MIP) for title complex
2o)] metal-organic framework is two-dimentional waviness layer structure; [Ni (4-bpah) is (H (5-MIP) for title complex
2o)] H
2o's is one dimension duplex structure; Title complex [Co (4-bpah) (5-MIP)] is a kind ofly to have (4
26) (4
368
410
2) the metal-organic framework structure of two-dimensional double-layer of (4) topological characteristic.Its beneficial effect is:
(1) synthetic method is simple, and synthesis material cost is low, and synthesis cycle is short, and power consumption is low, and in semi-rigid pair of pyridine bisamide part, the position of pyridine nitrogen hapto is adjustable;
(2) adopt oreinol dioctyl phthalate as anion ligand, bisamide group in semi-rigid pair of pyridine bisamide part is polar group, there is good good hydrophilic property, crystallisation process while having accelerated synthetic transition metal complex, shortened synthesis cycle, constant temperature time shortens, and power consumption reduces; In semirigid pair of pyridine bisamide part, hexanaphthene group is to exist with chair form or boat conformation, and two kinds of different conformations have increased the adaptive faculty of itself and transition metal ion coordination, have improved synthetic yield, have reduced synthetic cost;
(3) poorly water-soluble of synthetic transition metal complex under hydrothermal condition, has prevented the secondary pollution to environment;
(4) synthetic transition metal complex is strong to the affinity of multiple water miscible organic pollutant molecule, catalyzed degradation is effective, to the photocatalytic activity of methylenum coeruleum organic pollutant, can reach 55%～91%, to the photocatalytic activity of tropeolin-D organic pollutant, can reach 50%～78%, to the photocatalytic activity of rhodamine B organic pollutant, can reach 30%～40%, can be used as the photocatalyst material of Some Organic Pollutants.
Accompanying drawing explanation
Fig. 1 is [Cu (3-bpah) (5-MIP)] of the present invention 2H
2the XRD diffractogram of O;
Fig. 2 is [Ni (3-bpah) (5-MIP)] of the present invention H
2the XRD diffractogram of O;
Fig. 3 is [Co (3-bpah) (5-MIP)] of the present invention H
2the XRD diffractogram of O;
Fig. 4 is that of the present invention [Cu (4-bpah) is (H (5-MIP)
2o)] XRD diffractogram;
Fig. 5 is that of the present invention [Ni (4-bpah) is (H (5-MIP)
2o)] H
2the XRD diffractogram of O;
Fig. 6 is the XRD diffractogram of [Co (4-bpah) (5-MIP)] of the present invention;
Fig. 7 is the thermogram of the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and oreinol dioctyl phthalate of the present invention;
Fig. 8 is [Cu (3-bpah) (5-MIP)] of the present invention 2H
2the coordination environment figure of O;
Fig. 9 is [Cu (3-bpah) (5-MIP)] of the present invention 2H
2the two-dimensional layer structure iron of O;
Figure 10 is [Ni (3-bpah) (5-MIP)] of the present invention H
2the coordination environment figure of O;
Figure 11 is [Ni (3-bpah) (5-MIP)] of the present invention H
2the tomograph of O;
Figure 12 is [Ni (3-bpah) (5-MIP)] of the present invention H
2the three-dimensional topology structure iron of O;
Figure 13 is [Co (3-bpah) (5-MIP)] of the present invention H
2the coordination environment figure of O;
Figure 14 is that of the present invention [Cu (4-bpah) is (H (5-MIP)
2o)] coordination environment figure;
Figure 15 is that of the present invention [Cu (4-bpah) is (H (5-MIP)
2o)] two-dimensional network figure;
Figure 16 is that of the present invention [Ni (4-bpah) is (H (5-MIP)
2o)] H
2the coordination environment figure of O;
Figure 17 is that of the present invention [Ni (4-bpah) is (H (5-MIP)
2o)] H
2the one-dimensional chain structure iron of O;
Figure 18 is the coordination environment figure of [Co (4-bpah) (5-MIP)] of the present invention;
Figure 19 is the two-dirnentional structure figure of [Co (4-bpah) (5-MIP)] of the present invention;
Figure 20 adds [Cu (3-bpah) (5-MIP)] of the present invention 2H
2the photocatalytic degradation uv-absorbing figure of the methylenum coeruleum of O;
Figure 21 adds [Ni (3-bpah) (5-MIP)] of the present invention H
2the photocatalytic degradation uv-absorbing figure of the methylenum coeruleum of O;
Figure 22 adds [Co (3-bpah) (5-MIP)] of the present invention H
2the photocatalytic degradation uv-absorbing figure of the methylenum coeruleum of O;
Figure 23 adds that of the present invention [Cu (4-bpah) is (H (5-MIP)
2the photocatalytic degradation uv-absorbing figure of methylenum coeruleum O)];
Figure 24 adds that of the present invention [Ni (4-bpah) is (H (5-MIP)
2o)] H
2the photocatalytic degradation uv-absorbing figure of the methylenum coeruleum of O;
Figure 25 is the photocatalytic degradation uv-absorbing figure that adds the methylenum coeruleum of [Co (4-bpah) (5-MIP)] of the present invention;
Figure 26 is the degradation rate figure of the different UV-irradiation of aqueous solution of methylene blue under the time that adds six kinds of title complexs of the present invention;
Figure 27 adds [Cu (3-bpah) (5-MIP)] of the present invention 2H
2the photocatalytic degradation uv-absorbing figure of the tropeolin-D of O;
Figure 28 adds [Ni (3-bpah) (5-MIP)] of the present invention H
2the photocatalytic degradation uv-absorbing figure of the tropeolin-D of O;
Figure 29 adds [Co (3-bpah) (5-MIP)] of the present invention H
2the photocatalytic degradation uv-absorbing figure of the tropeolin-D of O;
Figure 30 adds that of the present invention [Cu (4-bpah) is (H (5-MIP)
2the photocatalytic degradation uv-absorbing figure of tropeolin-D O)];
Figure 31 adds that of the present invention [Ni (4-bpah) is (H (5-MIP)
2o)] H
2the photocatalytic degradation uv-absorbing figure of the tropeolin-D of O;
Figure 32 is the photocatalytic degradation uv-absorbing figure that adds the tropeolin-D of [Co (4-bpah) (5-MIP)] of the present invention;
Figure 33 is the degradation rate figure of the different UV-irradiation of methyl orange aqueous solution under the time that adds six kinds of title complexs of the present invention;
Figure 34 adds [Cu (3-bpah) (5-MIP)] of the present invention 2H
2the photocatalytic degradation uv-absorbing figure of the rhodamine B of O;
Figure 35 adds [Ni (3-bpah) (5-MIP)] of the present invention H
2the photocatalytic degradation uv-absorbing figure of the rhodamine B of O;
Figure 36 adds [Co (3-bpah) (5-MIP)] of the present invention H
2the photocatalytic degradation uv-absorbing figure of the rhodamine B of O;
Figure 37 adds that of the present invention [Cu (4-bpah) is (H (5-MIP)
2o)] the photocatalytic degradation uv-absorbing figure of rhodamine B;
Figure 38 adds that of the present invention [Ni (4-bpah) is (H (5-MIP)
2o)] H
2the photocatalytic degradation uv-absorbing figure of the rhodamine B of O;
Figure 39 is the photocatalytic degradation uv-absorbing figure that adds the rhodamine B of [Co (4-bpah) (5-MIP)] of the present invention;
Figure 40 is the degradation rate figure of the different UV-irradiation of the rhodamine B aqueous solution under the time that adds six kinds of title complexs of the present invention;
Figure 41 is the histogram of the methylenum coeruleum that adds six kinds of title complexs of the present invention, tropeolin-D, the degradation rate of the rhodamine B aqueous solution under UV-irradiation.
In figure: 1-[Cu (3-bpah) is (5-MIP)] 2H
2o, 2-[Ni (3-bpah) is (5-MIP)] H
2o, 3-[Co (3-bpah) is (5-MIP)] H
2o, 4-[Cu (4-bpah) is (H (5-MIP)
2o)], (5-MIP) (H of 5-[Ni (4-bpah)
2o)] H
2o, 6-[Co (4-bpah) is (5-MIP)].
Embodiment
Synthetic [Cu (3-bpah) (the 5-MIP)] 2H of embodiment 1
2o, wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, structural formula is:
, 5-MIP is oreinol dioctyl phthalate
By 0.1mmol CuCl
22H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.10mmol oreinol dioctyl phthalate and 7.8mL H
2o joins in 25mL beaker successively, at room temperature stir 30min, obtain suspended mixture, with the NaOH solution of 0.1mol/L, reconcile after the pH to 6.4 of suspended mixture, transfer in the autoclave of 25mL, heating rate with 15 ℃/h is warming up to 130 ℃, under hydrothermal condition, is incubated 48h, with the rate of temperature fall of 5 ℃/h, cools the temperature to room temperature, obtain blue bulk crystals, with deionized water and ethanol, alternately clean 3 times, under room temperature, naturally dry, obtain [Cu (3-bpah) (5-MIP)] 2H
2o, productive rate is 30%, as shown in Figure 1, as shown in Figure 8, its two-dimensional network figure is as shown in Figure 9 for coordination environment figure for its XRD diffracting spectrum.
Synthetic [Cu (3-bpah) (the 5-MIP)] 2H of embodiment 2
2o, wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
By 0.1mmol CuCl
22H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol oreinol dioctyl phthalate and 8.0mL H
2o joins in 25mL beaker successively, under room temperature, stir 40min, obtain suspended mixture, with the NaOH solution of 0.1mol/L, reconcile after the pH to 6.7 of suspended mixture, transfer in the autoclave of 25mL, heating rate with 15 ℃/h is warming up to 110 ℃, under hydrothermal condition, be incubated 96h, rate of temperature fall with 5 ℃/h cools the temperature to room temperature, obtain blue bulk crystals, with deionized water and ethanol, alternately clean 5 times, under room temperature, naturally dry, obtain [Cu (3-bpah) (5-MIP)] 2H2O, productive rate is 33%, its XRD diffracting spectrum as shown in Figure 1, coordination environment figure as shown in Figure 8, its two-dimensional network figure as shown in Figure 9.
Synthetic [Cu (3-bpah) (the 5-MIP)] 2H of embodiment 3
2o, wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
By 0.2mmol CuCl
22H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.2mmol oreinol dioctyl phthalate and 8.0mL H
2o joins in 25mL beaker successively, at room temperature stir 20min, obtain suspended mixture, with the NaOH solution of 0.1mol/L, reconcile after the pH to 7.0 of suspended mixture, transfer in the autoclave of 25mL, heating rate with 15 ℃/h is warming up to 120 ℃, under hydrothermal condition, is incubated 72h, with the rate of temperature fall of 5 ℃/h, cools the temperature to room temperature, obtain blue bulk crystals, with deionized water and ethanol, alternately clean 2 times, under room temperature, naturally dry, obtain [Cu (3-bpah) (5-MIP)] 2H
2o, productive rate is 39%, as shown in Figure 1, as shown in Figure 8, its two-dimensional network figure is as shown in Figure 9 for coordination environment figure for its XRD diffracting spectrum.
Synthetic [Ni (3-bpah) (the 5-MIP)] H of embodiment 4
2o, wherein 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
By 0.3mmol NiCl
26H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol oreinol dioctyl phthalate and 7.8mL H
2o joins in 25mL beaker successively, at room temperature stir 60min, obtain suspended mixture, with the NaOH solution of 0.1mol/L, reconcile after the pH to 6.5 of suspended mixture, transfer in the autoclave of 25mL, heating rate with 15 ℃/h is warming up to 120 ℃, under hydrothermal condition, be incubated 48h, rate of temperature fall with 5 ℃/h cools the temperature to room temperature, obtain green bulk crystals, with deionized water and ethanol, alternately clean 2 times, under room temperature, naturally dry, obtain [Ni (3-bpah) (5-MIP)] H2O, productive rate is 31%, its XRD diffracting spectrum as shown in Figure 2, coordination environment figure as shown in figure 10, its three-dimensional network figure as shown in figure 11, its three-dimensional topology structure as shown in figure 12.
Synthetic [Ni (3-bpah) (the 5-MIP)] H of embodiment 5
2o, wherein 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
By 0.3mmol NiCl
26H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol oreinol dioctyl phthalate and 8.0mL H
2o joins in 25mL beaker successively, at room temperature stir 30min, obtain suspended mixture, with the NaOH solution of 0.1mol/L, reconcile after the pH to 7.0 of suspended mixture, transfer in the autoclave of 25mL, heating rate with 10 ℃/h is warming up to 120 ℃, under hydrothermal condition, is incubated 60h, with the rate of temperature fall of 5 ℃/h, cools the temperature to room temperature, obtain green bulk crystals, with deionized water and ethanol, alternately clean 3 times, under room temperature, naturally dry, obtain [Ni (3-bpah) (5-MIP)] H
2o, productive rate is 38%, as shown in Figure 2, as shown in figure 10, as shown in figure 11, its three-dimensional topology structure is as shown in figure 12 for its three-dimensional network figure for coordination environment figure for its XRD diffracting spectrum.
Synthetic [Ni (3-bpah) (the 5-MIP)] H of embodiment 6
2o, wherein 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
By 0.2mmol NiCl
26H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol oreinol dioctyl phthalate and 8.0mL H
2o joins in 25mL beaker successively, at room temperature stir 20min, obtaining suspended mixture reconciles after the pH to 6.8 of suspended mixture with the NaOH solution of 0.5mol/L, transfer in the autoclave of 25mL, heating rate with 5 ℃/h is warming up to 120 ℃, under hydrothermal condition, be incubated 72h, rate of temperature fall with 2.5 ℃/h cools the temperature to room temperature, obtain green bulk crystals, with deionized water and ethanol, alternately clean 5 times, under room temperature, naturally dry, obtain [Ni (3-bpah) (5-MIP)] H2O, productive rate is 43%, its XRD diffracting spectrum as shown in Figure 2, coordination environment figure as shown in figure 10, its three-dimensional network figure as shown in figure 11, its three-dimensional topology structure as shown in figure 12.
Synthetic [Co (3-bpah) (the 5-MIP)] H of embodiment 7
2o, wherein 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
By 0.3mmol CoCl
26H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol oreinol dioctyl phthalate and 8.0mL H
2o joins in 25mL beaker successively, under room temperature, stir 40min, obtain suspended mixture, with the NaOH solution of 0.1mol/L, reconcile after the pH to 6.6 of suspended mixture, transfer in the autoclave of 25mL, heating rate with 5 ℃/h is warming up to 130 ℃, under hydrothermal condition, is incubated 96h, with the rate of temperature fall of 10 ℃/h, cools the temperature to room temperature, obtain pink colour bulk crystals, with deionized water and ethanol, alternately clean 3 times, under room temperature, naturally dry, obtain [Ni (3-bpah) (5-MIP)] H
2o, productive rate is 35%, its XRD diffracting spectrum as shown in Figure 3, coordination environment figure as shown in figure 13, its three-dimensional net structure and three-dimensional topology structure and [Ni (3-bpah) is (5-MIP)] H
2o is similar.
Synthetic [Co (3-bpah) (the 5-MIP)] H of embodiment 8
2o, wherein 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
By 0.1mmol CoCl
26H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol oreinol dioctyl phthalate and 7.8mL H
2o joins in 25mL beaker successively, at room temperature stir 30min, obtain suspended mixture, with the NaOH solution of 1mol/L, reconcile after the pH to 7.5 of suspended mixture, transfer in the autoclave of 25mL, heating rate with 10 ℃/h is warming up to 120 ℃, under hydrothermal condition, be incubated 68h, rate of temperature fall with 10 ℃/h cools the temperature to room temperature, obtain pink colour bulk crystals, with deionized water and ethanol, alternately clean 3 times, under room temperature, naturally dry, obtain [Ni (3-bpah) (5-MIP)] H2O, productive rate is 33%, its XRD diffracting spectrum as shown in Figure 3, coordination environment figure as shown in figure 13, its three-dimensional net structure and three-dimensional topology structure and [Ni (3-bpah) (5-MIP)] H
2o is similar.
Synthetic [Co (3-bpah) (the 5-MIP)] H of embodiment 9
2o, wherein 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
By 0.2mmol CoCl
26H
2o, 0.10mmol
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 0.15mmol oreinol dioctyl phthalate and 17.5mL H
2o joins in 25mL beaker successively, under room temperature, stir 30min, obtain suspended mixture, with the NaOH solution of 0.1mol/L, reconcile after the pH to 7.0 of suspended mixture, transfer in the autoclave of 25mL, heating rate with 10 ℃/h is warming up to 120 ℃, under hydrothermal condition, is incubated 72h, with the rate of temperature fall of 5 ℃/h, cools the temperature to room temperature, obtain pink colour bulk crystals, with deionized water and ethanol, alternately clean 3 times, under room temperature, naturally dry, obtain [Ni (3-bpah) (5-MIP)] H
2o, productive rate is 40%, its XRD diffracting spectrum as shown in Figure 3, coordination environment figure as shown in figure 13, its three-dimensional net structure and three-dimensional topology structure and [Ni (3-bpah) is (5-MIP)] H
2o is similar.
With
n,
n'-bis-(Isonicotinamide)-1,2-hexanaphthene replaces in embodiment 1
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, other condition is with embodiment 1, makes that [Cu (4-bpah) is (H (5-MIP)
2o)], productive rate is 44%, and as shown in Figure 4, as shown in figure 14, its two-dimensional network figure as shown in figure 15 for coordination environment figure for its XRD diffracting spectrum.
Embodiment 11 is synthetic, and [Ni (4-bpah) is (H (5-MIP)
2o)] H
2o, wherein 4-bpah is
n,
n'-bis-(Isonicotinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
With
n,
n'-bis-(Isonicotinamide)-1,2-hexanaphthene replaces in embodiment 4
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, other condition is with embodiment 4, makes that [Ni (4-bpah) is (H (5-MIP)
2o)] H
2o, productive rate is 35%, as shown in Figure 5, as shown in figure 16, its one dimension chain structure figure is as shown in figure 17 for coordination environment figure for its XRD diffracting spectrum.
Embodiment 12 synthetic [Co (4-bpah) (5-MIP)], wherein 4-bpah is
n,
n'-bis-(Isonicotinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate
With
n,
n'-bis-(Isonicotinamide)-1,2-hexanaphthene replaces in embodiment 7
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, other condition is with embodiment 7, make [Co (4-bpah) (5-MIP)], productive rate is 40%, and its XRD diffracting spectrum as shown in Figure 6, as shown in figure 18, its two-dimensional double-layer structure iron as shown in figure 19 for coordination environment figure.
The sign of the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and oreinol dioctyl phthalate
(1) powdery diffractometry characterizes the stability of phase purity and catalyzer
On Rigaku Ultima IV powder x-ray diffraction, collect powdered diffraction data, actuating current is 40 mA, and voltage is 40 kV.Adopt copper target X ray.Scanning constant, receiving slit wide is 0.1mm.Density data is collected and is used 2
θ/
θscan pattern, sweep limit 5
oto 60
o, sweep velocity is 5
o/ s, span is 0.02
o/ time.Data fitting is used Cerius2 program, and single crystal structure powdery diffractometry spectrum analog transforms and uses Mercury 1.4.1.
As shown in Fig. 1～Fig. 6, the powder x-ray diffraction spectrogram of the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and oreinol dioctyl phthalate and the PXRD spectrogram of matching are substantially identical, show that title complex is pure phase.
(2) thermogravimetric exosyndrome material stability
Thermostability adopts PE-Pyris Diamond S-II thermal analyzer to complete, 10 ℃/min of heating rate, 20 ℃～800 ℃ of temperature ranges.Fig. 7 shows that the decomposition temperature scope of the title complex that the present invention is synthetic is 240 ℃～620 ℃.
(3) crystal structure determination
With microscope, choose the monocrystalline of suitable size, under room temperature, adopt Bruker SMART APEX II diffractometer (graphite monochromator, Mo-K
a,
l=0.71073) collect diffraction data.Scan mode
w-φ, diffraction data is used SADABS program to carry out absorption correction.Reduction of data and structure elucidation are used respectively SAINT and SHELXTL program to complete.Method of least squares is determined whole non-hydrogen atom coordinates, and obtains hydrogen atom position with theoretical hydrogenation method.Adopt method of least squares to carry out refine to crystalline structure.Fig. 8～Figure 21 shows basic coordination situation and the expansion structure of the transition metal complex based on semi-rigid pair of pyridine bisamide organic ligand and oreinol dioctyl phthalate synthetic in embodiment 1～embodiment 12.The partial parameters of its crystallography point diffraction data gathering and structure refinement is as shown in the table:
The degradation experiment of the aqueous solution of methylenum coeruleum (MB), tropeolin-D (MO), rhodamine B (RhB) under UV-light
[Cu (3-bpah) (5-MIP)] 2H synthetic to embodiment 1～embodiment 3
2o (title complex 1), synthetic [Ni (3-bpah) (the 5-MIP)] H of embodiment 4～embodiment 6
2o (title complex 2), synthetic [Co (3-bpah) (the 5-MIP)] H of embodiment 7～embodiment 9
2o (title complex 3), embodiment 10 synthetic [Cu (4-bpah) is (H (5-MIP)
2o)] (title complex 4), embodiment 11 synthetic [Ni (4-bpah) is (H (5-MIP)
2o)] H
2o (title complex 5), embodiment 12 synthetic [Co (4-bpah) (5-MIP)] (title complexs 6) carry out respectively aqueous solution of methylene blue, methyl orange aqueous solution, the degradation experiment of the rhodamine B aqueous solution under UV-irradiation, and using respectively methylenum coeruleum, tropeolin-D, rhodamine B the aqueous solution to the characteristic absorption of UV-light as these three kinds of organic pollutant molecules of judgement there is foundation, for determining the degradation capability of 6 pairs of three kinds of water soluble contaminants of title complex 1～title complex.
The concrete steps of title complex 1～title complex 6 photocatalytic degradation methylenum coeruleum experiments are as follows:
It is 10.0 mgL that title complex 1～title complex 6 of 50mg is added respectively to 200mL concentration
– 1aqueous solution of methylene blue in as experimental group, and the aqueous solution of methylene blue of getting same volume is as a control group.The aqueous solution of methylene blue 30min of stirring test group obtains suspended substance, adopts while stirring mercury lamp to irradiate as the ultraviolet lamp of light source.Every 30min, take out 5mL solution and carry out centrifugation, obtain clarifying upper solution and carry out UV test.As shown in Figure 20～Figure 25, experimental group aqueous solution of methylene blue is after 240min UV-irradiation, and the characteristic absorbance of methylenum coeruleum significantly reduces, and shows that the major part of this material is decomposed.Wherein, the catalyzed degradation efficiency of title complex 1 is 60%, and the catalyzed degradation efficiency of title complex 2 is 75%, the catalyzed degradation efficiency of title complex 3 is 91%, the catalyzed degradation efficiency of title complex 4 is 55%, and the catalytic efficiency of title complex 5 is 70%, and the catalytic efficiency of title complex 6 is 85%.The aqueous solution of methylene blue of control group degradation rate after UV-irradiation 240min is 4%, show that this material almost cannot only degrade by UV-irradiation, but the katalysis that title complex 1～title complex 6 can play the degraded of methylenum coeruleum as catalyzer, especially more remarkable containing the title complex 3 of transition metals cobalt and the photocatalysis effect of 6 pairs of methylenum coeruleum of title complex, as shown in figure 26.
The concrete steps of title complex 1～title complex 6 photo-catalytic degradation of methyl-oranges (MO) experiment are as follows:
It is 10.0 mgL that title complex 1～title complex 6 of 50mg is added respectively to 200mL concentration
– 1methyl orange aqueous solution in as experimental group, and the methyl orange aqueous solution of getting same volume is as a control group.The methyl orange aqueous solution 30min of stirring test group obtains suspended substance, adopts while stirring mercury lamp to irradiate as the ultraviolet lamp of light source.Every 30min, take out 5mL solution and carry out centrifugation, obtain clarifying upper solution and carry out UV test.As shown in Figure 27～Figure 32, experimental group methyl orange aqueous solution is after 240min UV-irradiation, and the characteristic absorbance of tropeolin-D significantly reduces, and shows that the major part of this material is decomposed.Wherein, the catalyzed degradation efficiency of title complex 1 is 52%, and the catalyzed degradation efficiency of title complex 2 is 60%, the catalyzed degradation efficiency of title complex 3 is 75%, the catalyzed degradation efficiency of title complex 4 is 50%, and the catalytic efficiency of title complex 5 is 55%, and the catalytic efficiency of title complex 6 is 70%.The methyl orange aqueous solution of control group degradation rate after UV-irradiation 240min is 11%, while showing this material only by UV-irradiation, degradation rate is lower, but the katalysis that title complex 1～title complex 6 can play the degraded of tropeolin-D as catalyzer, especially more remarkable containing the title complex 3 of transition metals cobalt and the photocatalysis effect of 6 pairs of tropeolin-Ds, as shown in figure 33.
The concrete steps of title complex 1～title complex 6 photocatalytic degradation rhodamine B experiments are as follows:
It is 10.0 mgL that title complex 1～title complex 6 of 50mg is added respectively to 200mL concentration
– 1the rhodamine B aqueous solution in as experimental group, and the rhodamine B aqueous solution of getting same volume is as a control group.The rhodamine B aqueous solution 30min of stirring test group obtains suspended substance, adopts while stirring mercury lamp to irradiate as the ultraviolet lamp of light source.Every 30min, take out 5mL solution and carry out centrifugation, obtain clarifying upper solution and carry out UV test.As shown in Figure 34～Figure 39, the experimental group rhodamine B aqueous solution is after 240min UV-irradiation, and the characteristic absorbance of rhodamine B significantly reduces, and shows that the major part of this material is decomposed.Wherein, the catalyzed degradation efficiency of title complex 1 is 25%, and the catalyzed degradation efficiency of title complex 2 is 28%, the catalyzed degradation efficiency of title complex 3 is 40%, the catalyzed degradation efficiency of title complex 4 is 23%, and the catalytic efficiency of title complex 5 is 28%, and the catalytic efficiency of title complex 6 is 30%.The rhodamine B aqueous solution of control group degradation rate after UV-irradiation 240min is 3%, show that this material cannot only degrade by UV-irradiation, but the katalysis that title complex 1～title complex 6 can play the degraded of rhodamine B as catalyzer, especially more remarkable containing the title complex 3 of transition metals cobalt and the photocatalysis effect of 6 pairs of rhodamine Bs, as shown in figure 40.
Claims (10)
1. the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, is characterized in that: the molecular formula of this title complex is as follows:
[Cu(3-bpah)(5-MIP)]·2H
2O；
[Ni(3-bpah)(5-MIP)]·H
2O；
[Co(3-bpah)(5-MIP)]·H
2O；
[Cu(4-bpah)(5-MIP)(H
2O)]；
[Ni(4-bpah)(5-MIP)(H
2O)]·H
2O；
[Co(4-bpah)(5-MIP)]；
Wherein, 3-bpah is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene, 4-bpah is
n,
n'-bis-(Isonicotinamide)-1,2-hexanaphthene, 5-MIP is oreinol dioctyl phthalate.
2. as claimed in claim 1
onethe synthetic method of planting the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, is characterized in that:
Concrete steps are as follows:
By Cu
2+or Ni
2+or Co
2+muriate, the semi-rigid pair of pyridine bisamide part, oreinol dioctyl phthalate, add deionized water, at room temperature stir 20min～60min and form suspended mixture, the mol ratio of described semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate is 1:1～1:2, described semi-rigid pair of pyridine bisamide part and Cu
2+, Ni
2+, Co
2+muriatic mol ratio be 1:1～1:3, with NaOH solution, adjusting pH is 6.0～7.5, pour in autoclave and be warming up to 110 ℃～130 ℃, under hydrothermal condition, be incubated 48h～96h, cool to room temperature and obtain bulk crystals, with deionized water and ethanol, alternately clean 2 times～5 times, under room temperature, naturally dry, obtain the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate.
3. according to claim 2
onethe synthetic method of planting the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, is characterized in that: semi-rigid pair of described pyridine bisamide part is
n,
n'-bis-(Niacinamide)-1,2-hexanaphthene or
n,
n'-bis-(Isonicotinamide)-1,2-hexanaphthene.
4. according to claim 2
onethe synthetic method of planting the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, is characterized in that: described Cu
2+, Ni
2+, Co
2+the mol ratio of muriate, the semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate be 2:1:1.5.
5. according to claim 2
onethe synthetic method of planting the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, is characterized in that: described Cu
2+, Ni
2+, Co
2+muriate be respectively CuCl
22H
2o, NiCl
26H
2o, CoCl
26H
2o.
6. according to claim 2
onethe synthetic method of the transition metal complex kind based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, is characterized in that: during intensification, temperature rise rate is 5 ℃/h～15 ℃/h; During cooling, rate of temperature fall is 2.5 ℃/h～10 ℃/h.
7. according to claim 2
onethe synthetic method of planting the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, is characterized in that: the add-on of described deionized water is 30%～70% of autoclave volume.
8. according to claim 2
onethe synthetic method of planting the transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate, is characterized in that: the concentration of described NaOH solution is 0.1mol/L～1.0mol/L.
9. a kind of transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate as claimed in claim 1 is as the application in photocatalyst material.
10. a kind of transition metal complex based on semi-rigid pair of pyridine bisamide part and oreinol dioctyl phthalate according to claim 9 is as the application in the photocatalyst material of methylenum coeruleum organic pollutant, tropeolin-D organic pollutant and rhodamine B organic pollutant.
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| CN104310524A (en) * | 2014-09-30 | 2015-01-28 | 渤海大学 | Method for degrading rhodamine B and indigo organic pollutant |
| CN107617418A (en) * | 2016-07-16 | 2018-01-23 | 天津师范大学 | Application of thiocyanate radical Co (II) complexs based on 3 (oxadiazole of 5 methyl 1,3,4) pyridines in dyestuff is adsorbed |
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