CN103408600B - Semi-rigid double-imidazole organic-ligand-based transition metal compound containing N-S dicarboxylic acid, as well as synthetic method and application thereof - Google Patents
Semi-rigid double-imidazole organic-ligand-based transition metal compound containing N-S dicarboxylic acid, as well as synthetic method and application thereof Download PDFInfo
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Abstract
The molecular formula of a semi-rigid double-imidazole organic-ligand-based transition metal compound containing N-S dicarboxylic acid is [Co2 (L) 2 (2-CMSN) 2 (H2O)]. H2O; [Cd (L) (2-CMSN) (H2O)]; [Zn (L) (2-CMSN)]. 2 H2O; [Cd (L) (ADTZ) (H2O)]; [Zn (L) (ADTZ)]. H2O, wherein L represents 1, 4-bis ( imidazol-1-methylene ) benzene, 2-CMSN represents 2-carboxylic acid methylene group root, and ADTZ represents 2,2'-(1,3,4-thiadiazol oxazol-2,5-diyl) dithio diethyl dianion root. A synthetic method of the transition metal compound comprises the following steps: adding Co<2+> or Zn<2+> and Cd<2+> nitrate, semi-rigid double-imidazole ligands, dicarboxylic acid containing N and S into deionized water, stirring, using NaOH solution to adjust pH, pouring the mixture into a high-pressure reaction kettle, increasing the temperature to realize hydrothermal reaction, cooling to obtain a bulk crystal, and washing and drying the bulk crystal to obtain the target product. The synthetic method of the compound is simple, the synthesis productivity is high, the cost of synthetic raw materials is low, the synthetic period is short and the electrical energy consumption is low; the compound is high in affiliation capacity of water-soluble pollutants, good in catalysis and degradation effects and environmental-friendly, and can be used as photocatalytic materials.
Description
Technical field
The invention belongs to photocatalyst material and synthetic method field, particularly a kind of based on semi-rigid pair of imidazoles organic ligand with containing the transition metal complex of N-S dicarboxylic acid and synthetic method thereof and application.
Background technology
Transition metal functional complexes based on organic carboxyl acid and organic amine mixed ligand is a kind of inorganic functional material, has that structure-rich is various, catalytic performance is good, the feature of applied range.But the synthesis of this kind of title complex is subject to the restriction of the snappiness of organic ligand, the length of part, hapto quantity, coordination ability.Although synthesized, properties is excellent, the complex material of various structures, synthesizes this kind of complex material still more difficult.In addition, be used at present synthesizing the carboxylic acid derivative generally adopting arene structural unit to be connected with the Carboxylic acid ligand of the transition metal functional complexes of organic amine mixed ligand based on organic carboxyl acid, the rigidity of this analog derivative and sterically hindered larger, with show certain limitation during metallic ion coordination, make the transition metal functional complexes relative difficulty when crystallization based on such carboxylic acid derivative, the synthetic yield of transition metal functional complexes is caused to only have about 40%, synthetic yield is lower, and being photocatalyst material with polyacid base functional complexes, synthesis material cost is higher, consume electric energy larger, the secondary metals of Mo or W are easily caused to pollute, on the other hand, when after such carboxylic acid derivative and metallic ion coordination, add the hydrophobic nature of such part, this makes the affinity of transition metal functional complexes to water miscible organic pollutant constructed by such carboxylic acid poor, poor to the catalytic degradation effect of water-soluble organic pollutant.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of synthetic method is simple, synthetic yield is high, synthesis material cost is low, synthesis cycle is short, consume that electric energy is little, strong to water soluble contaminants affinity, catalytic degradation effect good, environment amenable based on semi-rigid pair of imidazoles organic ligand with containing the transition metal complex of N-S dicarboxylic acid and synthetic method thereof and application.
Technical solution of the present invention is:
Based on semi-rigid pair of imidazoles organic ligand and the transition metal complex containing N-S dicarboxylic acid, the molecular formula of this title complex is as follows:
[Co
2(L)
2(2-CMSN)
2(H
2O)]·H
2O；
[Cd(L)(2-CMSN)(H
2O)]；
[Zn(L)(2-CMSN)]·2H
2O；
[Cd(L)(ADTZ)(H
2O)]；
[Zn(L)(ADTZ)]·H
2O；
Wherein, L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root, and ADTZ is 2,2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio diethyl acid group.
Based on semi-rigid pair of imidazoles organic ligand and the synthetic method of transition metal complex containing N-S dicarboxylic acid, its concrete steps are:
By Zn
2+or Co
2+or Cd
2+nitrate, the semi-rigid pair of imidazole ligands, containing N and S dicarboxylic acid, add deionized water, at room temperature stir 20min ~ 60min and form suspended mixture, described semi-rigid couple of imidazole ligands L is 1:1 ~ 1:2 with the mol ratio containing N and S dicarboxylic acid, described semi-rigid couple of imidazole ligands L and Zn
2+, Co
2+, Cd
2+the mol ratio of nitrate be 1:1 ~ 1:3, pH is adjusted to be 5.1 ~ 7.0 by NaOH solution, pour in autoclave and be warming up to 90 DEG C ~ 105 DEG C, 24h ~ 60h is incubated under hydrothermal condition, cool to room temperature and obtain bulk crystals, replace cleaning 2 times ~ 5 times with deionized water and ethanol, naturally dry under room temperature, must based on semi-rigid pair of imidazoles organic ligand and the transition metal complex containing N-S dicarboxylic acid.
Semi-rigid pair of described imidazole ligands is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene.
Described is 2-carboxylic methylene radical sulfenyl nicotinic acid or 2,2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio oxalic acid containing N and S dicarboxylic acid.
Described Zn
2+, Co
2+, Cd
2+nitrate be respectively Zn (NO
3)
26H
2o, Co (NO
3)
26H
2o, Cd (NO
3)
24H
2o.
During intensification, temperature rise rate is 5 DEG C/h ~ 15 DEG C/h; During cooling, rate of temperature fall is 2.5 DEG C/h ~ 10 DEG C/h.
The add-on of described deionized water is 30% ~ 60% of autoclave volume.
The concentration of described NaOH solution is 0.1mol/L ~ 1.0mol/L.
A kind of based on semi-rigid pair of imidazoles organic ligand and containing the transition metal complex of N-S dicarboxylic acid as the application in photocatalyst material.
The present invention is with 1,4-bis-(imidazoles-1-methylene radical) benzene is as neutral organic ligand, with 2-carboxylic methylene radical sulfenyl nicotinic acid and 2,2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio oxalic acid is as anion ligand, the structural stability of title complex is increased by introducing semirigid Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene part; The wetting ability of carboxylic acid is increased by introducing pyridine and thiazolyl group introns in dicarboxylic acid; Adjust the snappiness of Carboxylic acid ligand by introducing S atom, and the radius changing the metal ion participating in coordination adjusts the structure of title complex, has synthesized 5 transition metal complexes from 2 d-to-3 d.Wherein, [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2o and [Cd (L) (2-CMSN) (H
2o)] be isostructural compounds, their inorganic-organic title complex skeleton is two-dimentional diamond check structure; [Zn (L) (2-CMSN)] 2H
2the title complex skeleton of O is the peanut shape trellis of two dimension; [Cd (L) (ADTZ) (H
2o) title complex skeleton] is two-dimentional wavy shaped configuration; [Zn (L) (ADTZ)] H
2the title complex skeleton of O is the quadruple interpenetrating structure that three-dimensional has diamond-type topology.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, carboxylic acid to join space of teeth adjustable;
(2) 2-carboxylic methylene radical sulfenyl nicotinic acid and 2 is adopted, 2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio oxalic acid as anion ligand, containing the pyridine of N and the good hydrophilic property of thiazole spacer groups, accelerate crystallisation process during synthesis transition metal complex, shorten synthesis cycle, constant temperature time shortens, and power consumption reduces; Snappiness containing S spacer groups is good, adds the coordination adaptive faculty of carboxylic acid coordination, improves synthetic yield, reduce synthesis cost; The poorly water-soluble of title complex, prevents the secondary pollution to environment;
(3) affinity of the transition metal complex synthesized to water miscible organic pollutant is strong, catalytic degradation effect good, can reach 85% ~ 98%, can apply as photocatalyst material the photocatalytic activity of methylenum coeruleum organic pollutant.
Accompanying drawing explanation
Fig. 1 is that the present invention synthesizes [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2o powder diagram;
Fig. 2 is that the present invention synthesizes [Cd (L) (2-CMSN) (H
2o)] powder diagram;
Fig. 3 is that the present invention synthesizes [Zn (L) (2-CMSN)] 2H
2o powder diagram;
Fig. 4 is that the present invention synthesizes [Cd (L) (ADTZ) (H
2o)] powder diagram;
Fig. 5 is that the present invention synthesizes [Zn (L) (ADTZ)] H
2o powder diagram;
Fig. 6 be the present invention synthesize based on semi-rigid pair of imidazoles organic ligand and the thermogram of transition metal complex containing N-S dicarboxylic acid;
In figure: 1-[Co
2(L)
2(2-CMSN)
2(H
2o)] H
2o, 2-[Cd (L) (2-CMSN) (H
2o)], 3-[Zn (L) (2-CMSN)] 2H
2o, 4-[Cd (L) (ADTZ) (H
2o)], 5-[Zn (L) (ADTZ)] H
2o;
Fig. 7 is that the present invention synthesizes [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2the coordination environment figure of O;
Fig. 8 is that the present invention synthesizes [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2the two-dimensional network figure of O;
Fig. 9 is that the present invention synthesizes [Cd (L) (2-CMSN) (H
2o) coordination environment figure];
Figure 10 is that the present invention synthesizes [Cd (L) (2-CMSN) (H
2o) two-dimensional network figure];
Figure 11 is that the present invention synthesizes [Zn (L) (2-CMSN)] 2H
2the coordination environment figure of O;
Figure 12 is that the present invention synthesizes [Zn (L) (2-CMSN)] 2H
2the two-dimensional network figure of O;
Figure 13 is that the present invention synthesizes [Cd (L) (ADTZ) (H
2o) coordination environment figure];
Figure 14 is that the present invention synthesizes [Cd (L) (ADTZ) (H
2o) two-dimensional network figure];
Figure 15 is that the present invention synthesizes [Zn (L) (ADTZ)] H
2the coordination environment figure of O;
Figure 16 is that the present invention synthesizes [Zn (L) (ADTZ)] H
2the tomograph of O;
Figure 17 is that the present invention synthesizes [Zn (L) (ADTZ)] H
2the three dimensional diamond type topology diagram of O;
Figure 18 is that the present invention synthesizes [Zn (L) (ADTZ)] H
2the three dimensional topology figure of the quadruple IPN of O;
Figure 19 is the photocatalytic degradation uv-absorbing figure of the methylenum coeruleum of catalyst-free;
Figure 20 adds the present invention's synthesis [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2the photocatalytic degradation uv-absorbing figure of the methylenum coeruleum of O;
Figure 21 adds the present invention's synthesis [Cd (L) (2-CMSN) (H
2the photocatalytic degradation uv-absorbing figure of methylenum coeruleum O)];
Figure 22 adds the present invention's synthesis [Zn (L) (2-CMSN)] 2H
2the photocatalytic degradation uv-absorbing figure of the methylenum coeruleum of O;
Figure 23 adds the present invention's synthesis [Cd (L) (ADTZ) (H
2the photocatalytic degradation uv-absorbing figure of methylenum coeruleum O)];
Figure 24 adds the present invention's synthesis [Zn (L) (ADTZ)] H
2the photocatalytic degradation uv-absorbing figure of the methylenum coeruleum of O.
Embodiment
Embodiment 1 synthesizes [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2o, wherein, L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and structural formula is:
, 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root
By 0.1mmol Co (NO
3)
26H
2o, 0.10mmol Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, 0.1mmol 2-carboxylic methylene radical sulfenyl nicotinic acid (structural formula is:
) and 7.5mL H
2o joins in 50mL beaker successively, stirred at ambient temperature 20min, adjust pH to 6 by the NaOH solution of 0.1mol/L, pour in the autoclave of 25mL, be warming up to 90 DEG C with the heating rate of 15 DEG C/h, 48h is incubated under hydrothermal condition, cool the temperature to room temperature with the rate of temperature fall of 5 DEG C/h, obtain pink colour bulk crystals, replace cleaning 2 times with deionized water and ethanol, naturally dry under room temperature, obtain [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2o, productive rate is 62%, and as shown in Figure 7, its two-dimensional network figure as shown in Figure 8 for its coordination environment figure.
Embodiment 2 synthesizes [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2o, wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root
By 0.2mmol Co (NO
3)
26H
2o, 0.10mmol Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, 0.14mmol 2-carboxylic methylene radical sulfenyl nicotinic acid and 12mL H
2o joins in 50mL beaker successively, stirred at ambient temperature 30min, adjust pH to 6.1 by the NaOH solution of 0.5mol/L, pour in the autoclave of 25mL, be warming up to 100 DEG C with the heating rate of 10 DEG C/h, 48h is incubated under hydrothermal condition, cool the temperature to room temperature with the rate of temperature fall of 2.5 DEG C/h, obtain pink colour bulk crystals, replace cleaning 5 times with deionized water and ethanol, naturally dry under room temperature, obtain [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2o, productive rate is 84%, and as shown in Figure 7, its two-dimensional network figure as shown in Figure 8 for its coordination environment figure.
Embodiment 3 synthesizes [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2o, wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root
By 0.3mmol Co (NO
3)
26H
2o, 0.10mmol Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, 0.2mmol 2-carboxylic methylene radical sulfenyl nicotinic acid and 14mL H
2o joins in 50mL beaker successively, stirred at ambient temperature 60min, adjust pH to 7.0 by the NaOH solution of 1mol/L, pour in the autoclave of 25mL, be warming up to 105 DEG C with the heating rate of 5 DEG C/h, 60h is incubated under hydrothermal condition, cool the temperature to room temperature with the rate of temperature fall of 8 DEG C/h, obtain pink colour bulk crystals, replace cleaning 3 times with deionized water and ethanol, naturally dry under room temperature, obtain [Co
2(L)
2(2-CMSN)
2(H
2o)] H
2o, productive rate is 74%, and as shown in Figure 7, its two-dimensional network figure as shown in Figure 8 for its coordination environment figure.
Embodiment 4 is synthesized [Cd (L) (2-CMSN) (H
2o)], wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root
By 0.11mmol Cd (NO
3)
24H
2o, 0.10mmol Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, 0.12mmol 2-carboxylic methylene radical sulfenyl nicotinic acid and 11mL H
2o joins in 50mL beaker successively, stirred at ambient temperature 25min, adjust pH to 5.1 by the NaOH solution of 0.1mol/L, pour in the autoclave of 25mL, be warming up to 105 DEG C with the heating rate of 15 DEG C/h, 36h is incubated under hydrothermal condition, cool the temperature to room temperature with the rate of temperature fall of 5 DEG C/h, obtain yellow bulk crystals, replace cleaning 3 times with deionized water and ethanol, naturally dry under room temperature, obtain [Cd (L) (2-CMSN) (H
2o)], productive rate is 60%, and as shown in Figure 9, its two-dimensional network figure as shown in Figure 10 for its coordination environment figure.
Embodiment 5 is synthesized [Cd (L) (2-CMSN) (H
2o)], wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root
By 0.22mmol Cd (NO
3)
24H
2o, 0.10mmol Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, 0.16mmol 2-carboxylic methylene radical sulfenyl nicotinic acid and 14mL H
2o joins in 50mL beaker successively, stirred at ambient temperature 30min, adjust pH to 6.4 by the NaOH solution of 0.5mol/L, pour in the autoclave of 25mL, be warming up to 105 DEG C with the heating rate of 10 DEG C/h, 24h is incubated under hydrothermal condition, cool the temperature to room temperature with the rate of temperature fall of 2.5 DEG C/h, obtain yellow bulk crystals, replace cleaning 4 times with deionized water and ethanol, naturally dry under room temperature, obtain [Cd (L) (2-CMSN) (H
2o)], productive rate is 85%, and as shown in Figure 9, its two-dimensional network figure as shown in Figure 10 for its coordination environment figure.
Embodiment 6 is synthesized [Cd (L) (2-CMSN) (H
2o)], wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root
By 0.3mmol Cd (NO
3)
24H
2o, 0.10mmol Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, 0.2mmol 2-carboxylic methylene radical sulfenyl nicotinic acid and 15mL H
2o joins in 50mL beaker successively, stirred at ambient temperature 40min, adjust pH to 7.0 by the NaOH solution of 1mol/L, pour in the autoclave of 25mL, be warming up to 95 DEG C with the heating rate of 15 DEG C/h, 60h is incubated under hydrothermal condition, cool the temperature to room temperature with the rate of temperature fall of 10 DEG C/h, obtain yellow bulk crystals, replace cleaning 3 times with deionized water and ethanol, naturally dry under room temperature, obtain [Cd (L) (2-CMSN) (H
2o)], productive rate is 74%, and as shown in Figure 9, its two-dimensional network figure as shown in Figure 10 for its coordination environment figure.
Embodiment 7 is synthesized [Zn (L) (2-CMSN)] 2H
2o, wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root
By 0.12mmol Zn (NO
3)
26H
2o, 0.10mmol Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, 0.12mmol 2-carboxylic methylene radical sulfenyl nicotinic acid and 12mL H
2o joins in 50mL beaker successively, stirred at ambient temperature 40min, adjust pH to 5.6 by the NaOH solution of 0.5mol/L, pour in the autoclave of 25mL, be warming up to 105 DEG C with the heating rate of 10 DEG C/h, 24h is incubated under hydrothermal condition, cool the temperature to room temperature with the rate of temperature fall of 5 DEG C/h, obtain yellow bulk crystals, replace cleaning 3 times with deionized water and ethanol, naturally dry under room temperature, obtain [Zn (L) (2-CMSN)] 2H
2o, productive rate is 72%, and as shown in figure 11, its two-dimensional network figure as shown in figure 12 for its coordination environment figure.
Embodiment 8 is synthesized [Zn (L) (2-CMSN)] 2H
2o, wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root
By 0.19mmol Zn (NO
3)
26H
2o, 0.10mmol Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, 0.14mmol 22-carboxylic methylene radical sulfenyl nicotinic acid and 14mL H
2o joins in 50mL beaker successively, stirred at ambient temperature 50min, adjust pH to 6.4 by the NaOH solution of 0.5mol/L, pour in the autoclave of 25mL, be warming up to 100 DEG C with the heating rate of 15 DEG C/h, 48h is incubated under hydrothermal condition, cool the temperature to room temperature with the rate of temperature fall of 2.5 DEG C/h, obtain yellow bulk crystals, replace cleaning 4 times with deionized water and ethanol, naturally dry under room temperature, obtain [Zn (L) (2-CMSN)] 2H
2o, productive rate is 83%, and as shown in figure 11, its two-dimensional network figure as shown in figure 12 for its coordination environment figure.
Embodiment 9 is synthesized [Zn (L) (2-CMSN)] 2H
2o, wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root
By 0.26mmol Zn (NO
3)
26H
2o, 0.10mmol Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, 0.18mmol 2-carboxylic methylene radical sulfenyl nicotinic acid and 12mL H
2o joins in 50mL beaker successively, stirred at ambient temperature 30min, adjust pH to 6.9 by the NaOH solution of 0.5mol/L, pour in the autoclave of 25mL, be warming up to 105 DEG C with the heating rate of 10 DEG C/h, 36h is incubated under hydrothermal condition, cool the temperature to room temperature with the rate of temperature fall of 5 DEG C/h, obtain yellow bulk crystals, replace cleaning 3 times with deionized water and ethanol, naturally dry under room temperature, obtain [Zn (L) (2-CMSN)] 2H
2o, productive rate is 70%, and as shown in figure 11, its two-dimensional network figure as shown in figure 12 for its coordination environment figure.
Embodiment 10 is synthesized [Cd (L) (ADTZ) (H
2o)], wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and ADTZ is 2,2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio diethyl acid group
With 2,2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio oxalic acid (structural formula is:
) replace 2-carboxylic methylene radical sulfenyl nicotinic acid in embodiment 4 ~ 6, the other the same as in Example 4 ~ 6, obtained [Cd (L) (ADTZ) (H
2o)], productive rate is 80%, and as shown in figure 13, its two-dimensional network figure as shown in figure 14 for its coordination environment figure.
Embodiment 11 is synthesized [Zn (L) (ADTZ)] H
2o, wherein L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and ADTZ is 2,2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio diethyl acid group
Replace 2-carboxylic methylene radical sulfenyl nicotinic acid in embodiment 7 ~ 9 with 2,2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio oxalic acid, other is with embodiment 7 ~ 9, obtained [Zn (L) (ADTZ)] H
2o, productive rate is 83%, and as shown in figure 15, as shown in figure 16, as shown in figure 17, the three dimensional topology figure of its quadruple IPN as shown in figure 18 for its three dimensional diamond type topology diagram for its three-dimensional network figure for its coordination environment figure.
Based on semi-rigid pair of imidazoles organic ligand and the sign of transition metal complex containing N-S dicarboxylic acid
(1) powdery diffractometry characterizes the stability of phase purity and catalyzer
Rigaku Ultima IV powder x-ray diffraction collects powdered diffraction data, and 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 collects use 2
θ/
θscan pattern, sweep limit 5
oto 60
o, sweep velocity is 5
o/ s, span is 0.02
o/ time.Data fitting uses Cerius2 program, and single crystal structure powdery diffractometry spectrum analog transforms and uses Mercury 1.4.1.
As shown in Fig. 1 ~ Fig. 5, based on semi-rigid pair of imidazoles organic ligand and containing the powder x-ray diffraction spectrogram of transition metal complex of N-S dicarboxylic acid and the XRD spectra of matching substantially identical, show that title complex is pure phase; After photocatalytic degradation experiment, based on semi-rigid pair of imidazoles organic ligand and substantially identical containing the diffraction spectrogram before the powder x-ray diffraction spectrogram of transition metal complex of N-S dicarboxylic acid and the XRD spectra of matching and catalyzed reaction, show that title complex keeps original structure in catalytic process, embody the stability of title complex in catalytic process.
(2) thermogravimetric exosyndrome material stability
Thermostability adopts PE-Pyris Diamond S-II thermal analyzer to complete, heating rate 10 DEG C/min, temperature range 30 DEG C ~ 800 DEG C.Fig. 6 shows that the decomposition temperature scope of the title complex that the present invention synthesizes is 200 DEG C ~ 550 DEG C.
(3) crystal structure determination
Choose the monocrystalline of suitable size with microscope, under room temperature, adopt Bruker SMART APEX II diffractometer (graphite monochromator, Mo-K
a,
l=0.71069) diffraction data is collected.Scan mode
w-φ, diffraction data uses SADABS program to carry out absorption correction.Reduction of data and structure elucidation use SAINT and SHELXTL program to complete respectively.Method of least squares determines whole non-hydrogen atom coordinate, and obtains hydrogen atom position with theoretical hydrogenation method.Method of least squares is adopted to carry out refine to crystalline structure.Fig. 7 ~ Figure 18 to show in embodiment 1 ~ embodiment 11 synthesis based on semi-rigid pair of imidazoles organic ligand with containing the basic coordination situation of the transition metal complex of N-S dicarboxylic acid and expansion structure.The partial parameters of its crystallography point diffraction data gathering and structure refinement is as shown in the table:
| Title complex | Embodiment 1 ~ 3 | Embodiment 4 ~ 6 | Embodiment 7 ~ 9 | Embodiment 10 | Embodiment 11 |
| Molecular weight | 1052.86 | 579.92 | 550.88 | 633.00 | 585.97 |
| Crystallographic system | Three is oblique | Three is oblique | Monocline | Monocline | Monocline |
| Spacer | P-1 | P-1 | C 2/c | P 21/c | P 21/c |
| Unit cell parameters | |||||
| a(?) | 8.8712(6) | 8.8471(8) | 28.327(3) | 5.1675(4) | 9.6083(16) |
| b(?) | 14.3134(9) | 11.0944(10) | 10.7619(11) | 26.7870(19) | 29.325(5) |
| c(?) | 18.1743(11) | 12.0063(11) | 16.2013(15) | 17.3981(12) | 9.1714(15) |
| α(°) | 77.7130(10) | 74.9200(10) | 90 | 90 | 90 |
| β(°) | 88.5260(10) | 78.820(2) | 99.994(2) | 97.8090(10) | 101.494(3) |
| γ(°) | 83.2400(10) | 88.547(2) | 90 | 90 | 90 |
| V(? 3) | 2239.2(2) | 1115.89(18) | 4864.1(8) | 2385.9(3) | 2532.4(7) |
| Z | 2 | 2 | 8 | 4 | 4 |
| Theoretical density (g cm –3) | 1.562 | 1.726 | 1.505 | 1.762 | 1.537 |
| Uptake factor (mm -1) | 0.905 | 1.118 | 1.143 | 1.224 | 1.260 |
| F(000) | 1084 | 584 | 2272 | 1272 | 1200 |
| Total point diffraction | 11501 | 5753 | 12146 | 13909 | 12188 |
| Independent point diffraction | 7901 | 3935 | 4344 | 5176 | 4458 |
| R int | 0.0131 | 0.0146 | 0.0477 | 0.0273 | 0.0231 |
| GOF | 1.059 | 1.005 | 1.011 | 1.024 | 1.048 |
| R 1(I>2σ(I)) | 0.0314 | 0.0272 | 0.0675 | 0.0338 | 0.0484 |
| wR 2(I>2σ(I)) | 0.0803 | 0.0668 | 0.2184 | 0.0810 | 0.1470 |
| △ρmax, e? -3 | 0.497 | 0.353 | 1.735 | 0.461 | 1.843 |
| △ρmin, e? -3 | -0.515 | -0.373 | -0.959 | -0.591 | -0.266 |
Aqueous solution of methylene blue degradation experiment under ultraviolet light
To [the Co that embodiment 1 ~ embodiment 3 is synthesized
2(L)
2(2-CMSN)
2(H
2o)] H
2o(compound 1), embodiment 4 ~ embodiment 6 synthesize [Cd (L) (2-CMSN) (H
2o)] [Zn (L) (2-CMSN)] 2H of (compound 2), embodiment 7 ~ embodiment 9 synthesis
2o(compound 3), embodiment 10 synthesize [Cd (L) (ADTZ) (H
2o)] [Zn (L) (ADTZ)] H of (compound 4), embodiment 11 synthesis
2o(compound 5) carry out aqueous solution of methylene blue degradation experiment under ultraviolet light, using aqueous solution of methylene blue to the characteristic absorption of UV-light as judging the foundation that methylenum coeruleum exists, for the degradation capability of deterministic compound 1 ~ compound 5 pairs of water soluble contaminants.
Specific experiment step is as follows:
It is 10.0 mgL that the compound 1 ~ compound 5 of 50mg is added 200mL concentration respectively
– 1aqueous solution of methylene blue in as experimental group, and the aqueous solution of methylene blue getting same volume is as a control group.The aqueous solution of methylene blue 30min of stirring test group obtains suspended substance, adopts mercury lamp to irradiate as the ultraviolet lamp of light source while stirring.Take out 5mL solution every 30min and carry out centrifugation, obtain clarification upper solution and carry out UV test.As shown in figure 19, aqueous solution of methylene blue uv-absorbing amount after UV-irradiation 150min of control group has almost no change, and shows that this material cannot be degraded only by UV-irradiation.As shown in Figure 20 ~ Figure 24, experimental group aqueous solution of methylene blue is after 360min UV-irradiation, and the characteristic absorbance of methylenum coeruleum disappears substantially, shows that this material has decomposed totally.Wherein, the catalytic degradation efficiency of compound 1 is 86%, and the catalytic degradation efficiency of compound 2 is 88%, and the catalytic degradation efficiency of compound 3 is 85%, and the catalytic degradation efficiency of compound 4 is 98%, and the catalytic efficiency of compound 5 is 94%.
Claims (7)
1., based on semi-rigid pair of imidazoles organic ligand and the transition metal complex containing N-S dicarboxylic acid, it is characterized in that:
The molecular formula of this title complex is as follows:
[Co
2(L)
2(2-CMSN)
2(H
2O)]·H
2O；
[Cd(L)(2-CMSN)(H
2O)]；
[Zn(L)(2-CMSN)]·2H
2O；
[Cd(L)(ADTZ)(H
2O)]；
[Zn(L)(ADTZ)]·H
2O；
Wherein, L is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene, and 2-CMSN is 2-carboxylic methylene radical sulfenyl nicotinic acid root, and ADTZ is 2,2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio diethyl acid group.
2. a kind of based on semi-rigid pair of imidazoles organic ligand and the synthetic method of transition metal complex containing N-S dicarboxylic acid as claimed in claim 1, it is characterized in that:
Concrete steps are as follows:
By Zn
2+or Co
2+or Cd
2+nitrate, the semi-rigid pair of imidazole ligands, containing N and S dicarboxylic acid, add deionized water, at room temperature stir 20min ~ 60min and form suspended mixture, described semi-rigid couple of imidazole ligands L is 1:1 ~ 1:2 with the mol ratio containing N and S dicarboxylic acid, described semi-rigid couple of imidazole ligands L and Zn
2+, Co
2+, Cd
2+the mol ratio of nitrate be 1:1 ~ 1:3, pH is adjusted to be 5.1 ~ 7.0 by NaOH solution, pour in autoclave and be warming up to 90 DEG C ~ 105 DEG C, 24h ~ 60h is incubated under hydrothermal condition, cool to room temperature and obtain bulk crystals, replace cleaning 2 times ~ 5 times with deionized water and ethanol, naturally dry under room temperature, must based on semi-rigid pair of imidazoles organic ligand and the transition metal complex containing N-S dicarboxylic acid;
Described semi-rigid pair of imidazole ligands is Isosorbide-5-Nitrae-two (imidazoles-1-methylene radical) benzene;
Described is 2-carboxylic methylene radical sulfenyl nicotinic acid or 2,2'-(1,3,4-thiadiazoles-2,5-bis-base) dithio oxalic acid containing N and S dicarboxylic acid.
3. according to claim 2 a kind of based on semi-rigid pair of imidazoles organic ligand and the synthetic method of transition metal complex containing N-S dicarboxylic acid, it is characterized in that: described Zn
2+, Co
2+, Cd
2+nitrate be respectively Zn (NO
3)
26H
2o, Co (NO
3)
26H
2o, Cd (NO
3)
24H
2o.
4. according to claim 2ly a kind ofly it is characterized in that: during intensification based on semi-rigid pair of imidazoles organic ligand and the synthetic method of transition metal complex containing N-S dicarboxylic acid, temperature rise rate is 5 DEG C/h ~ 15 DEG C/h; During cooling, rate of temperature fall is 2.5 DEG C/h ~ 10 DEG C/h.
5. according to claim 2 a kind of based on semi-rigid pair of imidazoles organic ligand and the synthetic method of transition metal complex containing N-S dicarboxylic acid, it is characterized in that: the add-on of described deionized water is 30% ~ 60% of autoclave volume.
6. according to claim 2 a kind of based on semi-rigid pair of imidazoles organic ligand and the synthetic method of transition metal complex containing N-S dicarboxylic acid, it is characterized in that: the concentration of described NaOH solution is 0.1mol/L ~ 1.0mol/L.
7. as claimed in claim 1 a kind of based on semi-rigid pair of imidazoles organic ligand and containing the transition metal complex of N-S dicarboxylic acid as the application in photocatalyst material.
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