CN102040632B - Metal coordination polymer and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a metal coordination polymer and a preparation method and application of the metal coordination polymer. The polymer has a general structure formula shown by the formula I, and in the general structure formula of the formula I, R is a tetrabutyl ammonium ion, a tetradecyl trimethyl ammonium ion, Na or Ni, and M is Zn, Ni, Cu, Au, Pd or Pt. The preparation method comprises the following steps of: firstly, under an inert atmosphere, reacting sodium methylate with 1,3,4,6-tetra-sulfur co-cyclopentadiene-2,5-dione in an organic solvent; secondly, adding organic solution of nickel chloride hexahydrate to continue reacting, and after that, adding organic solution of an ammonium salt to continue reacting; and finally, drying the mixture, and oxidizing the mixture with iodine or air to obtain the product. For the polymer, the electric conductivity at 320K reaches 12.4S/cm, the seebeck coefficient can reach 170 muV/K, the heat conductivity is 0.3 W/m/k, and the thermoelectric merit figure ZT can reach 0.04. So, the metal coordination polymer is an excellent p-type organic thermoelectric conversion material.
Description
Technical field
The present invention relates to a kind of organic thermoelectric material, particularly relate to a kind of metal coordinating polymer and preparation method thereof and application.
Background technology
1834, French physicist Pei Erjie (J.C.A.Peltier) found that thermoelectric material can provide the conversion between electric energy and heat energy; Nineteen twenty-three, Sai Beike (seebeck) has reported that the temperature difference can produce electromotive force (Seebeck effect), and without the mechanical part moving, electromotive force can produce the temperature difference (Peltier effect), has obtained people's extensive concern.Thermoelectric effect itself is reversible, both can be converted to heat energy by electric energy, can be also electric energy by thermal power transfer.Although scientific circles at that time attach great importance to the discovery of Pei Erjie and Sai Beike, find not to be converted into very soon application.This is because the conversion efficiency of thermoelectric of metal is conventionally very low.Until the 1950's, some semiconductor materials with good thermo-electric conversion performance are found, and the research of pyroelectric technology (thermoelectric refrigeration and thermoelectric power generation) just becomes a heat subject.
Compare with inorganic heat electric material, organic thermoelectric material has low cost, high seebeck coefficient, the features such as low thermal conductance.Inorganic semiconductor material has had more research, and Comparatively speaking, the research of organic thermoelectric material is also fewer.In recent years, organic thermoelectric material has been subject to very large attention, is one of prior development direction of thermoelectric material (Mildred S.Dresselhaus, Gang Chen, Adv.Mater., 2007,19,1043-1053; Yan H, Ohta T, Toshima N.Macromol.Mater.Eng., 2001,286 (3), 139-142; S.B.Riffat, X.Ma, AppliedThermal Engineering, 2003,3,913-935).
At present, the molecular material as organic thermoelectric material of better performances mainly contains following several: polyaniline, carbon pipe dopant material etc.But these material ubiquities seebeck coefficient is not high, electricity is led the problems such as not high.Therefore the outstanding organic thermoelectric material of, design synthesis performance is still the problem that needs research.
Summary of the invention
The object of this invention is to provide a kind of metal coordinating polymer and preparation method thereof and application.
Metal coordinating polymer provided by the invention, its general structure is suc as formula shown in I,
In formula I general structure, R is TBuA ion, tetradecyl trimethyl ammonium ion, Na, Cu or Ni, M is Zn, Ni, Cu, Au, Pd or Pt, m: n=1-2: 1-6, m: n specifically can be 1: 1-4,1-1.3: 1-4,1: 1,2: 1-6,2: 1,1.8: 1-6,1.8: 1-4,1.8: 1,1: 1-5,1: 5 or 1: 4-5; M specifically can be 1,1.3,1.8,2 or 17.67, n specifically can be 1,4,5 or 10; X=0-3, specifically can be any number between 0-2,1-2 or is 1 or 2; Y=0-2, specifically can be any number or 1 between 0-1; Z=0-5, specifically can be any number or 1,2 or 4.3 or 4.5 between 0-1,0-2,0-1.86,0-4.3,1-4.3,2-4.3 or 1-4.5.
The method of the above-mentioned metal coordinating polymer of preparation provided by the invention, comprises the steps:
1), under inert atmosphere, by sodium methylate and 1,3,4,6-, tetra-sulphur two cyclopentenes-2,5-diketone reacts in organic solvent;
2) described step 1) after completion of the reaction, the organic solution of metal-salt is joined to step 1) reaction system in proceed reaction;
3) described step 2) after completion of the reaction, the organic solution of ammonium salt is joined to described step 2) reaction system in proceed reaction;
4) by step 3) after the reaction product that obtains is dry, be scattered in methyl alcohol, with iodine or atmospheric oxidation, obtain metal coordinating polymer provided by the invention.
The step 1 of the method), in, inert atmosphere is nitrogen atmosphere, described sodium methylate and described 1,3,4, and 6-tetra-sulphur two cyclopentenes-2, the mass ratio of 5-diketone is 20-33: 20-21, preferably 28: 20; The concentration of described sodium methylate in described organic solvent is 11-15mg/mL, preferably 12mg/mL; Described organic solvent is methyl alcohol; Temperature of reaction is 10-30 ℃; Reaction times is 0.5-2 hour, preferably 1 hour;
Described step 2), in, described metal-salt is selected from least one in Nickel dichloride hexahydrate, cupric chloride, Palladous chloride and platinum chloride; In the organic solution of described metal-salt, solvent is methyl alcohol; The concentration 12-20mg/mL of the methanol solution of described metal-salt, preferably 15mg/mL; The temperature of reaction is 10-70 ℃, preferably 25 ℃; The time of reaction is 0.5-1 hour, preferably 0.5 hour;
Described step 3) in, described ammonium salt is Tetrabutyl amonium bromide, Tetradecyl Trimethyl Ammonium Bromide or 4 bromide, successively suc as formula shown in II; The mass ratio of described ammonium salt and described metal-salt is 31-35: 9-11, preferably 32: 10; The temperature of reaction is 10-30 ℃, preferably 25 ℃; The time of reaction is 0.5-3 hour, preferably 1 hour;
Described step 4) in, the amount ratio of described reaction product and methyl alcohol is 4-8mg: 1ml, preferably 6mg: 1ml; The mass ratio of described product and iodine is 10-15: 5-8.The temperature of oxidation is 10-30 ℃, preferably 25 ℃; The time of iodine oxidation is 2-5 hour, preferably 3 hours; The time of atmospheric oxidation is 7-13 days, preferably 12 days.
In addition, the application of above-mentioned metal coordinating polymer provided by the invention in the organic thermoelectric material of preparation, also belongs to protection scope of the present invention.
Metal coordinating polymer based on ethene four thiolate prepared by the present invention, there is good thermoelectricity capability, there are higher seebeck coefficient and very low thermal conductivity, and specific conductivity is moderate, can be up to 12.4S/cm under 320K, seebeck coefficient can reach 170 μ V/K, thermal conductivity is 0.3W/m/K, thermoelectric figure of merit ZT can reach 0.04, and in air stable in properties, be the organic thermo-electric converting material of a kind of good p-type.The method of the above-mentioned polymkeric substance of preparation provided by the invention, synthetic for wet method, technical process is short, with low cost, in organic thermoelectric material field, has broad application prospects.
Accompanying drawing explanation
Fig. 1 is that electricity that embodiment 1 prepares gained metal coordinating polymer is led and varied with temperature curve;
Fig. 2 is that the seebeck coefficient that embodiment 1 prepares gained metal coordinating polymer varies with temperature curve.
Fig. 3 is photoelectron spectrum (XPS) spectrogram that embodiment 1 prepares gained metal coordinating polymer.
Fig. 4 is photoelectron spectrum (XPS) spectrogram that embodiment 2 prepares gained metal coordinating polymer.
Fig. 5 is photoelectron spectrum (XPS) spectrogram that embodiment 3 prepares gained metal coordinating polymer.
Fig. 6 is photoelectron spectrum (XPS) spectrogram that embodiment 4 prepares gained metal coordinating polymer.
Fig. 7 is that electricity that embodiment 2 prepares gained metal coordinating polymer is led and varied with temperature curve;
Fig. 8 is that the seebeck coefficient that embodiment 2 prepares gained metal coordinating polymer varies with temperature curve;
Fig. 9 is that electricity that embodiment 4 prepares gained metal coordinating polymer is led and varied with temperature curve;
Figure 10 is that the seebeck coefficient that embodiment 4 prepares gained metal coordinating polymer varies with temperature curve.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
The method of the metal coordinating polymer of preparation provided by the invention based on ethene four thiolate, with 1,3,4,6-, tetra-sulphur two cyclopentenes-2,5-diketone is raw material, by alkali and metal-salt, generate metal complexes, then generate charge-transfer complex by ammonium salt or other metal ions, and by it oxidation, obtain final product, its synthetic route is as follows:
Material prepared by the present invention can be adopted the detection of carrying out with the following method thermoelectricity capability: product is carried out to the detection of thermoelectricity capability.Sample is carried out to compressing tablet, obtain regular rectangular parallelepiped, by the mode of four electrodes, measure, by low temp. electric, magnetic property system, measure the resistance under differing temps.By sample compressing tablet, with SeebeckMeasurement System (SB-100), sample is carried out to the measurement of seebeck coefficient equally.In addition, also sample has been carried out the measurement of thermal conductance.
Metal coordinating polymer based on ethene four thiolate shown in embodiment 1, preparation formula a
By 1,3,4,6-, tetra-sulphur two cyclopentenes-2,5-diketone (170mg) is put into 50ml there-necked flask, and the 20ml concentration that adds nitrogen protection is the methanol solution of 12mg/mL sodium methylate, stirs 1 hour under room temperature nitrogen protection.The methanol solution of the Nickel dichloride hexahydrate that is 13mg/mL by 15ml concentration is injected in above-mentioned solution, stirring at room half an hour.Adding 20mL concentration is the methanol solution of the Tetradecyl Trimethyl Ammonium Bromide of 27mg/mL, then stirring at room half hour.Suction filtration obtains solid, with first alcohol and water, washs.Vacuum-drying is spent the night.The solid obtaining is dissolved in 10mL methyl alcohol with the concentration of 4mg/mL, adds iodine 20mg, and Oxidation at room temperature 3 hours obtains the metal coordinating polymer 189mg based on ethene four thiolate shown in formula a, productive rate 42.7%.
Photoelectron spectrum (XPS) spectrogram as shown in Figure 3, as seen from the figure, Ni, I, N, S, there is (O is free oxygen in air) in C, and by it in conjunction with the known Ni valency of energy data, be+divalent in compound, and should with S phase bonding, S has two kinds of different valence state, I is-1 valency.
By organic element analysis, obtain the content of C, H, N, the content that obtains Ni by inductively coupled plasma atomic emission spectrometer device (ICP-OES) instrumental analysis is as follows:
Ultimate analysis: C:20.22, H:2.45, N:0.87, Ni:16.63
Theoretical value: C:20.29, H:2.79, N:1.02, Ni:16.47
Metal coordinating polymer based on ethene four thiolate shown in formula a is carried out to the detection of thermoelectricity capability:
Sample is carried out to compressing tablet, obtain regular rectangular parallelepiped, by the mode of four electrodes, measure, by low temp. electric, magnetic property system, measure the resistance under differing temps, when 322.5K, its specific conductivity is 0.45S/cm.Equally, by the metal coordinating polymer compressing tablet based on ethene four thiolate shown in formula a, with Seebeck MeasurementSystem (SB-100), carry out the measurement of seebeck coefficient, predicting can be up to 250 μ V/K, as shown in Figure 2 at 322.5Kseebeck coefficient.In addition, also the metal coordinating polymer based on ethene four thiolate shown in formula a has been carried out to the measurement of thermal conductance, under 322.5K, its thermal conductivity is 0.3W/K/m.Can when 322.5K, reach ZT=0.003 by its thermoelectric figure of merit, as shown in Figure 1.
Metal coordinating polymer based on ethene four thiolate shown in embodiment 2, synthesis type b
By 1,3,4,6-, tetra-sulphur two cyclopentenes-2,5-diketone (261mg) is put into 50ml there-necked flask, the methanol solution of the sodium methylate that the 20ml concentration that adds nitrogen protection is 15mg/mL, and under nitrogen protection, stirring at room is 1 hour.The methanol solution of the Nickel dichloride hexahydrate that is 20mg/mL by 15ml concentration is injected in above-mentioned solution, stirring at room 1 hour.Suction filtration obtains solid, with first alcohol and water, washs.Vacuum-drying is spent the night.The solid obtaining is dissolved in 10mL methyl alcohol with the concentration of 6mg/mL, is oxidized and after 13 days, obtains the metal coordinating polymer 200mg based on ethene four thiolate shown in formula b, productive rate 78.0% in air at room temperature.
Fig. 4 is the photoelectron spectrum figure of this compound, as seen from the figure, and Ni, Na, S, in compound, there is (O is free oxygen in air, and N is test pollution) in C, and by its in conjunction with can data known Ni valency be+divalent, and should with S phase bonding, S has two kinds of different valence state.
By organic element analysis, obtain the content of C, by inductively coupled plasma atomic emission spectrometer device (ICP-OES) instrumental analysis, obtain Ni, the content of Na is as follows:
Ultimate analysis: C 9.40, Na 16.09, and Ni 25.56
Theoretical value: C 9.33, Na 15.78, and Ni 25.08
Metal coordinating polymer based on ethene four thiolate shown in formula b is carried out to the detection of thermoelectricity capability:
Sample is carried out to compressing tablet, obtain regular rectangular parallelepiped, by the mode of four electrodes, measure, by low temp. electric, magnetic property system, measure the resistance under differing temps, during 320K, specific conductivity is up to 12.4S/cm.Equally, by the metal coordinating polymer compressing tablet based on ethene four thiolate shown in formula b, with Seebeck MeasurementSystem (SB-100), carry out the measurement of seebeck coefficient, predicting seebeck coefficient when 320K can be up to 106 μ V/K, as shown in Figure 8.In addition, also the metal coordinating polymer based on ethene four thiolate shown in formula b has been carried out to the measurement of thermal conductance, its thermal conductivity is 0.3W/K/m, can obtain thermoelectric figure of merit ZT=0.015, as shown in Figure 7.
Embodiment 3,
Metal coordinating polymer based on ethene four thiolate shown in synthesis type c
By 1,3,4,6-, tetra-sulphur two cyclopentenes-2,5-diketone (175mg) is put into 50ml there-necked flask, the methanol solution of the sodium methylate that the 20ml concentration that adds nitrogen protection is 12mg/mL, and under nitrogen protection, stirring at room is 1 hour.The methanol solution of the anhydrous cupric chloride that is 15mg/mL by 15ml concentration is injected in above-mentioned solution, heats 70 degree return stirring 1 hour.Suction filtration obtains solid, with methyl alcohol, water, hydrochloric acid, washs.Vacuum-drying is spent the night.Obtain the metal coordinating polymer 181mg based on ethene four thiolate shown in formula c, productive rate 65.1%.
Fig. 5 is the photoelectron spectrum figure of this compound, and as seen from the figure, Cu, O, S, C exist in compound, and by its in conjunction with can data known Cu valency be+divalent, and should with S phase bonding, S has two kinds of different valence state.
Ni, I, N, S, in compound, there is (O is free oxygen in air) in C, and by its in conjunction with can data known Ni valency be+divalent, and should with S phase bonding, S has two kinds of different valence state, I is-1 valency.
By organic element analysis, obtain the content of C, H, the content that obtains Cu by inductively coupled plasma atomic emission spectrometer device (ICP-OES) analysis is as follows:
Ultimate analysis: C 7.15, H 1.17, and Cu 38.03
Theoretical value: C 7.25, H 1.22, and Cu 38.35
Metal coordinating polymer based on ethene four thiolate shown in formula c is carried out to the detection of thermoelectricity capability:
Sample is carried out to compressing tablet, obtain regular rectangular parallelepiped, by the mode of four electrodes, measure, by low temp. electric, magnetic property system, measure the resistance under differing temps, during 320K, specific conductivity reaches 1.2S/cm.Equally, by the metal coordinating polymer compressing tablet based on ethene four thiolate shown in formula c, with Seebeck MeasurementSystem (SB-100), carry out the measurement of seebeck coefficient, predict seebeck coefficient when 320K and can reach 10 μ V/K in addition, also the metal coordinating polymer based on ethene four thiolate shown in formula c has been carried out to the measurement of thermal conductance, during 320K, thermal conductivity is 0.3W/K/m.Can obtain thermoelectric figure of merit ZT=1.3*10 under 320K
-5.
Embodiment 4,
Metal coordinating polymer based on ethene four thiolate shown in synthesis type d
By 1,3,4,6-, tetra-sulphur two cyclopentenes-2,5-diketone (166mg) is put into 50ml there-necked flask, the methanol solution of the sodium methylate that the 20ml concentration that adds nitrogen protection is 11mg/mL, and under nitrogen protection, stirring at room is 1 hour.The methanol solution of the Nickel dichloride hexahydrate that is 12mg/mL by 15ml concentration is injected in above-mentioned solution, stirring at room 1 hour.Suction filtration obtains solid, with first alcohol and water, washs.Vacuum-drying is spent the night.The solid obtaining is dissolved in 10mL methyl alcohol with the concentration of 8mg/mL, adds 42mg iodine, and Oxidation at room temperature obtains the metal coordinating polymer 166mg based on ethene four thiolate shown in formula d, productive rate 71.6%.
Fig. 6 is the photoelectron spectrum figure of this compound, as seen from the figure, and Ni, I, N, S, there is (O is free oxygen in air) in C, and by it in conjunction with the known Ni valency of energy data, be+divalent in compound, and should with S phase bonding, S has two kinds of different valence state, I is-1 valency.
By organic element analysis, obtain the content of C, H, N, the content that obtains Ni by inductively coupled plasma atomic emission spectrometer device (ICP-OES) analysis is as follows:
Ultimate analysis: C 20.60, H 2.30, and N 1.00, Ni18.96
Theoretical value: C 20.37, H 2.37, and N 0.91, Ni19.14
Metal coordinating polymer based on ethene four thiolate shown in formula d is carried out to the detection of thermoelectricity capability:
Sample is carried out to compressing tablet, obtain regular rectangular parallelepiped, by the mode of four electrodes, measure, by low temp. electric, magnetic property system, measure the resistance under differing temps, during 320K, specific conductivity reaches 0.26S/cm.Equally, by the metal coordinating polymer compressing tablet based on ethene four thiolate shown in formula d, with Seebeck MeasurementSystem (SB-100), carry out the measurement of seebeck coefficient, predicting seebeck coefficient when 320K can be up to 27 μ V/K, as shown in figure 10.In addition, also the metal coordinating polymer based on ethene four thiolate shown in formula d has been carried out to the measurement of thermal conductance, under 320K, thermal conductivity is 0.3W/K/m, can obtain the thermoelectric figure of merit ZT=2.0*10 of 320K
-5, as shown in Figure 9.
Claims (5)
1. the metal coordinating polymer shown in formula a, formula b or formula c structure,
2. a method of preparing metal coordinating polymer described in claim 1 Chinese style a, comprises the steps:
1), under inert atmosphere, by sodium methylate and 1,3,4,6-, tetra-sulphur two cyclopentenes-2,5-diketone reacts in organic solvent;
2) described step 1) after completion of the reaction, the organic solution of metal-salt is joined to step 1) reaction system in proceed reaction;
3) described step 2) after completion of the reaction, the organic solution of ammonium salt is joined to described step 2) reaction system in proceed reaction;
4) by step 3) after the reaction product that obtains is dry, be scattered in methyl alcohol, with iodine oxidation, obtain metal coordinating polymer described in claim 1 Chinese style a;
Step 1), in, described inert atmosphere is nitrogen atmosphere, described sodium methylate and described 1,3,4, and 6-tetra-sulphur two cyclopentenes-2, the mass ratio of 5-diketone is 20-33:20-21; The concentration of described sodium methylate in described organic solvent is 11-15mg/mL; Described organic solvent is methyl alcohol;
Step 2), in, described metal-salt is selected from Nickel dichloride hexahydrate; In the organic solution of described metal-salt, solvent is methyl alcohol;
Step 3), in, described ammonium salt is Tetradecyl Trimethyl Ammonium Bromide; The mass ratio of described ammonium salt and described metal-salt is 31-35:9-11;
Described step 4), in, the amount ratio of described reaction product and methyl alcohol is 4-8mg:1mL; The mass ratio of described product and iodine is 10-15:5-8;
Described step 1), in, temperature of reaction is 10-30 ℃; Reaction times is 0.5-2 hour;
Described step 2), in, the temperature of reaction is 10-70 ℃; The time of reaction is 0.5-1 hour;
Described step 3), in, the temperature of reaction is 10-30 ℃; The time of reaction is 0.5-3 hour;
Described step 4), in, the temperature of oxidation is 10-30 ℃; The time of iodine oxidation is 2-5 hour.
3. method according to claim 2, is characterized in that: described step 1), and described sodium methylate and described 1,3,4,6-tetra-sulphur two cyclopentenes-2, the mass ratio of 5-diketone is 28:20; The concentration of described sodium methylate in described organic solvent is 12mg/mL;
Described step 2), in, the concentration of the methanol solution of described metal-salt is 13mg/mL;
Described step 3), in, the mass ratio of described ammonium salt and described metal-salt is 32:10;
Described step 4), in, the amount ratio of described reaction product and methyl alcohol is 6mg:1mL.
4. method according to claim 2, is characterized in that: described step 1), temperature of reaction is 25 ℃; Reaction times is 1 hour;
Described step 2), in, the temperature of reaction is 25 ℃; The time of reaction is 0.5 hour;
Described step 3), in, the temperature of reaction is 25 ℃; The time of reaction is 1 hour;
Described step 4), in, the temperature of oxidation is 25 ℃; The time of iodine oxidation is 3 hours.
5. the application of metal coordinating polymer in the organic thermoelectric material of preparation described in claim 1.
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| CN103755606B (en) * | 2013-12-23 | 2016-04-20 | 中国科学院化学研究所 | A kind of Organic thermoelectric material cuprous based on ethene four mercaptan and preparation method thereof |
| CN104241515B (en) * | 2014-09-15 | 2017-10-03 | 中国科学院化学研究所 | Organic thermoelectric material based on the mercaptan nickel of ethene four and preparation method and application |
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| CN102040632A (en) | 2011-05-04 |
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