CN107698777B - Copper-coordinated porous polymer, preparation method and application - Google Patents
Copper-coordinated porous polymer, preparation method and application Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000013078 crystal Substances 0.000 claims abstract description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 13
- LJVQHXICFCZRJN-UHFFFAOYSA-N 1h-1,2,4-triazole-5-carboxylic acid Chemical compound OC(=O)C1=NC=NN1 LJVQHXICFCZRJN-UHFFFAOYSA-N 0.000 claims abstract description 12
- MVRGLMCHDCMPKD-UHFFFAOYSA-N 3-amino-1h-1,2,4-triazole-5-carboxylic acid Chemical compound NC1=NNC(C(O)=O)=N1 MVRGLMCHDCMPKD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013256 coordination polymer Substances 0.000 claims abstract description 10
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 10
- 239000011941 photocatalyst Substances 0.000 claims abstract description 10
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 8
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 3
- 230000005595 deprotonation Effects 0.000 claims abstract description 3
- 238000010537 deprotonation reaction Methods 0.000 claims abstract description 3
- 239000013259 porous coordination polymer Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000013110 organic ligand Substances 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052802 copper Inorganic materials 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 239000005431 greenhouse gas Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229910052751 metal Chemical class 0.000 description 5
- 239000002184 metal Chemical class 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 150000003852 triazoles Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000239290 Araneae Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ZXBVATFSHBMXOL-UHFFFAOYSA-N copper;2h-triazole Chemical compound [Cu].C=1C=NNN=1 ZXBVATFSHBMXOL-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000013354 porous framework Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B01J35/39—
-
- B01J35/60—
Abstract
A copper coordination porous polymer, a preparation method and application. The present invention belongs to coordination polymer material. Has a chemical formula of [ Cu3(Tra)2O2•7H2O]nMolecular structural formula is C24H32Cu12N36O38Wherein Tra is an anion obtained after deprotonation of 1,2, 4-triazole, Cu is a divalent copper ion, and the material is in a solid crystal form. The crystal of the polymer is a trigonal system, R-3C space group, and the porosity of the three-dimensional frame structure is 51.9%. The preparation method comprises the following steps: 1,2, 4-triazole-3-carboxylic acid, 5-amino-1, 2, 4-triazole-3-carboxylic acid and CuCl2The reaction is carried out under hydrothermal conditions to obtain dark green crystals. The invention can be used as a photocatalyst to convert greenhouse gas carbon dioxide into carbon monoxide. The preparation process is easy to implement, the product purity and yield are high, and the method has a good application prospect in the aspect of photocatalytic conversion of carbon dioxide.
Description
Technical Field
The invention belongs to coordination polymer materials, in particular to a porous coordination polymer and a preparation method and application thereof.
Background
Abundant fossil fuel resources such as petroleum, coal, etc. are contained on the earth. Due to the fact thatCombustion of fossil fuels releases large amounts of CO2Causing a number of serious environmental problems such as global warming. Introducing CO2The idea of reduction to chemical fuels is to address CO2An effective method of the problem. To achieve this, the CO can be catalytically reduced using visible light2Thereby reducing the emission of greenhouse gases and simultaneously obtaining new fuels such as CO, methane and the like. The efficient photocatalyst is sought to solve CO2The key to the reduction is (CN 103721738A; CN 105749914A; CN 103464172B). The traditional carbon dioxide photocatalyst generally selects cheap and abundant manganese, iron and other metal complexes (ACS Catal.,2015,5, 2521-2528; J.Am.chem.Soc.,2016,138, 4354-4357), but the complexes are compounds with small molecular structures, generally have no regular pore structures and have weak absorption to carbon dioxide. The 1,2, 4-triazole and the derivatives thereof are excellent ligands with a plurality of coordination sites, the ligands can form metal complexes with different structures and functions with transition metals, and the coordination modes are various, so that the possibility is provided for synthesizing a porous copper coordination compound with a novel structure; copper belongs to cheap metal, and the complex formed by copper ions has good application prospect in the fields of electricity, catalysis, optics and the like (CN 104646058A; CN 102532170B). However, the research on the application of the copper triazole coordination polymer to photocatalytic reduction of carbon dioxide is rarely reported at present.
Disclosure of Invention
The invention aims to prepare a novel porous copper coordination polymer by taking 1,2, 4-triazole-3-carboxylic acid and 5-amino-1, 2, 4-triazole-3-carboxylic acid as precursor ligands and copper ions as metal centers, and the coordination polymer is used as a catalyst and applied to reduction of photocatalytic carbon dioxide.
In order to solve the above technical problems, the technical solution of the present invention includes:
(one) a copper-coordinated porous polymer
The chemical formula of the polymer is [ Cu ]3(Tra)2O2·7H2O]nWherein Tra represents an anion of an organic ligand 1,2, 4-triazole after deprotonation, Cu is a copper ion, and the polymerHas a one-dimensional pore canal formed by bridging copper ions through oxygen atoms by a Tra ligand and further has a three-dimensional porous framework network; the polymer crystal belongs to a trigonal system, the space group is R-3C, and the unit cell parameters are respectively as follows:
b＝17.569(5)、
α＝β＝90°,γ＝120°,
further: the porosity of the three-dimensional framework structure of the porous polymer crystal was 51.9%; the decomposition temperature of the frame structure was 305 ℃.
(II) method for preparing the porous coordination polymer material
The method comprises the following steps:
(1) 1,2, 4-triazole-3-carboxylic acid, 5-amino-1, 2, 4-triazole-3-carboxylic acid and CuCl2Mixing in distilled water;
(2) sealing the obtained mixed liquid, carrying out hydrothermal reaction at 150-180 ℃ for 24-48 hours, and slowly cooling to room temperature at the speed of 5 ℃ per hour to obtain dark green needle crystals;
(3) washing the dark green needle crystal with ethanol, and naturally airing to prepare a single crystal sample of the porous coordination polymer;
(4) vacuum drying at 110 deg.c to obtain the porous coordination polymer.
Further: the 1,2, 4-triazole-3-carboxylic acid, 5-amino-1, 2, 4-triazole-3-carboxylic acid and CuCl in the step (1)2The molar ratio of (a) to (b) is 1:1:1 to 1:1: 2.
(III) application of porous copper coordination polymer of the invention
A method of using one of the copper-coordinated porous polymers as a photocatalyst.
Further: the coordination polymer is used as a photocatalyst for reducing carbon dioxide into carbon monoxide.
Compared with the traditional catalyst, the invention has the beneficial effects that:
firstly, the characteristic of multi-coordination sites of 1,2, 4-triazole-3-carboxylic acid and 5-amino-1, 2, 4-triazole-3-carboxylic acid is utilized to achieve the purpose of forming a coordination compound with copper ions. 1,2, 4-triazole-3-carboxylic acid and 5-amino-1, 2, 4-triazole-3-carboxylic acid undergo elimination of amino and carboxyl in hydrothermal reaction, and form an oxygen bridge with copper ions, so that a three-dimensional network framework is formed, and carbon dioxide can be adsorbed by high porosity.
The Cu complex is a giant molecule with a framework structure, has a regular pore structure and good porosity, has obvious absorption on carbon dioxide, and can also catalyze and reduce CO2The gas is CO.
Secondly, the copper coordination compound is adopted, and the characteristic that metal copper is cheap and easy to obtain is utilized. The compound has the great advantage of low cost when being used as a catalyst.
Thirdly, the photocatalyst material of the invention has simple preparation, good reproducibility, high yield and high product purity.
Fourthly, the photocatalyst of the invention has stable structure and high thermal stability.
Drawings
FIG. 1 is an infrared spectrum of the porous coordination polymer. In the infrared spectrogram of the porous coordination polymer, after copper ions are coordinated with N atoms in triazole, the distance between the copper ions and the N atoms is 1513cm-1Showing a stronger absorption. Indicating that the copper ions form a coordination compound with the ligand.
FIG. 2 is a graph of simulated powder diffraction contrast of a single crystal sample and a single crystal of the porous coordination polymer. The figure shows that: the diffraction of the single crystal samples of the prepared porous coordination polymers was essentially identical to that of the single crystal simulations, indicating that the purity of the prepared porous coordination polymer samples was relatively high.
FIG. 3 is a schematic diagram showing the coordination structure of the porous coordination polymer. In the figure, copper ions are coordinated with nitrogen atoms at 1,4 positions in triazole, and simultaneously the copper ions are linked with a triazole coordination unit through an oxygen bridge bond to form a three-dimensional framework structure. FIG. 4 is a three-dimensional structure packing diagram of the porous coordination polymer crystal. It can be found that after the one-dimensional pore channels are stacked in the three-dimensional space, the coordination polymer with the micropore structure is formed.
FIG. 5 shows fluorescence emission spectrum of the porous coordination polymer. It is shown that under UV excitation, the coordination polymer has the strongest emission peak at 467nm, which is the fluorescence emission when the triazole ligand absorbs energy and then returns to the ground state.
FIG. 6 shows the catalytic reduction of CO using the porous coordination polymer as a photocatalyst2Gas chromatography of (A) shows that CO is present under the action of a porous coordination polymer2Can be reduced to CO. The porous coordination polymer has a good effect on catalytic conversion of carbon dioxide. The photocatalytic cycle conversion number (TON) was 35.
FIG. 7 is an adsorption curve of the porous coordination polymer for carbon dioxide gas at a temperature of 273K, from which it can be found that the adsorption amount of the porous coordination polymer for carbon dioxide gas can reach 15.6cm3/g。
The present invention is further illustrated by the following specific examples. The examples include but do not limit the scope of the invention.
Detailed Description
(one) preparing the porous coordination polymer material
Example 1:
11.31 mg (0.1mmol) of 1,2, 4-triazole-3-carboxylic acid, 12.81 mg (0.1mmol) of 5-amino-1, 2, 4-triazole-3-carboxylic acid and 34.1 mg (0.2mmol) of CuCl2·2H2Adding O into 10m L distilled water, mixing uniformly, sealing the obtained mixed solution, carrying out hydrothermal reaction at 150 ℃ for 48 hours, cooling to room temperature at the speed of 5 ℃ per hour to obtain dark green blocky transparent crystals, washing with ethanol, naturally drying to obtain a single crystal sample of the porous coordination polymer, and drying in vacuum at 110 ℃ to obtain the porous coordination polymer.
Example 2:
11.31 mg (0.1mmol) of 1,2, 4-triazole-3-carboxylic acid, 12.81 mg (0.1mmol) of 5-amino-1, 2, 4-triazole-3-carboxylic acid and 34.1 mg (0.2mmol) of CuCl2·2H2Adding O into 10m L distilled water, mixing uniformly, sealing the obtained mixed solution, carrying out hydrothermal reaction at 160 ℃, reacting for 36 hours, cooling to room temperature at the speed of 5 ℃ per hour to obtain dark green blocky transparent crystals, washing with ethanol, naturally airing to obtain a single crystal sample of the porous coordination polymer, and drying in vacuum at 110 ℃ to obtain the porous coordination polymer.
Example 3:
11.31 mg (0.1mmol) of 1,2, 4-triazole-3-carboxylic acid, 12.81 mg (0.1mmol) of 5-amino-1, 2, 4-triazole-3-carboxylic acid and 25.6 mg (0.15mmol) of CuCl2·2H2Adding O into 10m L distilled water, mixing uniformly, sealing the obtained mixed solution, carrying out hydrothermal reaction at 170 ℃, reacting for 36 hours, cooling to room temperature at the speed of 5 ℃ per hour to obtain dark green blocky transparent crystals, washing with ethanol, naturally airing to obtain a single crystal sample of the porous coordination polymer, and drying in vacuum at 110 ℃ to obtain the porous coordination polymer.
Example 4:
11.31 mg (0.1mmol) of 1,2, 4-triazole-3-carboxylic acid, 12.81 mg (0.1mmol) of 5-amino-1, 2, 4-triazole-3-carboxylic acid and 25.6 mg (0.10mmol) of CuCl2·2H2Adding O into 10m L distilled water, mixing uniformly, sealing the obtained mixed solution, carrying out hydrothermal reaction at 180 ℃, reacting for 24 hours, cooling to room temperature at the speed of 5 ℃ per hour to obtain dark green blocky transparent crystals, washing with ethanol, naturally airing to obtain a single crystal sample of the porous coordination polymer, and drying in vacuum at 110 ℃ to obtain the porous coordination polymer.
Determination of Structure of porous coordination Polymer
Table 1: parameter table of porous coordination polymer crystals
Selecting single crystal with proper size under microscope, and monochromating with graphite monochromator on Rigaku R-AXISSPIDER diffractometer at T293 (2) K
The method comprises the steps of collecting diffraction data in an omega-phi mode, carrying out absorption correction through an ABSCOR program, analyzing and refining the structure by using a SHE L XT L program through a direct method, determining all non-hydrogen atom coordinates through a difference function method and a least square method, carrying out full matrix least square method correction on the non-hydrogen atom coordinates and anisotropic parameters, obtaining the hydrogen atom position of a main skeleton through a theoretical hydrogenation method, and refining the crystal structure through a least square method, wherein partial parameters of collection and structure refinement of the data of the crystallographic diffraction points are shown in the table 1.
The infrared spectroscopy experiments of the present invention were performed using BRUKER TENSOR 27.
Fluorescence spectroscopy experiments were performed using a Hitachi F-4600 fluorescence spectrometer.
Powder diffraction data collection was done on a Rigaku D-MAX 2200VPC diffractometer.
Single crystal diffraction was performed on a Rigaku R-AXIS SPIDER diffractometer.
Gas chromatography detection was done in SHIMADZU GC-2014C.
Claims (6)
1. A copper-coordinated porous polymer characterized by: the chemical formula of the polymer is [ Cu ]3(Tra)2O2·7H2O]nWherein Tra represents an anion of the organic ligand 1,2, 4-triazole after deprotonation, Cu is a copper ion, and the polymer has a one-dimensional pore channel formed by bridging the Tra ligand with the copper ion through an oxygen atom and has a three-dimensional porous skeleton network; the polymer crystal belongs to a trigonal system, the space group is R-3C, and the unit cell parameters are respectively as follows:
b＝17.569(5)、
α＝β＝90°,γ＝120°,
2. the porous polymer according to claim 1, characterized in that: the porosity of the three-dimensional framework structure of the porous polymer crystal was 51.9%; the decomposition temperature of the frame structure was 305 ℃.
3. A process for preparing one of the porous polymers of claim 1 or 2, comprising the steps of:
(1) 1,2, 4-triazole-3-carboxylic acid, 5-amino-1, 2, 4-triazole-3-carboxylic acid and CuCl2Mixing in distilled water;
(2) sealing the obtained mixed liquid, carrying out hydrothermal reaction at 150-180 ℃ for 24-48 hours, and slowly cooling to room temperature at the speed of 5 ℃ per hour to obtain dark green needle crystals;
(3) washing the dark green needle crystal with ethanol, and naturally airing to prepare a single crystal sample of the porous coordination polymer;
(4) vacuum drying at 110 deg.c to obtain the porous coordination polymer.
4. The production method according to claim 3, characterized in that: the 1,2, 4-triazole-3-carboxylic acid and 5-amino-1, 2, 4-triazole-3-carboxylic acid in the step (1) and CuCl2The molar ratio of (a) to (b) is 1:1:1 to 1:1: 2.
5. A method of using one of the copper-coordinated porous polymers as claimed in claim 1 or 2 as a photocatalyst.
6. The method of application according to claim 5, characterized in that: the coordination polymer is used as a photocatalyst for reducing carbon dioxide into carbon monoxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665006A (en) * | 2013-12-13 | 2014-03-26 | 南开大学 | Porous metal-organic framework hybrid material as well as preparation method and application thereof |
| CN105037742A (en) * | 2015-06-11 | 2015-11-11 | 山西大学 | Copper metal polymer, and preparation method and application thereof |
| CN104628751B (en) * | 2015-02-05 | 2016-07-06 | 云南师范大学 | A kind of luminous Porous coordination polymer and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103665006A (en) * | 2013-12-13 | 2014-03-26 | 南开大学 | Porous metal-organic framework hybrid material as well as preparation method and application thereof |
| CN104628751B (en) * | 2015-02-05 | 2016-07-06 | 云南师范大学 | A kind of luminous Porous coordination polymer and its preparation method and application |
| CN105037742A (en) * | 2015-06-11 | 2015-11-11 | 山西大学 | Copper metal polymer, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Design of novel three-dimensional coordination polymers based on triangular trinuclear copper 1,2,4-triazolate units;Quan-Guo Zhai,et al.;《CRYSTAL GROWTH & DESIGN》;20060421;第6卷(第6期);1393-1398 * |
| 基于1,2,4-三氮唑配体的配位聚合物的合成、结构和性能研究;苗少斌;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20150215(第2期);13-18 * |
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