CN107698777A - A kind of porous polymer of cupric coordination, preparation method and application - Google Patents
A kind of porous polymer of cupric coordination, preparation method and application Download PDFInfo
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- CN107698777A CN107698777A CN201710974705.7A CN201710974705A CN107698777A CN 107698777 A CN107698777 A CN 107698777A CN 201710974705 A CN201710974705 A CN 201710974705A CN 107698777 A CN107698777 A CN 107698777A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000013256 coordination polymer Substances 0.000 claims abstract description 10
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 10
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims abstract description 5
- 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 2
- 238000010537 deprotonation reaction Methods 0.000 claims abstract 2
- 239000013259 porous coordination polymer Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910001431 copper ion Inorganic materials 0.000 claims description 12
- 239000010949 copper Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- MVRGLMCHDCMPKD-UHFFFAOYSA-N 3-amino-1h-1,2,4-triazole-5-carboxylic acid Chemical class NC1=NNC(C(O)=O)=N1 MVRGLMCHDCMPKD-UHFFFAOYSA-N 0.000 claims description 9
- LJVQHXICFCZRJN-UHFFFAOYSA-N 1h-1,2,4-triazole-5-carboxylic acid Chemical class OC(=O)C1=NC=NN1 LJVQHXICFCZRJN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 150000003852 triazoles Chemical class 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 claims description 2
- 238000000354 decomposition reaction Methods 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
- 239000000463 material Substances 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 241000239290 Araneae Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- MOFINMJRLYEONQ-UHFFFAOYSA-N [N].C=1C=CNC=1 Chemical class [N].C=1C=CNC=1 MOFINMJRLYEONQ-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method 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
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 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
- 239000005431 greenhouse gas 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
- 239000003446 ligand Substances 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
- 239000011148 porous material Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 238000001179 sorption measurement Methods 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
- 238000004846 x-ray emission Methods 0.000 description 1
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]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Catalysts (AREA)
Abstract
A kind of porous polymer of cupric coordination, preparation method and application.The invention belongs to coordination polymer material.Its chemical formula is [Cu3(Tra)2O2•7H2O]n, molecular structural formula C24H32Cu12N36O38, wherein Tra is the anion after 1,2,4 triazole deprotonations, and Cu is bivalent cupric ion, and the form of material is solid crystals.The crystal structure of the polymer is trigonal system, and R 3C space groups, the porosity of its three-dimensional frame structure is 51.9%.Preparation is：By the carboxylic acid of 1,2,4 triazole 3 and the carboxylic acid of 5 amino, 1,2,4 triazole 3 and CuCl2React under hydrothermal conditions, obtain blackish green crystal.The present invention can be used as a kind of photochemical catalyst, and GHG carbon dioxide is changed into carbon monoxide.Preparation technology of the present invention is easily implemented, and product purity and yield are higher, is had a good application prospect in terms of photocatalytic conversion carbon dioxide.
Description
Technical field
The invention belongs to coordination polymer material, especially Porous coordination polymer and its preparation method and application.
Background technology
Contain abundant fossil fuel resource, such as oil, coal etc. on the earth.Because the burning of fossil fuel discharges
Go out substantial amounts of CO2, cause many serious environmental problems such as global warming.By CO2The imagination of chemical fuel is reduced to, is solution
Certainly CO2The effective ways of problem.In order to realize this purpose, visible light catalytic reduction CO can be utilized2, so as to reduce greenhouse gas
The discharge of body, while obtain such as CO, methane new fuel.It is to solve CO to seek efficient photochemical catalyst2The crucial institute of reduction
In (CN 103721738A；CN 105749914A；CN 103464172B).Traditional carbon dioxide photochemical catalyst is typically selected
The metal complexs such as cheap and rich content manganese, iron (ACS Catal., 2015,5,2521-2528；J.Am.Chem.Soc.,
2016,138,4354-4357), but these complexs are the compounds of small molecule structure, the general hole knot without rule
Structure, the absorption to carbon dioxide be not strong.1,2,4- triazole and its derivative are a kind of excellent parts with multiple coordination sites,
Such forms different structure and the metal complex of function with physical efficiency and transition metal, and coordination mode is various, is composite structure
Novel Porous Cu complex provides possibility；And copper belongs to cheap metal, the complex that selection is formed with copper ion exists
The fields such as electricity, catalysis, optics have a good application prospect (CN 104646058A；CN 102532170B).But three
The research that nitrogen azoles copper coordination polymer is applied to photocatalytic reduction of carbon oxide is also seldom seen in report at present.
The content of the invention
It is an object of the invention to using 1,2,4- triazole -3- carboxylic acids and 5- amino-1,2,4-triazol -3- carboxylic acids before
Part is driven, using copper ion as metal center, prepares the porous copper coordination polymer of novelty, and using the coordination polymer as catalysis
Agent, the reduction applied to photocatalysis carbon dioxide.
To solve above technical problem, technical scheme includes：
(1) a kind of porous polymer of cupric coordination
The polymer chemistry formula is [Cu3(Tra)2O2·7H2O]n, wherein, Tra represents the triazole of organic ligand 1,2,4- and gone
Anion after proton, Cu are copper ion, and the polymer has the one-dimensional hole that Tra parts are formed by oxygen atom bridging copper ion
Road, and further there is three-dimensional porous back bone network；The polymer crystals belong to trigonal system, space group R-3C, structure cell
Parameter is respectively：B=17.569 (5), α=β=90 °, γ=120 °,
Further：The porosity of the three-dimensional frame structure of the porous polymer crystal is 51.9%；The decomposition of frame structure
Temperature is 305 DEG C.
(2) method for preparing above-mentioned porous coordination polymer material
Comprise the following steps：
(1) by 1,2,4- triazole -3- carboxylic acids and 5- amino-1,2,4-triazol -3- carboxylic acids and CuCl2In distilled water
It is well mixed；
(2) hydro-thermal reaction will be carried out after the sealing of above-mentioned gained mixed liquor at 150~180 DEG C 24~48 hours, then with every
The speed of 5 DEG C of hour is slowly cooled to room temperature, and obtains blackish green acicular crystal；
(3) above-mentioned blackish green acicular crystal, naturally dry, the monocrystalline sample of the obtained Porous coordination polymer are washed with ethanol
Product；
(4) 110 DEG C of vacuum drying, you can the Porous coordination polymer is made.
Further：1,2,4- triazole -3- the carboxylic acids of the step (1), 5- amino-1,2,4-triazol -3- carboxylic acids with
CuCl2Mol ratio be 1:1:1~1:1:2.
(3) application of the porous copper coordination polymer of the present invention
Using a kind of method as photochemical catalyst of the porous polymer of described cupric coordination.
Further：Using the coordination polymer as carbon dioxide reduction into the photochemical catalyst of carbon monoxide.
Compared with traditional catalyst, the beneficial effects of the invention are as follows：
First, 1,2,4- triazole -3- carboxylic acids and 5- amino -1,2, more coordination sites of 4- triazole -3- carboxylic acids be make use of
The characteristics of, reach the purpose that complex is formed with copper ion.1,2,4- triazole -3- carboxylic acids and 5- amino -1,2,4- three
Nitrogen azoles -3- carboxylic acids undergo sloughing for amino and carboxyl in hydro-thermal reaction, oxygen bridge are formd with copper ion, so as to form three dimensional network
Network skeleton, higher porosity can be with absorbing carbon dioxides.
Cu complexs in the present invention are the huge molecules for having frame structure, have well-regulated pore structure and good hole
Gap rate, there is obvious absorption to carbon dioxide, while reduction CO can also be catalyzed2Gas is CO.
Secondly, using cupric coordination compound, the characteristics of make use of metallic copper cheap and easy to get.Such compound is as catalyst
With the cheap huge advantage of cost.
3rd, photocatalyst material of the invention prepares simple, favorable reproducibility, yield height, product purity height.
4th, photocatalyst structure of the invention is stable, and heat endurance is high.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the Porous coordination polymer.In figure, the infrared spectrogram of the Porous coordination polymer,
After copper ion participates in coordination with the N atoms in triazole, in 1513cm-1Show stronger absorption.Illustrate copper ion and part
Form complex.
Fig. 2 is the single crystal samples and the powder diffraction comparison diagram of monocrystalline simulation of the Porous coordination polymer.Show in figure：Institute
The diffraction of the single crystal samples of obtained Porous coordination polymer is substantially consistent with monocrystalline simulation, shows obtained porous match somebody with somebody
The purity of position polymer-like is higher.
Fig. 3 is the coordination structure figure of the Porous coordination polymer.In figure, copper ion and the Isosorbide-5-Nitrae position nitrogen-atoms in triazole
Coordination, while copper ion is chained up by oxygen bridge key and triazole list of coordination units, forms three dimensional skeletal structure.Fig. 4 is more for this
The three-dimensional structure accumulation graph of hole coordination polymer crystal.It can be found that after one-dimensional channels are accumulated in three dimensions, formation carries
The coordination polymer of microcellular structure.
Fig. 5 is the fluorescence emission spectrogram of compound of the Porous coordination polymer.Shown in figure, under burst of ultraviolel, coordination polymerization
Thing has most strong emission peak at 467nm, and this is that Triazole ligand absorbs energy, is then return to the fluorescent emission of ground state.
Fig. 6 is to be used as photochemical catalyst, catalysis reduction CO by the use of the Porous coordination polymer2Gas chromatographic detection figure, figure
In show, in the presence of Porous coordination polymer, CO2CO can be reduced to.Show the Porous coordination polymer to dioxy
Changing carbon catalyzed conversion has preferable effect.Photocatalysis conversion and cycle number (TON) is 35.
Fig. 7 be the Porous coordination polymer at a temperature of 273K, can from figure to the adsorption curve of carbon dioxide
To find, the Porous coordination polymer can reach 15.6cm to the adsorbance of carbon dioxide3/g。
With reference to specific embodiment, the present invention will be further described.Embodiment includes but does not limit what the present invention protected
Scope.
Embodiment
(1) porous coordination polymer material is prepared
Embodiment 1：
By 11.31 milligrams of (0.1mmol) 1,2,4- triazole -3- carboxylic acids, 12.81 milligrams of (0.1mmol) 5- amino -1,2,
4- triazole -3- carboxylic acids, the CuCl of 34.1 milligrams (0.2mmol)2·2H2O is added in 10mL distilled water and is well mixed；Institute
Hydro-thermal reaction is carried out at 150 DEG C after obtaining mixed liquor sealing, is reacted 48 hours, then room temperature is cooled to 5 DEG C per hour of speed,
Blackish green block transparent crystal is obtained, is washed with ethanol, naturally dry, the single crystal samples of the Porous coordination polymer are made.110
DEG C vacuum drying, you can the Porous coordination polymer is made.
Embodiment 2：
By 11.31 milligrams of (0.1mmol) 1,2,4- triazole -3- carboxylic acids, 12.81 milligrams of (0.1mmol) 5- amino -1,2,
4- triazole -3- carboxylic acids, the CuCl of 34.1 milligrams (0.2mmol)2·2H2O is added in 10mL distilled water and is well mixed；Institute
Hydro-thermal reaction is carried out at 160 DEG C after obtaining mixed liquor sealing, after reacting 36 hours, room is cooled to 5 DEG C per hour of speed
Temperature, blackish green block transparent crystal is obtained, is washed with ethanol, naturally dry, then the monocrystalline sample of the Porous coordination polymer is made
Product, 110 DEG C of vacuum dryings, you can the Porous coordination polymer is made.
Embodiment 3：
By 11.31 milligrams of (0.1mmol) 1,2,4- triazole -3- carboxylic acids, 12.81 milligrams of (0.1mmol) 5- amino -1,2,
4- triazole -3- carboxylic acids, the CuCl of 25.6 milligrams (0.15mmol)2·2H2O is added in 10mL distilled water and is well mixed；Institute
Hydro-thermal reaction is carried out at 170 DEG C after obtaining mixed liquor sealing, after reacting 36 hours, room is cooled to 5 DEG C per hour of speed
Temperature, blackish green block transparent crystal is obtained, is washed with ethanol, naturally dry, then the monocrystalline sample of the Porous coordination polymer is made
Product, 110 DEG C of vacuum dryings, you can the Porous coordination polymer is made.
Embodiment 4：
By 11.31 milligrams of (0.1mmol) 1,2,4- triazole -3- carboxylic acids, 12.81 milligrams of (0.1mmol) 5- amino -1,2,
4- triazole -3- carboxylic acids, the CuCl of 25.6 milligrams (0.10mmol)2·2H2O is added in 10mL distilled water and is well mixed；Institute
Hydro-thermal reaction is carried out at 180 DEG C after obtaining mixed liquor sealing, after reacting 24 hours, room is cooled to 5 DEG C per hour of speed
Temperature, blackish green block transparent crystal is obtained, is washed with ethanol, naturally dry, then the monocrystalline sample of the Porous coordination polymer is made
Product, 110 DEG C of vacuum dryings, you can the Porous coordination polymer is made.
(2) measure of Porous coordination polymer structure
Table 1：The parameter list of Porous coordination polymer crystal
Sizeable monocrystalline is chosen under the microscope, under temperature T=293 (2) K, in Rigaku R-AXIS
On SPIDER diffractometers, Mo-K rays are used with through graphite monochromator monochromatizationCollected in a manner of ω-φ
Diffraction data.Absorption correction is carried out by ABSCOR programs.Parsed using direct method using SHELXTL programs and refined structure.
Whole non-hydrogen atom coordinates first are determined with difference function method and least square method, non-hydrogen atom coordinate and anisotropic parameters are carried out
Complete matrix least square method amendment, then the hydrogen atom position of main body framework is obtained with theoretical hydrogenation method, then use least square method
Refine is carried out to crystal structure.The partial parameters of crystallography point diffraction Data Collection and structure refinement see the above table 1.
Infrared spectrum experiment of the present invention is completed using BRUKER TENSOR 27.
Fluorescence spectrum experiments are completed using Hitachi F-4600 XRFs.
Powder diffraction data is collected and completed on Rigaku D-MAX 2200VPC diffractometers.
Single crystal diffraction is completed on Rigaku R-AXIS SPIDER diffractometers.
Gas chromatographic detection is completed in SHIMADZU GC-2014C.
Claims (6)
- A kind of 1. porous polymer of cupric coordination, it is characterised in that：The polymer chemistry formula is [Cu3(Tra)2O2·7H2O]n, its In, Tra represents the anion after the triazole deprotonation of organic ligand 1,2,4-, and Cu is copper ion, and the polymer has Tra parts The one-dimensional channels formed by oxygen atom bridging copper ion, and further there is three-dimensional porous back bone network；The polymer is brilliant Body belongs to trigonal system, space group R-3C, and cell parameter is respectively：B=17.569 (5),α=β=90 °, γ=120 °,
- 2. according to claim 1 and described porous polymer, it is characterised in that：The three-dimensional framework knot of the porous polymer crystal The porosity of structure is 51.9%；The decomposition temperature of frame structure is 305 DEG C.
- 3. preparing a kind of method of porous polymer as claimed in claim 1 or 2, comprise the following steps：(1) by 1,2,4- triazole -3- carboxylic acids and 5- amino-1,2,4-triazol -3- carboxylic acids and CuCl2Mixed in distilled water Uniformly；(2) hydro-thermal reaction will be carried out after the sealing of above-mentioned gained mixed liquor at 150~180 DEG C 24~48 hours, then with per hour 5 DEG C speed be slowly cooled to room temperature, obtain blackish green acicular crystal；(3) above-mentioned blackish green acicular crystal, naturally dry, the single crystal samples of the obtained Porous coordination polymer are washed with ethanol；(4) 110 DEG C of vacuum drying, you can the Porous coordination polymer is made.
- 4. preparation method according to claim 3, it is characterised in that：1,2,4- triazole -3- the carboxylics of the step (1) Acid, 5- amino-1,2,4-triazol -3- carboxylic acids and CuCl2Mol ratio be 1:1:1~1:1:2.
- A kind of 5. method as photochemical catalyst of the porous polymer of application cupric coordination as claimed in claim 1 or 2.
- 6. application process according to claim 5, it is characterised in that：Using the coordination polymer as carbon dioxide reduction into The photochemical catalyst of carbon monoxide.
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| CN109897056A (en) * | 2019-04-12 | 2019-06-18 | 云南师范大学 | A kind of Metal cadmium complex and the preparation method and application thereof |
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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 |
| 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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| CN109897056A (en) * | 2019-04-12 | 2019-06-18 | 云南师范大学 | A kind of Metal cadmium complex and the preparation method and application thereof |
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