CN114853790A - Preparation method and application of copper-potassium complex - Google Patents
Preparation method and application of copper-potassium complex Download PDFInfo
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- methylene blue
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- VDNXILQBKLFION-UHFFFAOYSA-N [K].[Cu] Chemical compound [K].[Cu] VDNXILQBKLFION-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims abstract description 45
- 229960000907 methylthioninium chloride Drugs 0.000 claims abstract description 45
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006352 cycloaddition reaction Methods 0.000 claims abstract description 16
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 25
- 150000002118 epoxides Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003463 adsorbent Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 17
- 239000013078 crystal Substances 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 8
- 229940012189 methyl orange Drugs 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000000634 powder X-ray diffraction Methods 0.000 description 7
- 238000001144 powder X-ray diffraction data Methods 0.000 description 7
- 238000001429 visible spectrum Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- FRPHFZCDPYBUAU-UHFFFAOYSA-N Bromocresolgreen Chemical compound CC1=C(Br)C(O)=C(Br)C=C1C1(C=2C(=C(Br)C(O)=C(Br)C=2)C)C2=CC=CC=C2S(=O)(=O)O1 FRPHFZCDPYBUAU-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000008054 sulfonate salts Chemical class 0.000 description 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 2
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- -1 perchloric acid ketone hexahydrate Chemical class 0.000 description 1
- UFITZXXHLWZPNO-UHFFFAOYSA-N perchloric acid;hexahydrate Chemical compound O.O.O.O.O.O.OCl(=O)(=O)=O UFITZXXHLWZPNO-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
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- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- 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
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2252—Sulfonate ligands
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/13—Potassium
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
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Abstract
The invention discloses a preparation method and application of a copper-potassium complex, wherein the structural formula of the copper-potassium complex is { (Me) 2 NH 2 ) 2 [CuK 4 (BPDSDC) 2 ]Copper perchlorate as metal ion source and diphenyl-3, 3 '-disulfonyl-4, 4' -dicarboxylic acid dipotassium salt (H) 2 K 2 -BPDSDC) as ligand, and the preparation method comprises the steps of dissolving copper perchlorate and the ligand in a mixed solvent prepared by mixing N, N-dimethylformamide and water, and reacting under the heating condition to prepare the copper potassium complex. The reaction raw materials of the preparation method of the copper-potassium complex are cheap and easy to prepareThe preparation method has the advantages of high reaction selectivity, mild reaction conditions, easiness in operation, low energy consumption and environmental friendliness, and the prepared copper-potassium complex has good phase purity, thermal stability and solvent stability, can be used as a reaction catalyst for catalyzing carbon dioxide cycloaddition reaction, and can also be used as a selective adsorbent for methylene blue.
Description
Technical Field
The invention belongs to the field of inorganic chemistry science, and particularly relates to a preparation method of a novel copper-potassium complex and application of the novel copper-potassium complex in methylene blue adsorption and carbon dioxide cycloaddition catalysis.
Background
The complex has an inherent porous structure and adjustable functionality, and becomes a functional material in many application fields. The complex can remove the organic dye from the solution through the actions of static electricity, acid-base, hydrogen bond and the like, and can selectively adsorb the organic dye through the surface and pore channels of the complex channel. Meanwhile, the complex plays a key role in heterogeneous catalytic activity due to large specific surface area, customizable pore structure, adjustable functionality and high chemical and thermal stability. The main challenge is how to easily prepare stable complex materials with high porosity and desirable properties. In general, factors such as the configuration of the organic ligand, the geometry of the central metal ion, the molar ratio of the reactants, the solvent system, the pH, and the reaction temperature will all affect the structure of the complex. Among these factors, ligands often play a key role in determining the structure of the complex. Because of the good coordination capability of the oxygen atom of the carboxyl group, a great deal of research has focused on the construction of infinite frameworks based on polycarboxylic ligands and a central metal atom. Sulfonate salts are less studied for coordination chemistry than carboxyl groups because sulfonate salts are a poor ligand. However, recent studies have shown that the weaker linkage of the sulfonate group favors the formation of a crystalline product and may give solid state kinetics to the resulting backbone.
A novel copper potassium complex synthesized by using biphenyl-3, 3 '-disulfonyl-4, 4' -dicarboxylic acid dipotassium salt as a catalyst for catalyzing carbon dioxide cycloaddition and methylene blue adsorption is not reported at present. Therefore, the novel copper-potassium complex is used as a novel reaction catalyst to catalyze the cycloaddition of carbon dioxide, and the development of a method which has cheap and easily-obtained reaction raw materials, high reaction selectivity, mild reaction conditions and environmental friendliness has important research significance and application value. The novel copper-potassium complex has double functions, can also be used for selective adsorption of methylene blue, and has important research value and application significance for treatment of organic dye sewage.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel preparation method of a copper-potassium complex, which has the advantages of cheap and easily-obtained reaction raw materials, high reaction selectivity, mild reaction conditions and environmental friendliness, and researching the application of the copper-potassium complex in methylene blue adsorption and carbon dioxide cycloaddition catalysis.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a preparation method of a copper-potassium complex, wherein the structural formula of the copper-potassium complex is { (Me) 2 NH 2 ) 2 [CuK 4 (BPDSDC) 2 ]Copper perchlorate as metal ion source and diphenyl-3, 3 '-disulfonyl-4, 4' -dicarboxylic acid dipotassium salt (H) 2 K 2 -BPDSDC) as ligand, the preparation method comprising the steps of:
s1, mixing N, N-dimethylformamide and water according to a volume ratio of 7-9:1 to prepare a mixed solvent;
s2, dissolving copper perchlorate and a ligand in a mixed solvent, wherein the molar ratio of the copper perchlorate to the ligand is 2: 1, the proportion of the copper perchlorate to the mixed solvent is 0.1-0.4 mmol/mL;
s3, reacting for 15-20 h under the heating condition to obtain the copper-potassium complex { (Me) 2 NH 2 ) 2 [CuK 4 (BPDSDC) 2 ]}。
Preferably, the volume ratio of the N, N-dimethylformamide to the water in step S1 is 8: 1.
Preferably, the ratio of the copper perchlorate to the mixed solvent in the step S2 is 0.25 mmol/mL.
Preferably, in step S2, the copper perchlorate and the ligand are mixed with the solvent and stirred for 10-30 min.
Preferably, in step S3, the heating condition is heating to 110 ℃ to 130 ℃.
The copper-potassium complex prepared by the preparation method of the copper-potassium complex is applied to methylene blue adsorption. The copper potassium complex can selectively adsorb methylene blue in the dye.
The application of the copper-potassium complex in catalyzing the cycloaddition reaction of epoxide and carbon dioxide can catalyze the cycloaddition of carbon dioxide to convert into cyclic carbonate.
The invention has the following beneficial effects:
1. the reaction raw materials of the preparation method of the copper-potassium complex are cheap and easy to obtain, the reaction selectivity is high, the reaction condition is mild, the operation is easy, the energy consumption is low, and the preparation method is environment-friendly;
2. the prepared copper-potassium complex has good phase purity, good thermal stability at room temperature to 200 ℃, good solvent stability, and can be used as an excellent reaction catalyst for catalyzing carbon dioxide cycloaddition reaction and also as a selective adsorbent for methylene blue;
3. the copper-potassium complex has quick absorption on methylene blue, the absorption performance is obvious, and the absorption capacity can reach 224.64mg -1 Even if other dyes exist, the adsorption of the methylene blue is not influenced, and the adsorption rate is not obviously changed after 5 times of recycling.
4. The copper potassium complex catalyzes the addition reaction of epoxide and carbon dioxide ring, when 5 wt% of complex is added and the complex is synergistically catalyzed with tetrabutylammonium bromide, the conversion rate can be improved to more than 80%, the yield is not obviously reduced after 5 times of recycling, the reaction condition is mild, the operation is easy, and the expanded production of the reaction is facilitated.
Drawings
FIG. 1 is a crystal structure diagram of a copper potassium complex;
FIG. 2(a) is a three-dimensional structural diagram of a copper potassium complex, (b) is a three-dimensional spatial simulation structural diagram of a copper potassium complex;
FIG. 3 PXRD pattern of copper potassium complex;
FIG. 4 is a thermogravimetric analysis graph of a copper potassium complex;
FIG. 5 PXRD spectrum of copper potassium complex from room temperature to 250 ℃;
FIG. 6 PXRD patterns of copper potassium complexes after 20 days immersion in different solvents;
FIG. 7 comparison of different dyes before and after adsorption;
FIG. 8 is a graph of the absorption of copper potassium complex versus the time variation of the visible spectrum of methylene blue;
FIG. 9 is a graph of the concentration of methylene blue in solution as a function of time;
FIG. 10 is a graph showing the adsorption amount of a copper potassium complex to methylene blue as a function of time;
FIG. 11 is a schematic diagram showing the recoverability of methylene blue adsorbed by a copper potassium complex;
fig. 12 binary mixed dye absorption visible spectra (a) Methylene Blue (MB)/Methyl Orange (MO), (b) Methylene Blue (MB)/rhodamine b (rhb);
FIG. 13 catalysis of epoxide with CO by copper potassium complex 2 The reaction scheme of (1);
FIG. 14 catalysis of CO by copper potassium complexes 2 The cycloaddition reaction generates various yields of cyclic carbonates;
figure 15(a) recovery of copper potassium complex from 5 catalytic cycles and (b) PXRD pattern of copper potassium complex after each catalytic cycle.
Detailed Description
The present invention is further described with reference to the following examples and drawings, but the present invention is not limited thereto in any way, and any modifications or alterations based on the teaching of the present invention are within the scope of the present invention.
Example 1
Preparation of copper-potassium complex and phase purity analysis.
Mixing perchloric acid ketone hexahydrate and diphenyl-3, 3 '-disulfonyl-4, 4' -dicarboxylic acid dipotassium salt (H) 2 K 2 -BPDSDC) were dissolved in different ratios in N, N-Dimethylformamide (DMF) and water (DMF: water volume ratio 8: 1) in a mixed solvent of (2), at different temperatures and for different times to prepare the copper potassium complex { (Me) 2 NH 2 ) 2 [CuK 4 (BPDSDC) 2 ]}. The specific preparation scheme is shown in Table 1.
TABLE 1 preparation scheme of copper potassium complex
It can be seen that the perchlorate hexahydrate and the dipotassium salt of biphenyl-3, 3 '-disulfonyl-4, 4' -dicarboxylic acid (H) 2 K 2 BPDSDC) can prepare the copper potassium complex at 110-130 ℃. Performing single crystal X-ray analysis on the copper potassium complex crystal, and finding that the crystal belongs to a tetragonal space group and each structural unit contains one Cu according to a crystal structure diagram of the copper potassium complex shown in figure 1(II) ions, four K (I) ions and two fully deprotonated BPDSDC 4- A ligand. For charge balance, each [ CuK ] 4 (BPDSDC) 2 ]There should be two cations [ (Me) in the unit from the decomposition of DMF 2 NH 2 ] + . The Cu (II) and K (I) ions are connected by carboxylate and sulfonate groups to form a 1D band extending along the c-axis, all the K (I) ions are arranged at the edges of the band, and the Cu (II) ions are located inside the band. Each ribbon chain is connected to four adjacent chains by biphenyl linkers to form the final 3D frame. Fig. 2(a) is a three-dimensional structural diagram of the copper potassium complex, and fig. 2(b) is a three-dimensional simulated structural diagram of the copper potassium complex. Notably, the copper potassium complex has regular square channels along the c-axis (based on sulfonic acid oxygen atoms), is free of any solvent molecules, and has high porosity (PLATON calculated porosity 48.3%). The uncoordinated sulfonate oxygen atoms protrude into the square channels. This structural feature enables the framework to exhibit performance in dye adsorption, catalysis, and other areas without activation.
In the PXRD spectrum of the copper potassium complex shown in FIG. 3, the lower curve is the simulated powder X-ray diffraction spectrum of the copper potassium complex, and the upper curve is the powder X-ray diffraction spectrum of the copper potassium complex prepared by the invention. And comparing the two spectrograms, and no obvious impurity peak appears, so that the complex has good phase purity.
Example 2
And (4) analyzing the stability test of the copper potassium complex.
In order to examine the thermal stability of the copper-potassium complex, thermogravimetric analysis is carried out, and the result is shown in a thermogravimetric analysis graph of the copper-potassium complex in figure 4. When the temperature is lower than 200 ℃, the thermogravimetric analysis curve is not reduced, which indicates that the crystal structure of the copper-potassium complex is stable in the temperature range. When the temperature is higher than 250 ℃, weight loss begins to occur, solvent molecules in the pore canal begin to be removed, and the skeleton structure begins to collapse. PXRD (PXRD) spectrum of the copper-potassium complex from room temperature to 250 ℃ is shown in figure 5, X-ray diffraction spectra of powder of the copper-potassium complex processed at various temperatures further illustrate the thermal stability of the complex, and the crystal structure is matched with a simulation result within 200 ℃ to indicate that the crystal structure is stable. When the temperature reached 250 ℃, the PXRD peak disappeared, indicating that the crystal structure was destroyed by such high temperature, which is consistent with the thermogravimetric analysis results. The results show that the complexes have good thermal stability at room temperature to 200 ℃.
Samples of the crystals of the copper potassium complex are soaked in different organic solvents, such as N, N-Dimethylformamide (DMF), methanol (MeOH), ethanol (EtOH), dimethyl sulfoxide (DMSO), and deionized water (H) 2 O) for 20 days. As shown in fig. 6 by PXRD patterns of the copper potassium complex after 20 days soaking in different solvents, the complex recovered from the solvent possessed consistent PXRD data with the un-soaked complex, indicating good solvent stability of the copper potassium complex. According to literature reports, it is very rare that the heterometallic complexes have such excellent chemical and thermal stability.
Example 3
Selective adsorption performance test analysis of copper potassium complex on methylene blue
20mg of copper potassium complex is respectively dispersed in aqueous solution with the concentration of 240mg/L of rhodamine B (RhB), Methylene Blue (MB), Methyl Orange (MO), Congo Red (CR) and Bromocresol Green (BG) and the volume of 10mL, and after standing for 4h under dark condition, the result is shown in a comparison graph before and after different dyes are adsorbed in FIG. 7, and the copper potassium complex has obvious adsorption effect on the methylene blue.
Adsorption kinetics experiments were performed at room temperature by dispersing 20mg of copper potassium complex in 20mL of 240mg/L aqueous methylene blue, removing about 2mL of the solution at intervals with a syringe, and measuring the visible spectrum of the dye, as shown in FIG. 8, which is a graph of the adsorption of copper potassium complex on the visible spectrum of methylene blue as a function of time. The results show that the maximum absorption peak of methylene blue at 664nm within 4h is gradually reduced to be close to zero.
The result of calculating the adsorption amount of the copper potassium complex to methylene blue is shown in a graph of the change of the concentration of the methylene blue in the solution of FIG. 9 along with the time, and the result shows that the copper potassium complex can adsorb 62.3% of the methylene blue in the first 1h and has an adsorption rate of 93% in 4 h.
By mixing into a series of different concentrations (60 to 650mg/L)10mg of copper potassium complex was added to the methylene blue aqueous solution (20mL) of (1), and the adsorption isotherm was measured, and the adsorption amount of methylene blue by the copper potassium complex was plotted as a function of time as shown in FIG. 10. The result shows that the adsorption quantity of the methylene blue is rapidly increased within 1h and reaches the maximum value of 224.64mg g after 4h -1 。
The recovery of the copper potassium complex in methylene blue adsorption was investigated. Soaking the adsorbed copper-potassium complex in 20mL of saturated ammonium chloride aqueous solution for 2 hours to remove the dye, washing with deionized water, drying at 40 ℃ in vacuum, and repeatedly adsorbing methylene blue. The result is shown in a schematic diagram of the recoverability of the copper potassium complex for adsorbing methylene blue in fig. 11, and the result shows that the adsorption capacity of the copper potassium complex is not remarkably reduced after the copper potassium complex is recycled for 5 times, which indicates that the copper potassium complex has good reusability.
In addition, it is also of great interest to explore selective separations of different dyes. The selective adsorption performance of the copper-potassium complex is proved through adsorption research on methylene blue/methyl orange and methylene blue/rhodamine B binary mixed dye solution. As shown in fig. 12, the binary mixed dye absorption visible spectrum graph, graph (a) is a Methylene Blue (MB) and Methyl Orange (MO) mixed dye absorption visible spectrum graph, and graph (B) is a Methylene Blue (MB) and rhodamine B (rhb) mixed dye absorption visible spectrum graph, and when a spectrum graph is visible, a peak corresponding to the methylene blue almost disappears, and a peak of the methyl orange/rhodamine B does not change obviously. The phenomenon shows that the copper-potassium complex can selectively adsorb methylene blue in the binary mixed dye.
Example 4
The complex is analyzed by applying a performance test in catalyzing cycloaddition reaction of epoxide and carbon dioxide.
The copper-potassium complex is used for catalyzing the cycloaddition reaction of carbon dioxide and epoxide, and the experimental scheme is optimized by taking epoxy chloropropane as an example. The results show that CO is present when tetrabutylammonium bromide (TATB) is used as catalyst 2 The cycloaddition conversion was 6%; the conversion rate can be improved to 27% by using the copper-potassium complex as a catalyst; when the copper-potassium complex and TATB are catalyzed together, the conversion rate can reach 99%. Accordingly, it was determined that the copper potassium complex catalyzes the reaction of an epoxide with CO 2 The reaction scheme of (1) is as shown in FIG. 13, the copper potassium complex catalyzes the reaction of epoxide and CO 2 The reaction scheme of (a).
To further investigate the catalytic versatility of the copper potassium complex, CO was performed at 1atm and 60 ℃ using different epoxide substrates 2 And (3) performing cycloaddition reaction. The corresponding results are shown in FIG. 14, in which the copper potassium complex catalyzes CO 2 The yield of various cyclic carbonates generated by cycloaddition reaction shows that the copper potassium complex is in CO 2 High efficiency is shown in the cycloaddition reaction.
Recyclability is an important feature of the practical application of heterogeneous catalysts, and in order to examine the recyclability of the copper potassium complex catalyst, the model reaction mixture was filtered after completion of the reaction to isolate the catalyst. The catalyst was further washed with dichloromethane and dried in air and then reused for at least five cycles, see figure 15(a) recovery of copper potassium complex for 5 catalytic cycles without reduction in conversion. As shown in figure 15b PXRD pattern of copper potassium complex after each catalytic cycle, the PXRD pattern of the catalyzed copper potassium complex was completely consistent with the simulated pattern, indicating that framework integrity was maintained after five catalytic cycles.
Claims (8)
1. The preparation method of the copper-potassium complex is characterized in that the structural formula of the copper-potassium complex is { (Me) 2 NH 2 ) 2 [CuK 4 (BPDSDC) 2 ]Copper perchlorate as metal ion source and diphenyl-3, 3 '-disulfonyl-4, 4' -dicarboxylic acid dipotassium salt (H) 2 K 2 -BPDSDC) as ligand, the preparation method comprising the steps of:
s1, mixing N, N-dimethylformamide and water according to a volume ratio of 7-9:1 to prepare a mixed solvent;
s2, dissolving copper perchlorate and a ligand in a mixed solvent, wherein the molar ratio of the copper perchlorate to the ligand is 2: 1, the proportion of the copper perchlorate to the mixed solvent is 0.1-0.4 mmol/mL;
s3, reacting for 15-20 h under the heating condition to obtain the copper-potassium complex { (Me) 2 NH 2 ) 2 [CuK 4 (BPDSDC) 2 ]}。
2. The method according to claim 1, wherein the volume ratio of N, N-dimethylformamide to water in step S1 is 8: 1.
3. The method for preparing a copper potassium complex according to claim 1, wherein the ratio of the copper perchlorate to the mixed solvent in step S2 is 0.25 mmol/mL.
4. The method of claim 1, wherein in step S2, the mixture of copper perchlorate and ligand with solvent is stirred for 10-30 min.
5. The method of claim 1, wherein in step S3, the heating condition is heating to 110-130 ℃.
6. Use of the copper potassium complex prepared by the process according to claim 1 for methylene blue adsorption.
7. The use of a copper potassium complex for the adsorption of methylene blue as claimed in claim 7 wherein the copper potassium complex selectively adsorbs methylene blue from the dye.
8. Use of the copper potassium complex prepared according to the preparation process of claim 1 for catalyzing the cycloaddition reaction of an epoxide with carbon dioxide.
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| CN108649256A (en) * | 2018-05-12 | 2018-10-12 | 中国科学院山西煤炭化学研究所 | The preparation method and application of sulfonate polybenzimidazole proton exchange membrane |
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