CN114849778B - Hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst and preparation method and application thereof - Google Patents
Hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst and preparation method and application thereof Download PDFInfo
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- CN114849778B CN114849778B CN202110154874.2A CN202110154874A CN114849778B CN 114849778 B CN114849778 B CN 114849778B CN 202110154874 A CN202110154874 A CN 202110154874A CN 114849778 B CN114849778 B CN 114849778B
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- 239000013317 conjugated microporous polymer Substances 0.000 title claims abstract description 220
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 title claims abstract description 204
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 111
- 239000004332 silver Substances 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 239000000987 azo dye Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- -1 silver ions Chemical class 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 75
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 57
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 44
- 238000006722 reduction reaction Methods 0.000 claims description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 22
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 19
- 230000035484 reaction time Effects 0.000 claims description 18
- 239000012279 sodium borohydride Substances 0.000 claims description 16
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 16
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012153 distilled water Substances 0.000 claims description 12
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 11
- ZDRMMTYSQSIGRY-UHFFFAOYSA-N 1,3,5-triethynylbenzene Chemical compound C#CC1=CC(C#C)=CC(C#C)=C1 ZDRMMTYSQSIGRY-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 9
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical group [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims description 6
- 229940012189 methyl orange Drugs 0.000 claims description 6
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 238000000944 Soxhlet extraction Methods 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
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- 238000009736 wetting Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 18
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 29
- 230000009467 reduction Effects 0.000 description 27
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical group NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 24
- 238000005984 hydrogenation reaction Methods 0.000 description 24
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- JNWPRPLNUUMYCM-UHFFFAOYSA-N 5-bromo-2-(5-bromopyridin-2-yl)pyridine Chemical compound N1=CC(Br)=CC=C1C1=CC=C(Br)C=N1 JNWPRPLNUUMYCM-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
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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
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
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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
- B01J2531/17—Silver
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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Abstract
The invention discloses a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst, a preparation method and application thereof. The preparation method comprises the steps of preparing hydrophilic bipyridyl conjugated microporous polymer, adsorbing silver ions, preparing and loading elemental silver. The catalyst has the advantages of good water dispersibility, small silver nanoparticle size, high catalytic activity, good stability and the like, is a novel supported heterogeneous catalyst, has high application value, and the preparation method has the advantages of simple process, convenient operation, controllable reaction conditions, high economic benefit and the like, is suitable for large-scale preparation, and is beneficial to further popularization and application. The catalyst can efficiently and rapidly remove the nitroaromatic compounds and/or azo dyes in the water body, and has the advantages of simple operation, short treatment period, good treatment effect and the like, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of water body restoration, and relates to a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst, and a preparation method and application thereof.
Background
The pollution of organic pollutants to water environment is one of serious environmental threats due to the universality and high risk. Nitroaromatic compounds, such as p-nitrophenol, are dangerous organic pollutants from industry and agriculture, are widely used in leather, plastics, medicine, pesticides, paper industry and other industries, and are considered to cause serious damage to water environments. However, p-nitrophenol has strong light, heat stability and biodegradability resistance, and is difficult to completely remove. If accumulated for a long period of time, damage to aquatic organisms and humans can occur. Azo dyes are compounds containing one or more azo bonds, are highly toxic and resistant to biodegradation, and are also an organic contaminant. Azo dyes are widely used in textile manufacturing and other industries, are harmful to the environment and pose a risk of carcinogenesis to human health. Thus, there is an urgent need to obtain a method capable of effectively degrading nitroaromatic compounds and azo dyes in water.
The catalytic hydrogenation reaction has strong operability and high efficiency, and is considered to be the most effective technology for reducing p-nitrophenol. Meanwhile, the p-nitrophenol hydrogenation reduction product is p-aminophenol, is a beneficial precursor of synthetic drugs, drying agents and corrosion inhibitors, and provides higher economic benefits. At present, a main obstacle in removing p-nitrophenol in water by utilizing catalytic hydrogenation reaction is how to obtain a proper catalyst. Metallic silver nanoparticle catalysts have attracted great interest. The nanostructure and nanoscale materials have excellent catalytic properties independent of their volumetric counterparts. However, the prior art of silver nanoparticles has disadvantages in that they are very unstable during the catalytic process, are easily aggregated, lead to deactivation of catalytic activity, and are difficult to recover after the reaction. The conjugated microporous polymer has inherent microporous characteristics and can provide specific and limited space for the growth of metal nanoparticles, so that the conjugated microporous polymer can be used as a main body and a support of silver nanoparticles. However, the existing silver-loaded conjugated microporous polymer composite catalytic material still has the defects of poor solution dispersibility, poor hydrophilicity, poor stability and the like, so that the composite catalytic material is difficult to effectively disperse in aqueous solution, difficult to recycle, and unfavorable for the contact of the composite catalytic material with nitroaromatic compounds and azo dyes, thereby being unfavorable for improving the treatment efficiency and the reuse times of the nitroaromatic compounds and the azo dyes in water, and the existence of the problems limits the application of the silver-loaded conjugated microporous polymer composite catalytic material in removing the p-nitrophenol in the water. Therefore, the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst with good water dispersibility, small silver nanoparticle size, high catalytic activity and good stability and the preparation method matched with the silver catalyst have the advantages of simple process, convenient operation, controllable reaction conditions and high economic benefit, and have very important significance for improving the treatment efficiency and the removal effect of nitroaromatic compounds and azo dyes in water.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst with good water dispersibility, small silver nanoparticle size, high catalytic activity and good stability, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a silver catalyst loaded by hydrophilic bipyridyl conjugated microporous polymer comprises a hydrophilic bipyridyl conjugated microporous polymer, wherein superfine silver nano particles are loaded on the hydrophilic bipyridyl conjugated microporous polymer; the average grain diameter of the superfine silver nano-particles is less than or equal to 15nm.
The hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst is further improved, and the average particle size of the superfine silver nano particles is less than or equal to 5nm.
The hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst is further improved, and the mass percentage of ultrafine silver nano particles in the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst is 0.1-14wt%.
As a general technical conception, the invention also provides a preparation method of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst, which comprises the following steps:
S1, immersing a bipyridyl conjugated microporous polymer into a sulfuric acid solution saturated by ammonium persulfate, stirring, filtering, washing and drying to obtain a hydrophilic bipyridyl conjugated microporous polymer;
s2, mixing the hydrophilic bipyridyl conjugated microporous polymer obtained in the step S1 with silver ion solution, stirring, filtering and washing to obtain the hydrophilic bipyridyl conjugated microporous polymer adsorbed with silver ions;
s3, adding the hydrophilic bipyridyl conjugated microporous polymer adsorbed with silver ions obtained in the step S2 into deionized water, carrying out reduction reaction under the condition of illumination or reducing agent, filtering, washing and drying to obtain the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst.
In the further improved preparation method of the silver catalyst loaded on the hydrophilic bipyridyl conjugated microporous polymer, in the step S1, the preparation method of the bipyridyl conjugated microporous polymer comprises the following steps:
(1) Adding 1,3, 5-tri-ethynyl benzene, 5' -dibromo-2, 2' -bipyridine, 4' -dibromobiphenyl, tetrakis (triphenylphosphine) palladium (0) and cuprous iodide into a mixed solution of N, N-dimethylformamide and triethylamine, and stirring to obtain a bipyridyl conjugated microporous polymer precursor solution;
(2) Heating the bipyridyl conjugated microporous polymer precursor solution obtained in the step (1) to 80-90 ℃ for reaction, washing, filtering, purifying and drying to obtain the bipyridyl conjugated microporous polymer.
In the preparation method of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst, which is further improved, in the step (1), the molar ratio of the 1,3, 5-tri-ethynyl benzene to the 5,5' -dibromo-2, 2' -bipyridine to the 4,4' -dibromobiphenyl is 2:1.5 to 2:0 to 4; the mass ratio of the tetra (triphenylphosphine) palladium (0) to the cuprous iodide is 1:1 to 2.5:1, a step of; the volume ratio of the N, N' -dimethylformamide to the triethylamine is 1:1 to 1.5:1, a step of; the mass ratio of the cuprous iodide to the 1,3, 5-tri-ethynyl benzene is 1:14 to 1:15; the mass volume ratio of the 1,3, 5-tri-ethynyl benzene to the N, N' -dimethylformamide is 12g: 1L-14 g:1L; the stirring is carried out under nitrogen atmosphere; the stirring time is 80-100 min.
The preparation method of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst is further improved, and in the step (2), the reaction is carried out under the nitrogen atmosphere; the reaction time is 48-72 hours; the washing is to adopt chloroform, water, methanol and acetone to wash the reaction products for 3 to 5 times respectively; the purification adopts a Soxhlet extraction method; the extraction time is 24-72 hours; the drying is performed under vacuum; the drying temperature is 60-70 ℃; the drying time is 12-24 hours.
In the preparation method of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst, which is further improved, in the step S1, the following treatment is further included before immersing the bipyridyl conjugated microporous polymer in the sulfuric acid solution saturated by ammonium persulfate: placing the bipyridyl conjugated microporous polymer in ethanol, and performing wetting treatment on the surface of the bipyridyl conjugated microporous polymer; the molar concentration of sulfuric acid in the ammonium persulfate saturated sulfuric acid solution is 0.1 mol/L-1 mol/L; the stirring time is 12-24 hours; the washing is to wash the filtered product for 3 to 5 times by distilled water; the drying temperature is 60-70 ℃; the drying time is 8-12 h.
In the preparation method of the silver catalyst loaded by the hydrophilic bipyridyl conjugated microporous polymer, which is further improved, in the step S2, the mass volume ratio of the hydrophilic bipyridyl conjugated microporous polymer to the silver ion solution is 0.1g: 1L-1 g:1L; the molar concentration of silver ions in the silver ion solution is 0.1 mmol/L-10 mmol/L; the silver ion solution is silver nitrate solution; the stirring is performed under dark conditions; the stirring time is 8-12 h; the washing is to wash the filtered product 3-5 times by distilled water.
In the preparation method of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst, which is further improved, in the step S3, the volume mass ratio of the deionized water to the hydrophilic bipyridyl conjugated microporous polymer is 2 mL-4 mL:5 mg-10 mg; the mass volume ratio of the reducing agent to the deionized water is 0.1g: 1L-10 g:1L; the reducing agent is sodium borohydride; the time of the reduction reaction is 4-24 hours; the washing is to wash the filtered product for 3 to 5 times by distilled water; the drying is performed under vacuum; the drying temperature is 60-70 ℃; the drying time is 8-12 h.
As a general technical conception, the invention also provides an application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst or the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst prepared by the preparation method in removing nitroaromatic compounds and/or azo dyes in water.
The above application, further improved, comprising the steps of: mixing a silver catalyst loaded by a hydrophilic bipyridyl conjugated microporous polymer, sodium borohydride and a solution containing nitroaromatic compounds and/or azo dyes for catalytic hydrogenation reaction to remove the nitroaromatic compounds and/or azo dyes in the water body; the molar ratio of the sodium borohydride to the nitroaromatic compound or azo dye in the solution containing the nitroaromatic compound and/or azo dye is 100:1 to 1000:1, a step of; the mass volume ratio of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst to the nitroaromatic compound and/or azo dye containing solution is 0.1g: 1L-0.2 g:1L; the concentration of the nitroaromatic compound or azo dye in the solution containing the nitroaromatic compound and/or azo dye is less than or equal to 70mg/L.
In the application, the time of the catalytic hydrogenation reaction is further improved and is 1-30 min; the nitroaromatic compound is p-nitrophenol; the azo dye is methyl orange.
Compared with the prior art, the invention has the advantages that:
(1) The invention provides a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst, which comprises a hydrophilic bipyridyl conjugated microporous polymer, wherein superfine silver nano particles are supported on the hydrophilic bipyridyl conjugated microporous polymer, and the particle size of the superfine silver nano particles is less than or equal to 15nm. In the invention, the hydrophilic bipyridyl conjugated microporous polymer has the characteristics of good water dispersibility, stable physical and chemical properties, rich surface structure and the like, and on the basis, the hydrophilic bipyridyl conjugated microporous polymer is used as a carrier of the silver nano-particles, on one hand, because bipyridyl units of the hydrophilic bipyridyl conjugated microporous polymer have rich coordination groups, more anchoring sites can be provided for the silver nano-particles, and therefore, the silver nano-particles can be uniformly and stably dispersed on the hydrophilic bipyridyl conjugated microporous polymer; on the other hand, the hydrophilic bipyridyl conjugated microporous polymer has a stable nano microporous structure, and can provide limitation and support for the growth of silver nano particles, so that the aggregation of the nano silver particles can be prevented, the dispersibility and the fine size of the nano silver particles can be maintained, and the better catalytic activity and stability can be maintained. In addition, the hydrophilic bipyridyl conjugated microporous polymer has the characteristic of good water dispersibility, so that the composite catalyst can be better dispersed in an aqueous solution, and the contact opportunity of the active site of the composite catalyst and target pollutants is increased. In addition, the hydrophilic bipyridyl conjugated microporous polymer has stable physical and chemical properties, so that the composite catalyst can be recycled for multiple times, and the composite catalyst is favorable for wide application in the field of water treatment. More importantly, the particle size of the silver nano particles is optimized, and the performance of the silver nano particles can be better exerted by loading the superfine silver nano particles with the average particle size less than or equal to 15nm on the hydrophilic bipyridyl conjugated microporous polymer, so that the silver catalyst loaded by the hydrophilic bipyridyl conjugated microporous polymer has better catalytic performance. The hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst has the advantages of good water dispersibility, small silver nanoparticle size, high catalytic activity, good stability and the like, is a novel supported heterogeneous catalyst, and has high application value.
(2) The invention provides a preparation method of a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst, which adopts a bipyridyl conjugated microporous polymer with a nano microporous structure which is easier to disperse, is favorable for improving the dispersibility of the bipyridyl conjugated microporous polymer in a solution, is convenient for subsequent adsorption of silver ions and loading and application of silver nano particles, and utilizes a sulfuric acid solution saturated by ammonium persulfate to modify the bipyridyl conjugated microporous polymer to improve the hydrophilicity of the bipyridyl conjugated microporous polymer, is favorable for improving the dispersibility of the bipyridyl conjugated microporous polymer in an aqueous solution, is favorable for subsequent preparation of a composite catalyst with better water dispersibility, and based on the preparation method, the prepared hydrophilic bipyridyl conjugated microporous polymer and the silver ion solution are used as raw materials to prepare the silver nano particles and load the silver nano particles on the hydrophilic bipyridyl conjugated microporous polymer, and the preparation method comprises the following steps: the hydrophilic bipyridyl conjugated microporous polymer and silver ion solution are mixed and stirred, abundant coordination groups in bipyridyl units on the hydrophilic bipyridyl conjugated microporous polymer are used as binding sites of silver ions, silver ions are uniformly distributed on and stably dispersed in the hydrophilic bipyridyl conjugated microporous polymer by utilizing the interaction of the silver ions and-N groups in the hydrophilic bipyridyl, further, the hydrophilic bipyridyl conjugated microporous polymer adsorbed with the silver ions is subjected to reduction reaction, binding sites are provided for silver nanoparticles through the bipyridyl functional groups on the hydrophilic bipyridyl conjugated microporous polymer in the reduction reaction process, and limitation and support are provided for the silver nanoparticles through the nano microporous structure of the bipyridyl conjugated microporous polymer, so that the nano silver particles loaded in the bipyridyl conjugated microporous polymer keep uniform dispersion, and the hydrophilic bipyridyl conjugated microporous polymer loaded silver catalyst with the advantages of good water dispersibility, fine silver nanoparticle size, high catalytic activity, good stability and the like is finally prepared. The preparation method has the advantages of simple process, convenient operation, controllable reaction conditions, high economic benefit and the like, is suitable for large-scale preparation, and is favorable for further popularization and application.
(3) In the preparation method, the bipyridyl conjugated microporous polymer is prepared from 1,3, 5-tri-ethynyl benzene, 5 '-dibromo-2, 2' -bipyridine and 4,4 '-dibromobiphenyl, wherein the molar ratio of the 1,3, 5-tri-ethynyl benzene, 5' -dibromo-2, 2 '-bipyridine to the 4,4' -dibromobiphenyl is 2:1.5 to 2: 0-4, through adjusting the proportion of the monomers, the microscopic morphology of the bipyridyl conjugated microporous polymer is converted, so that the bipyridyl conjugated microporous polymer can be better dispersed in the solution, the contact opportunity of organic matters and catalytic active sites is increased, and finally, higher catalytic efficiency is obtained.
(4) The invention also provides application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in removing nitroaromatic compounds and/or azo dyes in water, which is characterized in that the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst, sodium borohydride and solution containing nitroaromatic compounds and/or azo dyes are mixed, and catalytic hydrogenation reduction reaction is carried out under the condition of normal temperature and normal pressure, so that the nitroaromatic compounds and/or azo dyes in the water can be removed efficiently and rapidly. Taking p-nitrophenol as an example, the removal principle is as follows: hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst is used as catalyst, wherein the existence of silver nano particles in the catalyst is helpful for BH 4 - Dissociation to produce H.radicals, positively charged nitrogen for attack on the nitro group of p-nitrophenol, catalyzing the hydrogenation of p-nitrophenol to the corresponding amine, thereby reducing the p-nitrophenol in water to the p-amino groupPhenol, and removing the p-nitrophenol in the water body. The method for removing the nitroaromatic compounds and/or azo dyes by using the silver-loaded hydrophilic bipyridyl conjugated microporous polymer provided by the invention can realize the rapid and efficient removal of the nitroaromatic compounds and/or azo dyes in the water body, has the advantages of simplicity and convenience in operation, small dosage of chemical agents, short treatment period, good treatment effect and the like, and simultaneously, the catalyst is easy to recover after the reaction is finished, so that the defect that the catalyst is difficult to recover in the traditional homogeneous reaction system is overcome.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is a process flow diagram of the preparation of hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst according to the present invention.
FIG. 2 is N of the bipyridyl conjugated microporous polymer (CMP-bpy 1) prepared in example 1 of the present invention 2 Adsorption and desorption graph.
FIG. 3 is a pore size distribution diagram of the bipyridyl conjugated microporous polymer (CMP-bpy 1) prepared in example 1 of the present invention.
FIG. 4 is an SEM image of a bipyridyl conjugated microporous polymer and a hydrophilic bipyridyl conjugated microporous polymer prepared in example 1 of the present invention, wherein a and b are bipyridyl conjugated microporous polymers, and c and d are hydrophilic bipyridyl conjugated microporous polymers.
FIG. 5 is a TEM image of the bipyridyl conjugated microporous polymer and the hydrophilic bipyridyl conjugated microporous polymer prepared in example 1 of the present invention, wherein a and c are bipyridyl conjugated microporous polymers, and b and d are hydrophilic bipyridyl conjugated microporous polymers.
Fig. 6 is an SEM image of a silver catalyst supported on a hydrophilic bipyridyl conjugated microporous polymer prepared in example 1 of the present invention.
FIG. 7 is a TEM image of a silver-supported hydrophilic bipyridyl conjugated microporous polymer prepared in example 1 of the present invention.
Fig. 8 is a graph showing a particle size distribution of ultrafine silver nanoparticles in a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst prepared in example 1 of the present invention.
FIG. 9 is N of bipyridyl conjugated microporous polymer (CMP-bpy 2) prepared in example 2 of the present invention 2 Adsorption and desorption graph.
FIG. 10 is a pore size distribution diagram of a bipyridyl conjugated microporous polymer (CMP-bpy 2) prepared in example 2 of the present invention.
FIG. 11 is a graph showing the ultraviolet spectrum of the solution of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst (HCMP-bpy 1-Ag) for catalyzing the hydrogenation reduction of p-nitrophenol according to the reaction time in example 3 of the present invention.
FIG. 12 is a graph showing the comparison of the p-nitrophenol solution catalyzed reaction in example 3 of the present invention.
FIG. 13 is a graph showing the ultraviolet spectrum of the solution of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst for catalyzing the hydrogenation reduction of p-nitrophenol according to the present invention in example 4, as a function of the reaction time.
FIG. 14 is a graph showing the ultraviolet spectrum of the solution for catalyzing the hydrogenation reduction of p-nitrophenol for the tenth time by using the silver catalyst supported on the hydrophilic bipyridyl conjugated microporous polymer in example 4 of the present invention, which shows the change of the ultraviolet spectrum with the reaction time.
FIG. 15 is a graph showing the ultraviolet spectrum of the solution of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst for catalyzing the hydrogenation reduction of p-nitrophenol according to the present invention in example 5, as a function of the reaction time.
FIG. 16 is a graph showing the ultraviolet spectrum of the solution of the biphenyl conjugated microporous polymer supported silver catalyst (CMPA-Ag) for catalyzing the hydrogenation reduction of p-nitrophenol in comparative example 2 according to the present invention, as a function of the reaction time.
FIG. 17 shows ln (C) at ambient temperature and pressure for a solution of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst (CMP-bpy 2-Ag) of example 5 and the biphenyl conjugated microporous polymer supported silver catalyst (CMPa-Ag) of comparative example 2 of the present invention catalyzing the hydrogenation reduction of p-nitrophenol t /C 0 ) And comparing the graph with a quasi-first-order curve of time.
FIG. 18 is a graph showing the ultraviolet spectrum of the solution for catalyzing the reduction of methyl orange by the silver catalyst supported on the hydrophilic bipyridyl conjugated microporous polymer in example 6 of the present invention, according to the reaction time.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
In the embodiment of the invention, the adopted raw materials and instruments are all commercially available. Unless otherwise specified, the process employed was conventional, the equipment employed was conventional, and the data obtained were averages of three or more replicates. The unit M is mol/L.
Example 1
A silver catalyst loaded by hydrophilic bipyridyl conjugated microporous polymer comprises a hydrophilic bipyridyl conjugated microporous polymer, wherein superfine silver nano particles are loaded on the hydrophilic bipyridyl conjugated microporous polymer, and the average particle size of the superfine silver nano particles is 4.12nm.
In this example, the mass percentage of the ultra-fine silver nano particles in the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst was 12.65wt%.
In this example, the hydrophilic bipyridyl conjugated microporous polymer has a microscopic morphology of nanospheres.
The preparation method of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in the embodiment, as shown in fig. 1, comprises the following steps:
(1) Synthesis of bipyridyl conjugated microporous Polymer:
(1.1) 300.36mg of 1,3, 5-triethylenebenzene, 627.96mg of 5,5' -dibromo-2, 2' -bipyridine and 1248mg of 4,4' -dibromobiphenyl, 40mg of tetrakis (triphenylphosphine) palladium (0) and 20mg of cuprous iodide were added to a mixed solution containing N, N-dimethylformamide and triethylamine (the volumes of N, N-dimethylformamide and triethylamine in the mixed solution were 25 mL), magnetically stirred and kept warm to 90℃under a nitrogen atmosphere, stirring was stopped after stirring for 90min, the reaction was continued at 90℃for 72 hours, and after the completion of the reaction, the bipyridyl-conjugated microporous polymer precipitate floc was carefully taken out with forceps.
(1.2) washing the bipyridyl conjugated microporous polymer precipitate floccules obtained in the step (1.1) with chloroform, water, methanol and acetone in sequence, washing for 4 times respectively, filtering the washed products with common qualitative filter paper, purifying the bipyridyl conjugated microporous polymer obtained by filtering with methanol as an extracting agent by a Soxhlet extraction method for 48 hours, and vacuum drying at 70 ℃ for 24 hours to obtain the bipyridyl conjugated microporous polymer with the number of CMP-bpy1.
(2) 200mg of the bipyridyl conjugated microporous polymer obtained in the step (1) is weighed, soaked in ethanol and sucked by filter paper to enable the bipyridyl conjugated microporous polymer to be in a semi-dry state, immersed into 20mL of saturated sulfuric acid solution (the concentration of sulfuric acid in the solution is 1 mol/L) for stirring reaction for 24 hours, filtered (vacuum filtered by a vacuum filter) after the reaction, a large amount of solution is removed, a residual sample is washed by a large amount of distilled water until a washing filtrate is neutral (washed 3 times), and finally dried for 12 hours at 70 ℃ to obtain the hydrophilic bipyridyl conjugated microporous polymer with the number of HCMP-bpy1. In the invention, the surface of the bipyridyl conjugated microporous polymer is wetted by ethanol, which is favorable for the sufficient contact between the bipyridyl conjugated microporous polymer and the sulfuric acid solution saturated by ammonium persulfate, so that the hydrophilic modification of the bipyridyl conjugated microporous polymer is easier to realize.
(3) Weighing 50mg of HCMP-bpy1 obtained in the step (2), adding into 50mL of 10mmol/L silver nitrate solution, stirring for 8h in the dark, filtering (vacuum filtering by a vacuum suction filter), taking a grey yellow sample, washing 3 times by distilled water, adding into 20mL of distilled water, stirring for 4h under irradiation of visible light, filtering (vacuum filtering by a vacuum suction filter), recovering, washing 3 times by distilled water, and vacuum drying at 60 ℃ for 12h to obtain the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst with the number of HCMP-bpy1-Ag.
FIG. 2 is N of the bipyridyl conjugated microporous polymer (CMP-bpy 1) prepared in example 1 of the present invention 2 Adsorption and desorption graph. Drawing of the figure3 is the pore size distribution diagram of the bipyridyl conjugated microporous polymer (CMP-bpy 1) prepared in example 1 of the present invention. As can be seen from FIG. 2, the BET specific surface area of CMP-bpy1 is 2.5001m 2 g -1 As can be seen from FIG. 3, the average pore size of CMP-bpy1 is 10.5109nm, and macropores are used as main pore channels.
FIG. 4 is an SEM image of a bipyridyl conjugated microporous polymer and a hydrophilic bipyridyl conjugated microporous polymer prepared in example 1 of the present invention, wherein a and b are bipyridyl conjugated microporous polymers, and c and d are hydrophilic bipyridyl conjugated microporous polymers. As can be seen from fig. 4, the bipyridyl conjugated microporous polymer and the hydrophilic bipyridyl conjugated microporous polymer both have a single nanosphere structure, which illustrates that the micro morphology and macro structure of the bipyridyl conjugated microporous polymer can be fundamentally controlled by adjusting the proportion of the synthetic monomers of the bipyridyl conjugated microporous polymer, which is beneficial to the practical application of the bipyridyl conjugated microporous polymer.
FIG. 5 is a TEM image of the bipyridyl conjugated microporous polymer and the hydrophilic bipyridyl conjugated microporous polymer prepared in example 1 of the present invention, wherein a and c are bipyridyl conjugated microporous polymers, and b and d are hydrophilic bipyridyl conjugated microporous polymers. As can be seen from fig. 5, both the bipyridyl conjugated microporous polymer and the hydrophilic bipyridyl conjugated microporous polymer are homogeneous molecular porous networks, exhibiting disordered amorphous structures.
As can be seen from fig. 4 and 5, the microscopic morphology and amorphous characteristics of the bipyridyl conjugated microporous polymer and the hydrophilic bipyridyl conjugated microporous polymer are not significantly changed, which indicates that the chemical oxidation modification can change the wettability of the bipyridyl conjugated microporous polymer without changing the morphological structure of the bipyridyl conjugated microporous polymer.
Fig. 6 is an SEM image of a silver catalyst supported on a hydrophilic bipyridyl conjugated microporous polymer prepared in example 1 of the present invention. FIG. 7 is a TEM image of a silver-supported hydrophilic bipyridyl conjugated microporous polymer prepared in example 1 of the present invention. Fig. 8 is a graph showing a particle size distribution of ultrafine silver nanoparticles in a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst prepared in example 1 of the present invention. As can be seen from fig. 6 to 8, silver nanoparticles are uniformly well supported on the hydrophilic bipyridyl conjugated microporous polymer, and the average diameter of the monodisperse silver nanoparticles is 4.12nm.
Example 2
A silver catalyst loaded by hydrophilic bipyridyl conjugated microporous polymer comprises a hydrophilic bipyridyl conjugated microporous polymer, wherein superfine silver nano particles are loaded on the hydrophilic bipyridyl conjugated microporous polymer.
In this example, the mass percentage of the ultrafine silver nanoparticles in the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst was 2.98wt%.
The preparation method of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in the embodiment comprises the following steps:
(1) Synthesis of bipyridyl conjugated microporous Polymer:
(1.1) 150.18mg of 1,3, 5-triethylenebenzene, 235.49mg of 5,5 '-dibromo-2, 2' -bipyridine, 25mg of tetrakis (triphenylphosphine) palladium (0) and 15mg of cuprous iodide were added to a mixed solution containing N, N-dimethylformamide and triethylamine (15 mL of each of the volumes of N, N-dimethylformamide and triethylamine), and the mixture was magnetically stirred under a nitrogen atmosphere and heated to 90℃for 90 minutes, and stirring was stopped, the reaction was continued at 90℃for 72 hours, and after the completion of the reaction, a bipyridyl-conjugated microporous polymer precipitate floccule was carefully taken out with forceps.
(1.2) washing the bipyridyl conjugated microporous polymer precipitate floccules obtained in the step (1.1) with chloroform, water, methanol and acetone in sequence, washing for 4 times respectively, filtering the washed products with common qualitative filter paper, purifying the bipyridyl conjugated microporous polymer obtained by filtering with methanol as an extracting agent by a Soxhlet extraction method for 48 hours, and vacuum drying at 70 ℃ for 24 hours to obtain the bipyridyl conjugated microporous polymer with the number of CMP-bpy2.
(2) Weighing 50mg of CMP-bpy2 obtained in the step (1), adding the obtained solution into 50mL of 1mmol/L silver nitrate solution, stirring for 4 hours in the dark, adding 100mg of sodium borohydride, stirring for 8 hours again, filtering (vacuum filtration by a vacuum suction filter), recovering, washing with distilled water for 3 times, and vacuum drying at 60 ℃ for 12 hours to obtain the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst with the number of CMP-bpy2-Ag.
FIG. 9 is N of bipyridyl conjugated microporous polymer (CMP-bpy 2) prepared in example 2 of the present invention 2 Adsorption and desorption graph. FIG. 10 is a pore size distribution diagram of a bipyridyl conjugated microporous polymer (CMP-bpy 2) prepared in example 2 of the present invention. As can be seen from FIG. 9, the BET specific surface area of CMP-bpy2 is 586.3099m 2 g -1 As can be seen from FIG. 10, the average pore size of CMP-bpy2 is 5.0090nm, and micropores and mesopores are used as main pore channels.
Comparative example 1
A preparation method of a biphenyl conjugated microporous polymer supported silver catalyst comprises the following steps:
(1) Synthesis of Biphenyl conjugated microporous Polymer:
(1.1) 150.18mg of 1,3, 5-triethylenebenzene, 234.01mg of 4,4' -dibromobiphenyl, 25mg of tetrakis (triphenylphosphine) palladium (0) and 15mg of cuprous iodide were added to a mixed solution containing N, N-dimethylformamide and triethylamine (15 mL of each of the N, N-dimethylformamide and triethylamine) and stirred magnetically under a nitrogen atmosphere and heated to 90℃for 90 minutes, stirring was stopped, the reaction was continued at 90℃for 72 hours, and after the completion of the reaction, a bipyridyl conjugated microporous polymer precipitate was carefully taken out using forceps.
(1.2) washing the diphenyl conjugated microporous polymer precipitate floccules obtained in the step (1.1) with chloroform, water, methanol and acetone in sequence, washing for 4 times respectively, filtering the washed products with common qualitative filter paper, purifying the diphenyl conjugated microporous polymer obtained by filtering with methanol as an extracting agent by adopting a Soxhlet extraction method for 48 hours, and vacuum drying at 70 ℃ for 24 hours to obtain the diphenyl conjugated microporous polymer with the number of CMPA.
(2) Weighing 50mg of the biphenyl conjugated microporous polymer obtained in the step (2), adding the biphenyl conjugated microporous polymer into 50mL of 1mmol/L silver nitrate solution, stirring in the dark for 4 hours, adding 100mg of sodium borohydride, stirring for 8 hours, filtering (vacuum filtration by a vacuum suction filter), recovering, washing with distilled water for 3 times, and vacuum drying at 60 ℃ for 12 hours to obtain the biphenyl conjugated microporous polymer supported silver catalyst with the number of CMPA-Ag.
Example 3
The application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in removing nitroaromatic compounds in water body, in particular to the application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in catalyzing the hydrogenation reduction of p-nitrophenol at room temperature, comprising the following steps:
(1) 0.0757g of sodium borohydride are weighed into 50mL of a 0.2mmol/L p-nitrophenol solution and stirred for a while until the solution turns from pale yellow to bright yellow.
(2) 8.4mg of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst (HCMP-bpy 1-Ag) prepared in the example 1 is weighed and added into the bright yellow solution in the step (1) to be mixed for catalytic hydrogenation reaction, so that the removal of p-nitrophenol in the water body is completed.
During the reaction, samples were filtered and UV spectrophotometric measurements were performed at time intervals.
FIG. 11 is a graph showing the ultraviolet spectrum of the solution of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst (HCMP-bpy 1-Ag) for catalyzing the hydrogenation reduction of p-nitrophenol according to the reaction time in example 3 of the present invention. As can be seen from FIG. 11, when HCMP-bpy1-Ag is present, the intensity of the absorption peak at 400nm (characteristic peak of p-nitrophenol) disappears at about 4min and the absorption peak at 300nm (characteristic peak of p-aminophenol) is formed, which indicates that the system can catalyze the reduction of p-nitrophenol to p-aminophenol in a short period of time.
FIG. 12 is a graph showing the comparison of the p-nitrophenol solution catalyzed reaction in example 3 of the present invention. As can be seen from FIG. 12, the absorption peak of the paranitrophenol stock solution is about 316 nm; after the sodium borohydride solution is added, the absorption peak of the mixed solution of the paranitrophenol and the sodium borohydride is shifted to 400nm, and the peak gradually decreases along with the progress of the reaction, which indicates that the paranitrophenol is continuously consumed; at the same time, an absorption peak of p-aminophenol occurs at 300nm, which indicates that p-nitrophenol is reduced to p-aminophenol in the solution after the catalytic reaction.
Example 4
The application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in removing nitroaromatic compounds in water body, in particular to the application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in catalyzing the hydrogenation reduction of p-nitrophenol at room temperature, comprising the following steps:
(1) 0.0757g of sodium borohydride was weighed into 50mL of a 0.2mmol/L p-nitrophenol solution and stirred for a short time until the solution turned from pale yellow to bright yellow.
(2) 8.4mg of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst (CMP-bpy 2-Ag) prepared in example 2 was weighed and added to the bright yellow solution in step (1) to be mixed for catalytic hydrogenation reaction.
(3) Filtering and recovering the residual CMP-bpy2-Ag in the step (2), and recycling the steps (1) and (2) for a plurality of times.
During the reaction, samples were filtered and UV spectrophotometric measurements were performed at time intervals.
FIG. 13 is a graph showing the ultraviolet spectrum of the solution of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst for catalyzing the hydrogenation reduction of p-nitrophenol according to the present invention in example 4, as a function of the reaction time. As can be seen from fig. 13, when CMP-bpy2-Ag was present, the intensity of the absorption peak at 400nm (characteristic peak of p-nitrophenol) was gradually weakened with the lapse of the reaction time, and the absorption peak at 300nm (characteristic peak of p-aminophenol) was formed, which suggests that the system is capable of catalyzing the hydrogenation reduction of p-nitrophenol to p-aminophenol. Meanwhile, as can be seen from a graph 13, the reaction system can catalyze and reduce p-nitrophenol into p-aminophenol in about 5 minutes, which shows that the system has higher catalytic activity.
FIG. 14 is a graph showing the ultraviolet spectrum of the solution for catalyzing the hydrogenation reduction of p-nitrophenol for the tenth time by using the silver catalyst supported on the hydrophilic bipyridyl conjugated microporous polymer in example 4 of the present invention, which shows the change of the ultraviolet spectrum with the reaction time. From the graph 14, after ten times of recycling, the reaction system can still catalyze and reduce p-nitrophenol to p-aminophenol in about 5 minutes, which proves that the system has very high catalytic stability.
Example 5
The application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in removing the p-nitrophenol in the water body, in particular to the application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in catalyzing the hydrogenation reduction of the p-nitrophenol at room temperature, comprising the following steps of:
(1) 0.3783g of sodium borohydride was weighed into 50mL of a 0.2mmol/L p-nitrophenol solution and stirred for a short time until the solution turned from pale yellow to bright yellow.
(2) 8.4mg of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst (CMP-bpy 2-Ag) prepared in example 2 was weighed and added to the bright yellow solution in step (1) and timed, and sampling filtration and ultraviolet spectrophotometry were performed at certain time intervals.
FIG. 15 is a graph showing the ultraviolet spectrum of the solution of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst for catalyzing the hydrogenation reduction of p-nitrophenol according to the present invention in example 5, as a function of the reaction time. As can be seen from fig. 15, when CMP-bpy2-Ag was present, the intensity of the absorption peak at 400nm (characteristic peak of p-nitrophenol) was gradually weakened with the lapse of the reaction time, and the absorption peak (characteristic peak of p-aminophenol) was formed at 300nm, which suggests that the system is capable of catalyzing the hydrogenation reduction of p-nitrophenol to p-aminophenol.
Comparative example 2
The application of the biphenyl conjugated microporous polymer supported silver catalyst in removing p-nitrophenol in water body, in particular to the application of the biphenyl conjugated microporous polymer supported silver catalyst in catalyzing the hydrogenation reduction of p-nitrophenol at room temperature, comprising the following steps:
(1) 0.3783g of sodium borohydride was weighed into 50mL of a 0.2mmol/L p-nitrophenol solution and stirred for a short time until the solution turned from pale yellow to bright yellow.
(2) 8.4mg of the biphenyl conjugated microporous polymer supported silver catalyst (CMPA-Ag) prepared in comparative example 2 is weighed and added into the bright yellow solution in step (1) to be mixed for catalytic hydrogenation reaction, so as to complete the removal of the p-nitrophenol in the water body.
During the reaction, samples were filtered and UV spectrophotometric measurements were performed at time intervals.
FIG. 16 is a graph showing the ultraviolet spectrum of the solution of the biphenyl conjugated microporous polymer supported silver catalyst (CMPA-Ag) for catalyzing the hydrogenation reduction of p-nitrophenol in comparative example 2 according to the present invention, as a function of the reaction time. As can be seen from fig. 16, when CMPA-Ag is present, the intensity of the absorption peak at 400nm (characteristic peak of p-nitrophenol) gradually becomes weaker with the lapse of reaction time, and the absorption peak (characteristic peak of p-aminophenol) is formed at 300nm, which indicates that the system is capable of catalyzing the hydrogenation reduction of p-nitrophenol.
FIG. 17 shows ln (C) at ambient temperature and pressure for a solution of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst (CMP-bpy 2-Ag) of example 5 and the biphenyl conjugated microporous polymer supported silver catalyst (CMPa-Ag) of comparative example 2 of the present invention catalyzing the hydrogenation reduction of p-nitrophenol t /C 0 ) And comparing the graph with a quasi-first-order curve of time. As can be seen from FIG. 17, the reaction rate constant of the system for catalyzing the hydrogenation reduction of the p-nitrophenol by the biphenyl conjugated microporous polymer supported silver catalyst (CMPa-Ag) is obviously lower than that of the system for catalyzing the hydrogenation reduction of the p-nitrophenol by the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst (CMP-bpy 2-Ag).
Example 6
The application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in removing azo dyes in water body, in particular to the application of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst in catalyzing p-nitrophenol hydrogenation reduction at room temperature, comprising the following steps:
(1) 0.0757g of sodium borohydride are weighed into 50mL, 0.2mmol/L methyl orange solution and stirred for a short time.
(2) 8.4mg of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst (CMP-bpy 2-Ag) prepared in the example 2 is weighed and added into the methyl orange solution in the step (1) to be mixed for catalytic hydrogenation reaction, so that the removal of methyl orange in the water body is completed.
During the reaction, samples were filtered and UV spectrophotometric measurements were performed at time intervals.
FIG. 18 is a graph showing the ultraviolet spectrum of the solution for catalyzing the reduction of methyl orange by the silver catalyst supported on the hydrophilic bipyridyl conjugated microporous polymer in example 6 of the present invention, according to the reaction time. From the graph 18, it can be seen that when CMP-bpy2-Ag exists, the intensity of the absorption peak (characteristic peak of p-nitrophenol) at 465nm gradually weakens along with the reaction time, and the degradation can be completed within about 10 minutes, which shows that the system can catalyze methyl orange reduction more efficiently.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (8)
1. The preparation method of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst is characterized by comprising the following steps of:
s1, immersing a bipyridyl conjugated microporous polymer into a sulfuric acid solution saturated by ammonium persulfate, stirring, filtering, washing and drying to obtain a hydrophilic bipyridyl conjugated microporous polymer; the method further comprises the following treatment before immersing the bipyridyl conjugated microporous polymer into the sulfuric acid solution saturated by ammonium persulfate: placing the bipyridyl conjugated microporous polymer in ethanol, and performing wetting treatment on the surface of the bipyridyl conjugated microporous polymer;
s2, mixing the hydrophilic bipyridyl conjugated microporous polymer obtained in the step S1 with silver ion solution, stirring, filtering and washing to obtain the hydrophilic bipyridyl conjugated microporous polymer adsorbed with silver ions;
S3, adding the hydrophilic bipyridyl conjugated microporous polymer adsorbed with silver ions obtained in the step S2 into deionized water, carrying out reduction reaction under the condition of illumination or reducing agent, filtering, washing and drying to obtain a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst;
the silver catalyst loaded by the hydrophilic bipyridyl conjugated microporous polymer comprises a hydrophilic bipyridyl conjugated microporous polymer, and superfine silver nano particles are loaded on the hydrophilic bipyridyl conjugated microporous polymer; the average particle size of the superfine silver nano particles is less than or equal to 15 nm; the mass percentage of the superfine silver nano particles in the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst is 12.65-14 wt%.
2. The method for preparing a silver catalyst supported on a hydrophilic bipyridyl conjugated microporous polymer according to claim 1, wherein in the step S1, the method for preparing a bipyridyl conjugated microporous polymer comprises the steps of:
(1) Adding 1,3, 5-tri-ethynyl benzene, 5' -dibromo-2, 2' -bipyridine, 4 ' -dibromobiphenyl, tetrakis (triphenylphosphine) palladium (0) and cuprous iodide into a mixed solution of N, N-dimethylformamide and triethylamine, and stirring to obtain a bipyridyl conjugated microporous polymer precursor solution;
(2) Heating the bipyridyl conjugated microporous polymer precursor solution obtained in the step (1) to 80-90 ℃ for reaction, washing, filtering, purifying and drying to obtain the bipyridyl conjugated microporous polymer.
3. The method for preparing a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst according to claim 2, wherein in the step (1), the molar ratio of 1,3, 5-tri-ethynyl benzene, 5' -dibromo-2, 2' -bipyridine to 4,4' -dibromobiphenyl is 2:1.5 to 2:0 to 4, and the molar weight of the 4,4' -dibromobiphenyl is not 0; the mass ratio of the tetra (triphenylphosphine) palladium (0) to the cuprous iodide is 1:1 to 2.5:1, a step of; the volume ratio of the N, N-dimethylformamide to the triethylamine is 1:1 to 1.5:1, a step of; the mass ratio of the cuprous iodide to the 1,3, 5-tri-ethynyl benzene is 1:14 to 1:15; the mass volume ratio of the 1,3, 5-tri-ethynyl benzene to the N, N-dimethylformamide is 12g: 1L-14 g:1L; the stirring is carried out under nitrogen atmosphere; the stirring time is 80-100 min;
in step (2), the reaction is carried out under a nitrogen atmosphere; the reaction time is 48-72 hours; the washing is to adopt chloroform, water, methanol and acetone to wash the reaction products for 3 to 5 times respectively; the purification adopts a Soxhlet extraction method; the extraction time is 24-72 hours; the drying is performed under vacuum; the drying temperature is 60-70 ℃; the drying time is 12-24 hours.
4. The method for preparing a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst according to any one of claims 1 to 3, wherein in step S1, the molar concentration of sulfuric acid in the ammonium persulfate-saturated sulfuric acid solution is 0.1mol/L to 1mol/L; the stirring time is 12-24 hours; the washing is to wash the filtered product for 3 to 5 times by distilled water; the drying temperature is 60-70 ℃; the drying time is 8-12 h;
in the step S2, the mass volume ratio of the hydrophilic bipyridyl conjugated microporous polymer to the silver ion solution is 0.1g: 1L-1 g:1L; the molar concentration of silver ions in the silver ion solution is 0.1 mmol/L-10 mmol/L; the silver ion solution is silver nitrate solution; the stirring is performed under dark conditions; the stirring time is 8-12 h; the washing is to wash the filtered product for 3 to 5 times by distilled water;
in the step S3, the volume mass ratio of the deionized water to the hydrophilic bipyridyl conjugated microporous polymer is 2 mL-4 mL:5 mg-10 mg; the mass volume ratio of the reducing agent to the deionized water is 0.1g: 1L-10 g:1L; the reducing agent is sodium borohydride; the time of the reduction reaction is 4-24 hours; the washing is to wash the filtered product for 3 to 5 times by distilled water; the drying is performed under vacuum; the drying temperature is 60-70 ℃; the drying time is 8-12 h.
5. The method for preparing a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst according to claim 1, wherein the average particle size of the ultrafine silver nanoparticles is not more than 5 nm.
6. Use of a hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst prepared by the preparation method according to any one of claims 1 to 5 for removing nitroaromatic compounds and/or azo dyes from water.
7. The use according to claim 6, characterized by the steps of: mixing a silver catalyst loaded by a hydrophilic bipyridyl conjugated microporous polymer, sodium borohydride and a solution containing nitroaromatic compounds and/or azo dyes for catalytic hydrogenation reaction to remove the nitroaromatic compounds and/or azo dyes in the water body; the molar ratio of the sodium borohydride to the nitroaromatic compound or azo dye in the solution containing the nitroaromatic compound and/or azo dye is 100:1 to 1000:1, a step of; the mass volume ratio of the hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst to the nitroaromatic compound and/or azo dye containing solution is 0.1g: 1L-0.2 g:1L; the concentration of the nitroaromatic compound or azo dye in the solution containing the nitroaromatic compound and/or azo dye is less than or equal to 70mg/L.
8. The use according to claim 7, wherein the catalytic hydrogenation reaction takes from 1min to 30min; the nitroaromatic compound is p-nitrophenol; the azo dye is methyl orange.
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| CN109400850A (en) * | 2018-11-15 | 2019-03-01 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and products thereof of ultra-fine silver nano-grain and micropore organic polymer composite material |
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