CN117659432B - Porous nickel porphyrin-based hydrogen bond organic framework material and preparation method and application thereof - Google Patents
Porous nickel porphyrin-based hydrogen bond organic framework material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117659432B CN117659432B CN202410139080.2A CN202410139080A CN117659432B CN 117659432 B CN117659432 B CN 117659432B CN 202410139080 A CN202410139080 A CN 202410139080A CN 117659432 B CN117659432 B CN 117659432B
- Authority
- CN
- China
- Prior art keywords
- porphyrin
- uranium
- organic framework
- based hydrogen
- framework material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- 239000013384 organic framework Substances 0.000 title claims abstract description 31
- RNGSTWPRDROEIW-UHFFFAOYSA-N [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Ni].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 RNGSTWPRDROEIW-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052770 Uranium Inorganic materials 0.000 claims abstract description 46
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 claims abstract description 46
- 230000001699 photocatalysis Effects 0.000 claims abstract description 41
- 239000002354 radioactive wastewater Substances 0.000 claims abstract description 29
- 230000009467 reduction Effects 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 150000004032 porphyrins Chemical class 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- AQIFPEIUSQBFJF-UHFFFAOYSA-N 4-[10,15,20-tris(4-cyanophenyl)-21,23-dihydroporphyrin-5-yl]benzonitrile Chemical compound N#Cc1ccc(cc1)-c1c2ccc(n2)c(-c2ccc(cc2)C#N)c2ccc([nH]2)c(-c2ccc(cc2)C#N)c2ccc(n2)c(-c2ccc(cc2)C#N)c2ccc1[nH]2 AQIFPEIUSQBFJF-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- OFAPSLLQSSHRSQ-UHFFFAOYSA-N 1H-triazine-2,4-diamine Chemical compound NN1NC=CC(N)=N1 OFAPSLLQSSHRSQ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 235000019260 propionic acid Nutrition 0.000 claims description 8
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 238000004065 wastewater treatment Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- WZWIQYMTQZCSKI-UHFFFAOYSA-N 4-cyanobenzaldehyde Chemical compound O=CC1=CC=C(C#N)C=C1 WZWIQYMTQZCSKI-UHFFFAOYSA-N 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 238000013032 photocatalytic reaction Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- -1 azo arsine Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 231100000045 chemical toxicity Toxicity 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The invention belongs to the technical field of material chemistry, and particularly relates to a porous nickel-porphyrin-based hydrogen bond organic framework material, a preparation method and application thereof. The Ni-pHOF has excellent photocatalytic reduction capability on hexavalent uranium, shows good anti-jamming ion capability and reusability, and has excellent uranium removal capability in the treatment of real uranium-containing radioactive wastewater.
Description
Technical Field
The invention belongs to the technical field of material chemistry, and particularly relates to a porous nickel porphyrin-based hydrogen bond organic framework material, and a preparation method and application thereof, which are mainly applied to treatment of uranium-containing radioactive wastewater.
Background
Uranium is the most important raw material of nuclear power plants, and uranium-containing radioactive wastewater is inevitably generated during exploitation and use. Because uranium has the characteristics of long-term radioactivity, chemical toxicity, easy environment migration and the like, the uranium has great threat to environmental safety and human health; removing uranium in uranium-containing wastewater is a key to realizing uranium resource reuse and sustainable development of nuclear energy. At present, the photocatalysis method has received high attention because of the advantages of quick dynamics, high selectivity and the like.
The hydrogen bond organic framework material (HOFs) is composed of organic monomers connected by intermolecular hydrogen bonds, and has the unique properties of structural diversity, porosity, modifiable property, high crystallinity, good chemical and thermal stability and hydrogen bond endowed; and the synthesis condition is mild, the solution processability is strong, and the repair and regeneration are easy. However, the weaker strength of action and stronger flexibility of hydrogen bonds often lead to the tendency of the HOFs structure to collapse.
Disclosure of Invention
The invention aims to provide a porous nickel porphyrin-based hydrogen bond organic framework material, and a preparation method and application thereof; the porous nickel porphyrin-based hydrogen bond organic framework material selects porphyrin as a rigid framework to prepare porous HOFs with excellent photocatalytic performance, and can be used for removing uranium in uranium-containing radioactive wastewater.
In order to achieve the above purpose, the invention adopts the following technical scheme:
step 1: preparation of 5,10,15, 20-tetra (4-cyanophenyl) porphyrin;
under the nitrogen atmosphere, adding 1 part by mass of 4-cyanobenzaldehyde into 20-80 parts by volume of propionic acid, and stirring; heating and refluxing for 2-6 hours under the light-shielding condition, and adding pyrrole with the volume ratio of 1:50-100 with propionic acid while keeping the reflux; then cooling to room temperature, adding methanol with the volume ratio of 1:0.8-1.5 to propionic acid, stirring, standing for 12-24 hours at the temperature of 5-8 ℃, filtering, washing, and vacuum drying to obtain 5,10,15, 20-tetra (4-cyanophenyl) porphyrin;
step 2: preparation of 5,10,15, 20-tetrakis (4- (2, 4-diaminotriazine) phenyl) porphyrin;
adding 2 parts by mass of 5,10,15, 20-tetra (4-cyanophenyl) porphyrin prepared in the step 1, 1 part by mass of dicyandiamide and 1 part by mass of potassium hydroxide into 20-80 parts by volume of anhydrous glycol monomethyl ether in a nitrogen atmosphere, stirring, heating and refluxing for 24-48 hours, evaporating to dryness under reduced pressure, washing and drying in vacuum to obtain 5,10,15, 20-tetra (4- (2, 4-diaminotriazine) phenyl) porphyrin;
step 3: preparing Ni/DAT-porphyrin;
heating and refluxing 5,10,15, 20-tetra (4- (2, 4-diaminotriazine) phenyl) porphyrin and nickel dichloride prepared in the step 2 with the mass ratio of 1:1-5 in 80-120 parts by volume of N, N-dimethylformamide for 6-12 hours, washing, and vacuum drying to obtain Ni/DAT-porphyrin;
step 4: preparing a porous nickel porphyrin-based hydrogen bond organic framework material;
placing 1 part by mass of Ni/DAT-porphyrin prepared in the step 3 and 20-70 parts by volume of mixed solvent into a pressure-resistant pipe, performing ultrasonic treatment at room temperature for 10-30 min, sealing, heating for 60-90 h, cooling to room temperature, filtering, washing, and performing vacuum drying to obtain a porous nickel-porphyrin-based hydrogen bond organic framework material; the mixed solvent comprises o-dichlorobenzene, n-butanol and acetic acid with the volume ratio of 3:0.1-1.5:0.01-0.15, wherein the concentration of the acetic acid is 4.5-7.5 mol/L.
The heating temperature is 100-180 ℃; the temperature of vacuum drying is 60-90 ℃.
The porous nickel porphyrin-based hydrogen bond organic framework material prepared by the preparation method.
The porous nickel porphyrin-based hydrogen bond organic framework material prepared by the method is applied to uranium-containing radioactive wastewater treatment.
According to the uranium-containing radioactive wastewater treatment method, the prepared porous nickel porphyrin-based hydrogen bond organic framework material is added into the uranium-containing radioactive wastewater to perform photocatalytic reaction under light irradiation, so that the photocatalytic reduction removal of hexavalent uranium in the uranium-containing radioactive wastewater is realized.
Further, the solid-to-liquid ratio of the porous nickel porphyrin-based hydrogen bond organic framework material to uranium-containing radioactive wastewater is 0.4g/L.
Further, the pH of the uranium-containing radioactive wastewater is adjusted to 5.
Further, the concentration of hexavalent uranium in the uranium-containing radioactive wastewater is adjusted to be 50mg/L.
Further, methanol or ethanol is added into the uranium-containing radioactive wastewater to serve as a hole trapping agent.
The beneficial effects of the invention are as follows: porphyrin is used as a rigid framework, transition metal nickel is introduced into the center of porphyrin ring, and the porous nickel porphyrin-based hydrogen bond organic framework material (Ni-pHOF) with stable structure is prepared. The Ni-pHOF has excellent photocatalytic reduction capability on hexavalent uranium, shows good anti-jamming ion capability and reusability, and has excellent uranium removal capability in the treatment of real uranium-containing radioactive wastewater.
Drawings
FIG. 1 is an SEM image of Ni-pHOF as in (a); (b) SEM image of pHOF.
FIG. 2 shows XRD patterns of Ni-pHOF and pHOF.
FIG. 3 shows the photocatalytic removal effect of Ni-pHOF and pHOF on U (VI) under light conditions.
FIG. 4 shows the photocatalytic removal effect of Ni-pHOF on U (VI) at different solid to liquid ratios.
FIG. 5 shows the photocatalytic removal effect of Ni-pHOF on U (VI) at different pH conditions.
FIG. 6 shows the photocatalytic removal of U (VI) by Ni-pHOF under different initial U (VI) concentrations.
FIG. 7 shows the photocatalytic removal effect of Ni-pHOF on U (VI) in the presence of different hole-trapping agents.
FIG. 8 shows the photocatalytic removal effect of Ni-pHOF on U (VI) in the presence of different cations.
FIG. 9 shows the photocatalytic removal effect of Ni-pHOF on U (VI) in the presence of different anions.
FIG. 10 shows the photocatalytic removal of U (VI) by Ni-pHOF over multiple cycles.
Detailed Description
Example 1
The embodiment provides a preparation method of a porous nickel porphyrin-based hydrogen bond organic framework material Ni-pHOF with stable structure, which comprises the following steps:
step 1: 200mL of propionic acid was used as a solvent under nitrogen atmosphere, 6.69g of 4-cyanobenzaldehyde was added thereto and stirred, the mixture was heated to 141℃under dark conditions, and after refluxing for 10 minutes, 3.25mL of pyrrole was slowly injected. And keeping reflux for 3 hours, cooling the obtained solution in air to room temperature, adding 200mL of methanol, stirring, placing in a refrigerator (the temperature is 5-8 ℃) for 24 hours, generating a large amount of precipitate, filtering, washing with methanol, and drying in vacuum at 80 ℃ to obtain 5,10,15, 20-tetra (4-cyanophenyl) porphyrin.
Step 2: 586mg of 5,10,15, 20-tetra (4-cyanophenyl) porphyrin, 345mg of dicyandiamide and 300mg of potassium hydroxide are added into 20mL of anhydrous ethylene glycol methyl ether under the nitrogen atmosphere, the mixture is heated to 125 ℃ and refluxed for 48 hours, the product is dried by decompression evaporation at 60 ℃ by a rotary evaporator, and then repeatedly washed by methanol and deionized water, and vacuum dried at 80 ℃ to obtain 5,10,15, 20-tetra (4- (2, 4-diaminotriazine) phenyl) porphyrin, which is called DAT-porphyrin for short.
Step 3: 1.05g of DAT-porphyrin and 3.1g of nickel dichloride were heated in 100mL of DMF at 153℃and refluxed for 8h, washed with deionized water, and dried in vacuo at 80℃to give Ni/DAT-porphyrin.
Step 4: 30mg of Ni/DAT-porphyrin and 1.1mL of mixed solvent (o-dichlorobenzene: n-butanol: acetic acid with the concentration of 6mol/L in a volume ratio of 3:1:0.1) are placed in a 10mL pressure-resistant tube, ultrasonic treatment is performed at room temperature for 15min, sealing is performed, heating is performed at 120 ℃ for 72h, cooling is performed to room temperature, filtering is performed, deionized water washing is performed, vacuum drying is performed at 80 ℃, and a porous nickel porphyrin-based hydrogen bond organic framework material Ni-pHOF with stable structure is obtained, wherein the Ni-pHOF is brown powder.
Comparative example 1
The present embodiment provides a preparation method of a porphyrin-based hydrogen bond organic framework material pHOF, which adopts the raw materials and the amounts substantially the same as those of embodiment 1, and only omits step 3, and specifically includes the following steps:
step 1: 200mL of propionic acid was used as a solvent under nitrogen atmosphere, 6.69g of 4-cyanobenzaldehyde was added thereto and stirred, the mixture was heated to 141℃under dark conditions, and after refluxing for 10 minutes, 3.25mL of pyrrole was slowly injected. And keeping reflux for 3 hours, cooling the obtained solution in air to room temperature, adding 200mL of methanol, stirring, placing in a refrigerator (the temperature is 5-8 ℃) for 24 hours, generating a large amount of precipitate, filtering, washing with methanol, and drying in vacuum at 80 ℃ to obtain 5,10,15, 20-tetra (4-cyanophenyl) porphyrin.
Step 2: 586mg of 5,10,15, 20-tetra (4-cyanophenyl) porphyrin, 345mg of dicyandiamide and 300mg of potassium hydroxide are added into 20mL of anhydrous ethylene glycol methyl ether under the nitrogen atmosphere, the mixture is heated and refluxed for 48 hours, the product is dried by decompression evaporation at 60 ℃ by a rotary evaporator, and then repeatedly washed by methanol and deionized water, and vacuum dried at 80 ℃ to obtain 5,10,15, 20-tetra (4- (2, 4-diaminotriazine) phenyl) porphyrin, which is called DAT-porphyrin for short.
Step 3: 30mg of DAT-porphyrin and 1.1mL of a mixed solvent (o-dichlorobenzene: n-butanol: 6mol/L acetic acid in a volume ratio of 3:1:0.1) are placed in a 10mL pressure-resistant tube, sonicated at room temperature for 15min, sealed, heated at 120 ℃ for 72h, cooled to room temperature, filtered, washed with deionized water, and dried in vacuo at 80 ℃ to obtain a much Kong Bulin-base hydrogen bonded organic framework material pHOF.
The topographical features of Ni-pHOF and pHOF were observed using a Gemini-300 field emission scanning electron microscope. FIG. 1 (a) is an SEM image of Ni-pHOF, and FIG. 1 (b) is an SEM image of pHOF, as can be seen from FIG. 1: a large amount of porous lamellar structure can be observed on the surface of Ni-pHOF material, while pHOF material exhibits a small amount of porous structure.
XRD patterns of Ni-pHOF and pHOF were obtained using a D8 VENTURE/QUEST X-ray powder diffractometer. As shown in FIG. 2, ni-pHOF has a strong diffraction peak, indicating that Ni-pHOF material has a high crystallinity; the diffraction peak position of Ni-pHOF is basically consistent with pHOF, which shows that Ni has almost no obvious effect on the crystal structure of the material after being introduced into porphyrin center ring.
Photocatalytic experiments (performed in a PCX-50C Discover multichannel photocatalytic reaction System)
Firstly, respectively taking 20mg of Ni-pHOF and pHOF, adding into a quartz photoreaction bottle, ultrasonically dispersing into 50mL of hexavalent uranium [ U (VI) ] solution (the concentration is 50 mg/L), adding 2.5mL of methanol as a hole capturing agent, adjusting the pH value by using 0.1mol/L NaOH or HCl solution with negligible volume, and injecting nitrogen into the solution for 30min to deoxidize.
Then, a 10W LED lamp was used to simulate a solar light source, and the irradiation was performed for 120min. And (3) separating the photocatalyst from the liquid phase within a certain time, measuring the concentration of U (VI) at 651nm by using a UV-2450 ultraviolet-visible light spectrophotometer by adopting an azo arsine III spectrophotometry, and calculating the removal rate. The method evaluates the influence of different solid-to-liquid ratios, pH, initial U (VI) concentration, hole trapping agent, interfering ions and the like on the U (VI) removal performance.
Finally, after each photocatalytic cycle, the photocatalyst was exposed to air for 12 hours and treated with 0.01mol/L HNO in a multiple cycle test 3 The solution was further treated, washed 3 times with deionized water, dried in vacuo at 80 ℃ and used for the next round of photocatalytic cycle experiments.
FIG. 3 shows the photocatalytic removal effect of Ni-pHOF and pHOF on U (VI) under light conditions; the photocatalytic removal rate of Ni-pHOF was 90.66%, and the removal rate of pHOF was 79.91%, and it was apparent that the photocatalytic removal rate of Ni-pHOF was higher than pHOF. Mainly because of the introduction of metallic nickel, the porphyrin ring can transfer free electrons to the nickel metal center through a ligand-metal charge transfer mechanism, which is favorable for the transmission and migration of electrons, thereby enhancing the photocatalytic U (VI) removal capability of the Ni-pHOF material.
FIG. 4 is the photocatalytic removal effect of Ni-pHOF on U (VI) at different solid to liquid ratios (m/V=0.1, 0.2, 0.4, 0.6, 0.8, 1.0 g/L); as can be seen from fig. 4: too much or insufficient photocatalyst usage will significantly affect the photocatalytic removal rate of U (VI); when the light is irradiated for 120min, the dosage of the Ni-pHOF catalyst is 0.4g/L, the highest photocatalytic removal rate of U (VI) is 98.17 percent.
FIG. 5 is the photocatalytic removal effect of Ni-pHOF on U (VI) at different pH conditions (pH=2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, m/V=0.4 g/L); as can be seen from fig. 5: when the pH value of the solution is increased from 2.0 to 5.0, the photocatalytic removal rate of U (VI) is increased from 7.36% to 86.57% under the irradiation of visible light, and then the photocatalytic removal rate of U (VI) is gradually reduced to 24.24% along with the continuous increase of the pH value of the solution. Mainly due to U (VI) and photo-generated holes at low pHh + Competing for photogenerated electrons on the surface of Ni-pHOF catalyste ‒ Hydrolysis of U (VI) at high pH interferes with the utilization of visible light by Ni-pHOF catalysts.
FIG. 6 is a graph of (C) at various initial U (VI) concentrations U(VI) =12.5, 25, 50, 100, 200, 400mg/L, m/v=0.4 g/L, ph=5.0) Ni-pHOF has photocatalytic removal effect on U (VI). As can be seen from fig. 6: as the initial U (VI) concentration increased from 12.5mg/L to 50mg/L, the photocatalytic removal rate of U (VI) increased from 27.42% to 93.27% under visible light irradiation, after which the photocatalytic removal rate of U (VI) gradually decreased to 82.87% as the initial U (VI) concentration continued to increase to 400 mg/L. The yellow color of the high-concentration U (VI) solution weakens the light transmittance of the solution, and reduces the photocatalytic removal efficiency of the U (VI).
FIG. 7 is a graph of the concentration of a different hole-trapping agent (methanol, ethanol, formic acid, acetic acid, ethylenediamine tetraacetic acid, m/v=0.4 g/L, pH=5.0, C) U(VI) =50 mg/L) photocatalytic removal effect of Ni-pHOF on U (VI). As can be seen from fig. 7: in the absence of a hole trapping agent, ni-pHOF has weaker photocatalytic removal capacity of U (VI) under irradiation of visible light; when a hole-capturing agent such as methanol or ethanol is added, the highest efficiency of removing U (VI) by Ni-pHOF photocatalysis is 97.00%, which shows that the alcohol hole-capturing agent and photo-generated holesh + The reaction between them can beEffectively reduce photo-generated electron-photo-generated holee ‒ -h + ) Is improved in the compounding process of (a)e ‒ Is used for the utilization of the system.
FIG. 8 shows the results in the presence of different cations (Na + 、K + 、Mg 2+ 、Ca 2+ 、Ce 3+ 、Sm 3+ 、Eu 3+ 、Gd 3+ The concentration of each cation was 50 mg/L) Ni-pHOF had a photocatalytic removal effect on U (VI). As can be seen from fig. 8: the effect of these cations on the photocatalytic removal of U (VI) by Ni-pHOF was almost negligible compared to the control (no cations), and the selectivity of the Ni-pHOF catalyst for U (VI) was still as high as 98.02%, exhibiting excellent selectivity.
FIG. 9 shows the reaction of (ClO) in the presence of different anions 4 ‒ 、Cl ‒ 、CO 3 2‒ 、SO 4 2‒ The concentration of each anion was 50 mg/L) Ni-pHOF had a photocatalytic removal effect on U (VI). As can be seen from fig. 9: clO compared to the control group (no anions) 4 ‒ 、Cl ‒ And CO 3 2‒ The effect on the photocatalytic removal of U (VI) by Ni-pHOF is negligible, while SO 4 2‒ A certain disturbance is exhibited.
FIG. 10 is the photocatalytic removal effect of Ni-pHOF on U (VI) over multiple cycles; as can be seen from fig. 10: after 5 times of circulation, the photocatalysis removal rate of the Ni-pHOF catalyst to U (VI) can still reach 86.36 percent, and the catalyst has excellent light stability, high recycling property and better economic benefit.
In order to further evaluate the practical application potential of Ni-pHOF in real uranium-containing radioactive wastewater, the Ni-pHOF photocatalyst prepared in example 1 was used for photocatalytic treatment of uranium-containing radioactive wastewater of certain uranium ores in southwest China. The result shows that the high concentration SO in the real uranium-containing radioactive wastewater 4 2‒ In the presence of (1483.20 mg/L), after visible light irradiation for 120min, the removal rate of U (VI) in the real uranium-containing radioactive wastewater can reach 86.74%, and the excellent practical application potential of the Ni-pHOF photocatalyst is shown.
The foregoing is merely a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification and substitution based on the technical scheme and the inventive concept provided by the present invention should be covered in the scope of the present invention.
Claims (10)
1. The preparation method of the porous nickel porphyrin-based hydrogen bond organic framework material is characterized by comprising the following steps of:
step 1: preparation of 5,10,15, 20-tetra (4-cyanophenyl) porphyrin;
under the nitrogen atmosphere, adding 1 part by mass of 4-cyanobenzaldehyde into 20-80 parts by volume of propionic acid, and stirring; heating and refluxing for 2-6 hours under the light-shielding condition, and adding pyrrole with the volume ratio of 1:50-100 with propionic acid while keeping the reflux; then cooling to room temperature, adding methanol with the volume ratio of 1:0.8-1.5 to propionic acid, stirring, standing for 12-24 hours at the temperature of 5-8 ℃, filtering, washing, and vacuum drying to obtain 5,10,15, 20-tetra (4-cyanophenyl) porphyrin;
step 2: preparation of 5,10,15, 20-tetrakis (4- (2, 4-diaminotriazine) phenyl) porphyrin;
adding 2 parts by mass of 5,10,15, 20-tetra (4-cyanophenyl) porphyrin prepared in the step 1, 1 part by mass of dicyandiamide and 1 part by mass of potassium hydroxide into 20-80 parts by volume of anhydrous glycol monomethyl ether in a nitrogen atmosphere, stirring, heating and refluxing for 24-48 hours, evaporating to dryness under reduced pressure, washing and drying in vacuum to obtain 5,10,15, 20-tetra (4- (2, 4-diaminotriazine) phenyl) porphyrin;
step 3: preparing Ni/DAT-porphyrin;
heating and refluxing 5,10,15, 20-tetra (4- (2, 4-diaminotriazine) phenyl) porphyrin and nickel dichloride prepared in the step 2 with the mass ratio of 1:1-5 in 80-120 parts by volume of N, N-dimethylformamide for 6-12 hours, washing, and vacuum drying to obtain Ni/DAT-porphyrin;
step 4: preparing a porous nickel porphyrin-based hydrogen bond organic framework material;
taking 1 part by mass of Ni/DAT-porphyrin prepared in the step 3 and 20-70 parts by volume of mixed solvent, placing the mixed solvent into a pressure-resistant pipe, performing ultrasonic treatment at room temperature for 10-30 min, sealing, heating to 100-180 ℃ and heating for 60-90 h; cooling to room temperature, filtering, washing and vacuum drying to obtain the porous nickel porphyrin-based hydrogen bond organic frame material; the mixed solvent comprises o-dichlorobenzene, n-butanol and acetic acid with the volume ratio of 3:0.1-1.5:0.01-0.15, wherein the concentration of the acetic acid is 4.5-7.5 mol/L.
2. The method for preparing the porous nickel porphyrin-based hydrogen bond organic framework material according to claim 1, wherein the heating reflux temperature is 100-180 ℃.
3. The method for preparing the porous nickel porphyrin-based hydrogen bond organic framework material according to claim 1, wherein the vacuum drying temperature is 60-90 ℃.
4. A porous nickel porphyrin-based hydrogen bond organic framework material prepared by the preparation method of any one of claims 1 to 3.
5. Use of the porous nickel porphyrin-based hydrogen bond organic framework material according to claim 4 in uranium-containing radioactive wastewater treatment.
6. The application of the porous nickel porphyrin-based hydrogen bond organic framework material in uranium-containing radioactive wastewater treatment according to claim 5, wherein the porous nickel porphyrin-based hydrogen bond organic framework material is added into the uranium-containing radioactive wastewater to perform photocatalytic reaction under light irradiation, so that photocatalytic reduction removal of hexavalent uranium in the uranium-containing radioactive wastewater is realized.
7. The use of the porous nickel porphyrin-based hydrogen bond organic framework material according to claim 6 in uranium-containing radioactive wastewater treatment, wherein the solid-to-liquid ratio of the porous nickel porphyrin-based hydrogen bond organic framework material to uranium-containing radioactive wastewater is 0.4g/L.
8. The use of a porous nickel porphyrin-based hydrogen bonding organic framework material according to claim 6 in the treatment of uranium-containing radioactive wastewater, wherein the pH of the uranium-containing radioactive wastewater is adjusted to 5.
9. The use of a porous nickel porphyrin-based hydrogen bonding organic framework material according to claim 6 in uranium-containing radioactive wastewater treatment, wherein the concentration of hexavalent uranium in the uranium-containing radioactive wastewater is adjusted to be 50mg/L.
10. The use of a porous nickel porphyrin-based hydrogen bonding organic framework material according to claim 6 in uranium-containing radioactive wastewater treatment, wherein methanol or ethanol is added to the uranium-containing radioactive wastewater as a hole scavenger.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410139080.2A CN117659432B (en) | 2024-02-01 | 2024-02-01 | Porous nickel porphyrin-based hydrogen bond organic framework material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410139080.2A CN117659432B (en) | 2024-02-01 | 2024-02-01 | Porous nickel porphyrin-based hydrogen bond organic framework material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117659432A CN117659432A (en) | 2024-03-08 |
| CN117659432B true CN117659432B (en) | 2024-04-02 |
Family
ID=90073522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410139080.2A Active CN117659432B (en) | 2024-02-01 | 2024-02-01 | Porous nickel porphyrin-based hydrogen bond organic framework material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117659432B (en) |
Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001089490A (en) * | 1999-09-16 | 2001-04-03 | Japan Science & Technology Corp | Compound having 2 to 4 porphyrins doubly bonded (condensed) by each meso-beta carbon/carbon |
| CN1935897A (en) * | 2002-09-09 | 2007-03-28 | 索尼株式会社 | Resin composition |
| CN103254426A (en) * | 2013-04-25 | 2013-08-21 | 中国石油大学(华东) | Novel porphyrin polymer and synthetic method thereof |
| CN106824108A (en) * | 2017-01-23 | 2017-06-13 | 四川大学 | A kind of preparation method of the functionalization hydro-thermal carbon material for for uranium in solution separate |
| CN110102300A (en) * | 2019-06-05 | 2019-08-09 | 中北大学 | Monatomic catalyst of a kind of flexibility carbon-based supports carried metal and its preparation method and application |
| CN111514937A (en) * | 2020-05-13 | 2020-08-11 | 中国石油大学(华东) | Preparation method of porphyrin-based metal organic framework material sensitized oxide catalyst |
| CN112121854A (en) * | 2020-09-29 | 2020-12-25 | 江南大学 | Self-assembled tetra (4-carboxyphenyl) porphyrin/oxygen-doped carbon nitride nanosheet heterojunction photocatalyst and preparation method and application thereof |
| KR20210019720A (en) * | 2019-08-13 | 2021-02-23 | 울산과학기술원 | Metal-organic framework as metamaterial and its manufacturing method |
| CN112473745A (en) * | 2020-11-27 | 2021-03-12 | 复旦大学 | Mesoporous metal organic framework multi-center catalyst and preparation method and application thereof |
| EP3871768A1 (en) * | 2020-02-27 | 2021-09-01 | Technische Universität Berlin | Semiconductive and proton-conductive porous hydrogen-bonded frameworks |
| CN113717382A (en) * | 2021-08-30 | 2021-11-30 | 浙江工业大学 | Porphyrin and pyrimidine-based high-density metallized covalent triazine polymer and preparation method and application thereof |
| CN115487866A (en) * | 2021-06-18 | 2022-12-20 | 浙江大学 | Covalent organic framework material coupled nano metal catalyst and preparation method thereof |
| WO2023282200A1 (en) * | 2021-07-06 | 2023-01-12 | 国立研究開発法人物質・材料研究機構 | Porphyrin metal complex and sensitive membrane material for chemical sensor |
| CN115894871A (en) * | 2022-11-01 | 2023-04-04 | 广东工业大学 | Metal porphyrin-based porous ionic polymer and preparation method and application thereof |
| CN116178448A (en) * | 2023-02-06 | 2023-05-30 | 苏州大学 | Porphyrin-based coordination molecular cage and preparation method and application thereof |
| CN116496461A (en) * | 2023-05-06 | 2023-07-28 | 北京市农林科学院 | Covalent organic framework material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112111070B (en) * | 2020-10-20 | 2022-02-25 | 苏州大学 | Metal coordination porphyrin-based conjugated polymer, preparation method thereof and application thereof in photocatalytic degradation of organic pollutants |
-
2024
- 2024-02-01 CN CN202410139080.2A patent/CN117659432B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001089490A (en) * | 1999-09-16 | 2001-04-03 | Japan Science & Technology Corp | Compound having 2 to 4 porphyrins doubly bonded (condensed) by each meso-beta carbon/carbon |
| CN1935897A (en) * | 2002-09-09 | 2007-03-28 | 索尼株式会社 | Resin composition |
| CN103254426A (en) * | 2013-04-25 | 2013-08-21 | 中国石油大学(华东) | Novel porphyrin polymer and synthetic method thereof |
| CN106824108A (en) * | 2017-01-23 | 2017-06-13 | 四川大学 | A kind of preparation method of the functionalization hydro-thermal carbon material for for uranium in solution separate |
| CN110102300A (en) * | 2019-06-05 | 2019-08-09 | 中北大学 | Monatomic catalyst of a kind of flexibility carbon-based supports carried metal and its preparation method and application |
| KR20210019720A (en) * | 2019-08-13 | 2021-02-23 | 울산과학기술원 | Metal-organic framework as metamaterial and its manufacturing method |
| EP3871768A1 (en) * | 2020-02-27 | 2021-09-01 | Technische Universität Berlin | Semiconductive and proton-conductive porous hydrogen-bonded frameworks |
| CN111514937A (en) * | 2020-05-13 | 2020-08-11 | 中国石油大学(华东) | Preparation method of porphyrin-based metal organic framework material sensitized oxide catalyst |
| CN112121854A (en) * | 2020-09-29 | 2020-12-25 | 江南大学 | Self-assembled tetra (4-carboxyphenyl) porphyrin/oxygen-doped carbon nitride nanosheet heterojunction photocatalyst and preparation method and application thereof |
| CN112473745A (en) * | 2020-11-27 | 2021-03-12 | 复旦大学 | Mesoporous metal organic framework multi-center catalyst and preparation method and application thereof |
| CN115487866A (en) * | 2021-06-18 | 2022-12-20 | 浙江大学 | Covalent organic framework material coupled nano metal catalyst and preparation method thereof |
| WO2023282200A1 (en) * | 2021-07-06 | 2023-01-12 | 国立研究開発法人物質・材料研究機構 | Porphyrin metal complex and sensitive membrane material for chemical sensor |
| CN113717382A (en) * | 2021-08-30 | 2021-11-30 | 浙江工业大学 | Porphyrin and pyrimidine-based high-density metallized covalent triazine polymer and preparation method and application thereof |
| CN115894871A (en) * | 2022-11-01 | 2023-04-04 | 广东工业大学 | Metal porphyrin-based porous ionic polymer and preparation method and application thereof |
| CN116178448A (en) * | 2023-02-06 | 2023-05-30 | 苏州大学 | Porphyrin-based coordination molecular cage and preparation method and application thereof |
| CN116496461A (en) * | 2023-05-06 | 2023-07-28 | 北京市农林科学院 | Covalent organic framework material and preparation method and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| "Porphyrin-based hydrogen-bonded organic framework for visible light driven photocatalytic removal of U(VI) from real low-level radioactive wastewater";Wu, Peng 等;《JOURNAL OF HAZARDOUS MATERIALS》;20231005;第459卷;132179 * |
| "Synthesis, crystal structure and photocatalytic property of a porphyrin-based coordination polymer";Jiang Wei，等;《INORGANIC AND NANO-METAL CHEMISTRY》;20210903;第51卷(第8期);1029-1035 * |
| "功能性氢键有机框架设计组装的研究进展";王小娟，等;《安徽工业大学学报（自然科学版）》;20221031;第39卷(第4期);391-402 * |
| "拓展卟啉与镍、锌配位行为及其发光性质的量化研究";龙威，等;《首都师范大学学报(自然科学版)》;20170831;第38卷(第4期);45-53 * |
| "铀(Ⅵ)在卟啉基MOF上的吸附行为";孙艳兵，等;《材料导报》;20200525;第34卷(第10期);10108-10113 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117659432A (en) | 2024-03-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN104525266B (en) | Preparation method of metal-organic framework material photocatalyst and application | |
| CN113275041B (en) | Preparation of COF-316/CAT-1 composite material and photocatalytic carbon dioxide reduction | |
| CN108479777B (en) | Preparation method and application of attapulgite composite photocatalyst | |
| CN111715300B (en) | Zinc ferrite/Bi-MOF/tannic acid composite visible light catalyst | |
| Chen et al. | The synthesis of a novel conjugated microporous polymer and application on photocatalytic removal of uranium (Ⅵ) from wastewater under visible light | |
| CN113045723A (en) | Preparation method of porous covalent organic framework and application of porous covalent organic framework in capture of uranyl ions | |
| CN111013608A (en) | Metallic nickel modified sulfur indium zinc photocatalyst and preparation method and application thereof | |
| CN108892783B (en) | Visible light driven hydrogen production metal-organic framework material based on eosin and preparation method thereof | |
| Wu et al. | Porphyrin-based hydrogen-bonded organic framework for visible light driven photocatalytic removal of U (VI) from real low-level radioactive wastewater | |
| CN105921153B (en) | A kind of composite photo-catalyst and preparation method thereof | |
| Chen et al. | Constructing redox-active 3D covalent organic frameworks with high-affinity hexameric binding sites for enhanced uranium capture | |
| CN117659432B (en) | Porous nickel porphyrin-based hydrogen bond organic framework material and preparation method and application thereof | |
| CN103739035B (en) | A kind of Rapid microwave treatment method of waste water from dyestuff | |
| CN108906125A (en) | Three dish alkene polymer DTP/ zinc-cadmium sulfide Cd of one kind0.5Zn0.5The preparation method of S composite photo-catalyst | |
| CN111234295B (en) | Molecularly imprinted photocatalytic material and preparation method and application thereof | |
| CN112642456A (en) | Preparation method of composite photocatalyst | |
| CN109865528B (en) | Semiconductor photocatalyst material and processing technology thereof | |
| CN103011287A (en) | Preparation for pyro-vanadic acid zinc hollow microsphere and application thereof | |
| CN114367312B (en) | Ag + -Ag 0 Graphite-phase-doped carbon nitride coupled cobalt oxime molecule composite photocatalyst and preparation method and application thereof | |
| CN112174964B (en) | Cationic non-porous macrocyclic organic compound and preparation method and application thereof | |
| CN109759071A (en) | A kind of preparation method of cerium dopping magnetic composite nano material | |
| CN104874401A (en) | Preparation and application of Nd3-xCoxTaO7-zeolite composite porous nano-catalyst material | |
| CN108722491A (en) | A kind of Ta/W mixed matching polyacid organic-inorganic hybrids and preparation method thereof with visible light catalysis activity | |
| CN109939740B (en) | Preparation method and application of gold nanoparticle-loaded two-dimensional nanosheet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |