CN111408413B - Modified carbon nitride/Fe-based MOF composite material and preparation method and application thereof - Google Patents
Modified carbon nitride/Fe-based MOF composite material and preparation method and application thereof Download PDFInfo
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 42
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 230000001699 photocatalysis Effects 0.000 claims abstract description 30
- GPNNOCMCNFXRAO-UHFFFAOYSA-N 2-aminoterephthalic acid Chemical compound NC1=CC(C(O)=O)=CC=C1C(O)=O GPNNOCMCNFXRAO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 238000007146 photocatalysis Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- CSNFMBGHUOSBFU-UHFFFAOYSA-N pyrimidine-2,4,5-triamine Chemical compound NC1=NC=C(N)C(N)=N1 CSNFMBGHUOSBFU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000227 grinding Methods 0.000 claims abstract description 3
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- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 9
- 239000002351 wastewater Substances 0.000 claims description 8
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 69
- 239000013206 MIL-53 Substances 0.000 description 58
- 239000011651 chromium Substances 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000006722 reduction reaction Methods 0.000 description 17
- 230000009467 reduction Effects 0.000 description 16
- 239000012621 metal-organic framework Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
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- 238000001816 cooling Methods 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000005576 amination reaction Methods 0.000 description 6
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
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- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
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- 239000002245 particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
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- 239000010453 quartz Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DFGKGUXTPFWHIX-UHFFFAOYSA-N 6-[2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]acetyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)C1=CC2=C(NC(O2)=O)C=C1 DFGKGUXTPFWHIX-UHFFFAOYSA-N 0.000 description 1
- 239000013179 MIL-101(Fe) Substances 0.000 description 1
- 239000013132 MOF-5 Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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Abstract
The invention discloses a modified carbon nitride/Fe-based MOF composite material, a preparation method thereof and application thereof in the field of photocatalysis, wherein the preparation method comprises the following steps: (1) uniformly mixing melamine and triaminopyrimidine according to a molar ratio of 1: 2-4, roasting at 450-550 ℃ in an inert atmosphere, grinding the obtained product, adding the ground product into dimethyl sulfoxide, ultrasonically stripping for 1-3 hours, centrifuging with distilled water, washing, and drying to obtain modified carbon nitride powder; (2) dispersing the modified carbon nitride powder obtained in the step (1) in N, N-dimethylformamide to form a dispersion solution, adding the dispersion solution into an N, N-dimethylformamide solution containing ferric chloride, terephthalic acid and amino terephthalic acid, uniformly mixing, and carrying out solvothermal reaction at 140-160 ℃ for 14-16 h to obtain the modified carbon nitride/Fe-based MOF composite material.
Description
Technical Field
The invention relates to the technical field of visible light catalysis, in particular to a modified carbon nitride/Fe-based MOF composite material and a preparation method and application thereof.
Background
Taking heavy metal chromium as an example, industries such as tanning, electroplating and the like generate a large amount of chromium-containing Cr (VI) organic wastewater every year, and the formed composite pollution is difficult to treat and the toxicity is enhanced. Therefore, how to effectively remove Cr (VI) in the water body is an urgent problem to be solved.
The conventional chemical reduction method requires stepwise treatment and produces a large amount of chromium-containing sludge. The photocatalysis is a clean environment-friendly technology, and can generate electron hole pairs under illumination, has oxidation-reduction property and can process Cr (VI) containing compounds in one step. However, much research on TiO is currently underway 2 The semiconductor catalysts still have some defects, such as small specific surface area, high band gap, poor photoresponse capability and the like, and the development of novel and efficient visible-light catalysts is urgently needed.
Metal-organic frameworks (MOFs) are a class of crystalline porous materials with a periodic network structure formed by the interconnection of inorganic metal centers (metal ions or metal clusters) and bridging organic ligands through self-assembly. The MOFs material has the advantages of large specific surface area and extremely high porosity, has great potential in the fields of sensing, adsorption, medicaments and the like and is widely concerned by people, and simultaneously, the MOFs is a material with catalytic property. MOFs, MOF-5, the first material to be synthesized in the laboratory since 1999, developed very rapidly, and thousands of MOFs have been reported.
In recent years, MOFs show good application prospects in the field of photocatalysis, particularly Fe-MOFs taking iron ions as metal centers, such as MIL-53(Fe), MIL-101(Fe), MIL-88(Fe) and the like, and the common point of the MOFs catalysts is that organic carboxylic acid groups are introduced into inorganic metal centers to form MOFs materials with stable properties, large specific surface areas and multi-hollow three-dimensional space structures. Because the MOFs material has diversity in structure and composition and strong adjustability, the structure of the MOFs can be designed and modified according to actual requirements.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a preparation method of a modified carbon nitride/Fe-based MOF composite material, which adopts a pre-functionalization method to modify carbon nitride (marked as g-C) 3 N 4 -M) as modifying substance, a novel modified carbon nitride/Fe-based MOF composite material (noted as g-C) is prepared 3 N 4 -M/NH 2 MIL-53(Fe) -X%), can be used as a photocatalyst and can be used for visible light catalytic reduction of Cr (VI). The performance test shows that a very small amount of modified carbon nitride g-C is added 3 N 4 NH of-M 2 The reduction efficiency of MIL-53(Fe) -X% under visible light to Cr (VI) is obviously better than that of the traditional g-C 3 N 4 Is composed ofComposite material g-C 3 N 4 /NH 2 -MIL-53(Fe) -X% and NH Only 2 -MIL-53(Fe) -X% and single g-C 3 N 4 -M, denotes g-C 3 N 4 -M and NH 2 There is a strong synergy between MIL-53(Fe) -X%.
A preparation method of a modified carbon nitride/Fe-based MOF composite material comprises the following steps:
(1) uniformly mixing melamine and triaminopyrimidine according to the molar ratio of 1: 2-4, roasting at 450-550 ℃ under an inert atmosphere, grinding the obtained product, adding the ground product into dimethyl sulfoxide (DMSO), ultrasonically stripping for 1-3 hours, centrifuging with distilled water, washing, and drying to obtain modified carbon nitride powder;
(2) dispersing the modified carbon nitride powder obtained in the step (1) in N, N-Dimethylformamide (DMF) to form a dispersion liquid, adding the dispersion liquid into an N, N-dimethylformamide solution containing ferric chloride, terephthalic acid and amino terephthalic acid, uniformly mixing, and carrying out solvothermal reaction at 140-160 ℃ for 14-16 h to obtain the modified carbon nitride/Fe-based MOF composite material.
The preparation process has simple process and mild reaction conditions, and the obtained composite material is g-C 3 N 4 -M/NH 2 -MIL-53(Fe) -X%, useful as a photocatalyst. Firstly, the invention prepares heterojunction type NH by amino terephthalic acid and terephthalic acid mixed ligand 2 MIL-53/MIL-53 (i.e., NH) 2 MIL-53(Fe) -X%, X% representing the amination fraction), it was found that amination of MIL-53 significantly affects the cycling stability of the material, and the fraction of amination also affects the change in photocatalytic activity. Then on the basis of the optimization, the invention prepares p-type semiconductor modified carbon nitride g-C 3 N 4 -M (Normal g-C) 3 N 4 Is an n-type semiconductor), further studies have found g-C 3 N 4 -M Fe-based MOF NH functionalized with conduction and valence bands and amino moieties 2 The conduction band and the valence band of MIL-53(Fe) -X% are matched, and a p-n type heterojunction can be formed, so that the synergistic effect of the two in photocatalysis can be further exerted, and the efficiency of photocatalytic reduction of Cr (VI) can be effectively improved. The composite material prepared by the invention has high photocatalytic activityConvenient preparation, low cost, easy recovery and the like.
The inert atmosphere is N 2 Rare gases, and the like.
Preferably, in the step (1), the roasting time is 1-3 h.
Preferably, in the step (2), the molar ratio of the ferric chloride to the terephthalic acid to the aminoterephthalic acid is 2:0.5 to 1.5, and the ratio of the molar amount of the ferric chloride to the sum of the molar amounts of the terephthalic acid and the aminoterephthalic acid is 1: 1.
Preferably, in the step (2), the ratio of the modified carbon nitride powder to the ferric chloride in the dispersion liquid is 0.5-2 mg:2 mmol. NH (NH) 2 After the-MIL-53 (Fe) -X% is compounded with a very small amount of modified carbon nitride, the photocatalytic performance can be remarkably improved.
The invention also provides the modified carbon nitride/Fe-based MOF composite material prepared by the preparation method, which can be used as a photocatalyst.
The invention also provides application of the modified carbon nitride/Fe-based MOF composite material in the field of photocatalysis. For example, the modified carbon nitride/Fe-based MOF composite material can be used as a photocatalyst or used for preparing the photocatalyst.
The invention also provides a treatment method of wastewater containing Cr (VI), which comprises the following steps: adding the modified carbon nitride/Fe-based MOF composite material into the wastewater containing Cr (VI), carrying out visible light irradiation after adsorption balance of dark reaction, and carrying out photocatalytic degradation.
Preferably, before dark reaction adsorption, ammonium oxalate is added into the Cr (VI) -containing wastewater, and the adding amount is 20-40 mg/L.
Compared with the prior art, the invention has the main advantages that: the synthesis method provided by the invention has the advantages of simple and feasible process and mild conditions, and is relatively suitable for large-scale production. The resulting composite g-C 3 N 4 -M/NH 2 MIL-53(Fe) can be used as photocatalyst. Different from the common g-C 3 N 4 g-C prepared according to the invention 3 N 4 M is a p-type semiconductor, due to its Fe group MOF NH with functionalized conduction band and valence band and amino moiety 2 The conduction band and the valence band of MIL-53(Fe) -X% are matched, a p-n type heterojunction can be formed, the synergistic effect of the two in photocatalysis is fully exerted, and therefore the efficiency of photocatalytic reduction of Cr (VI) can be effectively improved. The composite material prepared by the invention has the advantages of high photocatalytic activity, convenient synthesis, low cost, easy recovery and the like.
Drawings
FIG. 1 is a graph of NH prepared from starting amino terephthalic acid and terephthalic acid at different ratios in example 1 2 Comparison of MIL-53(Fe) -X% photocatalytic reduction Cr (VI) performance;
FIG. 2 shows the starting g-C in example 3 3 N 4 -M added volume of stripping solution to g-C 3 N 4 -M/NH 2 -MIL-53(Fe) -50% photocatalytic performance impact diagram;
FIG. 3 is a comparison of the performance of the different types of catalysts in example 4 for the photocatalytic reduction of Cr (VI), where (1) g-C 3 N 4 ，(2)g-C 3 N 4 -M，(3)MIL-53(Fe)，(4)NH 2 -MIL-53(Fe)，(5)NH 2 -MIL-53(Fe)-50％，(6)g-C 3 N 4 /NH 2 -MIL-53(Fe)-50％-1.5mL，(7)g-C 3 N 4 -M/NH 2 -MIL-53(Fe)-50％-1.5mL；
FIG. 4 shows the optimized preparation of g-C in example 5 3 N 4 -M/NH 2 -MIL-53(Fe) -50% -1.5mL of cyclic stability chart for treating chromium-containing wastewater.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
NH containing various proportions of amino terephthalic acid ligands 2 -MIL-53(Fe) -X% preparation
1)NH 2 MIL-53(Fe) -100% (i.e., NH) 2 Preparation of MIL-53(Fe))
First, 2mmol of FeCl 3 ·6H 2 Dissolving O and 2mmol of amino terephthalic acid in 40mL of N, N-dimethylformamide, magnetically stirring for 60min, transferring to a hydrothermal kettle, heating at 150 ℃ for 15h, naturally cooling to room temperature, centrifuging at 8000rpm for 5min, washing with DMF and methanol twice, and vacuum drying at 100 ℃ for 12h to obtain NH 2 -MIL-53(Fe)-100％。
2)NH 2 Preparation of-MIL-53 (Fe) -75%
First, 2mmol FeCl 3 ·6H 2 Dissolving O, 1.5mmol of amino terephthalic acid and 0.5mmol of terephthalic acid in 40mL of N, N-dimethylformamide, magnetically stirring for 60min, transferring to a hydrothermal kettle, heating at 150 ℃ for 15h, naturally cooling to room temperature, centrifuging at 8000rpm for 5min, washing with DMF and methanol twice, and vacuum drying at 100 ℃ for 12h to obtain NH 2 -MIL-53(Fe)-75％。
3)NH 2 Preparation of-MIL-53 (Fe) -50%
First, 2mmol of FeCl 3 ·6H 2 Dissolving O, 1mmol of amino terephthalic acid and 1mmol of terephthalic acid in 40mL of N, N-dimethylformamide, magnetically stirring for 60min, transferring to a hydrothermal kettle, heating at 150 ℃ for 15h, naturally cooling to room temperature, centrifuging at 8000rpm for 5min, washing with DMF and methanol twice, and vacuum drying at 100 ℃ for 12h to obtain NH 2 -MIL-53(Fe)-50％。
4)NH 2 Preparation of-MIL-53 (Fe) -25%
First, 2mmol of FeCl 3 ·6H 2 Dissolving O, 0.5mmol of amino terephthalic acid and 1.5mmol of terephthalic acid in 40mL of N, N-dimethylformamide, magnetically stirring for 60min, transferring to a hydrothermal kettle, heating at 150 ℃ for 15h, naturally cooling to room temperature, centrifuging at 8000rpm for 5min, washing with DMF and methanol twice, and vacuum drying at 100 ℃ for 12h to obtain NH 2 -MIL-53(Fe)-25％。
5)NH 2 Preparation of-MIL-53 (Fe) -0% (i.e. MIL-53(Fe))
First, 2mmol FeCl 3 ·6H 2 Dissolving O and 2mmol of terephthalic acid in 40mL of N, N-dimethylformamide, magnetically stirring for 60min, transferring to a hydrothermal kettle, heating at 150 ℃ for 15h, naturally cooling to room temperature, centrifuging at 8000rpm for 5min, washing with DMF and methanol twice, and vacuum drying at 100 ℃ for 12h to obtain NH 2 -MIL-53(Fe)-0％
6) Photocatalytic reduction Cr (VI) performance test
Taking 10mg of NH containing amino terephthalic acid ligands with different proportions 2 MIL-53(Fe) -X%, adding into a potassium dichromate solution (100mL) with Cr (VI) concentration of 80 mu mol/L, adding 3mg of ammonium oxalate as a coexisting organic matter and hole trapping agent, adjusting the pH to 4.7, carrying out a dark reaction for 30 minutes under the condition of magnetic stirring, turning on a xenon lamp light source, and carrying out a photocatalytic reaction under the action of visible light. After 20 minutes of irradiation with visible light, sampling and centrifugation were carried out, and the absorbance at 540nm of the supernatant was measured by a color development method, and the reduction ratio of Cr (VI) was calculated by comparing the absorbance before and after the reaction, and the results are shown in FIG. 1.
As can be seen from FIG. 1, NH of different amination ratios were compared 2 Ability of MIL-53(Fe) -X% for photocatalytic reduction of Cr (VI) with starting aminoterephthalic acid and terephthalic acid in a molar ratio of 1:1 to obtain NH 2 MIL-53(Fe) -50% exhibited the best photocatalytic performance. The photocatalytic performance of MIL-53(Fe) after complete amination is not as good as that of partial amination, and the NH prepared in situ by the method is shown 2 And a synergistic effect exists between MIL-53(Fe) and MIL-53(Fe), so that the photocatalytic performance is promoted to be improved.
In addition, in the experimental process, it is found that under the condition of adding ammonium oxalate, the MIL-53(Fe) without amino is poor in stability, easy to dissolve and incapable of being effectively separated and recovered, and the NH with amino is 2 The MIL-53(Fe) and the compound thereof have good stability and can be recycled and used stably.
Example 2
g-C 3 N 4 Preparation of the-M Dispersion (stripping liquid)
1)g-C 3 N 4 Preparation of (E) -M
Weighing the MelamineUniformly mixing amine and triaminopyrimidine in a molar ratio of 1:3, flatly paving on a quartz boat, heating in a tubular furnace in a nitrogen atmosphere at a heating rate of 5 ℃/min to 500 ℃, maintaining for 120min, and finally cooling to room temperature under nitrogen purging to obtain powdery g-C 3 N 4 -M, ground to powder, sonicated in pure DMSO for 120min to exfoliate g-C 3 N 4 M particles, collected after being centrifuged five times with distilled water at 8000rpm in a centrifuge and dried at 60 ℃ for 12 hours in a vacuum drying oven.
2)g-C 3 N 4 Preparation of the-M Dispersion
Weighing the good g-C prepared in the step 1) 3 N 4 50mg of the-M particles, which are added to DMF and sonicated for half an hour to give g-C at a concentration of 1mg/mL 3 N 4 -M dispersion.
Example 3
Preparation of multicomponent composite catalyst
1)g-C 3 N 4 -M/NH 2 Preparation of-MIL-53 (Fe) -50%
First, 2mmol FeCl 3 ·6H 2 O, 1mmol of aminoterephthalic acid and 1mmol of terephthalic acid were dissolved in 40mL of N-N-dimethylformamide, and g-C prepared in example 2 was added in different volumes (0.5mL, 1.0mL, 1.5mL, 2mL) 3 N 4 Magnetically stirring the-M dispersion liquid for 60min, transferring to a hydrothermal kettle, heating at 150 deg.C for 15h, naturally cooling to room temperature, centrifuging at 8000rpm for 5min, washing with DMF and methanol twice, and vacuum drying at 100 deg.C for 12h to obtain g-C 3 N 4 M g-C of different load ratios 3 N 4 -M/NH 2 -MIL-53(Fe)-50％。
2) Photocatalytic reduction Cr (VI) performance test
Taking 10mg g-C 3 N 4 M g-C of different load ratios 3 N 4 -M/NH 2 MIL-53(Fe) -50%, added to a potassium dichromate solution (100mL) of Cr (VI) concentration of 80. mu. mol/L, 3mg of ammonium oxalate was added as a coexisting organic substance/hole trap, the pH was adjusted to 4.7, and after a dark reaction for 30 minutes under magnetic stirring,and (3) turning on a xenon lamp light source, and carrying out photocatalytic reaction under the action of visible light. After the visible light irradiation for 20 minutes, sampling and centrifugal separation were carried out, and the absorbance at 540nm of the supernatant was measured by a color development method, and the reduction rate of Cr (VI) was calculated by comparing the absorbance before and after the reaction, and the results are shown in FIG. 2.
As can be seen from FIG. 2, comparison of g-C 3 N 4 The addition amount of the M dispersion to the photocatalytic reduction of Cr (VI) was 1.5mL of g-C 3 N 4 g-C prepared from-M stripping solution 3 N 4 -M/NH 2 MIL-53(Fe) -50% -1.5mL exhibited the best photocatalytic performance.
Example 4
Preparation of other control group catalysts
1)g-C 3 N 4 /NH 2 Preparation of-MIL-53 (Fe) -50% -1.5mL
First, 2mmol of FeCl 3 ·6H 2 O, 1mmol of aminoterephthalic acid and 1mmol of terephthalic acid were dissolved in 40mL of N-N-dimethylformamide, and 1.5mL of g-C was added 3 N 4 Stripping solution (preparation procedure was the same as that of g-C of example 2 except that triaminopyrimidine was not added 3 N 4 -M stripping solution), magnetically stirring for 60min, transferring to a hydrothermal kettle, heating at 150 deg.C for 15h, naturally cooling to room temperature, centrifuging at 8000rpm for 5min, washing with DMF and methanol twice, and vacuum drying at 100 deg.C for 12h to obtain g-C 3 N 4 /NH 2 -MIL-53(Fe)-50％。
2)g-C 3 N 4 Preparation of
Weighing melamine, spreading on a quartz boat, heating in a tube furnace at 5 deg.C/min under nitrogen atmosphere -1 Heating to 500 deg.C, maintaining for 120min, and cooling to room temperature under nitrogen purging to obtain powdery g-C 3 N 4 Ground into powder, and treated in ultrasonic bath in pure DMSO for 120min to strip g-C 3 N 4 The pellets were collected after being centrifuged five times with distilled water at 8000rpm in a centrifuge and dried at 60 ℃ for 12 hours in a vacuum oven.
3) Performance test of various catalysts for photocatalytic reduction of Cr (VI)
10mg of different catalysts are added into a potassium dichromate solution (100mL) with the concentration of Cr (VI) being 80 mu mol/L, 3mg of ammonium oxalate is added as a coexisting organic matter and hole trapping agent, the pH value is adjusted to be 4.7, a xenon lamp light source is turned on after dark reaction is carried out for 30 minutes under the condition of magnetic stirring, and the photocatalytic reaction is carried out under the action of visible light. After 20 minutes of irradiation with visible light, sampling and centrifugation were carried out, and the absorbance at 540nm of the supernatant was measured by a color development method, and the reduction ratio of Cr (VI) was calculated by comparing the absorbance before and after the reaction, and the results are shown in FIG. 3.
As can be seen from FIG. 3, in the case of photocatalytic reduction of Cr (VI), NH is added 2 MIL-53(Fe) -50% based on (starting aminoterephthalic acid to terephthalic acid molar ratio 1:1), in g-C 3 N 4 -M stripping liquid is additive (addition amount is 1.5mL), and the prepared multi-element composite catalyst g-C 3 N 4 -M/NH 2 MIL-53(Fe) -50% exhibited the best performance.
Invention g-C 3 N 4 The photocatalytic activity of-M is lower than that of ordinary g-C 3 N 4 And both have almost no photocatalytic activity, but when g-C is used in an extremely small amount 3 N 4 When the-M is compounded with the partially aminated MIL-53(Fe), the photocatalytic activity of the obtained composite material can be obviously improved and is obviously higher than that of the common g-C 3 N 4 And partially aminated MIL-53(Fe) to illustrate g-C 3 N 4 M forms a multi-element heterojunction with partially aminated MIL-53(Fe), and there is a strong synergy.
Example 5
Stability test for Recycling
To optimize the preparation of g-C 3 N 4 -M/NH 2 MIL-53(Fe) -50% as photocatalyst applied to photocatalytic reduction of Cr (VI), 5 cycles are carried out, the photocatalyst is centrifuged, washed with water and dried before each cycle, then is put into a new 80 mu mol/L Cr (VI) (100mL) solution again, 3mg of ammonium oxalate is added as coexisting organic matter and hole trapping agent, the pH is adjusted to 4.7, and the dark reaction is carried out for 30 minutes under the condition of magnetic stirringAfter the clock, the xenon lamp light source is turned on, and the photocatalytic reaction is carried out under the action of visible light. After the visible light irradiation is carried out for 20 minutes, sampling and centrifugal separation are carried out, the absorbance of the supernatant at 540nm is measured by a color development method, the reduction rate of Cr (VI) can be calculated by comparing the absorbance before and after the reaction, and the result is shown in figure 4, g-C 3 N 4 -M/NH 2 the-MIL-53 (Fe) -50% has better recycling stability, and the activity of the-MIL-53 (Fe) -50% is not obviously changed after 5 times of recycling, and is stabilized to be more than 90%.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (8)
1. A preparation method of a modified carbon nitride/Fe-based MOF composite material is characterized by comprising the following steps:
(1) uniformly mixing melamine and triaminopyrimidine according to a molar ratio of 1: 2-4, roasting at 450-550 ℃ in an inert atmosphere, grinding the obtained product, adding the ground product into dimethyl sulfoxide, ultrasonically stripping for 1-3 hours, centrifuging with distilled water, washing, and drying to obtain modified carbon nitride powder;
(2) dispersing the modified carbon nitride powder obtained in the step (1) in N, N-dimethylformamide to form a dispersion liquid, adding the dispersion liquid into an N, N-dimethylformamide solution containing ferric chloride, terephthalic acid and amino terephthalic acid, uniformly mixing, and carrying out solvothermal reaction at 140-160 ℃ for 14-16 h to obtain a modified carbon nitride/Fe-based MOF composite material;
the molar ratio of the ferric chloride to the terephthalic acid to the amino terephthalic acid is 2: 0.5-1.5.
2. The preparation method according to claim 1, wherein in the step (1), the roasting time is 1-3 h.
3. The process according to claim 1, wherein in the step (2), the ratio of the molar amount of ferric chloride to the sum of the molar amounts of terephthalic acid and aminoterephthalic acid is 1: 1.
4. The method according to claim 1 or 3, wherein in the step (2), the ratio of the modified carbon nitride powder to the ferric chloride in the dispersion liquid is 0.5-2 mg:2 mmol.
5. The modified carbon nitride/Fe-based MOF composite material prepared by the preparation method according to any one of claims 1 to 4.
6. Use of the modified carbon nitride/Fe-based MOF composite material according to claim 5 in the field of photocatalysis.
7. A method for treating wastewater containing Cr (VI) is characterized by comprising the following steps: adding the modified carbon nitride/Fe-based MOF composite material of claim 5 into the Cr (VI) -containing wastewater, and after dark reaction adsorption equilibrium, irradiating with visible light for photocatalytic degradation.
8. The treatment method according to claim 7, wherein before the adsorption of the dark reaction, ammonium oxalate is further added into the Cr (VI) -containing wastewater, and the addition amount is 20-40 mg/L.
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