CN111408413A - 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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- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000000463 material Substances 0.000 title claims abstract description 24
- 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 28
- 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 18
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 16
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 16
- 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
- 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
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 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 6
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 239000012298 atmosphere Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000004729 solvothermal method Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 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
- 239000007788 liquid Substances 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 69
- 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 18
- 230000009467 reduction Effects 0.000 description 17
- 239000013206 MIL-53 Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012621 metal-organic framework Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 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
- 238000003756 stirring Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013132 MOF-5 Substances 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
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
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- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 238000011065 in-situ storage Methods 0.000 description 1
- 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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- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
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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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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 both oxidation and reduction properties, and can process a Cr (VI) -containing compound in one step. However, much research on TiO is currently underway2The 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 meanwhile, the MOFs material 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 MI L-53 (Fe), MI L-101 (Fe), MI L-88 (Fe) and the like, 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 area and multi-cavity three-dimensional structures.
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)3N4-M) as modifying substance, a novel modified carbon nitride/Fe-based MOF composite material (noted as g-C) is prepared3N4-M/NH2MI L-53 (Fe) -X%), which can be used as photocatalyst for visible light catalytic reduction of Cr (VI) performance test shows that g-C with very little modified carbon nitride3N4NH of-M2The reduction efficiency of the-MI L-53 (Fe) -X% to Cr (VI) under visible light is obviously better than that of the traditional g-C3N4Constituting composite material g-C3N4/NH2-MI L-53 (Fe) -X% and NH Only2-MI L-53 (Fe) -X% and single g-C3N4-M, denotes g-C3N4-M and NH2There is a strong synergy between-MI L-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 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 (DMSO), ultrasonically stripping for 1-3 h, 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-C3N4-M/NH2-MIL-53(Fe) -X% can be used as photocatalyst. Firstly, the invention prepares heterojunction type NH by amino terephthalic acid and terephthalic acid mixed ligand2MI L-53/MI L-53 (i.e., NH)2MI L-53 (Fe) -X%, wherein X% represents amination proportion), the amination of MI L-53 is found to significantly influence the cycle stability of the material, and the amination proportion also influences the change of photocatalytic activity3N4-M (Normal g-C)3N4Is an n-type semiconductor), further studies have found g-C3N4-M Fe-based MOF NH functionalized with conduction and valence bands and amino moieties2The conduction band and the valence band of-MI L-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 inert atmosphere is N2Rare 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)2After the-MI L-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-C3N4-M/NH2MI L-53 (Fe) can be used as photocatalyst, unlike ordinary g-C3N4g-C prepared according to the invention3N4M is a p-type semiconductor, due to its Fe group MOF NH with functionalized conduction band and valence band and amino moiety2The conduction band and the valence band of-MI L-53 (Fe) -X% are matched, a p-n type heterojunction can be formed, and the synergistic effect of the two in photocatalysis is fully exerted, so that the efficiency of photocatalytic reduction of Cr (VI) can be effectively improved.
Drawings
FIG. 1 shows NH prepared from starting amino terephthalic acid and terephthalic acid in different ratios in example 12-MI L-53 (Fe) -X% photocatalytic reduction Cr (VI) performance comparison plot;
FIG. 2 shows the starting g-C in example 33N4-M added volume of stripping solution to g-C3N4-M/NH2-MI L-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-C3N4，(2)g-C3N4-M，(3)MIL-53(Fe)，(4)NH2-MIL-53(Fe)，(5)NH2-MIL-53(Fe)-50％，(6)g-C3N4/NH2-MIL-53(Fe)-50％-1.5mL，(7)g-C3N4-M/NH2-MIL-53(Fe)-50％-1.5mL；
FIG. 4 shows the optimized preparation of g-C in example 53N4-M/NH2-MI L-53 (Fe) -50% -1.5m L as a circular 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 ligands2-MI L-53 (Fe) -X% preparation
1)NH2-MI L-53 (Fe) -100% (i.e., NH)2Preparation of-MI L-53 (Fe))
First, 2mmol of FeCl3·6H2Dissolving O and 2mmol of amino terephthalic acid in 40m L N, N-dimethylformamide, 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 NH2-MIL-53(Fe)-100％。
2)NH2Preparation of-MI L-53 (Fe) -75%
First, 2mmol of FeCl3·6H2Dissolving O, 1.5mmol of amino terephthalic acid and 0.5mmol of terephthalic acid in 40m L N, N-dimethylformamide, 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 NH2-MIL-53(Fe)-75％。
3)NH2Preparation of-MI L-53 (Fe) -50%
First, 2mmol of FeCl3·6H2Dissolving O, 1mmol of aminoterephthalic acid and 1mmol of terephthalic acid in 40m L N, N-dimethylformamide, magnetically stirring for 60min, transferring to hydrothermal kettle, and heating at 150 deg.CHeating 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 NH2-MIL-53(Fe)-50％。
4)NH2Preparation of-MI L-53 (Fe) -25%
First, 2mmol of FeCl3·6H2Dissolving O, 0.5mmol of amino terephthalic acid and 1.5mmol of terephthalic acid in 40m L N, N-dimethylformamide, 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 NH2-MIL-53(Fe)-25％。
5)NH2Preparation of-MI L-53 (Fe) -0% (i.e. MI L-53 (Fe))
First, 2mmol of FeCl3·6H2Dissolving O and 2mmol of terephthalic acid in 40m L N, N-dimethylformamide, 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 NH2-MIL-53(Fe)-0％
6) Photocatalytic reduction Cr (VI) performance test
Taking 10mg of NH containing amino terephthalic acid ligands with different proportions2-MI L-53 (Fe) -X%, adding into a potassium dichromate solution (100m L) with Cr (VI) concentration of 80 μmol/L, adding 3mg ammonium oxalate as a coexisting organic matter and hole trapping agent, adjusting pH to 4.7, carrying out a dark reaction for 30 minutes under magnetic stirring, turning on a xenon lamp light source, and carrying out a photocatalytic reaction under visible light, irradiating with visible light for 20 minutes, then sampling, centrifuging, collecting the supernatant, measuring the absorbance at 540nm by a color development method, and calculating the reduction rate of Cr (VI) by comparing the absorbance before and after the reaction, wherein the result is shown in FIG. 1.
As can be seen from FIG. 1, NH of different amination ratios were compared2-MI L-53 (Fe) -X% Performance for photocatalytic reduction of Cr (VI), starting amino terephthalic acidNH prepared with terephthalic acid in a molar ratio of 1:12MI L-53 (Fe) -50% exhibited the best photocatalytic performance, the photocatalytic performance of MI L-53 (Fe) after total amination was not as good as that of partial amination, and it can be seen that NH prepared in situ by the method of the invention2the-MI L-53 (Fe) and the MI L-53 (Fe) have a synergistic effect, and the photocatalytic performance is promoted to be improved.
In addition, in the experimental process, the MI L-53 (Fe) without amino group is found to have poor stability, be easy to dissolve and be incapable of being effectively separated and recovered under the condition of adding ammonium oxalate, and the NH containing amino group2the-MI L-53 (Fe) and the compound thereof have good stability and can be recycled and used stably.
Example 2
g-C3N4Preparation of the-M Dispersion (stripping liquid)
1)g-C3N4Preparation of (E) -M
Weighing melamine and triaminopyrimidine, uniformly mixing the melamine and the triaminopyrimidine according to the molar ratio of 1:3, flatly paving the mixture on a quartz boat, heating the mixture in a tube furnace in the nitrogen atmosphere at the heating rate of 5 ℃/min to 500 ℃, maintaining the temperature for 120min, and finally cooling the mixture to room temperature under nitrogen purging to obtain powdery g-C3N4-M, ground to powder, sonicated in pure DMSO for 120min to exfoliate g-C3N4M particles, collected after centrifugation five times in a centrifuge with distilled water at 8000rpm and drying in a vacuum oven at 60 ℃ for 12 hours.
2)g-C3N4Preparation of the-M Dispersion
Weighing the good g-C prepared in the step 1)3N450mg of the-M particles, which after addition to DMF and sonication for half an hour gave g-C at a concentration of 1mg/M L3N4-M dispersion.
Example 3
Preparation of multicomponent composite catalyst
1)g-C3N4-M/NH2Preparation of-MI L-53 (Fe) -50%
First, 2mmol of FeCl3·6H2O, 1mmol of aminoterephthalic acid and 1mmol of terephthalic acid in 40m L N-N-dimethylformylTo the amine, different volumes (0.5m L, 1.0m L, 1.5m L, 2m L) of g-C prepared in example 2 were added3N4Magnetically 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-C3N4M g-C of different load ratios3N4-M/NH2-MIL-53(Fe)-50％。
2) Photocatalytic reduction Cr (VI) performance test
Taking 10mg g-C3N4M g-C of different load ratios3N4-M/NH2MI L-53 (Fe) -50%, adding into potassium dichromate solution (100m L) with Cr (VI) concentration of 80 μmol/L, adding 3mg ammonium oxalate as coexisting organic matter and hole trapping agent, adjusting pH to 4.7, under magnetic stirring, after dark reaction for 30 minutes, turning on xenon lamp light source, carrying out photocatalytic reaction under visible light action, after visible light irradiation for 20 minutes, sampling, centrifuging, taking supernatant, measuring absorbance at 540nm by using a color development method, and calculating the reduction rate of Cr (VI) by comparing absorbance before and after reaction, the result is shown in FIG. 2.
As can be seen from FIG. 2, comparison of g-C3N4The addition amount of the dispersion M to the photocatalytic reduction of Cr (VI) was 1.5M, L g-C3N4g-C prepared from-M stripping solution3N4-M/NH2MI L-53 (Fe) -50% -1.5m L exhibited the best photocatalytic performance.
Example 4
Preparation of other control group catalysts
1)g-C3N4/NH2Preparation of-MI L-53 (Fe) -50% -1.5m L
First, 2mmol of FeCl3·6H2O, 1mmol of aminoterephthalic acid and 1mmol of terephthalic acid are dissolved in 40m L N-N-dimethylformamide and 1.5m L g-C3N4Stripping solution (preparation procedure was the same as that of g-C of example 2 except that triaminopyrimidine was not added3N4-M stripper), magnetic stirring 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-C3N4/NH2-MIL-53(Fe)-50％。
2)g-C3N4Preparation of
Weighing melamine, spreading on a quartz boat, heating in a tube furnace at 5 deg.C/min under nitrogen atmosphere-1Heating to 500 deg.C, maintaining for 120min, and cooling to room temperature under nitrogen purging to obtain powdery g-C3N4Ground into powder, and treated in ultrasonic bath in pure DMSO for 120min to strip g-C3N4The 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 were added to a potassium dichromate solution (100m L) containing Cr (VI) at a concentration of 80. mu. mol/L, 3mg of ammonium oxalate was added as a coexisting organic substance/hole trapping agent, pH was adjusted to 4.7, and after a dark reaction for 30 minutes under magnetic stirring, a xenon lamp light source was turned on to carry out a photocatalytic reaction under visible light, and after 20 minutes of irradiation with visible light, sampling and centrifugal separation were carried out, and the supernatant was taken and the absorbance at 540nm 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 added2MI L-53 (Fe) -50% based (starting amino terephthalic acid to terephthalic acid molar ratio 1:1), in g-C3N4-M stripping liquid as additive (addition amount of 1.5M L), and prepared multi-component composite catalyst g-C3N4-M/NH2MI L-53 (Fe) -50% exhibited the best performance.
Invention g-C3N4The photocatalytic activity of-M is lower than that of ordinary g-C3N4And both have almost no photocatalytic activity, but when g-C is used in an extremely small amount3N4When the-M is compounded with the partially aminated MI L-53 (Fe), the photocatalytic activity of the obtained composite material can be obviously improved and is obviously higher than that of the common g-C3N4And partially aminated MI L-53 (Fe) indicating g-C3N4M forms a multi-element heterojunction with partially aminated MI L-53 (Fe), and there is a strong synergy.
Example 5
Stability test for Recycling
To optimize the preparation of g-C3N4-M/NH2-MI L-53 (Fe) -50% is a 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 put into a new 80 mu mol/L Cr (VI) (100m L) solution again, 3mg of ammonium oxalate is added as a coexisting organic matter and hole trapping agent, the pH is adjusted to 4.7, a xenon lamp light source is turned on after dark reaction for 30 minutes under the magnetic stirring condition, photocatalytic reaction is carried out under the action of visible light, after visible light irradiation for 20 minutes, sampling and centrifugal separation are carried out, the supernatant is taken and the absorbance at 540nm is measured by a color method, and the reduction rate of Cr (VI) can be calculated by comparing the absorbance before and after reaction, and the result is shown in figure 4, g-C3N4-M/NH2the-MI L-53 (Fe) -50% has better recycling stability, and the activity of the compound 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 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.
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 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.
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 added into the Cr (VI) -containing wastewater, and the addition amount is 20-40 mg/L.
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