CN111617806A - g-C with sodium citrate as matrix3N4MOFs composite photocatalytic material and preparation method and application thereof - Google Patents
g-C with sodium citrate as matrix3N4MOFs composite photocatalytic material and preparation method and application thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 title claims abstract description 44
- 239000001509 sodium citrate Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 66
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- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 54
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 39
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- -1 rare earth ions Chemical class 0.000 abstract description 14
- 239000013110 organic ligand Substances 0.000 abstract description 6
- 229920000877 Melamine resin Polymers 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000010900 secondary nucleation Methods 0.000 abstract description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 abstract 1
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 abstract 1
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 34
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 18
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- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 5
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- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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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
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- C—CHEMISTRY; METALLURGY
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- 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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- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/36—Yttrium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to g-C with sodium citrate as a matrix3N4MOFs composite photocatalytic material and preparation method and application thereof. Calcining melamine to obtain g-C3N4(ii) a Dissolving trimesic acid in a DMF solution; erbium nitrate, thulium nitrate, yttrium nitrate and prepared g-C3N4Adding into sodium citrate solution; mixing the two solutions, placing the mixture in a hydrothermal kettle for hydrothermal reaction to obtain g-C3N4The MOFs composite photocatalytic material. The invention is madeThe prepared composite photocatalytic material utilizes carboxyl groups provided by sodium citrate, can coordinate with organic ligands and rare earth ions, and can inhibit the rapid growth and secondary nucleation of crystals at the initial stage of crystal growth, so that a sample has better size uniformity, dispersibility and crystal configuration integrity, and has better photocatalytic effect under visible light.
Description
Technical Field
The invention belongs to the field of material chemistry, and particularly relates to a method for preparing lanthanide series metal organic framework materials MOFs with complete crystal configuration and uniform size by using sodium citrate as a matrix, wherein g-C is directly introduced in the process3N4The nanometer powder adopts a one-step solvothermal method to realize MOFs material and g-C3N4To obtain g-C3N4The MOFs composite photocatalytic material solves the problems of poor crystal configuration integrity and uneven size of the composite photocatalytic material.
Background
At present, the degradation of pollutants in wastewater through various technologies is one of the major measures for treating the environment, wherein the photocatalytic degradation is a green technical means for converting solar energy into chemical energy to eliminate water pollution, and is widely concerned by the society, so that the development and research of novel and efficient photocatalytic materials become the targets of researchers.
Metal organic framework Materials (MOFs) are semiconductor materials with porous structures, and are more catalytic due to larger specific surface areaThe advantages of activating active center sites, large contact range with a target object and the like are different from those of the traditional organic semiconductor, and the organic semiconductor is widely applied to the field of photocatalysis. Pure MOFs material can be excited by light to generate electron-hole pairs, but the generated electron-hole pairs have higher recombination rate and poorer stability, so that the photocatalysis efficiency is lower, and the pure MOFs material is used as graphite-like phase carbon nitride (g-C) of a non-metal semiconductor3N4) The catalyst has good stability and high catalytic activity, and can be compounded with other materials by utilizing a proper position of a valence band, good light absorption efficiency and strong electron transfer capacity, so that various heterojunction compound catalysts are formed, and the photocatalytic efficiency can be effectively improved. Simultaneously, mixing g-C3N4The research of preparing the composite photocatalytic material by compounding the composite photocatalytic material with the rare earth MOFs material prepared by taking sodium citrate as a matrix is not reported yet.
Disclosure of Invention
The invention aims to provide a method for synthesizing lanthanide series metal organic framework materials MOFs (metal organic frameworks) by utilizing sodium citrate to provide carboxyl groups, and the synthesis method is used for synthesizing the MOFs with g-C3N4Are compounded to form g-C3N4The MOFs composite photocatalytic material has the characteristics of good crystal configuration, uniform size and higher photocatalytic efficiency.
The technical scheme adopted by the invention is as follows: g-C with sodium citrate as matrix3N4the/MOFs composite photocatalytic material takes sodium citrate as a matrix, and g-C is directly introduced in the process of preparing lanthanide series metal organic framework material MOFs3N4Compounding by a one-step solvothermal method to obtain g-C3N4a/MOFs composite photocatalytic material; according to the mass ratio of g to C3N4:MOFs＝(0.5-2):1。
Further, g-C with sodium citrate as matrix3N4a/MOFs composite photocatalytic material, according to the mass ratio, g-C3N4:MOFs＝1:1。
g-C with sodium citrate as matrix3N4The preparation method of the MOFs composite photocatalytic material comprises the following steps:
1) mixing sodium citrate and deionized water, adding Er (NO)3)3、Tm(NO3)3、Y(NO3)3And g-C3N4Performing ultrasonic treatment on the nano powder for 30-50 min; then dropwise adding a mixed solution of trimesic acid and N, N-dimethylformamide, and violently stirring for 30-45min to obtain a yellow-white liquid;
2) pouring the yellowish white liquid obtained in the step 1) into a hydrothermal kettle, sealing, carrying out hydrothermal reaction at 60 ℃ for 24 hours, slowly cooling to room temperature, and centrifuging the reaction liquid to obtain a solid sample;
3) washing the solid sample obtained in the step 2) with DMF, activating the obtained product with methanol for 24h, centrifuging the activated product again to obtain a solid sample, and drying the solid sample in a vacuum oven at the temperature of 80 ℃ to obtain g-C3N4The MOFs composite photocatalytic material.
Further, the above production process, the g-C3N4The preparation method of the nano powder comprises the following steps: putting melamine powder with a certain mass into a muffle furnace, heating and calcining at room temperature, heating at 5 ℃ per minute from room temperature to 550 ℃, keeping the temperature for 4 hours, cooling to room temperature, taking out a light yellow solid, and grinding to obtain g-C3N4And (4) nano powder.
Furthermore, the preparation method comprises the following steps of (1) and (0.6) respectively mixing sodium citrate and trimesic acid according to a molar ratio.
Furthermore, the preparation method comprises the step of mixing 1:1 by mol ratio of sodium citrate and trimesic acid.
Further, the above preparation method, Er3+/Tm3+/Y3+The molar total amount of trimesic acid (1-3) is 1.
Further, the above preparation method, Er3+/Tm3+/Y3+The molar total amount of trimesic acid is 2: 1.
Further, in the above preparation method, step 3), the activation with methanol is performed for 24 hours, specifically, the obtained product is placed in methanol, and the methanol is replaced every 6 hours.
g-C with sodium citrate as matrix3N4The application of the MOFs composite photocatalytic material in photocatalytic degradation of organic pollutants in wastewater.
The invention has the beneficial effects that:
1) the invention uses sodium citrate as a substrate to participate in g-C3N4The preparation of the/MOFs composite photocatalytic material can provide a large number of carboxyl groups, the carboxyl groups are coordinated with trimesic acid ligands and rare earth ions, the rapid growth of individual crystals can be inhibited in the initial stage of crystal growth, and the secondary nucleation process of the crystals in a system can be inhibited, so that the g-C with good crystal configuration, uniform size and high photocatalytic efficiency is obtained3N4The MOFs composite photocatalytic material.
2) The invention makes use of g-C3N4The compound with MOFs material solves the problems of high recombination rate and poor stability of electron hole pairs. When g-C3N4g-C after forming a composite material with rare earth MOFs materials3N4The original appearance is broken up into small nano-block structures, and the small nano-block structures are attached to the rod-shaped MOFs, so that the specific surface area of the composite photocatalyst is increased, a heterojunction structure is formed, the separation of photon-generated carriers in the photocatalytic reaction process is facilitated, and the photocatalytic efficiency is improved.
3) The invention adopts a one-step solvothermal method to directly introduce g-C in the process of preparing lanthanide series metal organic framework material3N4The powder has the characteristics of simple process and low cost, and the used equipment is simple, the operation is simple and convenient, and the preparation flow is greatly simplified.
Drawings
FIG. 1 is an SEM photograph of a sample prepared in example 1;
wherein, a: MOFs, b: g-C3N4C and d: g-C3N4The MOFs composite photocatalytic material.
FIG. 2 is an XRD pattern of MOFs materials prepared with different qualities of sodium citrate in example 2;
wherein, a: juc-32MOF standard card; b: 0.5 mmol; c: 0.4 mmol; d: 0.3 mmol.
FIG. 3 is an SEM image of MOFs materials prepared from different qualities of sodium citrate in example 2;
wherein, a: 0.3mmol of sodium citrate; b: 0.4mmol of sodium citrate; c and d: 0.5mmol of sodium citrate.
FIG. 4 shows the sample (Er) in example 33+/Tm3+/Y3+Molar total amount of trimesic acid 2:1) nitrogen adsorption-desorption isotherms and pore size profiles.
FIG. 5 shows g-C in example 43N4MOFs and g-C3N4XRD diffraction pattern of the/MOFs composite photocatalytic material.
FIG. 6 is g-C under visible light in example 43N4Ultraviolet-visible absorption spectrum of catalytic degradation RhB.
FIG. 7 shows g-C under visible light in example 43N4UV-visible absorption spectrum diagram of catalytic degradation of RhB by MOFs-2.
FIG. 8 is a graph of the effect of different photocatalysts on RhB degradation in visible light for 80min in example 4.
FIG. 9 shows g-C in example 43N4A graph of the effect of five-cycle photocatalytic degradation of RhB by using a MOFs-2 sample.
Detailed Description
Example 1
g-C with sodium citrate as matrix3N4MOFs composite photocatalytic material
The preparation method comprises
1) Putting melamine solid powder with a certain mass into a semi-closed corundum crucible with the capacity of 50mL, heating and calcining in a low-temperature muffle furnace, heating the temperature to 5 ℃ per minute from room temperature until the temperature reaches 550 ℃, then preserving the temperature for 4 hours, naturally cooling the temperature to room temperature, taking out a light yellow solid, and grinding the light yellow solid to obtain light yellow g-C with amorphous nano particles3N4And (4) nano powder.
2) 0.14705g (0.5mmol) of sodium citrate dihydrate were weighed out and mixed with 10mL of deionized waterAfter homogenization, 6mL of Er (NO) with a concentration of 0.01mol/L was added in sequence3)3Solution, 2mL Tm (NO) at a concentration of 0.01mol/L3)3Solution, 4.6mL of Y (NO) at a concentration of 0.2mol/L3)3Solution and 0.28g of g-C3N4Mixing the nanometer powder, stirring, and ultrasonic treating for 30min (in mass ratio g-C)3N4MOFs is 1:1), and mixed liquor A is obtained.
0.10507g (0.5mmol) of organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution, and sonication was carried out for 30min, in this example Er3+/Tm3+/Y3+The total molar amount of trimesic acid is 2: 1.
Dropwise adding the mixed solution of the trimesic acid and the DMF into the obtained mixed solution A at the dropwise adding speed of 0.5mL/s, and violently stirring for 30min to obtain a yellow-white liquid.
3) Pouring the yellowish white liquid obtained in the step 2) into an 80mL hydrothermal kettle, sealing, and then putting into an oven at 60 ℃ for reaction for 24 hours. After the reaction is finished, after the oven is slowly cooled to the room temperature, the reaction kettle is taken out, and a solid sample is obtained through centrifugation.
4) The solid sample obtained by centrifugation in step 3) was washed repeatedly with DMF and the product was activated in 50mL of methanol for 24h (methanol was changed every 6 hours). Centrifuging the activated product again to obtain a solid sample, and drying the solid sample in a vacuum oven at 80 ℃ for 12h to obtain g-C3N4The MOFs composite photocatalytic material.
(II) comparative example
Preparing lanthanide series metal organic framework materials MOFs:
1) 0.14705g (0.5mmol) of sodium citrate dihydrate is weighed and mixed evenly with 10mL of deionized water, and 6mL of Er (NO) with the concentration of 0.01mol/L is added in turn3)3Solution, 2mL Tm (NO) at a concentration of 0.01mol/L3)3Solution and 4.6mL of Y (NO) at a concentration of 0.2mol/L3)3And uniformly stirring the solution, and carrying out ultrasonic treatment for 30min to obtain a mixed solution B.
0.10507g (0.5mmol) of organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution and sonicated for 30min, in this example the total molar amount of Er, Tm and Y, the molar amount of trimesic acid being 2: 1.
Dropwise adding the mixed solution of the trimesic acid and the DMF into the obtained mixed solution B at the dropwise adding speed of 0.5mL/s, and violently stirring for 30min to obtain a milky white liquid.
3) Pouring the milky white liquid obtained in the step 2) into an 80mL hydrothermal kettle, sealing, and then putting into an oven at 60 ℃ for reaction for 24 hours. After the reaction is finished, after the oven is slowly cooled to the room temperature, the reaction kettle is taken out, and a solid sample is obtained through centrifugation.
4) The solid sample obtained by centrifugation in step 3) was washed repeatedly with DMF and the product was activated in 50mL of methanol for 24h (methanol was changed every 6 hours). And centrifuging the activated product again to obtain a solid sample, and drying the obtained solid sample in a vacuum oven at 80 ℃ for 12h to obtain the lanthanide series metal organic framework materials MOFs.
(III) detection
FIG. 1 is a scanning electron microscope for observing MOFs (a), g-C3N4Powder (b) and g-C3N4The microscopic morphology and size of the/MOFs composite photocatalytic material (C and d), wherein (a) in FIG. 1 is the surface morphology of the pure rare earth MOFs material, and (b) in FIG. 1 is pure g-C3N4The (C) and (d) are prepared g-C3N4The surface appearance of the MOFs composite photocatalytic material under different magnification factors. As can be seen from FIG. 1, the pure rare earth MOFs material is a standard rod-like structure and is composed of a large number of spherical particles, and pure carbon, trinitrogen and tetranitrogen are layered structures formed by irregular blocky stacking.
As can be seen from FIG. 1, when g-C3N4g-C after being compounded with rare earth MOFs material to form composite material3N4The original appearance is broken up into small nano-bulk structures, and the small nano-bulk structures are attached with the rare earth MOFs materials with rod-like structures and pure g-C3N4Compared with the prior art, the composite photocatalyst g-C of the invention3N4The specific surface area of the/MOFs is greatly increased, more reactive active sites can be provided in the photocatalysis process, and meanwhile, the heterosis is formedThe structure of the proton junction is beneficial to the separation of photon-generated carriers in the process of photocatalytic reaction, and the photocatalytic efficiency is improved.
Example 2
Effect of sodium citrate addition on Crystal nucleation Properties
The preparation method comprises the following steps:
1) 0.08823g (0.3mmol), 0.11764g (0.4mmol) and 0.14705g (0.5mmol) of sodium citrate dihydrate are respectively weighed and evenly mixed with 10mL of deionized water, and 6mL of Er (NO) with the concentration of 0.01mol/L is added in turn3)3Solution, 2mL Tm (NO) at a concentration of 0.01mol/L3)3Solution, 4.6mL of Y (NO) at a concentration of 0.2mol/L3)3Stirring the solution evenly and carrying out ultrasonic treatment for 30min to obtain a mixed solution C0.3And a mixed solution C0.4And a mixed solution C0.5。
0.10507g (0.5mmol) of organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution and sonicated for 30 min.
Dropwise adding the mixed solution of the trimesic acid and the DMF into the obtained mixed solution C at the dropwise adding speed of 0.5mL/s0.3And a mixed solution C0.4And a mixed solution C0.5And vigorously stirring for 30min to obtain milky white liquid.
3) Pouring the milky white liquid obtained in the step 2) into an 80mL hydrothermal kettle, sealing, and then putting into an oven at 60 ℃ for reaction for 24 hours. After the reaction is finished, after the oven is slowly cooled to the room temperature, the reaction kettle is taken out, and a solid sample is obtained through centrifugation.
4) The solid sample obtained by centrifugation in step 3) was washed repeatedly with DMF and the product was activated in 50mL of methanol for 24h (methanol was changed every 6 hours). And centrifuging the activated product again to obtain a solid sample, and drying the obtained solid sample in a vacuum oven at 80 ℃ for 12h to respectively obtain the MOFs materials with different sodium citrate adding amounts.
(III) detection
FIG. 2 is an XRD pattern of MOFs materials prepared with different qualities of sodium citrate. Wherein, a is JUC-32MOF standard card, b is when the addition amount of sodium citrate is 0.5mmol, c is when the addition amount of sodium citrate is 0.4mmol, and d is when the addition amount of sodium citrate is 0.3 mmol. As can be seen from fig. 2, the phases exhibited by the MOFs materials become more and more distinct as the amount of sodium citrate increases, and the sample shows a pure phase when the amount of sodium citrate added is 0.5 mmol.
Fig. 3 is an SEM image of MOFs materials prepared with different qualities of sodium citrate. Wherein, a is 0.3mmol, b is 0.4mmol, c is 0.5mmol, and d is 0.5 mmol. As can be seen from FIG. 3, when the amount of sodium citrate is 0.3mmol, the crystal size is not uniform and clustering occurs; when the amount of the sodium citrate is increased to 0.5mmol, the crystal configuration of the MOFs material is complete, the size is uniform, and the dispersibility is good.
Therefore, the sodium citrate and the trimesic acid are 1:1 in the molar ratio.
Example 3
Influence of the proportion of the total doping amount of rare earth ions and trimesic acid on the specific surface area and the pore size distribution of the rare earth ions
The preparation method comprises the following steps:
1) putting melamine solid powder with a certain mass into a semi-closed corundum crucible with the capacity of 50mL, heating and calcining in a low-temperature muffle furnace, heating the temperature to 5 ℃ per minute from room temperature until the temperature reaches 550 ℃, then preserving the temperature for 4 hours, naturally cooling the temperature to room temperature, taking out a light yellow solid, and grinding the light yellow solid to obtain light yellow g-C with amorphous nano particles3N4And (3) powder.
2) 0.14705g (0.5mmol) of sodium citrate dihydrate are weighed out and mixed well with 10mL of deionized water. The total amount of rare earth ions doped affects the pore size and the BET specific surface area of the material, so three groups of samples with molar ratios of the total amount of rare earth ions to the amount of trimesic acid of 1:1, 2:1 and 3:1 were selected for the test in this example.
① Total molar amount of rare earth ions, i.e. the molar amount of trimesic acid is 1:1, namely 3mL of Er (NO) with concentration of 0.01mol/L is measured3)3Solution, 1mL Tm (NO) concentration of 0.01mol/L3)3Solution, 2.3mL of Y (NO) at a concentration of 0.2mol/L3)3A solution;
② total molar amount of rare earth ions trimesicThe molar weight of the acid is 2:1, namely 6mL of Er (NO) with the concentration of 0.01mol/L is measured3)3Solution, 2mL Tm (NO) at a concentration of 0.01mol/L3)3Solution, 4.6mL of Y (NO) at a concentration of 0.2mol/L3)3A solution;
③ Total molar amount of rare earth ions (3: 1 molar amount of trimesic acid), 9mL of Er (NO) with concentration of 0.01mol/L was measured3)3Solution, 3mL Tm (NO) at a concentration of 0.01mol/L3)3Solution, 6.9mL of Y (NO) at a concentration of 0.2mol/L3)3A solution;
three groups of rare earth solutions with different doping ratios and 0.28g of g-C3N4Adding the powder into sodium citrate solution, respectively, and performing ultrasonic treatment for 30min to obtain mixed solution D1:1And a mixed solution D2:1And a mixed solution D3:1。
0.10507g (0.5mmol) of organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution and sonicated for 30 min.
Respectively dropwise adding the mixed solution of the trimesic acid and the DMF into the mixed solution D at the dropwise adding speed of 0.5mL/s1:1And a mixed solution D2:1And a mixed solution D3:1And vigorously stirring for 30min to respectively obtain yellow-white liquids.
3) The obtained yellow-white liquid is poured into a 80mL hydrothermal kettle and sealed, and then the kettle is placed into a 60 ℃ oven for reaction for 24 hours. After the reaction, after the oven is slowly cooled to room temperature, the reaction kettle is taken out and centrifuged to obtain a solid sample.
4) The solid sample was washed repeatedly with DMF and the product was activated in 50mL of methanol for 24h (methanol was changed every 6 h). Centrifuging the activated product again to obtain a solid sample, and drying in a vacuum oven at 80 ℃ for 12h to obtain g-C with different doping ratios3N4/MOFs composite photocatalytic material, respectively marked as g-C3N4/MOFs-1:1、g-C3N4/MOFs-2:1、g-C3N4/MOFs-3:1。
(II) testing nitrogen adsorption-desorption isotherm and pore size distribution
To measureDetermining the influence of the total amount of the rare earth ions on the specific surface area of the composite material, performing nitrogen adsorption-desorption tests on samples with the molar ratios of 1:1, 2:1 and 3:1, and obtaining an adsorption-desorption isothermal curve (before measurement, degassing the samples at 200 ℃ for 12 hours). FIG. 4 shows the total molar amount of rare earth ions, 2:1 molar amount of trimesic acid, sample g-C3N4A nitrogen adsorption-desorption isotherm and a pore size distribution diagram of/MOFs-2: 1. As shown in FIG. 4, the sample is a class IV isothermal adsorption curve at 0 by comparison with the standard adsorption desorption isotherm<P/P0<There is a hysteresis loop of type H4 between 1, indicating that the sample has a porous structure.
g-C can be calculated by an adsorption-desorption isothermal curve3N4/MOFs-1:1、g-C3N4/MOFs-2:1、g-C3N4BET specific surface areas of 96.8m for/MOFs-3: 1, respectively2/g，112.7m2/g，115.3m2Each of which is greater than pure g-C3N4Specific surface area of 15.3m2And/g, the rare earth ions are mainly composed of micropores smaller than 2nm in Ln-MOFs, so that the doping of the rare earth ions has a certain regulation and control effect on the specific surface area of a sample, and finally when the molar total amount of the rare earth ions, namely the molar amount of trimesic acid is determined to be 2:1, the specific surface area is large and the utilization rate of the material is high.
Example 4
g-C3N4Influence of doping amount in composite photocatalytic material on photocatalytic performance
The preparation method comprises the following steps:
1) putting melamine solid powder with a certain mass into a semi-closed corundum crucible with the capacity of 50mL, heating and calcining in a low-temperature muffle furnace, heating the temperature to 5 ℃ per minute from room temperature until the temperature reaches 550 ℃, then preserving the temperature for 4 hours, naturally cooling the temperature to room temperature, taking out a light yellow solid, and grinding the light yellow solid to obtain light yellow g-C with amorphous nano particles3N4And (3) powder.
2) 0.14705g (0.5mmol) of sodium citrate dihydrate is weighed and mixed evenly with 10mL of deionized water, and 6mL of Er (NO) with the concentration of 0.01mol/L is added in turn3)3Solution, 2mL Tm (NO) at a concentration of 0.01mol/L3)3Solution, 4.6mL of Y (NO) at a concentration of 0.2mol/L3)3The solution was then added with 0.14g, 0.28g, 0.56g of g-C3N4Powder, evenly stirred and ultrasonically treated for 30min (according to the mass ratio g-C)3N4MOFs 0.5:1, 1:1 and 2:1) to obtain mixed liquor E0.5:1And mixed solution E1:1And mixed solution E2:1
0.10507g (0.5mmol) of organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution and sonicated for 30min, in this example the total molar amount of Y, Er and Tm was 2: 1.
Respectively dropwise adding the mixed solution of the trimesic acid and the DMF into the mixed solution E at the dropwise adding speed of 0.5mL/s0.5:1And mixed solution E1:1And mixed solution E2:1Stirring vigorously for 30min to obtain yellow-white liquids
3) The obtained yellow-white liquid is poured into a 80mL hydrothermal kettle and sealed, and then the kettle is placed into a 60 ℃ oven for reaction for 24 hours. After the reaction, after the oven is slowly cooled to room temperature, the reaction kettle is taken out and centrifuged to obtain a solid sample.
4) The solid sample was washed repeatedly with DMF and the product was activated in 50mL of methanol for 24h (methanol was changed every 6 h). Centrifuging the activated product again to obtain a solid sample, and drying in a vacuum oven at 80 ℃ for 12h to obtain g-C3N4g-C of different doping ratios3N4/MOFs composite photocatalytic material, respectively marked as g-C3N4/MOFs-1、g-C3N4/MOFs-2、g-C3N4/MOFs-3。
(II) detection
1) XRD detection:
for the analysis of the structure, composition and phase of the samples prepared in the experiment, g-C was measured3N4Lanthanide metal organic framework materials MOFs and three g-C3N4g-C of different doping ratios3N4/MOFs-1、g-C3N4/MOFs-2、g-C3N4the/MOFs-3 was subjected to XRD powder characterization as shown in FIG. 5. For pure g-C3N4In other words, two different diffraction peaks exist at different diffraction angles, such as two characteristic diffraction peaks of 13.07 degrees 2 theta and 27.54 degrees 2 theta in an XRD spectrum, which correspond to g-C respectively3N4The (100) crystal plane and the (002) crystal plane of (A).
When g-C3N4When the amount of doped (B) is small, g-C3N4XRD patterns of/MOFs g-C could not be clearly observed3N4May be g-C3N4The composite photocatalytic material is less doped, has weaker peak intensities at 27.54 degrees and 13.07 degrees, is covered by relevant diffraction peaks of MOFs (metal organic frameworks) serving as lanthanide series metal organic framework materials, and has higher refractive index along with g-C3N4The g-C can be seen by increasing the doping amount in the composite photocatalytic material3N4The MOFs samples gradually exhibited g-C3N4The characteristic diffraction peak at 27.54 degrees of 2 theta of the (002) crystal face is gradually enhanced, which indicates that the rare earth MOFs contains g-C3N4。
2) And (3) detecting the photocatalytic performance:
visible light with the wavelength of more than 420nm is used as a light source, a 300w xenon lamp is used as the light source, the current is 20A, dye rhodamine B (RhB) is selected as a pollutant, and g-C is subjected to liquid phase degradation experiment3N4Testing the performance of the MOFs composite photocatalytic material, wherein the concentration of RhB is 10mg/L, 0.05g of the composite photocatalyst is respectively added into a 100mL beaker, 50mL of rhodamine B solution to be degraded is then added, and finally the rhodamine B solution mixed with the photocatalytic material is stirred for 60min in a dark place, so that the catalyst and the dye are in full contact, errors caused by physical adsorption of the photocatalyst are reduced, and the stability of degradation reaction is improved. Sampling 3mL before illumination as an initial sample solution, sampling 3mL every 20min after illumination, taking four times, centrifuging the sample, taking out supernatant, measuring the concentration of the residual dye in the solution by using UV-3600, and evaluating the catalytic performance of the sample according to the absorbance of the solution.
FIG. 6 is a graph of g-C3N4Catalyst, FIG. 7 is a composite photocatalytic material g-C3N4The MOFs-2 is a catalyst, a spectrogram of the absorbance of pollutants sampled at different time intervals is shown in FIG. 7, under the irradiation of visible light, a characteristic absorption peak exists at 550nm in an RhB solution, the absorption intensity of the absorption peak gradually shifts left and decreases along with the lapse of irradiation time, the molecular structure of rhodamine B is damaged, the absorbance of the rhodamine B is reduced, and after the irradiation of the visible light for 60min, no obvious peak exists in the absorption spectrum.
To compare g-C3N4The photocatalytic activity of the composite photocatalyst samples prepared at different doping ratios is calculated through an experiment of degrading rhodamine B through photocatalysis to obtain the degradation efficiency of each catalyst, and the result is shown in FIG. 8. g-C3N4The degradation rate of the sample on RhB is 60%; g-C3N4The degradation rate of the MOFs-1 sample on RhB is 75%, g-C3N4The degradation rate of the MOFs-2 sample on RhB can reach 90 percent, and g-C3N4The degradation rate of the/MOFs-3 sample on RhB was 82%, from which it can be seen that g-C3N4The MOFs-2 sample has good visible light catalytic performance, and through comparison of degradation efficiency, g-C is found3N4The catalytic efficiency of the MOFs composite photocatalyst is higher than that of g-C3N4Has great improvement and enhancement.
3) And (3) detecting the photocatalytic stability:
the same photocatalyst g-C is repeatedly utilized by taking 10mg/L rhodamine B solution as a target pollutant3N4The stability of the photocatalysis is examined by the aid of/MOFs-2, 5 cycles are passed, and the experiment is recorded by taking 80min as a cycle period. As shown in FIG. 9, g-C after the fifth cycle experiment3N4The photocatalytic activity of the/MOFs-2 is reduced to some extent, but the photocatalytic activity can still reach 90% of the initial photocatalytic degradation efficiency, which indicates that the photocatalyst has higher stability in the photocatalytic degradation process.
Claims (10)
1. g-C with sodium citrate as matrix3N4The MOFs composite type photocatalytic material is characterized in that,sodium citrate is taken as a substrate, and g-C is directly introduced in the process of preparing lanthanide series metal organic framework materials MOFs3N4Compounding by one-step solvothermal method to obtain g-C3N4a/MOFs composite photocatalytic material; according to the mass ratio of g to C3N4:MOFs＝(0.5-2):1。
2. The sodium citrate-based g-C of claim 13N4the/MOFs composite photocatalytic material is characterized in that the g-C composite photocatalytic material is prepared by mixing the following components in percentage by mass3N4:MOFs＝1:1。
3. g-C with sodium citrate as matrix3N4The preparation method of the MOFs composite photocatalytic material is characterized by comprising the following steps of:
1) mixing sodium citrate and deionized water, adding Er (NO)3)3、Tm(NO3)3、Y(NO3)3And g-C3N4Performing ultrasonic treatment on the nano powder for 30-50 min; then dropwise adding a mixed solution of trimesic acid and N, N-dimethylformamide, and violently stirring for 30-45min to obtain a yellow-white liquid;
2) pouring the yellowish white liquid obtained in the step 1) into a hydrothermal kettle, sealing, carrying out hydrothermal reaction at 60 ℃ for 24 hours, slowly cooling to room temperature, and centrifuging the reaction liquid to obtain a solid sample;
3) washing the solid sample obtained in the step 2) with DMF, activating the obtained product with methanol for 24h, centrifuging the activated product again to obtain a solid sample, and drying the solid sample in a vacuum oven at the temperature of 80 ℃ to obtain g-C3N4The MOFs composite photocatalytic material.
4. The production method according to claim 3, characterized in that: the g to C3N4The preparation method of the nano powder comprises the following steps: putting melamine powder with a certain mass into a muffle furnace, heating and calcining at room temperature, heating to 5 ℃ per minute from room temperature to 550 ℃, preserving heat for 4 hours, and coolingCooling to room temperature, taking out the light yellow solid, and grinding to obtain g-C3N4And (4) nano powder.
5. The production method according to claim 3, characterized in that: sodium citrate, trimesic acid (0.6-1) and 1 according to the mol ratio.
6. The method of claim 5, wherein: according to the molar ratio, the ratio of sodium citrate to trimesic acid is 1: 1.
7. The production method according to claim 3, characterized in that: er3+/Tm3+/Y3+The molar total amount of trimesic acid (1-3) is 1.
8. The method of claim 7, wherein: er3+/Tm3+/Y3+The molar total amount of trimesic acid is 2: 1.
9. The production method according to claim 3, characterized in that: in the step 3), the activation is carried out for 24 hours by using methanol, specifically, the obtained product is placed in methanol, and the methanol is replaced every 6 hours.
10. The sodium citrate-based g-C of claim 13N4The application of the MOFs composite photocatalytic material in photocatalytic degradation of organic pollutants in wastewater.
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