CN111617806B - g-C with sodium citrate as matrix 3 N 4 MOFs composite photocatalytic material and preparation method and application thereof - Google Patents
g-C with sodium citrate as matrix 3 N 4 MOFs composite photocatalytic material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 64
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 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 38
- 239000001509 sodium citrate Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011159 matrix material Substances 0.000 title claims abstract description 13
- 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 64
- 239000013110 organic ligand Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 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
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 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 claims description 19
- 229940043267 rhodamine b Drugs 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 229960000999 sodium citrate dihydrate Drugs 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 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 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000002957 persistent organic pollutant Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 2
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 21
- 239000013078 crystal Substances 0.000 abstract description 16
- -1 rare earth ions Chemical class 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 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 38
- 239000000047 product Substances 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 239000013241 lanthanide-based metal–organic framework Substances 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 150000002910 rare earth metals Chemical class 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000007146 photocatalysis Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 239000011858 nanopowder Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000004729 solvothermal method Methods 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
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- 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
-
- 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
-
- 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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- B01J35/39—
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- B01J35/613—
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- B01J35/615—
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- B01J35/643—
-
- 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
-
- 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
-
- 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
- B01J2531/38—Lanthanides other than lanthanum
-
- 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
-
- 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 a g-C with sodium citrate as a matrix 3 N 4 MOFs composite photocatalytic material and preparation method and application thereof. Calcining melamine to obtain g-C 3 N 4 The method comprises the steps of carrying out a first treatment on the surface of the Dissolving trimesic acid in DMF solution; erbium nitrate, thulium nitrate, yttrium nitrate and prepared g-C 3 N 4 Adding into sodium citrate solution; mixing the two solutions, and placing the mixture in a hydrothermal kettle for hydrothermal reaction to obtain g-C 3 N 4 MOFs composite photocatalytic material. The composite photocatalytic material prepared by the invention can coordinate with organic ligands and rare earth ions by utilizing carboxyl groups provided by sodium citrate, and can inhibit the rapid growth and secondary nucleation process of crystals at the initial stage of crystal growth, so that a sample has good size uniformity, dispersibility and crystal configuration integrity, and has good photocatalytic effect under visible light.
Description
Technical Field
The invention belongs to the field of material chemistry, in particular to a method for preparing lanthanide metal organic framework material MOFs with complete crystal configuration and uniform size by using sodium citrate as a matrix, and directly introducing g-C in the process 3 N 4 Nanometer powder, MOFs material and g-C are realized by adopting a one-step solvothermal method 3 N 4 Is compounded to obtain g-C 3 N 4 The MOFs composite photocatalytic material solves the problems of poor structural integrity and uneven size of the composite photocatalytic material crystal.
Background
At present, degradation of pollutants in wastewater through various technologies is one of the great measures for environmental treatment, wherein photocatalytic degradation is taken as a green technical means for converting solar energy into chemical energy to eliminate water pollution, and is widely focused by society, so that development and research on novel high-efficiency photocatalytic materials are the targets of researchers.
The metal organic framework Materials (MOFs) are widely applied to the field of photocatalysis as a semiconductor material with a porous structure, because of the advantages of larger specific surface area, more catalytic active center sites, larger contact range with a target object and the like, unlike the traditional organic semiconductors. Pure MOFs materials can be photoexcited to generate electron-hole pairs, but the generated electron-hole pairs have higher recombination rate and poorer stability, resulting in lower photocatalytic efficiency, while graphite-like carbon nitride (g-C 3 N 4 ) The catalyst has good stability and high catalytic activity, and can be compounded with other materials by utilizing the proper conduction valence band position, good light absorption efficiency and strong electron transfer capability, so that various heterojunction composite catalysts are formed, and the photocatalytic efficiency can be effectively improved. At the same time, g-C 3 N 4 And sodium citrate as matrixThe research on preparing the composite photocatalytic material by compounding the prepared rare earth MOFs material is not reported yet.
Disclosure of Invention
The invention aims to provide a method for synthesizing lanthanide metal organic framework material MOFs by using sodium citrate to provide carboxyl groups and combining the MOFs with g-C 3 N 4 Compounding to form g-C 3 N 4 The 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 matrix 3 N 4 The composite photocatalytic material of MOFs is prepared with sodium citrate as matrix and through direct introduction of g-C during preparing organic skeleton material MOFs of lanthanide series 3 N 4 Compounding by one-step solvothermal method to obtain g-C 3 N 4 MOFs composite photocatalytic material; according to mass ratio, g-C 3 N 4 :MOFs＝(0.5-2):1。
Further, the sodium citrate is g-C as the matrix 3 N 4 MOFs composite photocatalytic material, g-C according to mass ratio 3 N 4 :MOFs＝1:1。
g-C with sodium citrate as matrix 3 N 4 The 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(NO 3 ) 3 、Y(NO 3 ) 3 And g-C 3 N 4 Performing ultrasonic treatment on the nano powder for 30-50min; then dropwise adding a mixed solution of trimesic acid and N, N-dimethylformamide, and vigorously stirring for 30-45min to obtain a yellow-white liquid;
2) Pouring the yellow-white liquid obtained in the step 1) into a hydrothermal kettle, sealing, performing 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 24 hours, and separating the activated product againThe solid sample obtained from the core is put into a vacuum oven at 80 ℃ for drying to obtain g-C 3 N 4 MOFs composite photocatalytic material.
Further, according to the preparation method, the g-C 3 N 4 The preparation method of the nano powder comprises the following steps: placing melamine powder with certain mass into a muffle furnace, heating and calcining at room temperature, heating to 5 ℃ per minute from room temperature until 550 ℃ and preserving heat for 4 hours, cooling to room temperature, taking out light yellow solid, grinding to obtain g-C 3 N 4 A nano powder.
Further, according to the preparation method, the molar ratio of sodium citrate to trimesic acid= (0.6-1) is 1.
Further, according to the preparation method, the molar ratio of sodium citrate to trimesic acid=1:1.
Further, the preparation method, er, comprises the steps of 3+ /Tm 3+ /Y 3+ Molar amount of trimesic acid = (1-3): 1.
Further, the preparation method, er, comprises the steps of 3+ /Tm 3+ /Y 3+ Molar amount of trimesic acid = 2:1.
Further, in the above preparation method, in 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 matrix 3 N 4 Application of MOFs composite photocatalytic material in photocatalytic degradation of organic pollutants in wastewater.
The beneficial effects of the invention are as follows:
1) The invention takes sodium citrate as a matrix to participate in g-C 3 N 4 The preparation of the MOFs composite type photocatalysis material can provide a large amount of carboxyl groups, coordinate with trimesic acid ligand and rare earth ions, inhibit the rapid growth of individual crystals at the initial stage of crystal growth and inhibit the secondary nucleation process of the crystals in a system, thereby obtaining g-C with good crystal configuration, uniform size and higher photocatalysis efficiency 3 N 4 MOFs composite photocatalytic material.
2) The invention utilizes g-C 3 N 4 The composite material is compounded with MOFs material, so that the problems of high electron-hole pair recombination rate and poor stability are solved. When g-C 3 N 4 g-C after forming composite material with rare earth MOFs material 3 N 4 The original morphology is scattered into a small nano block structure and is adhered to MOFs material with a rod-shaped structure, so that the specific surface area of the composite photocatalyst is increased, a heterojunction structure is formed, separation of photo-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 metal organic framework material 3 N 4 The 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 process is greatly simplified.
Drawings
FIG. 1 is an SEM image of a sample prepared in example 1;
wherein a: MOFs, b: g-C 3 N 4 C and d: g-C 3 N 4 MOFs composite photocatalytic material.
FIG. 2 is an XRD pattern of MOFs materials prepared from different amounts of sodium citrate in example 2;
wherein a: JUC-32MOF standard card; b:0.5mmol; c:0.4mmol; d:0.3mmol.
FIG. 3 is an SEM image of MOFs prepared from different amounts of sodium citrate in example 2;
wherein a: sodium citrate 0.3mmol; b: sodium citrate 0.4mmol; c and d: sodium citrate 0.5mmol.
FIG. 4 is a sample (Er) of example 3 3+ /Tm 3+ /Y 3+ Molar amount of trimesic acid = 2:1) of the pore size distribution map.
FIG. 5 is g-C of example 4 3 N 4 MOFs and g-C 3 N 4 XRD diffraction pattern of MOFs composite photocatalytic material.
FIG. 6 is g-C under visible light in example 4 3 N 4 Ultraviolet-visible absorption spectrum of catalytic degradation RhB.
FIG. 7 is g-C under visible light in example 4 3 N 4 Ultraviolet-visible absorption spectrum of the catalytic degradation RhB of MOFs-2.
FIG. 8 is a graph showing the degradation effect of different photocatalysts in example 4 on RhB under visible light for 80 min.
FIG. 9 is g-C of example 4 3 N 4 Effect graph of five cycles of photocatalytic degradation of RhB for MOFs-2 samples.
Detailed Description
Example 1
g-C with sodium citrate as matrix 3 N 4 MOFs composite photocatalytic material
The preparation method (one) is as follows
1) Placing melamine solid powder with a certain mass into a semi-closed corundum crucible with a capacity of 50mL, heating and calcining in a low-temperature muffle furnace, heating to 5 ℃ per minute from room temperature until 550 ℃, preserving heat for 4 hours, naturally cooling to room temperature, taking out light yellow solid, and grinding to obtain light yellow g-C with amorphous nano particles 3 N 4 A nano powder.
2) 0.14705g (0.5 mmol) of sodium citrate dihydrate and 10mL of deionized water are weighed and mixed uniformly, and 6mL of Er (NO) with the concentration of 0.01mol/L are added in sequence 3 ) 3 Solution, 2mL Tm (NO) with concentration of 0.01mol/L 3 ) 3 Solution, 4.6mL of Y (NO) at a concentration of 0.2mol/L 3 ) 3 Solution and 0.28g of g-C 3 N 4 The nano powder is stirred uniformly and treated by ultrasonic for 30min (according to the mass ratio g-C 3 N 4 Mofs=1:1) to obtain a mixed solution a.
0.10507g (0.5 mmol) of the organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution and sonicated for 30min, er in this example 3+ /Tm 3+ /Y 3+ Molar amount of trimesic acid = 2:1.
The mixed solution of the trimesic acid and the DMF is dropwise added into the obtained mixed solution A according to the dropping speed of 0.5mL/s, and the mixed solution A is vigorously stirred for 30min, so that the yellowish white liquid is obtained.
3) The yellow-white liquid obtained in the step 2) is poured into an 80mL hydrothermal kettle and sealed, and then is put into a 60 ℃ oven for reaction for 24 hours. And after the reaction is finished, taking out the reaction kettle after the baking oven is slowly cooled to room temperature, and centrifuging to obtain a solid sample.
4) The solid sample obtained by centrifugation in step 3) was repeatedly washed with DMF and the resulting product was activated in 50mL of methanol for 24h (methanol was replaced every 6 hours). Centrifuging the activated product again to obtain a solid sample, and drying the obtained solid sample in a vacuum oven at 80 ℃ for 12 hours to obtain g-C 3 N 4 MOFs composite photocatalytic material.
(II) comparative example
Preparation of lanthanide metal organic frameworks MOFs:
1) 0.14705g (0.5 mmol) of sodium citrate dihydrate and 10mL of deionized water are weighed and mixed uniformly, and 6mL of Er (NO) with the concentration of 0.01mol/L are added in sequence 3 ) 3 Solution, 2mL Tm (NO) with concentration of 0.01mol/L 3 ) 3 Solution and 4.6mL of Y (NO) at a concentration of 0.2mol/L 3 ) 3 Stirring the solution uniformly and carrying out ultrasonic treatment for 30min to obtain a mixed solution B.
0.10507g (0.5 mmol) of the organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution and sonicated for 30min, the total molar amount of Er and Tm and Y in this example: molar amount of trimesic acid = 2:1.
The mixed solution of trimesic acid and DMF was added dropwise to the obtained mixed solution B at a dropping rate of 0.5mL/s, and stirred vigorously for 30min to give a milky white liquid.
3) The milky white liquid obtained in step 2) was poured into an 80mL hydrothermal kettle and sealed, and then placed into an oven at 60 ℃ for reaction for 24 hours. And after the reaction is finished, taking out the reaction kettle after the baking oven is slowly cooled to room temperature, and centrifuging to obtain a solid sample.
4) The solid sample obtained by centrifugation in step 3) was repeatedly washed with DMF and the resulting product was activated in 50mL of methanol for 24h (methanol was replaced every 6 hours). And centrifuging the activated product again to obtain a solid sample, and putting the obtained solid sample into a vacuum oven at 80 ℃ to dry for 12 hours to obtain the lanthanide metal organic framework material MOFs.
(III) detection
FIG. 1 shows the observation of MOFs (a) and g-C by a scanning electron microscope 3 N 4 Powders (b) and g-C 3 N 4 The micro-morphology and the size of the MOFs composite photocatalytic material (C and d) are shown as (a) in figure 1 being the surface morphology of the pure rare earth MOFs material and (b) in figure 1 being pure g-C 3 N 4 (C) and (d) are prepared g-C 3 N 4 Surface morphology of the MOFs composite photocatalytic material under different magnification factors. As can be seen from fig. 1, the pure rare earth MOFs material has a standard rod-like structure, and is formed by combining a large number of spherical particles, and the pure carbon triazas is a layered structure formed by stacking irregular blocks.
As can be seen from FIG. 1, when g-C 3 N 4 After being compounded with rare earth MOFs material to form composite material, g-C 3 N 4 The original shape is scattered into a small nano block structure, and the nano block structure is adhered to a rare earth MOFs material with a rod-shaped structure and is combined with pure g-C 3 N 4 In contrast, the composite photocatalyst g-C of the present invention 3 N 4 The specific surface area of the MOFs is greatly increased, more reactive sites can be provided in the photocatalysis process, a heterojunction structure is formed, separation of photo-generated carriers in the photocatalysis reaction process is facilitated, and the photocatalysis efficiency is improved.
Example 2
Effect of the amount of sodium citrate added on Crystal nucleation
The preparation method comprises the following steps:
1) 0.08823g (0.3 mmol), 0.11764g (0.4 mmol) and 0.14705g (0.5 mmol) of sodium citrate dihydrate are respectively weighed and uniformly mixed with 10mL of deionized water, and 6mL of Er (NO) with the concentration of 0.01mol/L are sequentially added 3 ) 3 Solution, 2mL Tm (NO) with concentration of 0.01mol/L 3 ) 3 Solution, 4.6mL of Y (NO) at a concentration of 0.2mol/L 3 ) 3 Stirring the solution uniformly and performing ultrasonic treatment for 30min to obtain a mixed solution C 0.3 MixingLiquid C 0.4 Mixed solution C 0.5 。
0.10507g (0.5 mmol) of the organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution and sonicated for 30min.
Dripping the mixed solution of the trimesic acid and the DMF into the obtained mixed solution C at a dripping speed of 0.5mL/s 0.3 Mixed solution C 0.4 Mixed solution C 0.5 And stirring vigorously for 30min to give milky liquid.
3) The milky white liquid obtained in step 2) was poured into an 80mL hydrothermal kettle and sealed, and then placed into an oven at 60 ℃ for reaction for 24 hours. And after the reaction is finished, taking out the reaction kettle after the baking oven is slowly cooled to room temperature, and centrifuging to obtain a solid sample.
4) The solid sample obtained by centrifugation in step 3) was repeatedly washed with DMF and the resulting product was activated in 50mL of methanol for 24h (methanol was replaced every 6 hours). And (3) centrifuging the activated product again to obtain a solid sample, and putting the obtained solid sample into a vacuum oven at 80 ℃ to dry for 12 hours to obtain MOFs materials with different sodium citrate addition amounts respectively.
(III) detection
Figure 2 is an XRD pattern of MOFs material prepared from different mass of sodium citrate. Wherein a is a 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 0.3mmol. As can be seen from fig. 2, the MOFs material exhibited more and more pronounced phases as the amount of sodium citrate increased, and the sample exhibited a pure phase when the amount of sodium citrate added was 0.5mmol.
Fig. 3 is an SEM image of MOFs material prepared from different amounts of sodium citrate. Wherein a is 0.3mmol, b is 0.4mmol, c is 0.5mmol, and d is 0.5mmol. As can be seen from fig. 3, when sodium citrate is 0.3mmol, the crystal size is not uniform and a cluster phenomenon occurs; when the amount of sodium citrate is increased to 0.5mmol, the MOFs material can be seen to have complete crystal configuration, uniform size and better dispersibility.
Therefore, the invention preferably comprises sodium citrate and trimesic acid in a molar ratio of 1:1.
Example 3
Influence of the ratio of the total amount of rare earth ion doping to the trimesic acid on the specific surface area and the pore size distribution
The preparation method comprises the following steps:
1) Placing melamine solid powder with a certain mass into a semi-closed corundum crucible with a capacity of 50mL, heating and calcining in a low-temperature muffle furnace, heating to 5 ℃ per minute from room temperature until 550 ℃, preserving heat for 4 hours, naturally cooling to room temperature, taking out light yellow solid, and grinding to obtain light yellow g-C with amorphous nano particles 3 N 4 And (3) powder.
2) 0.14705g (0.5 mmol) of sodium citrate dihydrate was weighed and mixed well with 10mL of deionized water. The total amount of rare earth ions doped affects the pore size and BET specific surface area of the material, so in this example, three groups of samples were selected for testing, each having a molar ratio of total rare earth ions to trimesic acid of 1:1,2:1, and 3:1.
(1) Total molar weight of rare earth ions molar weight of trimesic acid=1:1, i.e. 3mL of Er (NO) with concentration of 0.01mol/L is measured 3 ) 3 Solution, 1mL Tm (NO) with concentration of 0.01mol/L 3 ) 3 Solution, 2.3mL of Y (NO) at a concentration of 0.2mol/L 3 ) 3 A solution;
(2) total molar weight of rare earth ions molar weight of trimesic acid=2:1, i.e. 6mL of Er (NO) with concentration of 0.01mol/L is measured 3 ) 3 Solution, 2mL Tm (NO) with concentration of 0.01mol/L 3 ) 3 Solution, 4.6mL of Y (NO) at a concentration of 0.2mol/L 3 ) 3 A solution;
(3) total molar weight of rare earth ions molar weight of trimesic acid=3:1, i.e. 9mL of Er (NO) with concentration of 0.01mol/L is measured 3 ) 3 Solution, 3mL Tm (NO) with concentration of 0.01mol/L 3 ) 3 6.9mL of solution Y (NO) at a concentration of 0.2mol/L 3 ) 3 A solution;
three groups of rare earth solutions with different doping ratios and 0.28g of g-C 3 N 4 Respectively adding the powder into sodium citrate solution, and performing ultrasonic treatment for 30min to obtain mixed solution D 1:1 Mixed solution D 2:1 Mixed solution D 3:1 。
0.10507g (0.5 mmol) of the organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution and sonicated for 30min.
Dripping the mixed solution of the trimesic acid and the DMF into the mixed solution D according to the dripping speed of 0.5mL/s 1:1 Mixed solution D 2:1 Mixed solution D 3:1 And stirring vigorously for 30min to obtain yellow-white liquid respectively.
3) The resulting yellow-white liquids were poured into 80mL hydrothermal kettles and sealed, respectively, and then put into an oven at 60 ℃ for reaction for 24 hours. After the reaction, after the baking oven is slowly cooled to room temperature, the reaction kettle is taken out, and the solid sample is obtained by centrifugation.
4) The solid sample was repeatedly washed with DMF and the resulting product was taken up in 50mL of methanol for 24h (methanol was replaced every 6 hours). Centrifuging the activated product again to obtain a solid sample, and placing the solid sample into a vacuum oven at 80 ℃ to be dried for 12 hours to obtain g-C with different doping ratios respectively 3 N 4 MOFs composite photocatalytic material, respectively named g-C 3 N 4 /MOFs-1:1、g-C 3 N 4 /MOFs-2:1、g-C 3 N 4 /MOFs-3:1。
(II) Nitrogen adsorption-Desorption isotherm and pore size distribution test
To determine the effect of the total amount of rare earth ions on the specific surface area of the composite, nitrogen adsorption-desorption tests were performed on samples with a molar ratio of 1:1,2:1,3:1, and adsorption-desorption isotherms were obtained (samples were degassed at 200 ℃ for 12h prior to measurement). FIG. 4 is a sample g-C of the total molar amount of rare earth ions: molar amount of trimesic acid=2:1 3 N 4 Nitrogen adsorption-desorption isotherms and pore size distribution plots of/MOFs-2:1. As shown in FIG. 4, the sample is an isothermal adsorption curve of class IV, at 0, by comparison with a standard adsorption/desorption isothermal curve<P/P 0 <The presence of a hysteresis loop of H4 type between 1 indicates that the sample has a porous structure.
By adsorption-desorption isothermal curve, g-C can be calculated 3 N 4 /MOFs-1:1、g-C 3 N 4 /MOFs-2:1、g-C 3 N 4 BET specific surface areas of the MOFs-3:1 were 96.8m, respectively 2 /g，112.7m 2 /g，115.3m 2 Per gram, all greater than pure g-C 3 N 4 Is 15.3m 2 And/g, and mainly comprises micropores smaller than 2nm in Ln-MOFs, which shows that the doping of rare earth ions has a certain regulation and control effect on the specific surface area of a sample, and when the molar total amount of the rare earth ions is finally determined to be equal to the molar amount of trimesic acid=2:1, the rare earth ions have larger specific surface area and have higher utilization rate on materials.
Example 4
g-C 3 N 4 Influence of the amount of the additive in the composite photocatalytic material on the photocatalytic performance
The preparation method comprises the following steps:
1) Placing melamine solid powder with a certain mass into a semi-closed corundum crucible with a capacity of 50mL, heating and calcining in a low-temperature muffle furnace, heating to 5 ℃ per minute from room temperature until 550 ℃, preserving heat for 4 hours, naturally cooling to room temperature, taking out light yellow solid, and grinding to obtain light yellow g-C with amorphous nano particles 3 N 4 And (3) powder.
2) 0.14705g (0.5 mmol) of sodium citrate dihydrate and 10mL of deionized water are weighed and mixed uniformly, and 6mL of Er (NO) with the concentration of 0.01mol/L are added in sequence 3 ) 3 Solution, 2mL Tm (NO) with concentration of 0.01mol/L 3 ) 3 Solution, 4.6mL of Y (NO) at a concentration of 0.2mol/L 3 ) 3 The solution was then added with 0.14g,0.28g,0.56g of g-C, respectively 3 N 4 The powder was stirred uniformly and sonicated for 30min (in mass ratio g-C 3 N 4 Mofs=0.5:1, 1:1 and 2:1) to obtain mixed solution E 0.5:1 Mixed solution E 1:1 Mixed solution E 2:1
0.10507g (0.5 mmol) of the organic ligand trimesic acid was weighed out and dissolved in 40mL of N, N-Dimethylformamide (DMF) solution and sonicated for 30min, the total molar amount of Y and Er and Tm in this example being the molar amount of trimesic acid=2:1.
A mixed solution of trimesic acid and DMF was taken up in 0.5mLDrop-rate/s, drop-by-drop into the mixture E 0.5:1 Mixed solution E 1:1 Mixed solution E 2:1 Stirring vigorously for 30min to obtain yellow-white liquid
3) The resulting yellow-white liquids were poured into 80mL hydrothermal kettles and sealed, respectively, and then put into an oven at 60 ℃ for reaction for 24 hours. After the reaction, after the baking oven is slowly cooled to room temperature, the reaction kettle is taken out, and the solid sample is obtained by centrifugation.
4) The solid sample was repeatedly washed with DMF and the resulting product was taken up in 50mL of methanol for 24h (methanol was replaced every 6 hours). Centrifuging the activated product again to obtain solid sample, and drying in vacuum oven at 80deg.C for 12 hr to obtain g-C respectively 3 N 4 g-C with different doping ratios 3 N 4 MOFs composite photocatalytic material, respectively named g-C 3 N 4 /MOFs-1、g-C 3 N 4 /MOFs-2、g-C 3 N 4 /MOFs-3。
(II) detection
1) XRD detection:
in order to analyze the structure, composition and phase of the samples prepared in the experiments, g-C was prepared 3 N 4 Lanthanide metal organic framework material MOFs and three g-C 3 N 4 g-C with different doping ratios 3 N 4 /MOFs-1、g-C 3 N 4 /MOFs-2、g-C 3 N 4 XRD powder characterization was performed on/MOFs-3, as shown in FIG. 5. For pure g-C 3 N 4 In other words, there are two different diffraction peaks at different diffraction angles, such as two characteristic diffraction peaks of 2θ=13.07° and 2θ=27.54° in the XRD spectrum, corresponding to g-C respectively 3 N 4 (100) crystal plane and (002) crystal plane.
When g-C 3 N 4 g-C when the doping amount is small 3 N 4 XRD patterns of the/MOFs were not clearly observed for g-C 3 N 4 Is possible to be g-C 3 N 4 The composite photocatalytic material has smaller doping amount, weaker peak intensity at 27.54 degrees and 13.07 degrees, and is covered by the relevant diffraction peak of the lanthanide metal organic framework material MOFs when followingg-C 3 N 4 The gradual increase of the doping amount in the composite photocatalytic material can be seen in g-C 3 N 4 The MOFs samples gradually exhibited g-C 3 N 4 Characteristic diffraction peak at 2θ=27.54° of (002) crystal face, and the diffraction peak was gradually enhanced, indicating that the rare earth MOFs structure contained g-C 3 N 4 。
2) And (3) detecting photocatalytic performance:
the visible light with the wavelength of more than 420nm is used as a light source, a xenon lamp with the wavelength of 300w is used as the light source, the current of 20A is used, a dye rhodamine B (RhB) is used as a pollutant, and the g-C is realized through a liquid phase degradation experiment 3 N 4 And (3) testing the performance of the MOFs composite photocatalytic material, wherein the concentration of RhB is 10mg/L, adding 0.05g of the composite photocatalyst into a 100mL beaker respectively, then adding 50mL of rhodamine B solution to be degraded, and finally stirring the rhodamine B solution mixed with the photocatalytic material for 60min in a dark place, so that the catalyst and the dye are fully contacted, the error of the photocatalyst due to physical adsorption is reduced, and the stability of degradation reaction is improved. 3mL of the sample is taken as an initial sample solution before illumination, 3mL of the sample is taken every 20min after illumination, the sample is taken four times, supernatant liquid is taken out after centrifugation, the concentration of residual dye in the solution is measured by using UV-3600, and the catalytic performance of the sample is evaluated according to the absorbance of the solution.
FIG. 6 is in g-C 3 N 4 Catalyst, FIG. 7 is a composite photocatalytic material g-C 3 N 4 MOFs-2 is a catalyst, and the spectrum of the absorbance of the pollutant sampled in time intervals is shown in FIG. 7, the RhB solution has a characteristic absorption peak at 550nm under the irradiation of visible light, and the absorption intensity of the absorption peak gradually moves leftwards and decreases along with the irradiation time, which indicates that the molecular structure of rhodamine B is destroyed, so that the absorbance of the rhodamine B is reduced, and after 60 minutes of irradiation, no obvious peak is basically generated in the absorption spectrum.
To compare g-C 3 N 4 The photocatalytic activity of the composite photocatalyst samples prepared in different doping ratios is calculated through experiments of photocatalytic degradation of rhodamine B, and the degradation efficiency of each catalyst is obtained through calculation, and the result is shown as a graphShown at 8. g-C 3 N 4 The degradation rate of the sample to RhB is 60%; g-C 3 N 4 The degradation rate of the MOFs-1 sample to RhB is 75%, g-C 3 N 4 The degradation rate of the MOFs-2 sample to RhB can reach 90%, g-C 3 N 4 The degradation rate of RhB by MOFs-3 sample was 82%, thus, g-C 3 N 4 The MOFs-2 sample has good visible light catalytic performance, and g-C is found through comparison of degradation efficiency 3 N 4 The catalytic efficiency of the MOFs composite photocatalyst is higher than that of g-C 3 N 4 Has larger improvement and improvement.
3) And (3) photocatalytic stability detection:
the rhodamine B solution with the concentration of 10mg/L is taken as a target pollutant, and the same photocatalyst g-C is repeatedly utilized 3 N 4 MOFs-2 was investigated for its photocatalytic stability by 5 cycles and the experiment was recorded with a cycle period of 80 min. As shown in FIG. 9, g-C after the fifth cycle experiment 3 N 4 The photocatalytic activity of the MOFs-2 is reduced, but the photocatalytic activity can still reach 90% of the primary photocatalytic degradation efficiency, which shows that the MOFs-2 has higher stability in the photocatalytic degradation process.
Claims (1)
1. g-C with sodium citrate as matrix 3 N 4 The application of the MOFs composite photocatalytic material in photocatalytic degradation of organic pollutants in wastewater is characterized in that the organic pollutants are rhodamine B, and sodium citrate is g-C of a matrix 3 N 4 the/MOFs composite photocatalytic material is g-C with nano block structure 3 N 4 Attached to MOFs material with rod-shaped structure, the preparation method comprises the following steps:
1) Placing melamine solid powder with certain mass into a semi-closed corundum crucible with capacity of 50mL, heating and calcining in a low-temperature muffle furnace, heating to 5 ℃ per minute from room temperature to 550 ℃ and then preserving heat for 4h, naturally cooling to room temperature, taking out light yellow solid, and grinding to obtain light yellow g-C with amorphous nano particles 3 N 4 A powder;
2) Weighing 0.14705g, uniformly mixing the sodium citrate dihydrate with 10mL deionized water, and sequentially adding 6mL Er (NO) with concentration of 0.01mol/L 3 ) 3 Tm (NO) of the solution at a concentration of 2mL of 0.01mol/L 3 ) 3 Solution, Y (NO) with concentration of 4.6. 4.6mL of 0.2mol/L 3 ) 3 The solution was then added with 0.28 g-C0.28 g 3 N 4 Uniformly stirring the powder, and performing ultrasonic treatment for 30min to obtain a mixed solution;
weighing 0.10507g organic ligand trimesic acid, dissolving in 40mL N, N-dimethylformamide solution, and performing ultrasonic treatment for 30min, wherein Er 3+ /Tm 3+ /Y 3+ Molar amount of trimesic acid = 2:1; dropwise adding the mixed solution of trimesic acid and DMF into the mixed solution according to the dropwise adding speed of 0.5mL/s, and vigorously stirring for 30min to obtain a yellowish white liquid;
3) Pouring the obtained yellow-white liquid into an 80mL hydrothermal kettle, sealing, and then placing into a 60 ℃ oven for reaction for 24 h; after the reaction, taking out the reaction kettle after the baking oven is slowly cooled to room temperature, and centrifuging to obtain a solid sample;
4) Repeatedly washing the solid sample with DMF, placing the obtained product in 50mL methanol for activation for 24h, and replacing methanol every 6 hours; centrifuging the activated product again to obtain solid sample, and drying in vacuum oven at 80deg.C for 12h to obtain g-C 3 N 4 MOFs composite photocatalytic material.
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