CN111229322B - BiOCl/C 3 N 4 /UiO-66 ternary composite photocatalytic material - Google Patents
BiOCl/C 3 N 4 /UiO-66 ternary composite photocatalytic material Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000013207 UiO-66 Substances 0.000 title claims abstract description 43
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 26
- 239000011206 ternary composite Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 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
- XINQFOMFQFGGCQ-UHFFFAOYSA-L (2-dodecoxy-2-oxoethyl)-[6-[(2-dodecoxy-2-oxoethyl)-dimethylazaniumyl]hexyl]-dimethylazanium;dichloride Chemical compound [Cl-].[Cl-].CCCCCCCCCCCCOC(=O)C[N+](C)(C)CCCCCC[N+](C)(C)CC(=O)OCCCCCCCCCCCC XINQFOMFQFGGCQ-UHFFFAOYSA-L 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 102000020897 Formins Human genes 0.000 claims description 3
- 108091022623 Formins Proteins 0.000 claims description 3
- 229910007926 ZrCl Inorganic materials 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000012719 thermal polymerization Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 22
- 239000004065 semiconductor Substances 0.000 description 15
- 229910052797 bismuth Inorganic materials 0.000 description 12
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000004098 Tetracycline Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229960002180 tetracycline Drugs 0.000 description 6
- 229930101283 tetracycline Natural products 0.000 description 6
- 235000019364 tetracycline Nutrition 0.000 description 6
- 150000003522 tetracyclines Chemical class 0.000 description 6
- 238000004566 IR spectroscopy Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 238000005452 bending Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
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- 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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Abstract
The invention provides BiOCl/C 3 N 4 The preparation method of the/UiO-66 ternary composite photocatalytic material comprises the following steps: 1) Preparation C 3 N 4 : preparation of C from melamine 3 N 4 (ii) a 2) Preparation of BiOCl/C 3 N 4 A complex; 3) By changing BiOCl/C 3 N 4 The proportion of the BiOCl to the UiO-66 controls the content of binary and monomer in the composite material to prepare BiOCl/C 3 N 4 a/UiO-66 ternary composite material; the prepared composite material has higher photocatalytic degradation performance.
Description
Technical Field
The invention relates to BiOCl/C 3 N 4 A/UiO-66 ternary composite photocatalytic material belongs to the technical field of catalysts.
Background
In recent years, the world is facing the difficult problems of energy shortage and environmental pollution, the photocatalytic technology is one of the most effective ways for directly converting solar energy into chemical energy, the photocatalytic technology has the advantages of low energy consumption, simple and convenient operation, mild reaction conditions, capability of being carried out at normal temperature and normal pressure, and becomes a research hotspot in the aspect of processing environmental problems.
The photocatalysis technology can convert inexhaustible low-density solar energy into high-density electrochemical energy to remove organic pollutants and CO in water or air 2 The fields of methane preparation by reduction, hydrogen preparation by water photolysis and the like are widely applied, and a clean and efficient new way is provided for solving the two problems of global environmental pollution and energy crisis. The core of the photocatalytic technology is a photocatalyst. However, conventional semiconductor photocatalysts (e.g. TiO) 2 ZnO, etc.) are difficult to be industrially applied on a large scale due to the defects of low light quantum efficiency and solar energy utilization rate, etc. In order to promote the development of the photocatalytic technology to commercialization and practicability and fully exert the advantages of the photocatalytic technology in the aspects of environmental protection and new energy utilization, the design and development of other novel efficient photocatalytic composite nanomaterial systems are inevitable trends in the development of the photocatalytic technology. In recent years, bismuth-based semiconductor materials have attracted much attention because of their unique band structures, their excellent photocatalytic properties, and their advantages such as low cost, stable physicochemical properties, and environmental friendliness.
Disclosure of Invention
The invention aims at the problems, thereby providing a BiOCl/C 3 N 4 the/UiO-66 ternary composite photocatalytic material.
The specific technical scheme is as follows:
BiOCl/C 3 N 4 The preparation method of the/UiO-66 ternary composite photocatalytic material comprises the following steps:
1) Preparation C 3 N 4 : preparation of C from melamine 3 N 4 ；
2) Preparation of BiOCl/C 3 N 4 A complex;
3) By changing BiOCl/C 3 N 4 The content of binary and monomer in the composite material is controlled by the proportion of the monomer to the UiO-66 to prepare the composite materialTo BiOCl/C 3 N 4 The ternary composite material of/UiO-66.
Further, step 1) C 3 N 4 The preparation method comprises the following steps:
1) 10g of melamine was weighed into a covered 50mL ceramic crucible and then heated from room temperature to 550 ℃ in a muffle furnace at a rate of about 20 ℃ for min -1 ；
2) After the thermal polymerization reaction is finished, taking out the crucible, naturally cooling to room temperature, finally grinding the product uniformly, and drying in an oven at 70 ℃ for 12 hours to obtain a final product C 3 N 4 。
Further, biOCl/C 3 N 4 The preparation method of the compound comprises the following steps:
1) 0.5g of C was weighed out separately 3 N 4 Dissolving 0.1491g of KCl in 50mL of deionized water, and fully performing ultrasonic treatment for 20min to obtain a solution A;
2) 0.9304g of Bi (NO) is weighed 3 ) 3 ·5H 2 Placing O in 50mL of glacial acetic acid solution, and stirring strongly for 30min to completely dissolve the O to obtain solution B;
3) Dropwise adding the solution B into the solution A, fully stirring the suspension for 1h after the dropwise adding step is finished, and standing for 4h;
4) Centrifuging, washing with water for 2 times and washing with ethanol for 2 times, drying the obtained precipitate at 60 deg.C to obtain BiOCl/C 3 N 4 And (c) a complex.
Further, biOCl/C 3 N 4 The preparation method of the/UiO-66 ternary composite material comprises the following steps:
1) 0.2149g of ZrCl 4 0.1532g of terephthalic acid, 0.5g of BiOCl/C 3 N 4 Adding the compound and 3.5mL of acetic acid into 42mL of DMF, performing ultrasonic treatment for 30min, and transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle to react for 24h at 120 ℃;
2) Cooling to room temperature, centrifuging, washing with DMF and ethanol for 3 times respectively, and drying at 80 deg.C to obtain BiOCl/C 3 N 4 The ternary composite material of/UiO-66.
The invention has the beneficial effects that:
1) BiOX has high photocatalytic activity mainly due to the fact that, on one hand, when electrons on a valence band are excited to a conduction band orbit, photo-generated electron-hole pairs are generated, biOX (X = Cl, br, I) has a unique layered structure and has enough space to polarize corresponding atoms and orbitals, and induced dipole moment can promote separation of the electron-hole pairs, so that the photocatalytic activity is greatly improved; in addition, the BiOX (X = Cl, br, I) is an indirect transition bandgap semiconductor, and excited electrons need to pass through a certain k layer to reach a valence band, so that recombination of the excited electrons and holes is reduced as much as possible. The combined action of the unique open structure and the indirect transition mode promotes the effective separation of the photo-generated electron-hole pairs, and the photo-generated carriers are quickly transferred, so that the BiOX has excellent photocatalytic performance.
2) The bismuth-based photocatalytic material has many advantages, mainly including the following two: first, bismuth has mainly two valence states, +3 and +5, and other intermediate valence states can be synthesized by different experimental methods. When the outer layer of electrons are lost, bismuth can be compounded and hybridized with other elements (such as O element) to form a valence band top end in a semiconductor, so that an s-p hybrid track is formed, the forbidden bandwidth of the S-p hybrid track is reduced, the transfer of photogenerated electrons and holes is facilitated, the recombination of photogenerated carriers is inhibited, and the photocatalytic performance can be improved. Secondly, the bismuth semiconductor material has a plurality of microscopic morphologies, most of the bismuth semiconductor material is of a multilayer structure, the specific surface area is high, and the bismuth semiconductor material is favorable for being compounded with other semiconductor materials, so that the photocatalytic performance of the bismuth semiconductor material is improved.
3) There is also room for improvement in the performance of bismuth-based semiconductor photocatalytic materials. The current research focus is to modify the bismuth semiconductor photocatalytic material to improve the photocatalytic performance of the bismuth semiconductor photocatalytic material. The modification of the bismuth-based photocatalytic material mainly focuses on synthesizing a novel semiconductor photocatalytic material, compounding the semiconductor photocatalytic material with other semiconductor photocatalysts to form a heterojunction and doping some elements for modification.
4) Graphite phase carbon nitride (g-C) 3 N 4 ) The molecular structure is similar to that of graphene, and the graphene is an organic polymer, high in cost performance and easy to synthesize; mono-lamellar g-C 3 N 4 Has large specific surface area, chemical stability and narrow band gapThe structure ensures that the photocatalyst has absorption capacity on visible light and has good application prospect in the field of photocatalysis.
5): the high specific surface area of MOFs disperses the active center to the maximum extent, and the regular and ordered pore channels increase the effective contact between the substrate and the active center; the pore structure is easy to functionalize, and catalytic active points are effectively fixed; the aperture is adjustable, the threshold limiting effect similar to that of a micro-reactor is realized, and the catalytic reaction efficiency is improved.
Drawings
FIG. 1 is C 3 N 4 (ii) an infrared spectrum;
FIG. 2 is an infrared spectrum of BiOCl;
FIG. 3 is an IR spectrum of UiO-66;
FIG. 4 shows BiOCl/C 3 N 4 (ii) an infrared spectrum;
FIG. 5 shows BiOCl/C 3 N 4 An IR spectrum of/UiO-66;
FIG. 6 is C 3 N 4 、BiOCl、UiO-66、BiOCl/C 3 N 4 And BiOCl/C 3 N 4 The XRD pattern of @ UiO-66;
FIG. 7 is C 3 N 4 、BiOCl、UiO-66、BiOCl/C 3 N 4 And BiOCl/C 3 N 4 @ UiO-66 degrades the photocatalytic activity of tetracycline under visible light.
Detailed Description
In order to make the technical scheme of the invention clearer and clearer, the invention is further described below by combining the attached drawings, and any scheme obtained by carrying out equivalent replacement and conventional reasoning on the technical characteristics of the technical scheme of the invention falls into the protection scope of the invention.
Example one
The specific technical scheme is as follows:
BiOCl/C 3 N 4 The preparation method of the/UiO-66 ternary composite photocatalytic material comprises the following steps:
1) Preparation C 3 N 4
(1) 10g of melamine was weighed into a covered 50mL ceramic crucible and then heated in a muffle furnace from room temperature to 550 ℃ at a rate of about 20 ℃ for min -1 ；
(2) After the thermal polymerization reaction is finished, taking out the crucible, naturally cooling to room temperature, finally grinding the product uniformly, and drying in an oven at 70 ℃ for 12 hours to obtain a final product C 3 N 4 ；
2) Preparation of BiOCl/C 3 N 4 Composite material
(1) 0.5g of C was weighed out separately 3 N 4 Dissolving 0.1491g of KCl in 50mL of deionized water, and fully performing ultrasonic treatment for 20min to obtain a solution A;
(2) 0.9304g of Bi (NO) is weighed 3 ) 3 ·5H 2 Placing O in 50mL of glacial acetic acid solution, and stirring strongly for 30min to completely dissolve the O to obtain solution B;
(3) dropwise adding the solution B into the solution A, fully stirring the suspension for 1h after the dropwise adding step is completed, and then standing for 4h;
(4) centrifuging, washing with water for 2 times and washing with ethanol for 2 times, drying the obtained precipitate at 60 deg.C to obtain BiOCl/C 3 N 4 Complexes of BiOCl with C 3 N 4 The theoretical mass ratio of (2);
3) Preparation of BiOCl/C 3 N 4 Ternary composite material of/UiO-66
(1) 0.2149g of ZrCl 4 0.1532g of terephthalic acid, 0.5g of BiOCl/C 3 N 4 Adding the compound and 3.5mL of acetic acid into 42mL of DMF, carrying out ultrasonic treatment for 30min, and transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle to react for 24h at 120 ℃;
(2) cooling to room temperature, centrifuging, washing with DMF and ethanol for 3 times respectively, and drying at 80 deg.C to obtain BiOCl/C 3 N 4 Ternary composite material/UiO-66, biOCl/C 3 N 4 The theoretical mass ratio to UiO-66 is 1.
Example two
Using infrared spectroscopy to C 3 N 4 Performing analysis and identification, and the result is shown in figure 1; as can be seen from FIG. 1, C 3 N 4 At 808cm -1 The absorption peak corresponds to the out-of-plane stretching vibration of the C-N ring, and is in the range of 1239-1638cm -1 The absorption peak at (A) corresponds to C-N aromatic ring vibration; absorb thereinHaving C in the peak 3 N 4 Characteristic peaks appear.
EXAMPLE III
Analyzing and identifying BiOCl by using infrared spectroscopy, wherein the result is shown in figure 2;
as can be seen from FIG. 2, the A2u type vibration peak of the Bi-O bond was located at 508cm -1 At least one of (1) and (b); 767cm -1 The absorption peak at (b) corresponds to the asymmetric tensile vibration of the Bi — O bond. Furthermore, 1626cm -1 The stronger absorption peak corresponds to the bending vibration of the O-H bond of the water molecule on the surface of the catalyst; a BiOCl characteristic peak appears in the absorption peak.
The preparation method of BiOCl comprises the following steps: 0.9304g Bi (NO) 3 ) 3 ·5H 2 O was dissolved in 50mL of water and 4.5mL of acetic acid was added thereto, followed by stirring thoroughly, followed by dropwise addition to 50mL of an aqueous solution containing 0.1495g of KCl, stirring at room temperature for 1 hour, and standing for 1 hour. And (3) centrifugally separating the solid product, washing the solid product for 3 times by using deionized water and ethanol respectively, and drying the solid product at 80 ℃ to obtain the product.
Example four
The UiO-66 was analyzed and identified by infrared spectroscopy, the results are shown in FIG. 3; as can be seen from FIG. 3, 3434cm -1 The broader peak at this point corresponds to the-OH absorption peak of UiO-66, indicating that the material contains a large amount of water, due to the water absorbed by the porous adsorbent material of UiO-66; 1656cm -1 Vibration absorption attributable to the carbon-oxygen double bond C = O in the carboxyl group; 1407cm -1 Is formed by COO - The absorption peak due to stretching vibration of (2) is derived from the carboxyl group on terephthalic acid in UiO-66. In this absorption peak, characteristic UiO-66 peak appears.
EXAMPLE five
BiOCl/C by infrared spectroscopy 3 N 4 The complex was analyzed and identified, and the results are shown in FIG. 4; as can be seen from FIG. 4, C 3 N 4 At 808cm -1 The absorption peak corresponds to the out-of-plane stretching vibration of the C-N ring, and is 1244-1639cm -1 The absorption peak at (a) corresponds to the C-N aromatic ring vibration. The A2u type vibration peak of the Bi-O bond is located at 508cm -1 To (3). 767cm -1 The absorption peak at (b) corresponds to the asymmetric tensile vibration of the Bi — O bond. Furthermore, 1639cm -1 Strong suction ofThe peak is contracted corresponding to the bending vibration of the O-H bond of the water molecule on the surface of the catalyst; in BiOCl/C 3 N 4 In the absorption peak of the binary complex, C is as described above 3 N 4 And characteristic peaks of BiOCl were present.
EXAMPLE six
BiOCl/C by infrared spectroscopy 3 N 4 the/UiO-66 ternary composite material is analyzed and identified, and the result is shown in figure 5;
as can be seen in FIG. 5, C 3 N 4 At 808cm -1 The absorption peak corresponds to the out-of-plane stretching vibration of the C-N ring, and is 1244-1639cm -1 The absorption peak corresponds to C-N aromatic ring vibration; the A2u type vibration peak of the Bi-O bond is located at 508cm -1 To (3).
Furthermore, 1639cm -1 The stronger absorption peak corresponds to the bending vibration of the O-H bond of the water molecule on the surface of the catalyst; 3407cm -1 The broader peak at (b) corresponds to the-OH absorption peak of UiO-66, indicating that the material contains a large amount of water, because UiO-66 is the porous adsorbent material which absorbs water; 1657cm -1 Vibration absorption attributable to the carbon-oxygen double bond C = O in the carboxyl group; 1402cm -1 Is the absorption peak due to stretching vibration of COO-, which is derived from the carboxyl group on terephthalic acid in UiO-66. In the absorption peak of the ternary complex, C is as described above 3 N 4 And characteristic peaks of BiOCl and UiO-66 were present.
In addition, the spectrum has three characteristic peaks of the monomer; however, some characteristic peaks were reduced in intensity, and the carboxyl peak of UiO-66 was slightly changed and combined to 1639cm -1 It is probably caused by the change of the environment of the carboxyl of the UiO-66 caused by the doping of acetic acid in the preparation process of the composite material. Meanwhile, the result is basically consistent with the result reported in the literature, and is 1575cm -1 Is the characteristic absorption peak of C-N bending vibration in the benzene ring.
EXAMPLE seven
Using XRD to C 3 N 4 、BiOCl、UiO-66、BiOCl/C 3 N 4 And BiOCl/C 3 N 4 The results of the structure identification with @ UiO-66 are shown in FIG. 6. Monomer C 3 N 4 XRD and theoretical XRD of BiOCl, uiO-66The spectrogram is well matched, and the purity is high. BiOCl/C 3 N 4 Can find C in the XRD spectrum of the product 3 N 4 And BiOCl corresponding to 2 theta angle. After UiO-66 compounding, biOCl/C 3 N 4 The @ UiO-66XRD spectrum can correspond to the 2 theta angles of three monomers.
Example eight
Evaluation of C by degradation of Tetracycline under visible light with Tetracycline as the target contaminant 3 N 4 、BiOCl、UiO-66、BiOCl/C 3 N 4 And BiOCl/C 3 N 4 @ Uio-66 photocatalytic activity. The self-degradation of tetracycline is almost negligible when no catalyst is present.
As shown in FIG. 7, uiO-66 mainly exhibits adsorption property, C 3 N 4 And BiOCl can photodegrade 23% and 56% of tetracycline in one hour. Binary compound BiOCl/C 3 N 4 The photocatalytic performance of (A) is improved, which is mainly C 3 N 4 The visible light absorption of BiOCl is widened after the composition. BiOCl/C is enhanced due to the adsorption property of UiO-66 3 N 4 The limited domain effect of/UiO-66, the material after ternary composition can degrade 95% of tetracycline in 1 hour.
Claims (1)
1. BiOCl/C 3 N 4 the/UiO-66 ternary composite photocatalytic material is characterized by comprising the following preparation methods:
1) Preparation C 3 N 4 : preparation of C from melamine 3 N 4 ；
2) Preparation of BiOCl/C 3 N 4 Complexes of BiOCl with C 3 N 4 The mass ratio of (1) is 2;
3) By changing BiOCl/C 3 N 4 The proportion of the BiOCl to the UiO-66 controls the content of the binary and the monomer in the composite material to prepare BiOCl/C 3 N 4 a/UiO-66 ternary composite material; biOCl/C 3 N 4 The mass ratio of the compound to UiO-66 is 1;
step 1) C 3 N 4 The preparation method comprises the following steps:
1) Balance10g of melamine was placed in a covered 50mL ceramic crucible and then heated from room temperature to 550 ℃ in a muffle furnace at a heating rate of 20 ℃ for min -1 ；
2) After the thermal polymerization reaction is finished, taking out the crucible, naturally cooling to room temperature, finally grinding the product uniformly, and drying in an oven at 70 ℃ for 12 hours to obtain a final product C 3 N 4 ；
BiOCl/C 3 N 4 The preparation method of the compound comprises the following steps:
1) Respectively weighing 0.5gC 3 N 4 Dissolving 0.1491g of KCl in 50mL of deionized water, and fully performing ultrasonic treatment for 20min to obtain a solution A;
2) 0.9304g of Bi (NO) is weighed out 3 ) 3 .5H 2 Placing O in 50mL of glacial acetic acid solution, and stirring strongly for 30min to completely dissolve the O to obtain solution B;
3) Dropwise adding the solution B into the solution A, fully stirring the suspension for 1h after the dropwise adding step is finished, and standing for 4h;
4) Centrifuging, washing with water for 2 times and washing with ethanol for 2 times, drying the obtained precipitate at 60 deg.C to obtain BiOCl/C 3 N 4 A complex;
BiOCl/C 3 N 4 the preparation method of the/UiO-66 ternary composite material comprises the following steps:
1) 0.2149g of ZrCl 4 0.1532g of terephthalic acid, 0.5g of BiOCl/C 3 N 4 Adding the compound and 3.5mL of acetic acid into 42mL of DMF, carrying out ultrasonic treatment for 30min, and transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle to react for 24h at 120 ℃;
2) Cooling to room temperature, centrifuging, washing with DMF and ethanol for 3 times respectively, and drying at 80 deg.C to obtain BiOCl/C 3 N 4 the/UiO-66 ternary composite material.
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| CN109847780A (en) * | 2019-01-30 | 2019-06-07 | 太原理工大学 | A kind of AgBr/BiOI/g-C3N4The preparation method and applications of tri compound catalysis material |
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| CN109847780A (en) * | 2019-01-30 | 2019-06-07 | 太原理工大学 | A kind of AgBr/BiOI/g-C3N4The preparation method and applications of tri compound catalysis material |
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