CN112090450A - In2S3/rGO/UiO-66 sandwich type composite catalyst and preparation method thereof - Google Patents
In2S3/rGO/UiO-66 sandwich type composite catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN112090450A CN112090450A CN201910527964.4A CN201910527964A CN112090450A CN 112090450 A CN112090450 A CN 112090450A CN 201910527964 A CN201910527964 A CN 201910527964A CN 112090450 A CN112090450 A CN 112090450A
- Authority
- CN
- China
- Prior art keywords
- uio
- rgo
- preparation
- visible light
- type composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013207 UiO-66 Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 239000003054 catalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000008367 deionised water Substances 0.000 claims abstract description 41
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 238000000227 grinding Methods 0.000 claims abstract description 15
- 229910007926 ZrCl Inorganic materials 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000000967 suction filtration Methods 0.000 claims abstract description 12
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 8
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 36
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000005485 electric heating Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 9
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 239000011941 photocatalyst Substances 0.000 description 7
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000001055 reflectance spectroscopy Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000008394 flocculating agent Substances 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007131 hydrochloric acid regeneration reaction Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002471 indium Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011807 nanoball Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment 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
Images
Classifications
-
- 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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of inorganic functional materials, and particularly relates to In2S3the/rGO/UiO-66 sandwich type composite visible light catalyst and the preparation method thereof are as follows: firstly, GO is prepared by a Hummer method, and is added into deionized water, and ZrCl is respectively added4Adding terephthalic acid into the aqueous solution of GO, moving the mixture into a reaction kettle, cooling after the reaction is finished, performing suction filtration, washing, drying and grinding; 2) redispersing rGO/UiO-66 In deionized water, In (NO)3)3·5H2Adding O into the aqueous solution of rGO/UiO-66, stirring, adding Na2S·9H2Adding O, stirring, transferring into a reaction kettle, and after the reaction is finishedCooling, suction filtering, washing with deionized water, drying and grinding. The preparation method has the advantages of simple preparation process, mild preparation conditions, environmental protection, no pollution, low equipment requirement and strong operability.
Description
Technical Field
The invention belongs to the field of inorganic functional materials, and relates to a catalyst for degrading organic matters In wastewater, In particular to In2S3a/rGO/UiO-66 sandwich type composite catalyst and a preparation method thereof.
Background
With the increasing severity of water eutrophication problems and the increasingly strict discharge standards of ammonia nitrogen and organic matters, the technology for advanced wastewater treatment has become a subject of wide attention by domestic and foreign scholars. Wherein cold rolling mill units in the steel industry all relate to the pickling of strip steel, and acid regeneration units are designed and arranged for realizing the recycling of waste acid. Most hydrochloric acid regeneration units are provided with a silicon removal process, and NH in wastewater is inevitably brought when a silicon removal device runs3-N is out of limits (NH)3N is mainly from ammonia water in a silicon removal process) and organic matters exceed the standard (the organic matters are mainly from a flocculating agent in the silicon removal process), and the application of a mature ammonia nitrogen removal and organic matter rapid degradation technology in acid-containing wastewater is not seen so far. The photocatalyst researched by the technology can effectively degrade organic matters in the wastewater, and the organic matters in the wastewater can be discharged up to the standard.
Among the technical means, photocatalysis is considered as the most promising method for solving the energy and environmental problems due to the characteristics of low energy consumption, environmental friendliness and high efficiency. At present, a single semiconductor material is used for photocatalysis to meet the requirements of practical application more and more, and the development of a composite photocatalyst with good effect, strong practicability and environmental protection is urgent.
Metal-organic frameworks (MOFs) are three-dimensional network crystal materials formed by self-assembly of metal central ions and organic ligands, and have the characteristics of large specific surface area, high porosity, excellent thermal stability and chemical stability, designable structure and the like, so that great attention is paid to the field of photocatalysis. The UiO-66 is a typical MOFs material, has good stability, can be maintained in water for several months without damaging the structure, and is very beneficial to catalytic degradation of organic pollutants in water by the UiO-66. Moreover, the larger specific surface area of UiO-66 makes it have good dispersion effect on the nano-particles loaded on the surface. In addition, the UiO-66 has semiconductor properties, but the pure UiO-66 has a wider band gap and can only respond to ultraviolet light, so that the practical application of the UiO-66 is limited.
In2S3Is a typical n-type semiconductor and has the characteristics of high carrier mobility, low toxicity and high stability. In2S3Has a band gap width of about 1.9-2.2eV, can respond to a wide range of visible light, and is a visible light type catalyst, and therefore, In2S3Has very wide application prospect in the field of photocatalysis. However, In of a single component2S3The photogenerated carriers are easily recombined after being irradiated by light, and In is prepared by a simple hydrothermal method2S3The nano particles are easy to agglomerate, so that the specific surface area is reduced, the active sites are reduced during the photocatalytic reaction, and the factors cause In2S3The effect is poor in practical application. In addition, indium salts are relatively expensive and these disadvantages limit the single component In2S3In practice, on a large scale. Thus, In2S3The material is compounded with other materials, on one hand, the recombination of photogenerated electrons and holes is slowed down by constructing a heterojunction, and on the other hand, In is improved2S3The dispersibility of the nano particles and the increase of reaction active sites, thereby improving the catalytic performance are of great significance.
The prior art has the problems that:
1) organic matters in the wastewater of the acid regeneration unit mainly come from a flocculating agent in a silicon removal process, and the prior technology for removing the organic matters in the wastewater mainly adopts a chemical agent degradation method, so that secondary pollution is easily caused by the technology, and the application of the technology in the field is restricted;
2) photocatalysis is considered to be the most promising method for solving energy and environmental problems due to the characteristics of low energy consumption, environmental friendliness and high efficiency. At present, a single semiconductor material is used for photocatalysis to meet the requirements of practical application more and more, and the development of a composite photocatalyst with good effect, strong practicability and environmental protection is urgent.
Comparison between typical patents in the same field
Application No. CN201610516561.6 discloses an RGO/In2S3Method for preparing composite material, In the composite system2S3No heterojunction is constructed between the composite material and other semiconductor materials, the electrical performance of the composite material is tested, and the photocatalytic capability is not evaluated. Application number is CN201410231420.0, and discloses a CuS/g-C3N4The preparation method of the nano ball flower compound catalyst is characterized In that In2S3/g-C3N4The construction of the heterojunction prolongs the transfer path of photo-generated electrons-holes, so that the composite visible light catalyst is more than single In2S3Has better photocatalysis effect, but g-C3N4The preparation of the urea is obtained by calcining urea at the high temperature of 550 ℃, and the preparation process is complex, has high cost and is not beneficial to energy conservation and environmental protection.
Disclosure of Invention
The present invention provides an In2S3/rGO/UiO-66 sandwich type composite visible light catalyst and preparation method thereof, In2S3The preparation method of the/rGO/UiO-66 sandwich type composite visible-light-driven photocatalyst mainly solves the technical problems of complex preparation process, harsh preparation conditions and limited catalytic effect of the visible-light-driven photocatalyst in the prior art, effectively degrades organic matters in wastewater, and realizes standard emission of the organic matters in the wastewater.
The technical scheme of the invention is as follows:
in2S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst comprises the following steps:
1) firstly, GO (graphene oxide) is prepared by a Hummer method, and then GO is addedAdding into deionized water, performing ultrasonic treatment to disperse GO, and respectively adding ZrCl4Adding terephthalic acid into a GO aqueous solution, stirring the materials, transferring the materials into a reaction kettle, reacting at 120-180 ℃ for 20-24 h, cooling to room temperature (20-25 ℃) after the reaction is finished, performing suction filtration, washing with deionized water, drying and grinding (preferably grinding for 15-30min) to obtain a rGO/UiO-66 matrix material;
2) redispersing rGO/UiO-66 In deionized water, then In (NO)3)3·5H2O was added to an aqueous solution of rGO/UiO-66, followed by Na after stirring2S·9H2Adding O, continuously stirring, finally moving into a reaction kettle, reacting for 12-16 h at 160-200 ℃, cooling to room temperature (20-25 ℃) after the reaction is finished, performing suction filtration, washing with deionized water, drying and grinding (preferably grinding for 15-30min) to obtain In2S3a/rGO/UiO-66 composite material.
Further, performing ultrasonic treatment for 1-2 hours in the step (1).
Further, ZrCl is separately added in the step (1)4And adding terephthalic acid into the aqueous solution of GO, stirring the materials for 1-2h, and then transferring the materials into a reaction kettle.
Further, GO, deionized water and ZrCl in the step (1)4The material ratio of terephthalic acid to terephthalic acid is as follows: 0.1g of 40-60 ml of 1-2 mmol of 1-2.4 mmol.
Further, washing with deionized water 3 to 6 times in the steps (1) and (2).
Further, In (NO) is added In step (2)3)3·5H2Adding O into the aqueous solution of rGO/UiO-66, and stirring for 2-4 h; then Na is added2S·9H2And adding O, and continuously stirring for 1-2 h.
Further, drying is carried out by adopting an oven for electric heating, the heating temperature is 80-100 ℃, and the drying time is 1-2 h.
Further, rGO/UiO-66, deionized water, In (NO) described In step (2)3)3·5H2O、Na2S·9H2The material ratio of O is 0.1g to 40-60 ml to 0.2-0.3 mmol to 0.3-0.9 mmol.
In according to the above2S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst can amplify or reduce the material ratio in the same proportion.
The invention also provides In2S3the/rGO/UiO-66 sandwich type composite visible light catalyst is prepared from one of the In2S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst comprises the steps of covering a layer of UiO-66 on the surface of GO (graphene), and covering a layer of In on the outermost layer2S3And preparing the sandwich type composite visible light catalyst.
The catalyst is designed into three sandwich type structure catalysts, and then a layer of UiO-66 is coated on the surface of GO (graphene) by a sol-gel method, and then a layer of In is coated on the outermost layer2S3Preparing the catalyst with sandwich structure
The invention provides In2S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst comprises the following steps:
1) firstly, GO (graphene oxide) is prepared by a Hummer method, then the GO is added into deionized water, ultrasonic treatment is carried out for 1-2 hours to disperse the GO, and then ZrCl is respectively added4And terephthalic acid is added into the aqueous solution of GO, the materials are stirred for 1-2h and then are moved into a reaction kettle to react for 20-24 h at 120-180 ℃, and the GO, the deionized water and the ZrCl are4The material ratio of the terephthalic acid to the terephthalic acid is 0.1g: 40-60 ml: 1-2 mmol: 1-2.4 mmol. After the reaction is finished, cooling to room temperature, carrying out suction filtration, washing for 3 times by using deionized water, drying and grinding to obtain a rGO/UiO-66 matrix material;
2) redispersing rGO/UiO-66 In deionized water, then In (NO)3)3·5H2Adding O into the aqueous solution of rGO/UiO-66, stirring for 2-4 h, and then adding Na2S·9H2Adding O, continuously stirring for 1-2h, finally moving to a reaction kettle, and reacting for 12-16 h at 160-200 ℃, wherein the rGO/UiO-66, deionized water and In (NO)3)3·5H2O、Na2S·9H2The material ratio of O is 0.1g to 40About 60ml, 0.2 to 0.3mmol, 0.3 to 0.9 mmol. After the reaction is finished, cooling to room temperature, carrying out suction filtration, washing for 3 times by using deionized water, drying and grinding to obtain In2S3a/rGO/UiO-66 composite material.
The invention prepares In by a simple hydrothermal method2S3the/rGO/UiO-66 sandwich type composite visible light catalyst. Firstly, loading UO-66 on GO nano-sheets by a hydrothermal method, and reducing GO into rGO in a hydrothermal reaction process, thereby obtaining an rGO/UO-66 composite material; then further using a hydrothermal method, taking rGO/UiO-66 as a matrix, and using the characteristic of high porosity of UiO-66 to adsorb In3+To make it In2S3Thereby obtaining In2S3the/rGO/UiO-66 sandwich type composite visible light catalyst.
The technical effects of the beneficial effects are as follows:
the invention passes In2S3The catalytic efficiency of the catalyst is improved by constructing a ternary system of rGO and UiO-66. Because UiO-66 has larger specific surface area and higher porosity, organic molecules can be adsorbed first and then degraded, so that the system is in dynamic balance of adsorption-degradation-adsorption, and the dynamic balance can effectively accelerate the catalytic process; at the same time, In2S3And UiO-66, and In can prolong the transfer path of photogenerated electrons-holes2S3The catalyst is uniformly dispersed on the surface, so that more catalytic reaction active sites can be provided; in addition, the rGO has excellent electrical properties, which is beneficial to electron transmission in a composite system, so that the recombination of photogenerated electrons and holes is inhibited, and the catalytic performance of the composite catalyst is greatly improved due to the factors.
Meanwhile, In of the present invention2S3the/rGO/UiO-66 sandwich type composite visible-light-driven photocatalyst has the advantages of simple preparation process, mild preparation conditions, environmental protection, no pollution, low equipment requirement and strong operability. In of the invention2S3The visible light catalytic material with the UiO-66 core-shell structure has good degradation effect on organic pollutants under the drive of visible light, does not generate secondary pollutants, and can be applied to large-scale industrializationThe application is as follows.
Drawings
FIG. 1(a) In alone2S3The scanning electron microscope image of (a),
(b) in obtained In example 12S3Scanning electron microscope images of/rGO/UiO-66 composite materials,
(c) in obtained In example 22S3Scanning electron microscope images of/rGO/UiO-66 composite materials,
(d) in obtained In example 32S3Scanning electron microscope images of/rGO/UiO-66 composite materials.
FIG. 2 In alone2S3Pure UiO-6 and different examples.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the invention, 15mg/L methyl orange is used as a target degradation product, a 500W xenon lamp with an additional optical filter (lambda is more than 420nm) is used as a light source, and the catalytic performance of the photocatalyst is examined. Before illumination, stirring in dark for 40min to make the system reach absorption-desorption equilibrium. The photocatalysis experiment is carried out in a special double-layer container, circulating water is filled in an interlayer of the container to ensure that the temperature of the system is kept at room temperature, and magnetic stirring is carried out simultaneously. 3mL of the reaction solution is taken every 10 minutes, centrifuged at 8000rpm for 5 minutes by using a centrifuge, the supernatant is filtered by using a 0.22 micron filter, and the change of the concentration of methyl orange in the solution is determined according to the change of the absorbance of the solution at 465nm by using an Shimadzu UV-3600 ultraviolet spectrophotometer.
Example 1
1) Firstly, GO (graphene oxide) is prepared by a Hummer method, then GO is added into deionized water, ultrasonic treatment is carried out for 1h to disperse GO, and then ZrCl is respectively added4And terephthalic acid is added into the aqueous solution of GO, the materials are stirred for 1h and then are moved into a reaction kettle to react for 20h at the temperature of 120 ℃, and the GO, the deionized water and the ZrCl are added4The material ratio of terephthalic acid to terephthalic acid was 0.1g:40ml:1mmol:1 mmol. Reaction junctionCooling to room temperature after the reaction, performing suction filtration, washing with deionized water for 3 times, drying and grinding for 25min to obtain a rGO/UiO-66 matrix material;
2) redispersing rGO/UiO-66 In deionized water, then In (NO)3)3·5H2O was added to an aqueous solution of rGO/UiO-66, stirred for 2h, then Na was added2S·9H2Adding O, continuously stirring for 1h, finally moving to a reaction kettle, and reacting for 12h at 160 ℃, wherein the rGO/UiO-66, the deionized water and the In (NO) are3)3·5H2O、Na2S·9H2The material ratio of O was 0.1g:40ml:0.2mmol:0.3 mmol. After the reaction is finished, cooling to room temperature, carrying out suction filtration, washing for 3 times by using deionized water, drying and grinding to obtain In2S3a/rGO/UiO-66 composite material.
The XRD spectrum of the obtained sample was measured by using German Bruker D8 Advance, and as a result, UiO-66 and In were simultaneously appeared In the XRD spectrum of the obtained sample as shown In FIG. 12S3Characteristic peaks of (A), indicating UiO-66 and In2S3The compounding is successful.
The sample was subjected to uv-vis diffuse reflectance spectroscopy using Agilent Cary 5000, australia, and the results are shown in the figure, indicating that the sample responded in both the uv-vis range, indicating that it can be used for visible light catalysis.
In prepared In this example2S3the/UiO-66 core-shell structure visible light catalyst is added into 15mg/L methyl orange solution according to the proportion of 0.5g/L, after dark reaction for 40min, and then under the irradiation of visible light, the methyl orange solution can be degraded by 96% within 60 min.
Example 2
1) Firstly, GO (graphene oxide) is prepared by a Hummer method, then GO is added into deionized water, ultrasonic treatment is carried out for 1.5h to disperse GO, and then ZrCl is respectively added4And terephthalic acid is added into the aqueous solution of GO, the materials are stirred for 1.5h and then are moved into a reaction kettle to react for 22h at the temperature of 150 ℃, and the GO, the deionized water and the ZrCl are added4The material ratio of terephthalic acid to terephthalic acid was 0.1g:50ml:1.5mmol:1.6 mmol. Cooling to room temperature after the reaction is finished, carrying out suction filtration,meanwhile, washing the substrate with deionized water for 3 times, and drying and grinding the substrate to obtain a rGO/UiO-66 substrate material;
2) redispersing rGO/UiO-66 In deionized water, then In (NO)3)3·5H2O was added to an aqueous solution of rGO/UiO-66, stirred for 3h, then Na was added2S·9H2Adding O, continuously stirring for 1.5h, finally moving to a reaction kettle, and reacting for 14h at 180 ℃, wherein the rGO/UiO-66, the deionized water and the In (NO) are3)3·5H2O、Na2S·9H2The material ratio of O was 0.1g:50ml:0.25mmol:0.6 mmol. After the reaction is finished, cooling to room temperature, carrying out suction filtration, washing for 3 times by using deionized water, drying and grinding to obtain In2S3a/rGO/UiO-66 composite material.
SEM morphology analysis of the obtained sample by Hitachi S-4800II of Japan revealed that UiO-66 regular octahedral shape, good dispersion and In were observed In FIG. 12S3The nano particles are uniformly loaded on the surface of UiO-66, and no obvious agglomeration occurs.
The sample was subjected to uv-vis diffuse reflectance spectroscopy using Agilent Cary 5000, australia, and the results are shown in fig. 2, indicating that the sample responded in both uv-vis range, indicating that it can be used for visible light catalysis.
In prepared In this example2S3the/UiO-66 core-shell structure visible light catalyst is added into 15mg/L methyl orange solution according to the proportion of 0.5g/L, after dark reaction for 40min, and then under the irradiation of visible light, the methyl orange solution can be degraded by 97% in 60 min.
Example 3
1) Firstly, GO (graphene oxide) is prepared by a Hummer method, then the GO is added into deionized water, ultrasonic treatment is carried out for 2 hours to disperse the GO, and then ZrCl is respectively added4And terephthalic acid is added into the aqueous solution of GO, the materials are stirred for 2h and then are moved into a reaction kettle to react for 24h at 180 ℃, and the GO, the deionized water and the ZrCl are4The material ratio of terephthalic acid to terephthalic acid was 0.1g:60ml:2mmol:2.4 mmol. Cooling to room temperature after reaction, suction filtering, washing with deionized water for 3 times, drying, and grindingThen obtaining a rGO/UiO-66 matrix material;
2) redispersing rGO/UiO-66 In deionized water, then In (NO)3)3·5H2O was added to an aqueous solution of rGO/UiO-66, stirred for 4h, then Na was added2S·9H2Adding O, continuously stirring for 2h, finally moving to a reaction kettle, and reacting for 16h at 200 ℃, wherein the rGO/UiO-66, the deionized water and the In (NO) are3)3·5H2O、Na2S·9H2The material ratio of O was 0.1g:60ml:0.3mmol:0.9 mmol. After the reaction is finished, cooling to room temperature, carrying out suction filtration, washing for 3 times by using deionized water, drying and grinding to obtain In2S3a/rGO/UiO-66 composite material.
The sample was subjected to uv-vis diffuse reflectance spectroscopy using Agilent Cary 5000, australia, and the results are shown in the figure, indicating that the sample responded in both the uv-vis range, indicating that it can be used for visible light catalysis.
In prepared In this example2S3the/UiO-66 core-shell structure visible light catalyst is added into 15mg/L methyl orange solution according to the proportion of 0.5g/L, after dark reaction for 40min, and then under the irradiation of visible light, the methyl orange solution can be degraded by 95% within 60 min.
Claims (10)
1. In2S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst is characterized by comprising the following steps:
1) firstly, GO is prepared by a Hummer method, then GO is added into deionized water, ultrasonic treatment is carried out to disperse GO, and then ZrCl is respectively added4Adding terephthalic acid into a GO aqueous solution, stirring the materials, transferring the materials into a reaction kettle, reacting at 120-180 ℃ for 20-24 h, cooling to room temperature after the reaction is finished, performing suction filtration, washing with deionized water, drying, and grinding to obtain a rGO/UiO-66 base material;
2) redispersing rGO/UiO-66 In deionized water, then In (NO)3)3·5H2O was added to an aqueous solution of rGO/UiO-66, followed by Na after stirring2S·9H2Adding O, continuously stirring, finally moving into a reaction kettle, reacting for 12-16 h at 160-200 ℃, cooling to room temperature after the reaction is finished, carrying out suction filtration, washing with deionized water, drying and grinding to obtain In2S3a/rGO/UiO-66 composite material.
2. An In according to claim 12S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst is characterized by carrying out ultrasonic treatment for 1-2 hours in the step (1).
3. An In according to claim 12S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst is characterized in that ZrCl is respectively added in the step (1)4And adding terephthalic acid into the aqueous solution of GO, stirring the materials for 1-2h, and then transferring the materials into a reaction kettle.
4. An In according to claim 12S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst is characterized in that the GO, the deionized water and the ZrCl in the step (1)4The material ratio of terephthalic acid to terephthalic acid is as follows: 0.1g of 40-60 ml of 1-2 mmol of 1-2.4 mmol.
5. An In according to claim 12S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst is characterized in that deionized water is used for washing for 3-6 times in the steps (1) and (2).
6. An In according to claim 12S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst is characterized In that In (NO) is added In the step (2)3)3·5H2Adding O into the aqueous solution of rGO/UiO-66, and stirring for 2-4 h; then Na is added2S·9H2And adding O, and continuously stirring for 1-2 h.
7. According to claim1 In of one kind2S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst is characterized in that drying is carried out by adopting electric heating of an oven, the heating temperature is 80-100 ℃, and the drying time is 1-2 h.
8. An In according to claim 12S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst is characterized In that the rGO/UiO-66, deionized water and In (NO) In the step (2)3)3·5H2O、Na2S·9H2The material ratio of O is 0.1g to 40-60 ml to 0.2-0.3 mmol to 0.3-0.9 mmol.
9. An In according to claim 4 or 82S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst is characterized in that the material ratio can be amplified or reduced in the same proportion.
10. In2S3A/rGO/UiO-66 sandwich type composite visible light catalyst, characterized In that it is formed by one of the In of claims 1 to 92S3The preparation method of the/rGO/UiO-66 sandwich type composite visible light catalyst comprises the steps of covering a layer of UiO-66 on the surface of GO and then covering a layer of In on the outermost layer2S3And preparing the sandwich type composite visible light catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910527964.4A CN112090450A (en) | 2019-06-18 | 2019-06-18 | In2S3/rGO/UiO-66 sandwich type composite catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910527964.4A CN112090450A (en) | 2019-06-18 | 2019-06-18 | In2S3/rGO/UiO-66 sandwich type composite catalyst and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112090450A true CN112090450A (en) | 2020-12-18 |
Family
ID=73749021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910527964.4A Pending CN112090450A (en) | 2019-06-18 | 2019-06-18 | In2S3/rGO/UiO-66 sandwich type composite catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112090450A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113030308A (en) * | 2021-03-02 | 2021-06-25 | 浙江省农业科学院 | Detection method of sulfonamide antibiotics in biogas slurry and sample treatment method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190470A (en) * | 2014-08-26 | 2014-12-10 | 福州大学 | Sandwiched Zr-MOFs (Metal-organic Frameworks)/graphene composite photocatalyst as well as preparation method and application thereof |
| CN105344327A (en) * | 2015-11-26 | 2016-02-24 | 中国科学院生态环境研究中心 | Preparation method of MOFs graphene composite material |
| CN107029672A (en) * | 2017-05-10 | 2017-08-11 | 上海师范大学 | Based on the NH of UIO 662With the graphene synthesis adsorption photochemical catalysis composite of assembling altogether in situ |
| WO2018197715A1 (en) * | 2017-04-28 | 2018-11-01 | Cambridge Enterprise Limited | Composite metal organic framework materials, processes for their manufacture and uses thereof |
| CN108786923A (en) * | 2018-05-08 | 2018-11-13 | 上海应用技术大学 | A kind of preparation method of kernel-shell structure, visible light catalyst |
-
2019
- 2019-06-18 CN CN201910527964.4A patent/CN112090450A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190470A (en) * | 2014-08-26 | 2014-12-10 | 福州大学 | Sandwiched Zr-MOFs (Metal-organic Frameworks)/graphene composite photocatalyst as well as preparation method and application thereof |
| CN105344327A (en) * | 2015-11-26 | 2016-02-24 | 中国科学院生态环境研究中心 | Preparation method of MOFs graphene composite material |
| WO2018197715A1 (en) * | 2017-04-28 | 2018-11-01 | Cambridge Enterprise Limited | Composite metal organic framework materials, processes for their manufacture and uses thereof |
| CN107029672A (en) * | 2017-05-10 | 2017-08-11 | 上海师范大学 | Based on the NH of UIO 662With the graphene synthesis adsorption photochemical catalysis composite of assembling altogether in situ |
| CN108786923A (en) * | 2018-05-08 | 2018-11-13 | 上海应用技术大学 | A kind of preparation method of kernel-shell structure, visible light catalyst |
Non-Patent Citations (3)
| Title |
|---|
| DUANDUAN LIU ET AL.: "Light harvesting and charge management by Ni4S3 modified metal organic frameworks and rGO in the process of photocatalysis", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| KUN-YI ANDREW LIN ET AL.: "Zr-Metal Organic Framework and Derivatives for Adsorptive and Photocatalytic Removal of Acid Dyes", 《WATER ENVIRONMENT RESEARCH》 * |
| XIAOLEI ZHANG ET AL.: "Synthesis of In2S3/UiO-66 hybrid with enhanced photocatalytic activity towards methyl orange and tetracycline hydrochloride degradation under visible-light irradiation", 《MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113030308A (en) * | 2021-03-02 | 2021-06-25 | 浙江省农业科学院 | Detection method of sulfonamide antibiotics in biogas slurry and sample treatment method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108786923B (en) | Preparation method of core-shell structure visible light catalyst | |
| Fang et al. | Facile synthesis of anatase/rutile TiO2/g-C3N4 multi-heterostructure for efficient photocatalytic overall water splitting | |
| Xiao et al. | Synthesis of EDTA-bridged CdS/g-C3N4 heterostructure photocatalyst with enhanced performance for photoredox reactions | |
| CN110152711B (en) | CeO (CeO)2@MoS2/g-C3N4Ternary composite photocatalyst and preparation method thereof | |
| Gao et al. | A regenerable Cu2O/BiOBr S-scheme heterojunction photocatalysts for efficient photocatalytic degradation of mixed organic pollutants | |
| Bi et al. | Direct Z-scheme CoS/g-C3N4 heterojunction with NiS co-catalyst for efficient photocatalytic hydrogen generation | |
| Huang et al. | Construction of a novel Z-scheme V2O5/NH2-MIL-101 (Fe) composite photocatalyst with enhanced photocatalytic degradation of tetracycline | |
| Xu et al. | MOFs-derived C-In2O3/g-C3N4 heterojunction for enhanced photoreduction CO2 | |
| CN112844484B (en) | Boron nitride quantum dot/porous metal organic framework composite photocatalytic material and preparation method and application thereof | |
| Zheng et al. | Preparation and characterization of CuxZn1-xS nanodisks for the efficient visible light photocatalytic activity | |
| CN111185210B (en) | Titanium carbide/titanium dioxide/black phosphorus nanosheet composite photocatalyst and preparation method and application thereof | |
| Huang et al. | Organic-inorganic TCPP/BiOCl hybrids with accelerated interfacial charge separation for boosted photocatalytic performance | |
| CN114522709B (en) | Three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst and preparation method and application thereof | |
| Lou et al. | A facility synthesis of bismuth-iron bimetal MOF composite silver vanadate applied to visible light photocatalysis | |
| CN112717958B (en) | Oxygen-rich vacancy BiOBr/HNb3O8Preparation method and application of nanosheet photocatalyst | |
| CN102580727B (en) | Preparation method of active carbon loaded titanium dioxide silver-doped photochemical catalyst | |
| CN113351231A (en) | Preparation method and catalytic application of high-performance bismuth oxyhalide/graphene nanocomposite | |
| Chen et al. | Immobilization of Bi-based metal-organic framework on g-C3N4 for efficient photocatalytic removal of tetracycline | |
| CN112090450A (en) | In2S3/rGO/UiO-66 sandwich type composite catalyst and preparation method thereof | |
| Luo et al. | Facile synthesis of δ-Bi 2 O 3 particles/rod-like Bi 4 O 7 composite with enhanced visible light-driven photocatalytic performance | |
| CN110586149B (en) | Bismuth molybdate/titanium carbide heterojunction two-dimensional photocatalytic material and preparation method and application thereof | |
| Cao et al. | Construction of nanosized MoP decorated highly crystalline carbon nitride sphere as an excellent photocatalyst for boosted photocatalytic hydrogen production | |
| CN102553591B (en) | A kind of visible light-responded CuAl2o4the preparation and application of-graphene photo-catalyst | |
| CN115608367A (en) | Zn1-xCuxO/TiO with core-shell structure 2 Preparation method and application of photocatalytic composite material | |
| CN112916014B (en) | All-solid-state vector Z mechanism composite photocatalyst CaTiO3/Cu/TiO2Preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201218 |