CN113731411B - Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst - Google Patents
Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst Download PDFInfo
- Publication number
- CN113731411B CN113731411B CN202111120789.0A CN202111120789A CN113731411B CN 113731411 B CN113731411 B CN 113731411B CN 202111120789 A CN202111120789 A CN 202111120789A CN 113731411 B CN113731411 B CN 113731411B
- Authority
- CN
- China
- Prior art keywords
- mos
- solution
- stirring
- composite catalyst
- ternary 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 239000011206 ternary composite Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 101100069231 Caenorhabditis elegans gkow-1 gene Proteins 0.000 title description 2
- 239000011218 binary composite Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 29
- 239000012153 distilled water Substances 0.000 claims description 23
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 238000002835 absorbance Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 6
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000013032 photocatalytic reaction Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 230000000593 degrading effect Effects 0.000 claims 1
- 239000003517 fume Substances 0.000 claims 1
- 229940107698 malachite green Drugs 0.000 claims 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims 1
- 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 1
- 229940043267 rhodamine b Drugs 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000011941 photocatalyst Substances 0.000 abstract 1
- 230000001699 photocatalysis Effects 0.000 description 18
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/682—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium, tantalum or polonium
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
-
- B01J35/39—
-
- 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
Abstract
The invention discloses a Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g‑C 3 N 4 The preparation method and application of the ternary composite catalyst are characterized in that the catalyst is prepared from the following raw materials in parts by weight: cu (Cu) 2 MoS 2 O 4 : 1-10 parts of Ag 2 V 4 O 11 /g‑C 3 N 4 :10 parts. The preparation method comprises the following steps: (1) Cu (Cu) 2 MoS 2 O 4 Is prepared by the steps of (1); (2) Ag (silver) 2 V 4 O 11 /g‑C 3 N 4 Preparing a binary composite material; (3) Cu (Cu) 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g‑C 3 N 4 And (3) preparing the ternary composite catalytic material. The invention synthesizes Cu by wet impregnation method 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g‑C 3 N 4 The ternary photocatalyst has the advantages of convenient operation, low cost, good effect on organic wastewater and good prospect in practical production and commercial application.
Description
Technical Field
The invention relates to a Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 A preparation method and application of a ternary composite catalyst belong to the technical field of catalyst preparation and application.
Background
The generation of printing and dyeing wastewater is an inevitable hazard in the development process of modern industries such as textile, paper making and the like. The printing and dyeing wastewater has strong toxicity, high chromaticity and difficult degradation under natural conditions, so the treatment process is always focused on by researchers. The photocatalysis technology is characterized by green environmental protection, low cost and no secondary pollution, and is a distinct treatment technology.
Graphite phase carbon nitride (g-C) 3 N 4 ) The semiconductor photocatalytic material has the advantages of wide application, low cost and low production cost, is easy to obtain raw materials, has visible light activity and high chemical and thermal stability, and is used in the fields of photocatalytic decomposition of water, degradation of organic pollutants and the like. However, g-C 3 N 4 The forbidden bandwidth is wide (2.7 eV), the specific surface area is small, the visible light response range is narrow, and the photocatalytic performance is greatly limited. Thus, modifying g-C 3 N 4 To overcome the defects and improve the photocatalytic activity of g-C 3 N 4 One of the focus of the study.
Disclosure of Invention
The present invention aims to provide a Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst and Cu used in preparation method 2 MoS 2 O 4 And Ag 2 V 4 O 11 Co-modification of g-C 3 N 4 To improve its photocatalytic efficiency.
In the invention, ag 2 V 4 O 11 Belongs to transition V-group oxide, has narrow forbidden band width (only 1.45 eV), proper energy band structure and strong electron transfer rate, and is one of the emerging photocatalytic materials. Cu (Cu) 2 MoS 2 O 4 Is Bi in 2 MoS 2 O 4 Is based on CuThe sulfur oxide formed instead of Bi, sulfur, can shorten the band gap of the semiconductor. Cu (Cu) 2 MoS 2 O 4 The monomer does not have photocatalytic activity, but after heterojunction is formed with other semiconductors, the photocatalytic activity of the semiconductor can be effectively improved.
The invention provides a Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary composite catalyst consists of the following raw materials in parts by weight:
Cu 2 MoS 2 O 4 :1 to 10 parts of a compound containing,
Ag 2 V 4 O 11 /g-C 3 N 4 :10 parts of Ag 2 V 4 O 11 ：g-C 3 N 4 The mass ratio of (1-100): 100.
the invention provides the Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The preparation method of the ternary composite catalyst is characterized by comprising the following steps:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.5-0.8 g (NH) 4 ） 6 Mo 7 O 24 ·12H 2 O is dissolved in 60-150 mL of distilled water, and then 3.8-5.4 g of Na is added 2 S, stirring was continued until a clear yellow color was obtained. HCl was added dropwise to produce a brown substance and to give off a pungent odor. When the pH is adjusted to 6-8, stirring for 10-30 min, adding 3.6-5.6 g Cu (NO) 3 ） 2 ·3H 2 O, after stirring uniformly, condensing and refluxing for 9-12 hours at 60-80 ℃, collecting an obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 50-80 ℃ for 10-24 hours, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 10-20 mL of distilled water to form a solution A, wherein the concentration is 1-6 mmol/L. Under the condition of heating and magnetic stirring, NH 4 VO 3 Dissolving in 30And (3) in distilled water of 60-mL, a pale yellow clear solution is formed, and is regarded as a solution B, and the concentration is 0.5-2 mmol/L. And adding the solution A into the solution B to generate yellow floccules, wherein the solution A is 0.8-1.2 parts, and the solution B is 1 part.
By HNO 3 And adjusting the pH value of the solution to be 2.2-2.6, and deepening the color of the solution to be orange. Stirring is continued for 30-60 min under heating, and the solution turns to be brownish red. At room temperature, 0.1-2 g g-C is added 3 N 4 Ultrasonic treatment is carried out for 30-60 min, stirring is carried out for 10-24 h, hydrothermal reaction is carried out, reaction products are respectively washed for a plurality of times by distilled water and absolute ethyl alcohol, and drying is carried out for 8-24 h at 50-80 ℃. Ag in the product 2 V 4 O 11 ：g-C 3 N 4 The mass ratio is 1-100: 100;
（3）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 preparation of a ternary composite catalyst:
weighing 0.02-1.0 g of monomer Cu 2 MoS 2 O 4 And 0.4-1.0 g Ag 2 V 4 O 11 /g-C 3 N 4 Placing the mixture into a beaker, adding 30-100 mL of solution, performing ultrasonic dispersion for 60-120 min, and stirring for 2-14 h. Centrifuging the obtained product for 5-10 min at 8000-10000 r/min, taking the precipitate, drying in an oven at 50-80 ℃ for 10-24 h, and grinding to obtain the ternary composite catalyst.
The Cu mentioned above 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The preparation method of the ternary composite catalyst comprises the steps of (2) heating the solution at 20-60 ℃ and performing hydrothermal reaction at 160-190 ℃.
The Cu mentioned above 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method of ternary composite catalyst, cu in step (3) 2 MoS 2 O 4 And Ag 2 V 4 O 11 /g-C 3 N 4 The mass ratio of (2) is 1-10:10.
The Cu mentioned above 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The preparation method of the ternary composite catalyst comprises the step (3), wherein the solution is distilled water, methanol or distilled water/methanol mixture.
The invention provides the Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary composite catalyst is applied to catalytic degradation of organic dye under the condition of visible light.
Taking organic dye active blue 19 as an example, 250 mL active blue 19 with the concentration of 20 mg/L is prepared, and then 0.05-0.12 g Cu is weighed 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp and adding a 420 nm optical filter as a visible light source to carry out photocatalytic reaction, taking one sample every 10 min for the total time of the photocatalytic reaction to be 40 min, taking supernatant after centrifugal separation to measure the absorbance, and calculating a corresponding concentration value according to the absorbance value; the removal rate of active blue 19 was obtained according to the removal rate formula (1):
（1）
wherein: c (C) 0 Is the initial concentration of active blue 19, mg.L -1 ；
C t The concentration of active blue 19 after time t is mg.L -1 。
The removal rate achieved by the method is 98-100%.
The invention has the beneficial effects that:
(1) The invention synthesizes Cu 2 MoS 2 O 4 And narrow bandgap Ag 2 V 4 O 11 And is used for modifying g-C 3 N 4 The visible light response range is widened, the light absorption intensity is enhanced, the photon-generated carrier recombination rate is inhibited, and the g-C is improved 3 N 4 Is used for the photocatalytic performance of the catalyst.
(2) The preparation method provided by the invention is simple and convenient, low in cost, easy to operate and has practical application significance.
(3) Cu in the invention 2 MoS 2 O 4 Effectively improves the binary Ag 2 V 4 O 11 /g-C 3 N 4 The crystallization condition of the catalyst further improves the photocatalysis performance.
(4) Cu synthesized by the invention 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary catalyst can degrade 20 mg/L active blue 19 solution within 40 min, and the degradation rate can reach more than 99%.
Drawings
FIG. 1 is a graph of g-C prepared in example 1 3 N 4 、Cu 2 MoS 2 O 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 X-ray diffraction pattern of ternary composite catalyst;
FIG. 2 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 An ultraviolet-visible diffuse reflection spectrogram of the ternary composite catalyst;
FIG. 3 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Band gap diagram of ternary composite catalyst;
FIG. 4 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Of ternary complex catalystsA fluorescence spectrum;
FIG. 5 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The degradation effect of the ternary composite catalyst on 20 mg/L active blue 19 is shown.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
Example 1:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.6621 g (NH 4 ） 6 Mo 7 O 24 ·12H 2 O was dissolved in 80. 80 mL distilled water, followed by addition of 4.6. 4.6 g Na 2 S, stirring was continued until a clear yellow color was obtained. HCl was added dropwise to produce a brown substance and to give off a pungent odor. When the pH was adjusted to 7, cu (NO) of 4.6375 g was added after stirring for 15 min 3 ） 2 ·3H 2 O, after stirring to be uniform, condensing and refluxing 10 h at 70 ℃, collecting the obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 60 ℃ for 12 h, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 10 mL distilled water to obtain solution A; concentration of 1.2 mmol/L, NH was added under magnetic stirring at 40 ℃ 4 VO 3 Dissolved in 50 mL distilled water to form a pale yellow clear solution, designated solution B, at a concentration of 2.4 mmol/L. Solution a was added to solution B to produce a yellow floc.
By HNO 3 The pH of the solution was adjusted to 2.45, and the color of the solution was then darkened to orange. Stirring continuously for 30 min under heating; the solution turned brownish red. 0.2955 g of C was added at room temperature 3 N 4 Ultrasonic treatment for 60 min, stirring for 11 h; carrying out hydrothermal reaction, and respectively using distilled water and absolute ethyl alcohol to obtain reaction productsWashed three times and dried at 60℃to 14 h.
（3）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation of a ternary composite catalytic material:
weigh 0.24 and g Cu 2 MoS 2 O 4 Mixing with 20A/CN of 0.4. 0.4 g in 30 mL water, ultrasonic treating for 60 min, stirring for 12 h, washing with water and absolute ethanol for several times, centrifuging at 8000 r/min for 6 min, collecting precipitate, drying in oven at 60deg.C for 12 h, and grinding to obtain ternary composite catalytic material.
Preparing 250 mL active blue 19 with the concentration of 20 mg/L, and weighing 0.05-0.12 g Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp and adding a 420 nm optical filter as a visible light source to carry out photocatalysis reaction, taking one sample every 10 min for the total time of the photocatalysis reaction, taking supernatant after centrifugal separation to measure the absorbance, and calculating a corresponding concentration value according to the absorbance value, wherein the total time of the photocatalysis reaction is 40 min, and the concentration value is shown in figure 5.
FIG. 1 is a graph of g-C prepared in example 1 3 N 4 、Cu 2 MoS 2 O 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 X-ray diffraction pattern of ternary composite catalyst. As can be seen by comparison with standard cards (JCPCDS 87-1526 and JCPCDS 49-0166), the alloy is made of Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 g-C was found in the XRD pattern of (C) 3 N 4 And Ag 2 V 4 O 11 Is equivalent to Cu 2 MoS 2 O 4 Characteristic peaks corresponding to monomers can also be found therein, indicating Ag 2 V 4 O 11 And Cu 2 MoS 2 O 4 Successful complexing to g-C 3 N 4 Is a kind of medium.
FIG. 2 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Ultraviolet-visible diffuse reflection spectrogram of ternary composite catalyst. g-C 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Is 470 nm,495 nm and 520 nm, respectively. Indicating Ag 2 V 4 O 11 And Cu 2 MoS 2 O 4 Load of (C) is g-C 3 N 4 The light absorbing edge is red shifted.
FIG. 3 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Band gap diagram of ternary composite catalyst. Ag (silver) 2 V 4 O 11 Let g-C 3 N 4 The band gap is reduced from 2.74 eV to 2.64 eV, cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The formation of the three-way composite catalyst further reduces its bandgap to 2.5 eV.
FIG. 4 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 PL diagram of ternary composite catalyst. Cu (Cu) 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary composite material has the lowest fluorescence intensity, which shows that the synthesis thereof effectively inhibits g-C 3 N 4 Is a photo-generated electron-hole recombination rate.
FIG. 5 is a graph of g-C prepared in example 1 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The degradation effect of the ternary composite catalyst on 20 mg/L active blue 19 is shown. g-C under 40 min photoreaction conditions 3 N 4 、Ag 2 V 4 O 11 /g-C 3 N 4 And Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Degradation rates for active blue 19 were 37.04%, 77.78% and 99.99%, respectively, for Ag 2 V 4 O 11 And Cu 2 MoS 2 O 4 Load of (2) increases g-C 3 N 4 Is a component of the photocatalytic activity of the catalyst.
Example 2:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.8. 0.8 g (NH 4 ） 6 Mo 7 O 24 ·12H 2 O was dissolved in 120. 120 mL distilled water, followed by addition of 5.2. 5.2 g Na 2 S, stirring was continued until a clear yellow color was obtained. HCl was added dropwise to give a brown material. When the pH was adjusted to 8, after stirring for 30 min, cu (NO) of 5 g was added 3 ） 2 ·3H 2 O, after stirring to be uniform, condensing and refluxing 11 h at 70 ℃, collecting the obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 80 ℃ for 18 h, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 20 mL distilled water to obtain solution A; concentration of 3 mmol/L, NH was added under magnetic stirring at 50deg.C 4 VO 3 Dissolved in 40 mL distilled water to form a pale yellow clear solution, which was regarded as solution B, at a concentration of 6 mmol/L. Solution a was added to solution B to produce a yellow floc.
By HNO 3 The pH of the solution was adjusted to 2.5, and the color of the solution was then darkened to orange. Under heating conditionsStirring for 50 min; the solution turned brownish red. At room temperature, 1 g of C-C was added 3 N 4 Ultrasonic for 50 min, stirring for 15 h; the hydrothermal reaction was carried out, and the reaction product was washed three times with distilled water and absolute ethanol, respectively, and dried at 75℃for 24 h.
（3）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation of a ternary composite catalytic material:
weigh 0.7. 0.7 g Cu 2 MoS 2 O 4 Mixing with 20A/CN of 0.6 g in 70 mL water, ultrasonic treating for 100 min, stirring for 8 h, washing with water and absolute ethanol for several times, centrifuging at 10000 r/min for 10 min, collecting precipitate, drying in oven at 80deg.C for 15 h, and grinding to obtain ternary composite catalytic material.
Preparing 250 mL active blue 19 with the concentration of 20 mg/L, and weighing 0.05-0.12 g Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp and adding a 420 nm optical filter as a visible light source to carry out photocatalysis reaction, taking one sample every 10 min for 40 min, taking supernatant after centrifugal separation to measure the absorbance, calculating a corresponding concentration value according to the absorbance value, and preparing a concentration C t Curves over time t to test their photocatalytic effect. Experiments show that: under the light reaction condition of 40 min, cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The degradation rate for active blue 19 was 99%.
Example 3:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.7. 0.7 g (NH 4 ） 6 Mo 7 O 24 ·12H 2 O was dissolved in 100 mL distilled water, followed by addition of 5 g Na 2 S, stirring was continued until a clear yellow color was obtained. Drop (D)HCl was added to give a brown material. When the pH was adjusted to 6, after stirring for 20 min, cu (NO) of 4.2. 4.2 g was added 3 ） 2 ·3H 2 O, after stirring to be uniform, condensing and refluxing 9 h at 65 ℃, collecting the obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 70 ℃ for 14 h, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 15 mL distilled water to obtain solution A; concentration of 2 mmol/L, NH was added under magnetic stirring at 40 ℃ 4 VO 3 Dissolved in 60 mL distilled water to form a pale yellow clear solution, which was regarded as solution B, at a concentration of 4 mmol/L. Solution a was added to solution B to produce a yellow floc.
By HNO 3 The pH of the solution was adjusted to 2.3, and the color of the solution was then darkened to orange. Stirring continuously under heating for 40 min; the solution turned brownish red. At room temperature, 0.5 g of C-C was added 3 N 4 Ultrasonic treatment for 40 min, stirring for 18 h; carrying out hydrothermal reaction, washing the reaction product with distilled water and absolute ethyl alcohol for three times respectively, and drying at 70 ℃ for 18 h;
（3）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 preparation of a ternary composite catalytic material:
weigh 0.5. 0.5 g Cu 2 MoS 2 O 4 Mixing with 20A/CN of 0.8. 0.8 g in 50 mL water, ultrasonic treating for 80 min, stirring for 10 h, washing with water and absolute ethanol for several times, centrifuging at 9000 r/min for 8 min, collecting precipitate, drying in oven at 70deg.C for 10 h, and grinding to obtain ternary composite catalytic material.
Preparing 250 mL active blue 19 with the concentration of 20 mg/L, and weighing 0.05-0.12 g Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; later is collectedPerforming photocatalytic reaction with 300W xenon lamp and 420 nm filter as visible light source for 40 min, taking one sample every 10 min, centrifuging, collecting supernatant, measuring absorbance, calculating corresponding concentration value according to absorbance value, and making concentration C t Curves over time t to test their photocatalytic effect. Experiments show that: under the light reaction condition of 40 min, cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The degradation rate for active blue 19 was 98.89%.
Claims (6)
1. Cu (copper) alloy 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary composite catalyst is characterized by comprising the following raw materials in parts by weight:
Cu 2 MoS 2 O 4 :1 to 10 parts of a compound containing,
Ag 2 V 4 O 11 /g-C 3 N 4 :10 parts of Ag therein 2 V 4 O 11 ：g-C 3 N 4 The mass ratio of (1-100): 100;
the Cu is 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The preparation method of the ternary composite catalyst comprises the following steps:
（1）Cu 2 MoS 2 O 4 is prepared from the following steps:
under magnetic stirring, 0.5-0.8 g (NH) 4 ） 6 Mo 7 O 24 ·12H 2 O is dissolved in 60-150 mL of distilled water, and then 3.8-5.4 g of Na is added 2 S, continuously stirring until the mixture is clear yellow; dripping HCl to generate brown substances and giving off pungent odor; when the pH is adjusted to 6-8, stirring for 10-30 min, adding 3.6-5.6 g Cu (NO) 3 ） 2 ·3H 2 O, after stirring uniformly, condensing and refluxing for 9-12 hours at 60-80 ℃, collecting an obtained sample, washing the sample with water and absolute ethyl alcohol for several times, drying the sample at 50-80 ℃ for 10-24 hours, and grinding the sample;
（2）Ag 2 V 4 O 11 /g-C 3 N 4 preparation of binary composite material:
AgNO is to be carried out 3 Dissolving in 10-20 mL of distilled water to form a solution A, wherein the concentration is 1-6 mmol/L; NH was stirred under heated magnetic force 4 VO 3 Dissolving the solution in 30-60 mL of distilled water to form a pale yellow clear solution, wherein the pale yellow clear solution is regarded as solution B, and the concentration is 0.5-2 mmol/L; adding the solution A into the solution B to generate yellow floccules, wherein the mass ratio of the solution A to the solution B is 0.8-1.2: 1, a step of;
by HNO 3 Adjusting the pH value of the solution to be 2.2-2.6, and deepening the color of the solution to be orange; continuously stirring for 30-60 min under heating, and changing the solution into brownish red; at room temperature, 0.1-2 g g-C is added 3 N 4 Performing ultrasonic treatment for 30-60 min, stirring for 10-24 h, performing hydrothermal reaction, washing the reaction product with distilled water and absolute ethyl alcohol for several times, and drying at 50-80 ℃ for 8-24 h;
（3）Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 preparation of a ternary composite catalyst:
weighing quantitative monomer Cu 2 MoS 2 O 4 And 0.4-1.0 g Ag 2 V 4 O 11 /g-C 3 N 4 Placing the mixture in a beaker, adding 30-100 mL of solution, performing ultrasonic dispersion for 60-120 min, and stirring for 2-14 h in a fume hood; centrifuging the obtained product for 5-10 min at 8000-10000 r/min, taking the precipitate, drying in an oven at 50-80 ℃ for 10-24 h, and grinding.
2. Cu according to claim 1 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 The ternary composite catalyst is characterized in that the heating temperature of the solution in the step (2) is 20-60 ℃, and the heating temperature of the hydrothermal reaction is 160-190 ℃.
3. Cu according to claim 1 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Ternary elementThe composite catalyst is characterized in that the solution used in the step (3) is one or a mixture of distilled water and methanol.
4. A Cu according to claim 1 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Application of ternary composite catalyst in catalyzing and degrading organic dye under visible light condition.
5. The use according to claim 4, characterized in that: the organic dye comprises one of active blue 19, rhodamine B and malachite green.
6. The use according to claim 5, characterized in that: preparing 250 mL active blue 19 with the concentration of 20 mg/L, and weighing 0.05-0.12 g Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Adding a three-way catalyst into the active blue 19 solution, performing ultrasonic treatment under dark condition for 10 min to uniformly disperse the catalyst, and then performing magnetic stirring in a dark box for 30 min to make the solution reach adsorption-desorption equilibrium; then adopting a 300W xenon lamp and adding a 420 nm optical filter as a visible light source to carry out photocatalytic reaction, taking one sample every 10 min for the total time of the photocatalytic reaction to be 40 min, taking supernatant after centrifugal separation to measure the absorbance, and calculating a corresponding concentration value according to the absorbance value; the removal rate of active blue 19 was obtained according to the removal rate formula (1):
（1）
wherein: c (C) 0 Is the initial concentration of active blue 19, mg.L -1 ；
C t The concentration of active blue 19 after time t is mg.L -1 。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111120789.0A CN113731411B (en) | 2021-09-24 | 2021-09-24 | Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111120789.0A CN113731411B (en) | 2021-09-24 | 2021-09-24 | Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113731411A CN113731411A (en) | 2021-12-03 |
| CN113731411B true CN113731411B (en) | 2023-12-19 |
Family
ID=78740760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111120789.0A Active CN113731411B (en) | 2021-09-24 | 2021-09-24 | Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113731411B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076384A (en) * | 2016-06-12 | 2016-11-09 | 江苏大学 | A kind of tri compound catalysis material and its production and use |
| CN108262054A (en) * | 2018-03-06 | 2018-07-10 | 内蒙古大学 | A kind of preparation method of silver vanadate/nitride porous carbon heterojunction composite photocatalyst |
| CN109225304A (en) * | 2018-10-25 | 2019-01-18 | 聊城大学 | A kind of visible light-responded Ag4V2O7/g-C3N4The preparation method of catalysis material |
| CN109806900A (en) * | 2019-02-20 | 2019-05-28 | 江苏大学 | A kind of molecular imprinting Ag/Ag3VO4The preparation method and application of/CN nanometer sheet composite photo-catalyst |
| CN113058601A (en) * | 2021-03-26 | 2021-07-02 | 华东理工大学 | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting |
-
2021
- 2021-09-24 CN CN202111120789.0A patent/CN113731411B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076384A (en) * | 2016-06-12 | 2016-11-09 | 江苏大学 | A kind of tri compound catalysis material and its production and use |
| CN108262054A (en) * | 2018-03-06 | 2018-07-10 | 内蒙古大学 | A kind of preparation method of silver vanadate/nitride porous carbon heterojunction composite photocatalyst |
| CN109225304A (en) * | 2018-10-25 | 2019-01-18 | 聊城大学 | A kind of visible light-responded Ag4V2O7/g-C3N4The preparation method of catalysis material |
| CN109806900A (en) * | 2019-02-20 | 2019-05-28 | 江苏大学 | A kind of molecular imprinting Ag/Ag3VO4The preparation method and application of/CN nanometer sheet composite photo-catalyst |
| CN113058601A (en) * | 2021-03-26 | 2021-07-02 | 华东理工大学 | Preparation method and application of ternary composite catalyst for photocatalytic hydrogen production by water splitting |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113731411A (en) | 2021-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111453804B (en) | Preparation method of iron-doped graphite-like phase carbon nitride/graphene multifunctional nano composite material | |
| CN109589989B (en) | ZnIn2S4Nanosheet-wrapped beta-Bi2O3Core-shell heterogeneous composite photocatalyst and preparation method and application thereof | |
| CN108993604B (en) | High visible light activity AgIn5S8/UIO-66-NH2Composite material and preparation method and application thereof | |
| CN108816268B (en) | Composite photocatalytic nanomaterial and preparation method thereof, and pollutant degradation method | |
| CN106944074B (en) | A kind of visible-light response type composite photo-catalyst and its preparation method and application | |
| CN109225273B (en) | Copper sulfide/tungsten sulfide composite photocatalyst and preparation method thereof | |
| CN110385146B (en) | Ni0.85Se/PDA/g-C3N4Composite photocatalyst and application thereof | |
| CN109317137B (en) | Hydrotalcite and bismuth molybdate heterojunction composite photocatalyst and preparation method and application thereof | |
| CN108855131B (en) | Preparation and application of silver-nickel bimetal doped titanium dioxide nano composite material | |
| CN108355700B (en) | Polyoxometallate and compound, preparation method and application thereof | |
| CN113457663A (en) | 3D nano flower-shaped Zn3(VO4)2Preparation method and application thereof | |
| CN113731451A (en) | Ternary composite catalytic material for removing tetracycline in wastewater and preparation method thereof | |
| CN113578313B (en) | Manganese-doped sillenite photocatalyst, preparation method thereof and application thereof in synchronous degradation of hexavalent chromium and organic pollutants | |
| CN106362742B (en) | A kind of Ag/ZnO nano-complex and its preparation method and application | |
| CN114192102A (en) | One-step preparation of polyacid-modified graphite-phase carbon nitride material and application thereof | |
| CN107899594B (en) | Carbon-point-modified copper hydroxyphosphate photocatalytic material and preparation method thereof | |
| CN113731411B (en) | Cu 2 MoS 2 O 4 /Ag 2 V 4 O 11 /g-C 3 N 4 Preparation method and application of ternary composite catalyst | |
| CN111939957A (en) | Preparation method of photocatalytic nitrogen fixation material porous carbon nitride nanofiber/graphene | |
| CN112495420A (en) | Preparation method of nitrogen-rich graphite phase carbon nitride/silver metavanadate composite photocatalyst | |
| CN109569569B (en) | Photocatalyst with ternary heterojunction structure and preparation method and application thereof | |
| CN109833887B (en) | Preparation method of visible light degradation organic dye composite catalyst | |
| CN110694655A (en) | Preparation method of silver sulfide/silver phosphate/graphene oxide composite photocatalyst | |
| CN114602450B (en) | Co/Zn-g-C 3 N 4 Photocatalytic material, preparation and application thereof | |
| CN115608388A (en) | Shell-core type Cs 3 PMo 12 O 40 /MnIn 2 S 4 Composite photocatalyst and preparation method and application thereof | |
| CN115069271A (en) | Composite material photocatalyst for efficiently treating chromium-containing wastewater and preparation method 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |