CN116586111B - Floatable photocatalytic material and preparation method and application thereof - Google Patents
Floatable photocatalytic material and preparation method and application thereof Download PDFInfo
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 40
- 239000002033 PVDF binder Substances 0.000 claims abstract description 39
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 238000002791 soaking Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 239000004201 L-cysteine Substances 0.000 claims description 5
- 235000013878 L-cysteine Nutrition 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 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
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 4
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002336 sorption--desorption measurement Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000011941 photocatalyst Substances 0.000 abstract description 8
- 241000282326 Felis catus Species 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 150000007974 melamines Chemical class 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- HHDOORYZQSEMGM-UHFFFAOYSA-L potassium;oxalate;titanium(4+) Chemical compound [K+].[Ti+4].[O-]C(=O)C([O-])=O HHDOORYZQSEMGM-UHFFFAOYSA-L 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002699 waste material Substances 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0242—Coating followed by impregnation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
Abstract
The invention relates to a floatable photocatalytic material, a preparation method and application thereof, belonging to the technical field of high-added-value chemical and catalyst production. The preparation method comprises the following steps: obtaining In by hydrothermal method 2 S 3 Micro-flowers, and synthesizing micro-flower NiCo by solvothermal method 2 S 4 /In 2 S 3 Photocatalyst by incorporating NiCo 2 S 4 /In 2 S 3 The floatable photocatalytic material NiCo is obtained by being loaded on PVDF modified Melamine Sponge (MS) 2 S 4 /In 2 S 3 PVDF/MS, irradiated for 1.5h with visible light, by overcoming O in water 2 Is a floatable photocatalytic material NiCo 2 S 4 /In 2 S 3 H of PVDF/MS 2 O 2 The production rate can reach 842.7 mu mol g cat ‑1 ·h ‑1 . The invention is H 2 O 2 Provides a feasible way for the photocatalytic production of the catalyst, and improves the circularity of the catalyst and the stability of the catalytic application.
Description
Technical Field
The invention belongs to the technical field of high-added-value chemicals and catalyst production, and particularly relates to a floatable photocatalytic material and a preparation method and application thereof.
Background
The photocatalysis technology is a mature green technology which is energy-saving and environment-friendly, and has potential application prospect in green production and green pollutant degradation.
Hydrogen peroxide (H) 2 O 2 ) As an environment-friendly oxidizing agent using only water and oxygen as by-products, attention has been paid. It is not only wideIs widely applied to the fields of organic synthesis, disinfection, pulp bleaching, fuel cells and the like, as an important component of Fenton reagent, the compound can be applied to environmental remediation. Currently, H 2 O 2 The production of (a) mainly adopts the traditional anthraquinone method with high energy consumption and dense waste, and the method is not sustainable from the aspects of energy conservation and environmental protection. In recent years, H is produced by photocatalysis 2 O 2 The process only needs water, oxygen and sunlight as raw materials, and has the advantages of no secondary pollution, simple equipment, low cost, high yield and the like. Photocatalytic production of H using conventional powder catalysts 2 O 2 Easy occurrence of difficult recovery of catalyst, poor cyclic stability and H 2 O 2 The problems of difficult complete separation from the powder catalyst, etc., and the related modification of the photocatalytic material combining the Melamine Sponge (MS) substrate and the powder photocatalyst can effectively overcome these drawbacks.
The research shows that the micro-flower photocatalyst generally has better visible light absorption capacity and visible light utilization efficiency, and the MS has the advantages of three-dimensional structure, large porosity, low cost, good flexibility, easy modification, environmental friendliness and the like, and is a very good substrate candidate material. Therefore, the design and construction of floatable photocatalytic material will be a very effective one for the production of H 2 O 2 Is a policy of (2).
Disclosure of Invention
In order to solve the problems, the invention provides a floatable photocatalytic material, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a floatable photocatalytic material is prepared by the following steps:
1) InCl is added to 3 ·4H 2 Dissolving O and L-cysteine In deionized water to form uniform solution, adjusting pH to 8.0, transferring into autoclave for reaction, naturally cooling to room temperature, centrifuging the precipitate, washing with water and ethanol for several times, and oven drying to obtain In 2 S 3 ；
2) In is to 2 S 3 Dispersed inAdding Ni (NO) into ethylene glycol 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、CH 4 N 2 S and CH 3 Uniformly stirring COONa, transferring into an autoclave for reaction, naturally cooling to room temperature, collecting a sample, washing with deionized water and ethanol for several times, and drying to obtain NiCo 2 S 4 /In 2 S 3 ；
3) Dispersing PVDF in a mixed solution of water and ethanol by ultrasonic waves to prepare a dispersion liquid A; niCo is prepared 2 S 4 /In 2 S 3 Dispersing in a mixed solution of water and ethanol by ultrasonic waves to prepare a dispersion liquid B; soaking melamine sponge in the dispersion liquid A, and calcining to obtain PVDF/MS; then soaking PVDF/MS in the dispersion liquid B, and calcining to obtain NiCo 2 S 4 /In 2 S 3 /PVDF/MS。
Further, in the above floatable photocatalytic material, in step 1), the ratio of the moles of the InCl is 3 ·4H 2 O:L-cysteine＝1:4。
Further, in the above floatable photocatalytic material, in step 1), the reaction is performed by heating at 180 ℃ for 10 hours.
Further, in the above-mentioned floatable photocatalytic material, in the step 2), in the following mass ratio 2 S 3 :Ni(NO 3 ) 2 ·6H 2 O:Co(NO 3 ) 2 ·6H 2 O:CH 4 N 2 S:CH 3 COONa＝72:7.7:15.3:10:5.3。
Further, in step 2) of the floatable photocatalytic material described above, the reaction is performed by heating at 200℃for 12 hours.
Further, in the above floatable photocatalytic material, in step 3), the soaking time is 5-15min.
Further, in the above floatable photocatalytic material, in step 3), the calcination is performed at 240 ℃ for 0.5h.
Use of a floatable photocatalytic material according to any of the preceding claims for the photocatalytic production of hydrogen peroxide.
Further, the application method comprises the following steps: placing floatable photocatalytic material in quartz reaction container, under the condition of ambient temperature 25 deg.C adopting 300W xenon lamp to simulate sunlight irradiation, the xenon lamp lambda is greater than or equal to 420nm, in deionized water containing ethyl alcohol regulating pH value to acidity so as to make O 2 Bubbling continuously and uniformly in the solution, magnetically stirring for 30min in the dark to reach adsorption-desorption balance before irradiation, and then reacting under the drive of light to catalyze and synthesize H 2 O 2 。
Further, the above application, the pH adjustment is performed by using HClO 4 The pH was adjusted to 3.
The beneficial effects of the invention are as follows: the invention uses powder photocatalyst NiCo 2 S 4 /In 2 S 3 In combination with porous melamine sponge, further promote O 2 Mass transfer, increase O at reaction interface 2 Concentration, thereby improving the photocatalytic production of H 2 O 2 Is a compound of formula (I). With the method of the invention, the light irradiation and O are performed under the condition of visible light 2 H of floatable photocatalytic material under bubbling for 1.5H 2 O 2 The production rate can reach 842.7 mu mol g cat -1 ·h -1 Higher than the powder photocatalyst NiCo 2 S 4 /In 2 S 3 H of (2) 2 O 2 Production rate, H 2 O 2 Green synthetic routes and sustainable technology are provided.
Drawings
FIG. 1 is a scanning electron microscope image of the sample of example 1, in which (a) is an SEM image of PVDF/MS and (b) is NiCo 2 S 4 /In 2 S 3 SEM image and enlarged image of PVDF/MS, (c) SEM image and enlarged image of PVDF microsphere surface, and (d) SEM image and enlarged image of MS skeleton surface.
FIG. 2 is NiCo 2 S 4 /In 2 S 3 XRD diffraction pattern of PVDF.
FIG. 3 is NiCo 2 S 4 /In 2 S 3 Linear Sweep Voltammogram (LSV) plots in different gaseous environments.
FIG. 4 is a powder catalyst NiCo 2 S 4 /In 2 S 3 And floatable photocatalytic material NiCo 2 S 4 /In 2 S 3 PVDF/MS photocatalytic synthesis of H 2 O 2 Yield comparison graph.
FIG. 5 is a powder catalyst NiCo 2 S 4 /In 2 S 3 And floatable photocatalytic material NiCo 2 S 4 /In 2 S 3 Comparison of recycling performance of PVDF/MS.
FIG. 6 is a powder catalyst NiCo 2 S 4 /In 2 S 3 And floatable photocatalytic material NiCo 2 S 4 /In 2 S 3 PVDF/MS utilization O 2 Photocatalytic production of H 2 O 2 Is a schematic diagram of (a).
Detailed Description
The invention is further described below in connection with specific examples.
EXAMPLE 1 floatable photocatalytic material NiCo 2 S 4 /In 2 S 3 Preparation of PVDF/MS (one) micro-flower-like In 2 S 3 Is prepared from
0.5mmol of InCl was weighed out separately 3 ·4H 2 O and 2mmol of L-cysteine are dissolved In 80mL of deionized water, stirred to form a clear solution, the pH of the solution is adjusted to 8.0, then the solution is transferred into an autoclave, reacted for 10 hours at 180 ℃, naturally cooled to room temperature, the product is collected by centrifugation, washed with deionized water and ethanol for several times, and dried for 12 hours at 60 ℃ to obtain In 2 S 3 。
(II) micro-flower NiCo 2 S 4 /In 2 S 3 Is prepared from
Weigh 0.072g In 2 S 3 Dispersing in 60mL glycol, sequentially adding a certain amount of Co (NO) 3 ) 2 ·6H 2 O、Ni(NO 3 ) 2 ·6H 2 O、CH 4 N 2 S and CH 3 COONa, in 2 S 3 、Ni(NO 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、CH 4 N 2 S and CH 3 The mass ratio of COONa is 72:7.7:15.3:10:5.3, stirring is continued for 1h, then the solution is transferred into an autoclave, heating is carried out for 12h at 200 ℃, precipitate is collected by centrifugation after natural cooling to room temperature, deionized water and ethanol are used for washing for several times, and drying is carried out at 60 ℃ for 12h, thus obtaining the micro-flower NiCo 2 S 4 /In 2 S 3 。
(III) floatable NiCo 2 S 4 /In 2 S 3 Preparation of PVDF/MS
45mg of PVDF is weighed and dispersed in 15mL of mixed solution of ethanol and water, melamine sponge MS is soaked in the mixed solution for 5-15min, and the reaction is carried out for 0.5h at the temperature of 240 ℃ in a muffle furnace, so that PVDF modified MS (PVDF/MS) is obtained; weigh 5mg of NiCo 2 S 4 /In 2 S 3 Dispersing in 5mL ethanol and water mixed solution, soaking PVDF/MS in the mixed solution for 5-15min, and reacting in a muffle furnace at 240 ℃ for 0.5h to obtain floatable NiCo 2 S 4 /In 2 S 3 /PVDF/MS。
(IV) test
1. As shown in FIG. 1, (a) - (d) are PVDF/MS, niCo respectively 2 S 4 /In 2 S 3 PVDF/MS, morphology of PVDF microsphere surface and MS backbone surface. It can be observed that PVDF/MS has a smooth surface, niCo 2 S 4 /In 2 S 3 The PVDF/MS surface becomes quite rough, and the micro-flower NiCo grows on the PVDF microsphere and the MS skeleton surface 2 S 4 /In 2 S 3 。
2. As shown in FIG. 2, niCo was determined by XRD diffraction patterns 2 S 4 /In 2 S 3 The crystalline structure of PVDF confirms the successful synthesis of the catalyst.
EXAMPLE 2 photocatalytic production of H 2 O 2
The method comprises the following steps:
NiCo obtained in example 1 2 S 4 /In 2 S 3 Powder photocatalyst and floatable NiCo 2 S 4 /In 2 S 3 PVDF/MS was used as the photocatalytic material and was placed in 20mL containing ethyleneIn deionized water of alcohol, 0.5mol/L HClO was used 4 Regulating the pH value of the solution to 3, and continuously introducing O into the solution under the dark condition 2 30min, under the condition of 25 ℃ of ambient temperature, adopting a 300W xenon lamp to irradiate simulated solar light, lambda is more than or equal to 420nm, taking out 0.5mL of solution every 30min in the process of photo-driven catalytic reaction, and detecting H by using a titanium potassium oxalate colorimetric method 2 O 2 Is a product of the above process.
(one) by subjecting NiCo to different gas environments 2 S 4 /In 2 S 3 Linear Sweep Voltammogram (LSV) test was performed
NiCo is prepared 2 S 4 /In 2 S 3 At O 2 And N 2 A Linear Sweep Voltammogram (LSV) test was performed in an atmosphere and the results are shown in FIG. 3 at O 2 The Oxygen Reduction Reaction (ORR) peak at-0.5V vs SCE appears in the atmosphere, while N 2 No ORR peak in the atmosphere, indicating NiCo 2 S 4 /In 2 S 3 At O 2 Oxygen reduction reactions may occur in the atmosphere.
(II) NiCo 2 S 4 /In 2 S 3 Photocatalyst and floatable NiCo 2 S 4 /In 2 S 3 Production of H by PVDF/MS photocatalytic material 2 O 2 Comparison
Determination of NiCo 2 S 4 /In 2 S 3 Photocatalyst and floatable NiCo 2 S 4 /In 2 S 3 PVDF/MS photocatalytic material for producing H under same experimental conditions 2 O 2 As shown in FIG. 4, niCo was irradiated with visible light for 1.5 hours 2 S 4 /In 2 S 3 H of (2) 2 O 2 The production rate reaches 394.2 mu mol g cat -1 ·h -1 By overcoming O in water 2 NiCo, transmission limit of (C) 2 S 4 /In 2 S 3 H of PVDF/MS 2 O 2 The production rate can reach 842.7 mu mol g cat -1 ·h -1 。
(III) carrying out photocatalysis to generate H 2 O 2 Is evaluated by the cycle test of (2)Valence NiCo 2 S 4 /In 2 S 3 Powdered catalyst and floatable NiCo 2 S 4 /In 2 S 3 Stability and recyclability of PVDF/MS
As shown in fig. 5, both catalytic materials can be recycled at least four times without significant performance degradation.
(IV) utilize O 2 Photocatalytic production of H 2 O 2 Is based on the principle of the following
As shown in FIG. 6, O is formed by coating a PVDF gas diffusion layer on the MS of porous network structure 2 Can be rapidly transferred to NiCo 2 S 4 /In 2 S 3 The catalyst layer greatly increases the oxygen concentration on the surface of the catalyst. In brief, in floatable NiCo 2 S 4 /In 2 S 3 In the PVDF/MS system, niCo 2 S 4 /In 2 S 3 Can be directly connected with O in the diffusion layer 2 Fully contact, not with dissolved oxygen in water, thus O 2 The utilization rate is high, and the oxygen reduction reaction is enhanced.
Claims (10)
1. A floatable photocatalytic material characterized in that the preparation method comprises the following steps:
1) InCl is added to 3 ·4H 2 Dissolving O and L-cysteine In deionized water to form uniform solution, adjusting pH to 8.0, transferring into autoclave for reaction, naturally cooling to room temperature, centrifuging the precipitate, washing with water and ethanol for several times, and oven drying to obtain In 2 S 3 ；
2) In is to 2 S 3 Dispersing in glycol, and sequentially adding Ni (NO) 3 ) 2 ·6H 2 O、Co(NO 3 ) 2 ·6H 2 O、CH 4 N 2 S and CH 3 Uniformly stirring COONa, transferring into an autoclave for reaction, naturally cooling to room temperature, collecting a sample, washing with deionized water and ethanol for several times, and drying to obtain NiCo 2 S 4 /In 2 S 3 ；
3) Ultrasound dispersion of PVDF in water and ethanolPreparing a dispersion liquid A in the mixed solution; niCo is prepared 2 S 4 /In 2 S 3 Dispersing in a mixed solution of water and ethanol by ultrasonic waves to prepare a dispersion liquid B; soaking melamine sponge in the dispersion liquid A, and calcining to obtain PVDF/MS; then soaking PVDF/MS in the dispersion liquid B, and calcining to obtain NiCo 2 S 4 /In 2 S 3 /PVDF/MS。
2. A floatable photocatalytic material according to claim 1, characterized in that in step 1), in molar ratio, inCl 3 ·4H 2 O:L-cysteine＝1:4。
3. A floatable photocatalytic material according to claim 1, characterized in that in step 1) the reaction is heated at 180 ℃ for 10 hours.
4. A floatable photocatalytic material according to claim 1, characterized In that In step 2) In terms of mass ratio, in 2 S 3 :Ni(NO 3 ) 2 ·6H 2 O:Co(NO 3 ) 2 ·6H 2 O:CH 4 N 2 S:CH 3 COONa＝72:7.7:15.3:10:5.3。
5. A floatable photocatalytic material according to claim 1, characterized in that in step 2) the reaction is heated at 200 ℃ for 12 hours.
6. A floatable photocatalytic material according to claim 1, characterized in that in step 3), the soaking time is 5-15min.
7. A floatable photocatalytic material according to claim 1, characterized in that in step 3) the calcination is performed at 240 ℃ for 0.5h.
8. Use of a floatable photocatalytic material according to any of the claims 1-7 for the photocatalytic production of hydrogen peroxide.
9. The use according to claim 8, characterized in that the method is as follows: placing the floatable photocatalytic material according to any of claims 1-7 in a quartz reaction vessel, under the condition of ambient temperature of 25 deg.C using 300W xenon lamp to simulate sunlight irradiation, the lambda of xenon lamp is greater than or equal to 420nm, in deionized water containing alcohol, regulating pH to acidity to make O 2 Bubbling continuously and uniformly in the solution, magnetically stirring for 30min in the dark to reach adsorption-desorption balance before irradiation, and then reacting under the drive of light to catalyze and synthesize H 2 O 2 。
10. The use according to claim 9, wherein the pH adjustment is performed by HClO 4 The pH was adjusted to 3.
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| CN116586111B true CN116586111B (en) | 2024-03-26 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337485A (en) * | 2020-11-12 | 2021-02-09 | 中国矿业大学 | Dicobalt tetrasulfide-diindium tetrasulfide compound, preparation method and application |
| CN112844415A (en) * | 2020-12-15 | 2021-05-28 | 沂水鸿羽环境科技中心 | Ecological environment restoration agent |
| CN115970765A (en) * | 2023-02-13 | 2023-04-18 | 吉林大学 | Bionic floatable photocatalytic material with 3D three-phase interface, preparation method and application of material in ammonia synthesis by photocatalytic nitrogen reduction |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112337485A (en) * | 2020-11-12 | 2021-02-09 | 中国矿业大学 | Dicobalt tetrasulfide-diindium tetrasulfide compound, preparation method and application |
| CN112844415A (en) * | 2020-12-15 | 2021-05-28 | 沂水鸿羽环境科技中心 | Ecological environment restoration agent |
| CN115970765A (en) * | 2023-02-13 | 2023-04-18 | 吉林大学 | Bionic floatable photocatalytic material with 3D three-phase interface, preparation method and application of material in ammonia synthesis by photocatalytic nitrogen reduction |
Non-Patent Citations (2)
| Title |
|---|
| "Mechanistic insights into efficient photocatalytic H2O2 production of 2D/ 2D g-C3N4/In2S3 photocatalyst by tracking charge flow direction";Huabin Chen et al.;《Chemical Engineering Journal》;第462卷;第1-15页 * |
| "Hierarchical NiCo2S4/ZnIn2S4 heterostructured prisms: High-efficient photocatalysts for hydrogen production under visible-light";Kai Wu et al.;《Journal of Colloid and Interface Science》;第619卷;第339-347页 * |
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