CN115069273B - Surface oleophylic sulfur indium zinc-based photocatalyst for fuel denitrification and preparation method and application thereof - Google Patents
Surface oleophylic sulfur indium zinc-based photocatalyst for fuel denitrification and preparation method and application thereof Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 22
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011941 photocatalyst Substances 0.000 title abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000000295 fuel oil Substances 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 10
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 6
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims abstract description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 3
- 239000011592 zinc chloride Substances 0.000 claims abstract description 3
- 238000007540 photo-reduction reaction Methods 0.000 claims abstract 2
- 239000002994 raw material Substances 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 238000013461 design Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- -1 nitrogen-containing compound Chemical class 0.000 abstract description 5
- 238000012546 transfer Methods 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 5
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 4
- 238000000643 oven drying Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 241000282412 Homo Species 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- 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
- 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
- B01J27/045—Platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G32/00—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms
- C10G32/04—Refining of hydrocarbon oils by electric or magnetic means, by irradiation, or by using microorganisms by particle radiation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a preparation method and application of a surface oleophylic sulfur indium zinc-based photocatalyst for fuel denitrification, and belongs to the fields of catalyst design preparation and liquid phase nitride removal. The surface oleophilic Pt/ZnIn 2 S 4 The composite catalyst takes zinc chloride, indium nitrate and thioacetamide as raw materials to hydrothermally synthesize ZnIn 2 S 4 The method comprises the steps of carrying out a first treatment on the surface of the To prepare ZnIn 2 S 4 The surface oleophylic Pt/ZnIn is prepared by modifying Pt with different proportions by a method through photoreduction and modifying cetyl trimethyl ammonium bromide 2 S 4 . In the obtained catalyst, the introduction of Pt provides an active site for the selective adsorption of the nitrogen-containing compound on the surface of the catalyst; the design of the surface oleophilic structure provides a guarantee for efficient mass transfer of the catalyst in a fuel system. Therefore, the catalyst prepared by design shows excellent performance in the denitrification of photocatalytic fuel oil. The preparation method of the invention has simple operation, high catalyst activity and stability and great application potential.
Description
Technical Field
The invention belongs to the field of catalyst design preparation and liquid phase nitride removal, and particularly relates to a preparation method and application of a surface oleophylic sulfur indium zinc-based photocatalyst for fuel oil denitrification.
Background
With the rapid development of society, the demand for fossil fuels by humans is increasing. Among them, environmental problems are increasingly raised due to the consumption of a large amount of fuel. In particular to nitrogen-containing compounds in fuel oil, which can generate highly toxic NO after combustion x Resulting in the formation of photochemical smog and acid rain, which seriously threatens the atmospheric environment and the life health of human beings. The search for effective fuel denitrification technology is significant. Currently, hydrodenitrogenation techniques widely used in industry are required to be performed under high-temperature and high-pressure conditions, and in addition, are highly required for equipment. Therefore, developing a green sustainable fuel denitrification process under mild conditions is a very challenging task.
The photocatalytic fuel oil denitrification technology can directly convert nitrogen-containing organic compounds in fuel oil into NH under mild conditions by taking sunlight as driving force 3 And is considered to be one of the most desirable denitrification pathways. However, the photocatalytic fuel oil denitrification technology is still rarely reported at present. This is mainly due to the challenges with solar denitrification processes: firstly, the problem of selective adsorption of the nitrogen-containing compound on the surface of the catalyst is solved, and how to realize the selective adsorption of the nitrogen-containing compound by the design of the catalyst structure plays an important role in improving the denitrification efficiency; secondly, the dispersibility of the catalyst in an oil phase system is poor, and most of photocatalysts are difficult to participate in the reaction due to poor dispersibility in a fuel oil system caused by surface hydrophilicity; thirdly, the photocatalyst carrier utilization rate is not high.
Based on the above, it is necessary to develop a novel composite surface oleophilic photocatalyst to achieve selective adsorption of nitrogen-containing compounds and high solar energy utilization.
Disclosure of Invention
The invention aims at: aiming at the problems existing in the prior art, the surface oleophilic Pt modified ZnIn is provided 2 S 4 The composite photocatalyst promotes the selective adsorption of nitrogen-containing compounds, improves the mass transfer efficiency of the catalyst in a fuel system, improves the sunlight utilization rate, and realizes the high-efficiency photocatalytic fuel denitrification performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
surface oleophylic Pt modified ZnIn for fuel denitrification 2 S 4 The preparation method of the composite photocatalyst comprises the following steps:
(1) Adding zinc chloride, indium nitrate and thioacetamide into deionized water according to a certain molar ratio, and stirring until the components are completely dissolved to obtain a mixed transparent clear solution;
(2) Transferring the solution to a high-pressure reaction kettle, reacting at 160 ℃ for 12 hours, cooling to room temperature after the reaction is finished, centrifugally separating, washing precipitate with distilled water and ethanol respectively, and vacuum drying at 60 ℃ to obtain ZnIn 2 S 4 ；
(3) Taking a certain amount of ZnIn 2 S 4 And H 2 PtCl 6 Dispersing in 20mL of methanol aqueous solution (the volume ratio of methanol to water is 1:4), continuously introducing nitrogen into the mixed system for 30min, then turning on a lamp to illuminate for 1h, and centrifugally washing after the reaction is finished;
(4) Dispersing the fresh precipitate obtained in the step (3) in 20mL of deionized water, adding 0.2g of cetyltrimethylammonium bromide into the solution, vigorously stirring for 4 hours under a nitrogen atmosphere, washing with deionized water, and drying to obtain surface oleophilic Pt-ZnIn 2 S 4 A composite catalyst.
The invention also comprises a surface oleophilic Pt-ZnIn 2 S 4 The composite catalyst is applied to photocatalytic fuel denitrification reaction.
The invention has the remarkable advantages that:
(1) The invention has simple preparation conditions, and the table is firstly providedSurface oleophilic Pt/ZnIn 2 S 4 The method is used in the field of photocatalytic fuel denitrification.
(2) The load and ZnIn 2 S 4 The Pt species on the surface effectively promotes the selective adsorption of the nitrogen-containing compound on the surface of the catalyst, thereby improving the denitrification performance of the fuel.
(3) The invention creatively proposes that Pt/ZnIn with lipophilic surface is obtained by modifying hexadecyl trimethyl ammonium bromide 2 S 4 The catalyst improves the mass transfer efficiency of the catalyst in the oil phase.
(4) The whole process is simple and easy to control, the production process is environment-friendly and low in energy consumption, the denitrification of the fuel oil under mild conditions can be effectively realized, a potential solution is provided for environmental pollution, and the method has a high application prospect.
Drawings
FIG. 1 shows the 1% Pt/ZnIn obtained in example 5 2 S 4 Is a scanning electron microscope image of (1).
FIG. 2 shows ZnIn obtained in example 2 2 S 4 Is a transmission electron microscope image of (a).
FIG. 3 is a 1% Pt/ZnIn solution obtained in example 5 2 S 4 Is a transmission electron microscope image of (a).
Fig. 4 is a graph of contact angle measurements for the samples obtained in example 1 (left) and example 2 (right).
FIG. 5 is a plot of the surface hydrophilic and surface lipophilic ZnIn obtained in examples 1-2 2 S 4 The photocatalytic fuel denitrification activity map.
FIG. 6 shows the surface oleophilic Pt/ZnIn obtained in examples 2-6 2 S 4 The photocatalytic fuel denitrification activity map.
Detailed Description
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
Example 1
13.63mg of ZnCl is taken 2 41.33mg of In (NO) 3 ·4H 2 O and 60.10mg of CH 3 CSNH 2 In a beaker, 60ml of distilled water was added and stirred0.5h until the solid is completely dissolved. Transferring the obtained transparent clear solution into a high-pressure reaction kettle, performing hydrothermal reaction at 160 ℃ for 12 hours, cooling to room temperature after the reaction is finished, taking out yellow precipitate, washing with deionized water until the solution ion concentration is lower than 10ppm, and drying to obtain ZnIn with hydrophilic surface 2 S 4 Labeled as Hy-ZnIn 2 S 4 。
Example 2
13.63mg of ZnCl is taken 2 41.33mg of In (NO) 3 ·4H 2 O and 60.10mg of CH 3 CSNH 2 In a beaker, 60ml of distilled water was added and stirred for 0.5h until the solid was completely dissolved. Transferring the obtained transparent clear solution into a high-pressure reaction kettle, carrying out hydrothermal reaction for 12 hours at 160 ℃, taking out yellow precipitate after the reaction is finished and cooling to room temperature, and washing the yellow precipitate with deionized water until the ion concentration of the solution is lower than 10ppm; dispersing fresh precipitate in 20mL deionized water, adding 0.2g cetyl trimethyl ammonium bromide into the solution, vigorously stirring for 4h under nitrogen atmosphere, washing with deionized water, and oven drying to obtain surface oleophilic ZnIn 2 S 4 Catalyst, marked ZnIn 2 S 4 。
Example 3
13.63mg of ZnCl is taken 2 41.33mg of In (NO) 3 ·4H 2 O and 60.10mg of CH 3 CSNH 2 In a beaker, 60ml of distilled water was added and stirred for 0.5h until the solid was completely dissolved. Transferring the obtained transparent clear solution into a high-pressure reaction kettle, performing hydrothermal reaction at 160 ℃ for 12 hours, cooling to room temperature after the reaction is finished, taking out yellow precipitate, washing the yellow precipitate with deionized water until the solution ion concentration is lower than 10ppm, and performing vacuum drying at 60 ℃ to obtain ZnIn 2 S 4 A sample; 0.1g of ZnIn is taken 2 S 4 And 25. Mu.L of H 2 PtCl 6 (Pt 4+ Dispersing the solution with the concentration of 10mg/mL in 20mL of methanol aqueous solution (the volume ratio of methanol to water is 1:4), continuously introducing nitrogen into the mixed system for 30min (the nitrogen flow is 100 mL/min), then turning on a lamp to illuminate for 1h, and centrifugally washing with deionized water until the ion concentration of the solution is lower than 10ppm after the reaction is finished; dispersing the fresh precipitate in 20mL deionized water, adding to the solutionAdding 0.2g of cetyl trimethyl ammonium bromide, vigorously stirring for 4 hours under nitrogen atmosphere, washing with deionized water, and drying to obtain the surface oleophilic 0.25% Pt/ZnIn 2 S 4 A composite catalyst.
Example 4
13.63mg of ZnCl is taken 2 41.33mg of In (NO) 3 ·4H 2 O and 60.10mg of CH 3 CSNH 2 In a beaker, 60ml of distilled water was added and stirred for 0.5h until the solid was completely dissolved. Transferring the obtained transparent clear solution into a high-pressure reaction kettle, performing hydrothermal reaction at 160 ℃ for 12 hours, cooling to room temperature after the reaction is finished, taking out yellow precipitate, washing the yellow precipitate with deionized water until the solution ion concentration is lower than 10ppm, and performing vacuum drying at 60 ℃ to obtain ZnIn 2 S 4 A sample; 0.1g of ZnIn is taken 2 S 4 And 50. Mu.L of H 2 PtCl 6 (Pt 4+ Dispersing the solution with the concentration of 10mg/mL in 20mL of methanol aqueous solution (the volume ratio of methanol to water is 1:4), continuously introducing nitrogen into the mixed system for 30min (the nitrogen flow is 100 mL/min), then turning on a lamp to illuminate for 1h, and centrifugally washing with deionized water until the ion concentration of the solution is lower than 10ppm after the reaction is finished; dispersing fresh precipitate in 20mL deionized water, adding 0.2g cetyl trimethyl ammonium bromide into the solution, vigorously stirring for 4h under nitrogen atmosphere, washing with deionized water, and oven drying to obtain surface oleophilic 0.5% Pt/ZnIn 2 S 4 A composite catalyst.
Example 5
13.63mg of ZnCl is taken 2 41.33mg of In (NO) 3 ·4H 2 O and 60.10mg of CH 3 CSNH 2 In a beaker, 60ml of distilled water was added and stirred for 0.5h until the solid was completely dissolved. Transferring the obtained transparent clear solution into a high-pressure reaction kettle, performing hydrothermal reaction at 160 ℃ for 12 hours, cooling to room temperature after the reaction is finished, taking out yellow precipitate, washing the yellow precipitate with deionized water until the solution ion concentration is lower than 10ppm, and performing vacuum drying at 60 ℃ to obtain ZnIn 2 S 4 A sample; 0.1g of ZnIn is taken 2 S 4 And 100. Mu.L of H 2 PtCl 6 (Pt 4+ A solution having a concentration of 10mg/mL was dispersed in 20mL of an aqueous methanol solution (methanol)And water volume ratio is 1:4), continuously introducing nitrogen into the mixed system for 30min (nitrogen flow is 100 mL/min), then turning on a lamp to illuminate for 1h, and centrifugally washing with deionized water until the ion concentration of the solution is lower than 10ppm after the reaction is finished; dispersing fresh precipitate in 20mL deionized water, adding 0.2g cetyl trimethyl ammonium bromide into the solution, vigorously stirring for 4h under nitrogen atmosphere, washing with deionized water, and oven drying to obtain surface oleophilic 1% Pt/ZnIn 2 S 4 A composite catalyst.
Example 6
13.63mg of ZnCl is taken 2 41.33mg of In (NO) 3 ·4H 2 O and 60.10mg of CH 3 CSNH 2 In a beaker, 60ml of distilled water was added and stirred for 0.5h until the solid was completely dissolved. Transferring the obtained transparent clear solution into a high-pressure reaction kettle, performing hydrothermal reaction at 160 ℃ for 12 hours, cooling to room temperature after the reaction is finished, taking out yellow precipitate, washing the yellow precipitate with deionized water until the solution ion concentration is lower than 10ppm, and performing vacuum drying at 60 ℃ to obtain ZnIn 2 S 4 A sample; 0.1g of ZnIn is taken 2 S 4 And 200. Mu.L of H 2 PtCl 6 (Pt 4+ Dispersing the solution with the concentration of 10mg/mL in 20mL of methanol aqueous solution (the volume ratio of methanol to water is 1:4), continuously introducing nitrogen into the mixed system for 30min (the nitrogen flow is 100 mL/min), then turning on a lamp to illuminate for 1h, and centrifugally washing with deionized water until the ion concentration of the solution is lower than 10ppm after the reaction is finished; dispersing fresh precipitate in 20mL deionized water, adding 0.2g cetyl trimethyl ammonium bromide into the solution, vigorously stirring for 4h under nitrogen atmosphere, washing with deionized water, and oven drying to obtain surface oleophilic 2% Pt/ZnIn 2 S 4 A composite catalyst.
FIG. 1 shows the 1% Pt/ZnIn obtained in example 5 2 S 4 As can be seen from fig. 1, the sample is represented by a nanoplatelet assembly structure.
FIG. 2 shows ZnIn obtained in example 2 2 S 4 As can be seen from fig. 2, the sample exhibits an ultra-thin nanoplatelet structure.
FIG. 3 is a 1% Pt/ZnIn solution obtained in example 5 2 S 4 As can be seen from fig. 3,the composite sample maintained ZnIn 2 S 4 The nanoplatelet structure and the presence of Pt nanoparticles is clearly observed.
Fig. 4 is a graph of contact angle measurements for the samples obtained in example 1 (left) and example 2 (right). As can be seen from the figure, compared with Hy-ZnIn 2 S 4 ，ZnIn 2 S 4 Increases the contact angle and increases the lipophilicity.
FIG. 5 is a plot of the surface hydrophilic and surface lipophilic ZnIn obtained in examples 1-2 2 S 4 The photocatalytic fuel denitrification activity map. As can be seen from the figure, the surface hydrophilicity and lipophilicity are those of ZnIn 2 S 4 The denitrification performance of the photocatalytic fuel oil has obvious influence. The lipophilic surface is more favorable for the dispersion of the catalyst in the fuel oil, improves the mass transfer efficiency, and further shows more excellent denitrification performance. Wherein, the surface is oleophilic ZnIn 2 S 4 The denitrification efficiency reaches 45 percent.
FIG. 6 shows the surface oleophilic Pt/ZnIn obtained in examples 2-6 2 S 4 The photocatalytic fuel denitrification activity map. As can be seen from the graph, the introduction of the metal Pt greatly improves the denitrification performance of the fuel oil, and the performance of the composite photocatalyst shows a trend of rising before reducing along with the increase of the Pt modification amount, wherein the surface is oleophylic by 1% of Pt/ZnIn 2 S 4 The composite catalyst has the highest denitrification performance and the efficiency reaches 81 percent.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (9)
1. A preparation method of a surface oleophylic sulfur indium zinc-based catalyst for denitrification of fuel oil is characterized by comprising the following steps: zinc chloride, indium nitrate and thioacetamide are used as raw materials to hydrothermally synthesize ZnIn 2 S 4 The method comprises the steps of carrying out a first treatment on the surface of the In ZnIn by photo-reduction 2 S 4 Surface modification of Pt and modification with cetyl trimethyl ammonium bromide to obtain surface oleophylic Pt/ZnIn 2 S 4 。
2. The method for preparing the surface oleophylic sulfur indium zinc-based catalyst for denitrification of fuel oil according to claim 1, which is characterized in that: the loading of Pt is 0.25% -2%.
3. The method for preparing the surface oleophylic sulfur indium zinc-based catalyst for fuel denitrification according to claim 1, which is characterized by comprising the following steps:
(1) ZnIn of 0.1. 0.1g was taken 2 S 4 Catalyst and 25-200 mu L of H 2 PtCl 6 Dispersing the solution in a 20mL methanol aqueous solution, continuously introducing nitrogen into the mixed system for 30min, then turning on a lamp to illuminate for 1h, and centrifugally washing with deionized water until the ion concentration of the solution is lower than 10ppm after the reaction is finished to obtain a precipitate;
(2) Dispersing the precipitate in the step (1) in 20mL deionized water, adding 0.2g hexadecyl trimethyl ammonium bromide into the solution, vigorously stirring for 4h under nitrogen atmosphere, washing with deionized water, and drying to obtain surface oleophilic Pt/ZnIn 2 S 4 A composite catalyst.
4. The method for preparing a surface oleophilic sulfur indium zinc-based catalyst for fuel denitrification as claimed in claim 3, wherein ZnIn 2 S 4 The preparation method of the catalyst comprises the following steps: znCl of 13.63 and mg was taken 2 In (NO) of 41.33mg 3 ) 3 ·4H 2 O and CH of 60.10mg 3 CSNH 2 Adding 60mL distilled water, stirring for 0.5h until the solid is completely dissolved, performing hydrothermal reaction at 160deg.C for 12h, and centrifuging and washing to obtain ZnIn 2 S 4 A catalyst;
5. the method for preparing the surface oleophylic sulfur-indium-zinc-based catalyst for fuel denitrification according to claim 4, wherein the method comprises the following steps: the H is 2 PtCl 6 Pt in (V) 4+ The concentration was 10 mg/mL.
6. The method for preparing the surface oleophylic sulfur-indium-zinc-based catalyst for fuel denitrification according to claim 5, wherein the method is characterized in that: and in the step (1), the volume ratio of the methanol to the water is 1:4.
7. The method for preparing the surface oleophylic sulfur indium zinc-based catalyst for denitrification of fuel oil according to claim 6, wherein the method is characterized in that: the nitrogen flow rate in the step (1) is 100 mL/min.
8. A surface oleophilic sulfur indium zinc-based catalyst made by the method of any of claims 1-7.
9. Use of a surface oleophilic sulfur indium zinc-based catalyst prepared by the method of any of claims 1-7 in photocatalytic fuel denitrification.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104525238A (en) * | 2015-01-09 | 2015-04-22 | 江苏大学 | Carbon nitride/sulfur indium zinc composite nanometer material and preparation method and application thereof |
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