CN114887645B - Preparation of amorphous FeOOH/GaN nanosheet heterojunction and application of amorphous FeOOH/GaN nanosheet heterojunction in photocatalytic synthesis of lactic acid by using biomass monosaccharide - Google Patents
Preparation of amorphous FeOOH/GaN nanosheet heterojunction and application of amorphous FeOOH/GaN nanosheet heterojunction in photocatalytic synthesis of lactic acid by using biomass monosaccharide Download PDFInfo
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000004310 lactic acid Substances 0.000 title claims abstract description 63
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 63
- 229910002588 FeOOH Inorganic materials 0.000 title claims abstract description 60
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 28
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 24
- 239000002135 nanosheet Substances 0.000 title claims abstract description 24
- 239000002028 Biomass Substances 0.000 title claims abstract description 23
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 23
- 150000002772 monosaccharides Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000011941 photocatalyst Substances 0.000 claims abstract description 45
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 30
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 17
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- 238000007146 photocatalysis Methods 0.000 claims abstract description 10
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 229910002601 GaN Inorganic materials 0.000 claims description 75
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 4
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229930182830 galactose Natural products 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 239000002064 nanoplatelet Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 239000003054 catalyst Substances 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 20
- 238000005286 illumination Methods 0.000 abstract description 11
- 230000002194 synthesizing effect Effects 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 50
- 230000000694 effects Effects 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007071 enzymatic hydrolysis Effects 0.000 description 2
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a preparation method of an amorphous FeOOH/GaN nanosheet heterojunction photocatalyst and application of the amorphous FeOOH/GaN nanosheet heterojunction photocatalyst in biomass-based monosaccharide photocatalysis synthesis of lactic acid, and belongs to the technical field of catalysis. The preparation method of the catalyst comprises the following steps: feCl is added 3 And (3) dropwise adding the precursor into the GaN suspension, and obtaining the amorphous FeOOH/GaN nanosheet heterojunction photocatalyst through a mixing-stirring-filtering-washing-freeze-drying method. The application process of the catalyst in the photocatalytic synthesis of lactic acid by biomass-based monosaccharide is as follows: mixing FeOOH/GaN photocatalyst, xylose and alkaline solution, and carrying out visible light illumination reaction for 5-180 min at 10-100 ℃. The photocatalyst with high catalytic activity and good thermal stability is prepared by a simple, green and low-cost method; the method has the advantages of good universality, recyclability, industrial application prospect and the like when being applied to synthesizing lactic acid by photocatalytic biomass-based monosaccharide.
Description
Technical Field
The invention relates to a preparation method of an amorphous FeOOH/GaN nano-sheet heterojunction photocatalyst and application thereof in biomass-based monosaccharide photocatalysis synthesis of lactic acid, and belongs to the technical field of catalysis.
Background
With the increasing exhaustion of non-renewable resources such as petroleum and the increasing emphasis of environmental problems, resource utilization is continually shifted to the use of non-fossil, clean and renewable resources. Biomass, which is an important renewable resource, has the advantages of rich sources, renewable and biodegradable properties, and has become one of the energy sources for replacing fossil fuels. Xylose, an important biomass-based monosaccharide, can be converted into various biomass-based high-value chemicals, and is favored in the fields of biology, medicine, chemical industry, materials and the like. Therefore, efficient utilization and conversion of xylose has an important impact on the economic benefit and commercial production of lignocellulosic feedstock biorefinery industrial production systems.
Lactic Acid (LA) is an important carboxylic acid, which can be converted from various biomass-based materials. As a multifunctional platform chemical, lactic acid has wide application prospect in the fields of food, pharmacy, medical treatment, cosmetics and the like. Currently, lactic acid is mainly obtained by enzymatic hydrolysis of sugars. However, the preparation of lactic acid by enzyme catalytic hydrolysis reaction has the problems of low reaction rate, low yield, high energy consumption, difficult purification of products and the like. Therefore, the development of an efficient and environment-friendly method for synthesizing lactic acid has important significance.
Currently, the synthesis methods of lactic acid mainly include biological methods and chemical methods. In biological methods, lactic acid is mainly prepared by enzymatic hydrolysis of carbohydrates, but the method has certain limitations, such as slow enzymolysis reaction rate, low yield, high energy consumption, difficult purification of products and the like. The product obtained by synthesizing lactic acid by chemical method has high purity, white color, good heat resistance, and no sugar impurity, and is especially suitable for preparing high-quality bread additive. However, the reaction temperature required for synthesizing lactic acid by the chemical method is high at present, which limits the application of lactic acid to a certain extent. Therefore, the development of an efficient and environment-friendly method for synthesizing lactic acid has become one of the main targets of the research and development efforts. At present, the photocatalysis technology is widely used in the fields of carbon dioxide reduction, nitrogen reduction, photolysis water, degradation of organic matters and the like due to the advantages of no toxicity, safety, good stability, high catalytic activity, quick response, low energy consumption, reusability and the like. Application of the photocatalysis technology to the synthesis of lactic acid will open up a new way to synthesize lactic acid.
Disclosure of Invention
The invention aims to overcome the defects of the existing lactic acid synthesis, and provides a preparation method of a novel and efficient amorphous FeOOH/GaN nanosheet heterojunction photocatalyst and application of the novel and efficient amorphous FeOOH/GaN nanosheet heterojunction photocatalyst in biomass-based monosaccharide photocatalysis synthesis of lactic acid. The invention uses FeCl 3 The precursor is added dropwise to the GaN suspension by mixing-stirring-filtering-washingThe amorphous FeOOH/GaN nano-sheet heterojunction photocatalyst is prepared by a freeze-drying method, and the preparation method is simple, green and safe. And then the prepared FeOOH/GaN is used as a photocatalyst, and biomass-based monosaccharide is catalyzed and oxidized into lactic acid through an illumination reaction. The catalyst synthesis method of the invention is simple and easy to control, low in cost and pollution-free.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the amorphous FeOOH/GaN nanosheet heterojunction photocatalyst for synthesizing lactic acid by biomass-based monosaccharide photocatalysis comprises the following steps:
(1) FeCl is added 3 Ultrasonic dissolving in deionized water to obtain FeCl 3 Solution as FeCl 3 A precursor. Wherein the FeCl 3 The proportion of the deionized water is 0.01 to 0.60g: 1.0-20.0 mL;
(2) And (3) dispersing GaN in ethanol by ultrasonic to obtain GaN suspension. Wherein the ratio of GaN to ethanol is 0.01-0.60 g: 10.0-200.0 mL;
(3) Under continuous stirring, feCl obtained in step (1) is added 3 Precursor (FeCl) 3 The solution) is dripped into the GaN suspension obtained in the step (2), and the mixture is continuously stirred for 6 to 24 hours, and the liquid phase becomes transparent, so that granular precipitate is generated. Wherein FeCl 3 The mass ratio of the silicon nitride to GaN is 0.5-2: 0.5 to 2.
(4) And (3) filtering the product obtained in the step (3), washing the obtained solid, and freeze-drying to obtain the amorphous FeOOH/GaN nanosheet heterojunction photocatalyst (FeOOH/GaN photocatalyst).
According to the above technical scheme, in the preferred case, in the step (1), the FeCl 3 The ratio of deionized water was 0.3g:10.0mL.
According to the above technical solution, in the preferred case, in the step (2), the ratio of gallium nitride to ethanol is 0.3g:100.0mL.
According to the above technical scheme, in the preferred case, in the step (3), feCl 3 The mass ratio of GaN to GaN is 1:1.
according to the above technical scheme, in the step (3), stirring is preferably performed continuously for 12 hours.
The invention uses FeCl 3 The precursor is dripped into GaN suspension, an amorphous FeOOH/GaN nanosheet heterojunction photocatalyst is obtained through a mixing-stirring-filtering-washing-freeze-drying method, and the obtained FeOOH/GaN photocatalyst is characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, solid ultraviolet diffuse reflection, nitrogen absorption and desorption, infrared spectrum and the like, and is used as a good photocatalyst to be applied to photocatalytic oxidation to synthesize lactic acid.
The amorphous FeOOH/GaN nanosheet heterojunction photocatalyst prepared by the method is applied to photocatalytic synthesis of lactic acid by biomass-based monosaccharide, and the reaction process is as follows: mixing the amorphous FeOOH/GaN nano-sheet heterojunction photocatalyst, biomass-based monosaccharide and alkaline solution, and reacting under visible light; filtering to remove catalyst, and measuring lactic acid content of the filtrate by high performance liquid chromatography.
According to the above technical solution, preferably, the biomass-based monosaccharide includes at least one of xylose, arabinose, galactose, glucose, mannose, and fructose.
According to the above-described technical scheme, preferably, the alkaline solution is a water-soluble alkaline solution, such as potassium hydroxide solution, sodium hydroxide solution, barium hydroxide solution, sodium carbonate solution, potassium carbonate solution, sodium bicarbonate solution, and the like, and preferably potassium hydroxide solution.
According to the technical scheme, the reaction temperature is preferably 10-100 ℃, preferably 60 ℃; the reaction time is 5.0 to 180.0min, preferably 100min.
According to the above-described embodiments, the concentration of the alkaline solution is preferably 0.01 to 8.0mol/L, more preferably 0.1 to 5.0mol/L, and still more preferably 3mol/L.
According to the technical scheme, preferably, the ratio of the biomass-based monosaccharide to the alkaline solution to the amorphous FeOOH/GaN nanosheet heterojunction photocatalyst is 0.05-0.5 g: 5-15 mL:2 to 80mg, preferably 0.1g:10mL:5 to 70mg, more preferably 0.1g:10mL:50mg.
The application of the amorphous FeOOH/GaN nanosheet heterojunction photocatalyst in synthesizing lactic acid by photocatalysis of biomass-based monosaccharides optimizes experimental conditions in aspects of catalyst dosage, reaction time, KOH concentration, reaction temperature and the like; the recyclability of the FeOOH/GaN photocatalyst was investigated under the optimum reaction conditions (0.1 g xylose, 10mL of 3.0mol/L KOH solution, 50mg of FeOOH/GaN photocatalyst, and reaction temperature of 60℃and reaction time of 100 min).
The amorphous FeOOH/GaN nanosheet heterojunction photocatalyst prepared by the method can be used in the reaction of synthesizing lactic acid by biomass-based monosaccharide photocatalysis, and the obtained catalyst can simply and efficiently catalyze and synthesize lactic acid and has good application prospect. The lactic acid synthesized by the photocatalytic oxidation of the FeOOH/GaN photocatalyst can be used as a new energy source and a high-value chemical. The reaction condition for synthesizing lactic acid by FeOOH/GaN photocatalytic oxidation is mild. The process and the reaction conditions are simple and easy to control, the method is environment-friendly, and the obtained lactic acid plays an important role in the aspects of medicines, cosmetics, foods and the like, so that the pressure of the environment and energy sources is reduced to a certain extent.
The synthesis method of the invention has the following advantages:
(1) The lactic acid synthesized by the invention is a chemical product with high value, and is an important chemical intermediate;
(2) The preparation method of the catalyst is simple and easy to control, is green, has no pollution, has universality and can be produced in a large scale;
(3) The preparation raw materials of the catalyst are relatively cheap and easy to obtain, and the catalyst is suitable for industrial production;
(4) The photocatalyst prepared by the invention has the advantages of good thermal stability, higher catalytic activity, recycling and the like;
(5) The method for synthesizing lactic acid is safe, nontoxic, quick in effect and low in energy consumption;
(6) The amplification of the FeOOH/GaN photocatalytic lactic acid synthesis process is achieved, and the 1000-time amplification experimental result shows that the lactic acid synthesis process has a certain potential for industrial production and implementation;
(7) The product obtained by the invention provides an effective way for solving the energy crisis.
Drawings
Fig. 1 is an XRD spectrum of the comparative GaN photocatalyst and the amorphous FeOOH/GaN heterojunction photocatalyst prepared in example 1.
FIG. 2 is a graph showing the effect of different amounts of catalyst on the photocatalytic synthesis of lactic acid by FeOOH/GaN in example 2.
FIG. 3 is a graph showing the effect of different illumination times on the photocatalytic synthesis of lactic acid from FeOOH/GaN in example 3 and example 2.
FIG. 4 is a graph showing the effect of different KOH solution concentrations on the photocatalytic synthesis of lactic acid by FeOOH/GaN in example 4 and example 3.
FIG. 5 is a graph showing the effect of different reaction temperatures on the photocatalytic synthesis of lactic acid by FeOOH/GaN in example 5 and example 4.
Detailed Description
The invention will be further illustrated by the following examples for better understanding of technical features of the invention, but the scope of the invention is not limited thereto.
Gallium nitride (GaN) in the following examples and comparative examples was purchased from mikrin.
Example 1
(1) Accurately weigh 0.3g FeCl 3 Ultrasonic dissolving in 10mL deionized water to obtain FeCl 3 Solution as FeCl 3 A precursor;
(2) Accurately weighing 0.3g of GaN, and dispersing the GaN in 100mL of ethanol by ultrasonic waves to obtain a GaN suspension;
(3) Under continuous stirring, feCl obtained in step (1) is added 3 The precursor is dripped into the GaN suspension obtained in the step (2), and the mixture is continuously stirred for 12 hours, so that the liquid phase becomes transparent, and granular precipitate is generated.
(4) And filtering the obtained product, washing with ethanol and deionized water, and freeze-drying to obtain the amorphous FeOOH/GaN nano-sheet heterojunction photocatalyst.
Comparative example
Gallium nitride (GaN) from mikrin was directly used as a photocatalyst.
Example 2
(1) 0.1g of xylose, 10mL of 2mol/L KOH solution and the FeOOH/GaN photocatalyst prepared in example 1 are taken and added into a pressure-resistant bottle, and the dosages of the photocatalyst are respectively 5mg, 10mg, 20mg, 30mg, 40mg, 50mg, 60mg and 70mg;
(2) Sealing the system in the step (1), carrying out illumination reaction for 30min by using a 300W xenon lamp at the reaction temperature of 50 ℃, and filtering to remove the FeOOH/GaN photocatalyst;
(3) And (3) measuring the yield of the lactic acid from the filtrate obtained in the step (2) by using a high performance liquid chromatography.
Example 3
(1) Maintaining the FeOOH/GaN photocatalyst amount at 50mg, otherwise as in step (1) of example 2;
(2) Setting the illumination time of the system to be 10min, 50min, 70min, 90min, 100min, 110min and 120min respectively, and carrying out the step (2) in the embodiment 2;
(3) And (3) measuring the yield of the lactic acid from the filtrate obtained in the step (2) by using a high performance liquid chromatography.
Example 4
(1) The KOH solution concentrations were set to 0.1mol/L, 0.5mol/L, 1.0mol/L, 4.0mol/L, 5.0mol/L, respectively, in the same manner as in step (1) of example 3;
(2) Setting the illumination time of the system to 100min, and performing the step (2) in the embodiment 3;
(3) And (3) measuring the yield of the lactic acid from the filtrate obtained in the step (2) by using a high performance liquid chromatography.
Example 5
(1) The KOH solution was set at a concentration of 3mol/L in the same manner as in step (1) of example 4;
(2) Setting the reaction temperature of the system to 20 ℃, 30 ℃, 40 ℃, 60 ℃, 70 ℃,80 ℃, 90 ℃ respectively, and otherwise carrying out the step (2) of example 4;
(3) And (3) measuring the yield of the lactic acid from the filtrate obtained in the step (2) by using a high performance liquid chromatography.
Example 6
(1) 0.1g of xylose, 10mL of 3mol/L KOH solution and 50mg of the FeOOH/GaN photocatalyst prepared in example 1 were taken and added to a pressure-resistant bottle;
(2) Sealing the system in the step (1), and carrying out illumination reaction for 100min at 60 ℃ by using a 300W xenon lamp; filtering to remove FeOOH/GaN photocatalyst;
(3) Measuring the conversion rate of xylose and the yield of lactic acid of the filtrate obtained in the step (2) by a high performance liquid chromatography method;
(4) After the reaction of the step (2) is finished, filtering the FeOOH/GaN photocatalyst, continuously washing with deionized water until the filtrate is neutral, and continuously using the filtrate for the next circulation of the steps (1) - (3) after drying overnight at 80 ℃ for ten times.
Example 7
(1) 100g of xylose, 10L of KOH solution (3 mol/L) and 50g of FeOOH/GaN photocatalyst prepared in example 1 were taken and added to a beaker;
(2) Mechanically stirring the system in the step (1) uniformly;
(3) Mechanically stirring the step (2) for 100min at room temperature under sunlight illumination; filtering to remove FeOOH/GaN photocatalyst;
(4) And (3) measuring the yield of the lactic acid from the filtrate obtained in the step (3) by using a high performance liquid chromatography.
FIG. 1 is an XRD spectrum of the comparative GaN catalyst and the FeOOH/GaN catalyst prepared in example 1. It can be seen from fig. 1 that GaN exhibits distinct diffraction peaks at 32.3 °, 34.5 °, 36.7 °, 48.0 °, 57.7 °, 63.3 °, 69.0 ° and 70.4 °, corresponding to the (100), (002), (101), (102), (110), (103), (112) and (201) crystal planes of hexagonal GaN (JCPDS 50-0792), respectively. Notably, no characteristic peak of the original FeOOH was detected in FeOOH/GaN, indicating that FeOOH has amorphous characteristics in the composite photocatalyst. For amorphous FeOOH/GaN nanosheet heterojunction photocatalysts, the high-crystallinity phase of the GaN substrate is more conducive to charge transfer and separation, while the amorphous phase of FeOOH is more conducive to adsorption and activation of reactive molecules.
FIG. 2 is a graph showing the effect of different amounts of catalyst on the synthesis of lactic acid by FeOOH/GaN photocatalytic xylose in example 2. As the FeOOH/GaN catalyst amount increases, the lactic acid yield increases. However, when the FeOOH/GaN catalyst is used in an amount of more than 50mg, the yield of lactic acid is somewhat decreased. This may be due to the formation of intermediates on the catalyst surface by the reactants, which reduces the activation energy of the reaction. Therefore, the amount of the catalyst to be used is preferably 50mg.
FIG. 3 is a graph showing the effect of different illumination times on the synthesis of lactic acid by FeOOH/GaN photocatalytic xylose in example 3 and example 2. Wherein, the illumination time in the example 3 is respectively 10min, 50min, 70min, 90min, 100min, 110min and 120min, the catalyst dosage in the example 2 is 50mg, and the illumination time is 30min. Under the condition of the optimal catalyst dosage, the influence of the reaction time on the synthesis of lactic acid by the FeOOH/GaN photocatalysis xylose is explored. It was found that as the reaction time increased from 10min to 120min, the yield of lactic acid tended to rise and then decrease. At 100min, the yield was maximized. This is probably due to the fact that under the same conditions, the lactic acid produced is further reacted to produce other by-products as the reaction time is prolonged.
FIG. 4 is a graph showing the effect of different KOH solution concentrations in examples 4 and 3 on the synthesis of lactic acid by FeOOH/GaN photocatalytic oxidation, wherein the KOH solution concentrations in example 4 are 0.1mol/L, 0.5mol/L, 1.0mol/L, 2.0mol/L, 4.0mol/L and 5.0mol/L, respectively, the catalyst amount in example 3 is 50mg, and the KOH solution concentration in example 3 is 3mol/L. The effect of KOH concentration on photocatalytic conversion of xylose to lactic acid was investigated. When the KOH concentration was increased from 0.1mol/L to 3mol/L, the yield of lactic acid was increased from 14.4% to 82.3%. However, the KOH concentration was further increased to 3 to 5mol/L, and the yield of lactic acid was somewhat lowered, which was attributable to the gradual increase of byproducts. Therefore, the optimal KOH concentration in the reaction system was 3mol/L.
FIG. 5 is a graph showing the effect of different reaction temperatures on the synthesis of lactic acid by FeOOH/GaN photocatalytic xylose in example 5 and example 4. Wherein the reaction temperature in example 5 was 20 ℃, 30 ℃, 40 ℃, 60 ℃, 70 ℃,80 ℃, 90 ℃ and the KOH solution in example 4 was 3mol/L and the reaction temperature was 50 ℃, respectively. When the reaction temperature was increased from 20℃to 60℃the yield of lactic acid was gradually increased, however, with further increase in temperature, the yield of lactic acid was somewhat decreased. This is probably because lactic acid reacts at high temperature to form other by-products. Therefore, 60℃was chosen as the optimal reaction temperature.
The foregoing examples are illustrative of part of the practice of the invention, but the invention is not limited to the embodiments, and any other changes, substitutions, combinations, and simplifications that depart from the spirit and principles of the invention are intended to be equivalent thereto and are within the scope of the invention.
Claims (8)
1. The application of the amorphous FeOOH/GaN nano-sheet heterojunction photocatalyst in biomass-based monosaccharide photocatalysis synthesis of lactic acid is characterized in that the preparation method of the amorphous FeOOH/GaN nano-sheet heterojunction photocatalyst comprises the following steps:
(1) FeCl is added 3 Ultrasonic dissolving in deionized water to obtain FeCl 3 Solution as FeCl 3 A precursor;
wherein the FeCl 3 The proportion of the deionized water is 0.01 to 0.60g: 1.0-20.0 mL;
(2) Dispersing GaN in ethanol by ultrasonic waves to obtain GaN suspension;
wherein the ratio of GaN to ethanol is 0.01-0.60 g: 10.0-200.0 mL;
(3) Stirring the FeCl obtained in the step (1) 3 Dropwise adding the solution into the GaN suspension obtained in the step (2), and stirring for 6-24 h;
wherein FeCl 3 The mass ratio of the silicon nitride to GaN is 0.5-2: 0.5 to 2;
(4) And (3) filtering, washing and freeze-drying the product obtained in the step (3) to obtain the amorphous FeOOH/GaN nanosheet heterojunction photocatalyst.
2. The use according to claim 1, wherein in step (1), feCl 3 The ratio of deionized water was 0.3g:10.0mL.
3. The use according to claim 1, characterized in that in step (2) the ratio of gallium nitride to ethanol is 0.3g:100.0mL.
4. The use according to claim 1, wherein the biomass-based monosaccharides comprise at least one of xylose, arabinose, galactose, glucose, mannose, fructose.
5. The use according to claim 1, characterized in that the amorphous FeOOH/GaN nanoplatelet heterojunction photocatalyst, biomass-based monosaccharide and alkaline solution are mixed and reacted under visible light.
6. The use according to claim 1, wherein the synthesis temperature is 10-100 ℃ and the synthesis time is 5.0-180.0 min.
7. The use according to claim 5, wherein the alkaline solution is a water-soluble alkaline solution, and the concentration of the alkaline solution is 0.01-8.0 mol/L.
8. The use according to claim 5, characterized in that the ratio of biomass-based monosaccharides, alkaline solutions, amorphous FeOOH/GaN nanoplatelet heterojunction photocatalysts is between 0.05 and 0.5g: 5-15 mL: 2.0-80.0 mg.
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| CN109772355A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | Amorphous FeOOH/alum acid bismuth composite photocatalyst material preparation method |
| CN113145169A (en) * | 2021-02-23 | 2021-07-23 | 大连工业大学 | Preparation of photocatalytic hydrogel and application of photocatalytic hydrogel in synthesis of lactic acid by photocatalytic oxidation of xylose |
| CN113441145A (en) * | 2021-07-30 | 2021-09-28 | 陕西科技大学 | Preparation method of barium titanate/iron oxyhydroxide photocatalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2015167882A (en) * | 2014-03-05 | 2015-09-28 | 国際石油開発帝石株式会社 | Photocatalyst production method, photocatalyst, and hydrogen generation method |
| CN109772355A (en) * | 2019-03-11 | 2019-05-21 | 辽宁石油化工大学 | Amorphous FeOOH/alum acid bismuth composite photocatalyst material preparation method |
| CN113145169A (en) * | 2021-02-23 | 2021-07-23 | 大连工业大学 | Preparation of photocatalytic hydrogel and application of photocatalytic hydrogel in synthesis of lactic acid by photocatalytic oxidation of xylose |
| CN113441145A (en) * | 2021-07-30 | 2021-09-28 | 陕西科技大学 | Preparation method of barium titanate/iron oxyhydroxide photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| Design of graphene-like gallium nitride and WS2/WSe2 nanocomposites for photocatalyst applications;Ruishen Meng et al.;《Science China Materials》;第59卷(第12期);第1027-1036页 * |
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