CN111889130A - Preparation of modified carbon nitride photocatalyst and application of modified carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of glucose - Google Patents
Preparation of modified carbon nitride photocatalyst and application of modified carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of glucose Download PDFInfo
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- CN111889130A CN111889130A CN202010752663.4A CN202010752663A CN111889130A CN 111889130 A CN111889130 A CN 111889130A CN 202010752663 A CN202010752663 A CN 202010752663A CN 111889130 A CN111889130 A CN 111889130A
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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 122
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000004310 lactic acid Substances 0.000 title claims abstract description 61
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 61
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 53
- 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 title claims abstract description 44
- 239000008103 glucose Substances 0.000 title claims abstract description 44
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 40
- 230000003647 oxidation Effects 0.000 title claims abstract description 26
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title description 9
- 238000003786 synthesis reaction Methods 0.000 title description 9
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000001354 calcination Methods 0.000 claims abstract description 32
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 29
- QEVGBDAVCSPCLP-UHFFFAOYSA-N acetic acid;boric acid Chemical compound CC(O)=O.OB(O)O QEVGBDAVCSPCLP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000013032 photocatalytic reaction Methods 0.000 claims abstract description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 57
- 238000000227 grinding Methods 0.000 claims description 26
- 229920000877 Melamine resin Polymers 0.000 claims description 20
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 20
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 16
- 239000004327 boric acid Substances 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 abstract description 49
- 238000011065 in-situ storage Methods 0.000 abstract description 16
- 229910052796 boron Inorganic materials 0.000 abstract description 15
- 238000003756 stirring Methods 0.000 abstract description 14
- 230000002194 synthesizing effect Effects 0.000 abstract description 11
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 abstract description 10
- 238000001914 filtration Methods 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000706 filtrate Substances 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 44
- 239000000047 product Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 28
- 229960000583 acetic acid Drugs 0.000 description 23
- 239000012362 glacial acetic acid Substances 0.000 description 15
- 238000005303 weighing Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910052573 porcelain Inorganic materials 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 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
- 229920000704 biodegradable plastic Polymers 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001308 synthesis method Methods 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
- 230000004913 activation Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000003625 amylolytic 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
- 238000005452 bending Methods 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000013048 microbiological method Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining 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
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
- B01J27/24—Nitrogen compounds
-
- 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
- C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
Abstract
The invention discloses a preparation method of a modified carbon nitride photocatalyst and application of the modified carbon nitride photocatalyst in synthesizing lactic acid by photocatalytic oxidation of glucose, and belongs to the technical field of catalysis. The preparation method of the catalyst comprises the following steps: and uniformly stirring the nitrogen-containing compound precursor and a boric acid-acetic acid solution, calcining, and further calcining to obtain the in-situ boron and oxygen heteroatom doped modified carbon nitride material. The application process of the catalyst in synthesizing lactic acid by photocatalytic oxidation of glucose is as follows: mixing the modified carbon nitride photocatalyst, glucose and an alkaline solution, and carrying out photocatalytic reaction; filtering to remove catalyst, and measuring lactic acid content of filtrate by high performance liquid chromatograph. The method for preparing the catalyst has better universality, the used catalyst has the advantages of high catalytic activity, good stability, recycling and the like, the method is simple and efficient in catalyzing glucose to synthesize lactic acid, and has good application prospect.
Description
Technical Field
The invention relates to preparation of a modified carbon nitride photocatalyst and application of the modified carbon nitride photocatalyst in synthesizing lactic acid by photocatalytic oxidation of glucose, and belongs to the technical field of catalysis.
Background
With the increasing exhaustion of non-renewable resources such as petroleum, the production of chemical products from renewable biomass as a raw material has become a trend of realizing sustainable development of chemical industry. The eu white paper proposes a policy related to biomass conversion and utilization in the 2030 european bioscience, and the 2012 us white house "national bioscience blueprint" is also proposed. Lactic acid is an important high-value chemical produced by biomass refining, and is mainly used in the fields of food, pharmaceutical industry, manufacturing of biodegradable plastics (such as polylactic acid) and the like. In a sustainable society, the market demand for lactic acid is increasing. At present, the main production process of lactic acid is obtained from amylolytic glucose fermentation by using transgenic enzyme. However, the biological process has the defects of low yield, harsh reaction conditions (temperature and pH value), complicated control of microbial population and the like. Therefore, the development of an efficient and environment-friendly method for synthesizing the lactic acid is of great significance.
Disclosure of Invention
The invention aims to provide a preparation method of a modified carbon nitride photocatalytic material and application of the modified carbon nitride photocatalytic material in synthesizing lactic acid by photocatalytic oxidation of glucose aiming at the defects of the existing lactic acid synthesis. The invention prepares the modified carbon nitride photocatalyst by a simple method, and then takes the modified carbon nitride as the photocatalyst to oxidize the first carbohydrate glucose in nature into lactic acid by photocatalytic reaction. The method for preparing the catalyst has universality and can be used for large-scale production. The catalyst used in the invention has the advantages of good stability, high catalytic activity, recyclability and the like. The synthesis method of the invention is simple and easy to control, low in cost, green and pollution-free.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a modified carbon nitride photocatalyst for synthesizing lactic acid by photocatalytic oxidation of glucose comprises the following steps:
(1) uniformly mixing a nitrogen-containing compound precursor with a boric acid-acetic acid solution and water, and calcining at the temperature of 300.0-450.0 ℃ for 1.0-3.0 h; wherein the concentration of boric acid in the boric acid-acetic acid solution is 0.8mol/L, and the volume concentration of acetic acid is 0.5-7.5% (v/v); the proportion of the nitrogen-containing compound precursor, the boric acid-acetic acid solution and water is 3.0 g: 0-3.0 mL: 0-3.0 mL;
(2) calcining the product obtained in the step (1) at the temperature of 500.0-600.0 ℃ for 1.0-3.0 h to obtain the in-situ boron and oxygen heteroatom doped modified carbon nitride photocatalytic material.
According to the above technical solution, in step (1), the nitrogen-containing compound precursor is preferably urea, thiourea, dicyanodiamine, melamine, or the like.
According to the above technical solution, in step (1), the calcination temperature is preferably 400.0 ℃, and the calcination time is preferably 2.0 h.
According to the above-mentioned means, in step (1) and step (2), the calcination is preferably followed by grinding.
According to the above technical solution, in step (2), the calcination temperature is preferably 560.0 ℃, and the calcination time is preferably 2.0 hours.
The modified carbon nitride photocatalytic material doped with boron and oxygen heteroatoms in situ is characterized by means of X-ray diffraction, infrared spectrum and the like, and is used as a good photocatalyst to be applied to photocatalytic oxidation of glucose to synthesize lactic acid.
The modified carbon nitride photocatalyst prepared by the method is applied to the photocatalytic oxidation of glucose to generate lactic acid, and the reaction process is as follows: uniformly mixing the modified carbon nitride photocatalyst, glucose and an alkaline solution, and carrying out photocatalytic reaction at the temperature of 20.0-90.0 ℃ for 30.0-180.0 min; filtering to remove catalyst, and measuring lactic acid content of filtrate by high performance liquid chromatograph.
According to the above technical solution, the alkaline solution is preferably a water-soluble alkaline solution, such as a potassium hydroxide solution, a sodium hydroxide solution, a barium hydroxide solution, a sodium carbonate solution, a potassium carbonate solution, a sodium bicarbonate solution, and the like, and preferably a potassium hydroxide solution.
According to the above technical solution, the concentration of the alkaline solution is preferably 0.1 to 5.0mol/L, and preferably 2.0 mol/L.
According to the above technical solution, preferably, the ratio of the glucose, the alkaline solution and the catalyst is 0.1 g: 10.0 mL: 5.0-70.0 mg, preferably 0.1 g: 10.0 mL: 30.0 mg.
According to the above technical means, the reaction temperature is preferably 60.0 ℃.
According to the above technical solution, preferably, the reaction time is 90 min.
The application of the modified carbon nitride photocatalyst in the synthesis of lactic acid by photocatalysis of glucose optimizes experimental conditions in the aspects of reaction time, reaction temperature, catalyst dosage, KOH concentration and the like; and the cyclic usability of the modified carbon nitride photocatalyst is researched under the optimal reaction condition.
The principle of the invention is as follows:
the modified carbon nitride photocatalyst is used for catalyzing and oxidizing glucose to synthesize lactic acid, and the lactic acid can be used as a new energy source and a high-value chemical.
The modified carbon nitride photocatalyst prepared by the invention is used in the reaction of generating lactic acid by photo-catalytic oxidation of glucose, and the method for preparing the modified carbon nitride photocatalyst has universality and can be used for large-scale production; the used catalyst has the advantages of good stability, high catalytic activity, good recyclability and the like, is simple and efficient in catalyzing glucose to synthesize lactic acid, and has good application prospect; the process of synthesizing lactic acid by the photocatalytic oxidation of glucose by the modified carbon nitride has the advantages of safety, no toxicity, quick response, low energy consumption and the like, solves a series of problems of lactic acid prepared by the current microbiological method, and provides a brand-new way for synthesizing lactic acid. The reaction conditions for synthesizing lactic acid by photocatalytic oxidation of glucose by modified carbon nitride are mild. The invention has simple process and easily controlled reaction conditions, and the obtained lactic acid is widely applied to food, pharmaceutical engineering and the manufacture of biodegradable plastics (such as polylactic acid).
The synthesis method of the invention has the following advantages:
(1) the lactic acid synthesized by the method is a chemical with high value and an important chemical intermediate;
(2) the preparation method of the catalyst has universality and can be used for large-scale production;
(3) the preparation raw materials of the catalyst are relatively cheap and easily available, and the catalyst is suitable for industrial production;
(4) the modified carbon nitride prepared by the invention is used as a catalyst, and has the advantages of good thermal stability, high catalytic activity, recyclability and the like;
(5) the method for synthesizing the lactic acid has the advantages of safety, no toxicity, quick response, low energy consumption and the like;
(6) the process for preparing the lactic acid by the photocatalytic oxidation of the modified carbon nitride can be amplified, and the 1000-time amplification experiment result shows that the process for synthesizing the lactic acid has the potential of industrial production;
(7) the product of the invention provides an effective way for solving the problem of energy crisis.
Drawings
FIG. 1 is an XRD spectrum of a modified carbon nitride photocatalyst, wherein a is the modified carbon nitride catalyst in which the nitrogen-containing compound of example 4 is melamine, b is the modified carbon nitride catalyst in which the nitrogen-containing compound of example 3 is melamine, c is the modified carbon nitride catalyst in which the nitrogen-containing compound of example 2 is melamine, and d is the modified carbon nitride catalyst prepared in example 1 in which glacial acetic acid is 10 mL.
FIG. 2 is a FT-IR spectrum of a modified carbon nitride photocatalyst, wherein a is the modified carbon nitride catalyst of example 4 in which the nitrogen-containing compound is melamine, b is the modified carbon nitride catalyst of example 3 in which the nitrogen-containing compound is melamine, c is the modified carbon nitride catalyst of example 2 in which the nitrogen-containing compound is melamine, and d is the modified carbon nitride catalyst prepared in example 1 in which glacial acetic acid is 10 mL.
FIG. 3 is a graph showing the effect of different reaction temperatures on the photocatalytic oxidation of glucose by a modified carbon nitride photocatalyst to synthesize lactic acid in example 9.
FIG. 4 is a graph showing the effect of different KOH concentrations on the photocatalytic oxidation of glucose by a modified carbon nitride photocatalyst to synthesize lactic acid in examples 10 and 9.
FIG. 5 is a graph showing the effect of different catalyst amounts on the photocatalytic oxidation of glucose by a modified carbon nitride photocatalyst to synthesize lactic acid in examples 11 and 10.
FIG. 6 is a graph showing the effect of different reaction times on the photocatalytic oxidation of glucose by a modified carbon nitride photocatalyst to synthesize lactic acid in examples 12 and 11.
FIG. 7 is a diagram showing the cyclic utilization of the catalyst in the synthesis of lactic acid by the photocatalytic oxidation of glucose with a modified carbon nitride photocatalyst in example 13.
Detailed Description
The present invention will be further described below by way of examples for better understanding of the technical features of the present invention, but the scope of the present invention claimed is not limited thereto.
Example 1
(1) Accurately measuring glacial acetic acid with the volumes of 1.0mL, 3.0mL, 5.0mL, 8.0mL, 10.0mL and 15.0mL respectively, adding deionized water to prepare 200.0mL of acetic acid solutions with different concentrations, then accurately weighing 10.0g of boric acid, adding the boric acid into the system, and preparing boric acid-acetic acid solutions with different concentrations for later use;
(2) accurately weighing 3.0g of melamine and 3.0mL of the boric acid-acetic acid solution prepared in the step (1), adding the solution into a porcelain boat, and stirring the mixture uniformly at room temperature;
(3) calcining the product obtained in the step (2) at 400.0 ℃ for 2.0h, and then grinding the obtained solid;
(4) and (3) calcining the product obtained by grinding in the step (3) at the temperature of 560.0 ℃ for 2.0h, and then grinding the obtained product into powder to obtain the in-situ doped boron and oxygen heteroatom modified carbon nitride photocatalytic material.
Example 2
(1) Accurately measuring 10.0mL of glacial acetic acid, adding deionized water to prepare 200.0mL of acetic acid solution, then accurately weighing 10.0g of boric acid, adding the boric acid into the system, and preparing boric acid-acetic acid solution for later use;
(2) accurately weighing 3g of nitrogen-containing compound precursor (melamine, thiourea, urea and dicyanodiamide respectively) and 2mL of boric acid-acetic acid solution prepared in the step (1), adding 1mL of water into a porcelain boat, and uniformly stirring at room temperature;
(3) calcining the product obtained in the step (2) at 400.0 ℃ for 2.0h, and then grinding the obtained solid;
(4) and (3) calcining the product obtained by grinding in the step (3) at the temperature of 560.0 ℃ for 2.0h, and then grinding the obtained product into powder to obtain the in-situ doped boron and oxygen heteroatom modified carbon nitride photocatalytic material.
Example 3
(1) Accurately measuring 10.0mL of glacial acetic acid, adding deionized water to prepare 200.0mL of acetic acid solution, then accurately weighing 10.0g of boric acid, adding the boric acid into the system, and preparing boric acid-acetic acid solution for later use;
(2) accurately weighing 3g of nitrogen-containing compound precursor (melamine, thiourea, urea and dicyanodiamide respectively) and 1mL of boric acid-acetic acid solution, adding 2mL of water into a porcelain boat, and uniformly stirring at room temperature;
(3) calcining the product obtained in the step (2) at 400.0 ℃ for 2.0h, and then grinding the obtained solid;
(4) and (3) calcining the product obtained by grinding in the step (3) at the temperature of 560.0 ℃ for 2.0h, and then grinding the obtained product into powder to obtain the in-situ doped boron and oxygen heteroatom modified carbon nitride photocatalytic material.
Example 4
(1) Accurately weighing 3g of nitrogen-containing compound precursor (melamine, thiourea, urea and dicyanodiamide respectively) and 3mL of water, adding into a porcelain boat, and stirring uniformly at room temperature;
(2) calcining the product obtained in the step (1) at 400.0 ℃ for 2.0h, and then grinding the obtained solid;
(3) and (3) calcining the product obtained by grinding in the step (2) at the temperature of 560.0 ℃ for 2.0h, and then grinding the obtained product into powder to obtain the in-situ doped boron and oxygen heteroatom modified carbon nitride photocatalytic material.
Example 5
(1) Accurately measuring 10.0mL of glacial acetic acid, adding deionized water to prepare 200.0mL of acetic acid solution, then accurately weighing 10.0g of boric acid, adding the boric acid into the system, and preparing boric acid-acetic acid solution for later use;
(2) accurately weighing 3.0g of melamine and 3.0mL of the boric acid-acetic acid solution prepared in the step (1), adding the solution into a porcelain boat, and stirring the mixture uniformly at room temperature;
(3) calcining the product obtained in the step (2) at 300.0 ℃, 350.0 ℃ and 450.0 ℃ for 2.0h respectively, and then grinding the obtained solid;
(4) and (3) calcining the product obtained by grinding in the step (3) at the temperature of 560.0 ℃ for 2.0h, and then grinding the obtained product into powder to obtain the in-situ doped boron and oxygen heteroatom modified carbon nitride photocatalytic material.
Example 6
(1) Accurately measuring 10.0mL of glacial acetic acid, adding deionized water to prepare 200.0mL of acetic acid solution, then accurately weighing 10.0g of boric acid, adding the boric acid into the system, and preparing boric acid-acetic acid solution for later use;
(2) accurately weighing 3.0g of thiourea and 3.0mL of the boric acid-acetic acid solution prepared in the step (1), adding the solution into a porcelain boat, and stirring the solution uniformly at room temperature;
(3) calcining the product obtained in the step (2) at 400.0 ℃ for 1.0h, 2.0h and 3.0h respectively, and then grinding the obtained solid;
(4) and (3) calcining the product obtained by grinding in the step (3) at the temperature of 560.0 ℃ for 2.0h, and then grinding the obtained product into powder to obtain the in-situ doped boron and oxygen heteroatom modified carbon nitride photocatalytic material.
Example 7
(1) Accurately measuring 10.0mL of glacial acetic acid, adding deionized water to prepare 200.0mL of acetic acid solution, then accurately weighing 10.0g of boric acid, adding the boric acid into the system, and preparing boric acid-acetic acid solution for later use;
(2) accurately weighing 3.0g of dicyanodiamine and 3.0mL of boric acid-acetic acid solution prepared in the step (1), adding the solution into a porcelain boat, and stirring the solution uniformly at room temperature;
(3) calcining the product obtained in the step (2) at 400.0 ℃ for 2.0h, and then grinding the obtained solid;
(4) and (3) respectively calcining the product obtained by grinding in the step (3) at the temperature of 500.0 ℃, 520.0 ℃, 540.0 ℃, 560.0 ℃, 580.0 ℃ and 600.0 ℃ for 2.0h, and then grinding the obtained product into powder to obtain the in-situ boron-doped and oxygen-heteroatom-doped modified carbon nitride photocatalytic material.
Example 8
(1) Accurately measuring 1.0mL of glacial acetic acid, adding deionized water, preparing 200.0mL of acetic acid solutions with different concentrations, then accurately measuring 10.0g of boric acid, adding the boric acid into the system, and preparing a boric acid-acetic acid solution for later use;
(2) accurately weighing 3.0g of melamine and 3.0mL of the boric acid-acetic acid solution prepared in the step (1), adding the solution into a porcelain boat, and stirring the mixture uniformly at room temperature;
(3) calcining the product obtained in the step (2) at 400.0 ℃ for 2.0h, and then grinding the obtained solid; (ii) a
(4) And (3) calcining the product obtained by grinding in the step (3) at the temperature of 560.0 ℃ for 1.0h and 3.0h respectively, and then grinding the obtained product into powder to obtain the in-situ doped boron and oxygen heteroatom modified carbon nitride photocatalytic material.
Example 9
(1) Adding 0.1g of glucose, 10.0mL of a 3.0mol/L KOH solution and 50.0mg of a modified carbon nitride photocatalyst prepared from a boric acid-acetic acid solution prepared from 10.0mL of glacial acetic acid in example 1 into a pressure-resistant bottle;
(2) adding a magneton into the system in the step (1), and stirring for 5 min;
(3) sealing the system in the step (2), respectively carrying out a reaction for 60min at 20.0 ℃, 40.0 ℃, 50.0 ℃, 60.0 ℃, 70.0 ℃, 80.0 ℃ and 90.0 ℃ by using a 300W xenon lamp for illumination, and filtering to remove the modified carbon nitride photocatalyst;
(4) and (4) measuring the synthetic amount of the lactic acid by using the filtrate obtained in the step (3) through a high performance liquid chromatograph.
Example 10
(1) Adding 0.1g of glucose, 10.0mL of KOH solutions with different concentrations (the concentrations are 0.1, 1.0mol/L, 4.0mol/L and 5.0mol/L respectively) and 50.0mg of the modified carbon nitride photocatalyst prepared from the boric acid-acetic acid solution prepared from 10.0mL of glacial acetic acid in example 1 into a pressure-resistant bottle;
(2) adding a magneton into the system in the step (1), and stirring for 5 min;
(3) sealing the system in the step (2), performing a reaction for 60min at 60.0 ℃ by using a 300W xenon lamp for illumination, and filtering to remove the modified carbon nitride photocatalyst;
(4) and (4) measuring the synthetic amount of the lactic acid by using the filtrate obtained in the step (3) through a high performance liquid chromatograph.
Example 11
(1) Adding 0.1g of glucose, 10.0mL of 2.0mol/L KOH solution and different amounts of the modified carbon nitride photocatalyst prepared from the boric acid-acetic acid solution prepared from 10.0mL of glacial acetic acid in the example 1 into a pressure-resistant bottle; wherein, the dosage of the modified carbon nitride photocatalyst is respectively set to be 5.0mg, 10.0mg, 20.0mg, 30.0mg, 40.0mg, 60.0mg and 70.0 mg;
(2) adding a magneton into the system in the step (1), and stirring for 5 min;
(3) sealing the system in the step (2), performing a reaction for 60min at 60.0 ℃ by using a 300W xenon lamp for illumination, and filtering to remove the modified carbon nitride photocatalyst;
(4) and (4) measuring the synthetic amount of the lactic acid by using the filtrate obtained in the step (3) through a high performance liquid chromatograph.
Example 12
(1) Adding 0.1g of glucose, 10.0mL of 2.0mol/L KOH solution and 30.0mg of modified carbon nitride photocatalyst prepared from boric acid-acetic acid solution prepared from 10.0mL of glacial acetic acid in example 1 into a pressure-resistant bottle;
(2) adding a magneton into the system in the step (1), and stirring for 5 min;
(3) sealing the system in the step (2), respectively reacting for 30.0min, 90.0min, 120.0min, 150.0min and 180.0min at 60.0 ℃ by using 300W xenon lamp illumination, and filtering to remove the modified carbon nitride photocatalyst;
(4) and (4) measuring the synthetic amount of the lactic acid by using the filtrate obtained in the step (3) through a high performance liquid chromatograph.
Example 13
(1) Centrifugally filtering the modified carbon nitride photocatalyst obtained by filtering after reacting for 90.0min in the example 12, washing the obtained product to be neutral by using deionized water, and drying the product overnight;
(2) adding 0.1g of glucose, 10.0mL of KOH solution (2.0mol/L) and 30.0mg of modified carbon nitride recovery photocatalyst into a pressure-resistant bottle;
(3) adding a magneton into the system in the step (1), and stirring for 5 min;
(4) sealing the system in the step (2), reacting for 90min at 60.0 ℃, and filtering to remove the modified carbon nitride photocatalyst;
(5) and (4) measuring the synthetic amount of the lactic acid by using a high performance liquid chromatograph.
(6) Repeating the steps (1) to (5) for 10 times of circulation on the modified carbon nitride photocatalyst obtained by filtering in the step (4).
FIG. 1 is an XRD spectrum of a modified carbon nitride catalyst, wherein a is the modified carbon nitride catalyst in which the nitrogen-containing compound of example 4 is melamine, b is the modified carbon nitride catalyst in which the nitrogen-containing compound of example 3 is melamine, c is the modified carbon nitride catalyst in which the nitrogen-containing compound of example 2 is melamine, and d is the modified carbon nitride catalyst prepared in example 1 in which glacial acetic acid is 10 mL. From the figure, the spectrum and g-C of the modified carbon nitride catalyst can be seen3N4Very similar spectra of the catalysts, g-C3N4The catalyst has obvious characteristic peaks at two positions of 13.0 DEG and 27.5 DEG, and is assigned to g-C3N4The (100) and (002) crystal faces of the catalyst respectively represent g-C3N4In-plane stacking and interfacial stacking of the catalyst. As the B, O element is doped in situ, the transverse peak of the (002) crystal face is shifted to a lower 2 theta angle, which shows that g-C3N4The stacking distance between the nanosheets gradually decreases. In addition, with the B, O element in-situ doping, the two peaks of the (100) and (002) crystal planes are bothBroadening and tapering, which indicates that elemental doping can be done with g-C during thermal polymerization3N4(or molecular precursors thereof) to cause a change in the ordered structure within the backbone.
FIG. 2 is a FT-IR spectrum of a modified carbon nitride catalyst, wherein a is the modified carbon nitride catalyst of example 4 in which the nitrogen-containing compound is melamine, b is the modified carbon nitride catalyst of example 3 in which the nitrogen-containing compound is melamine, c is the modified carbon nitride catalyst of example 2 in which the nitrogen-containing compound is melamine, and d is the modified carbon nitride catalyst prepared in example 1 in which glacial acetic acid is 10 mL. From the figure, the spectrogram and g-C of the modified carbon nitride photocatalyst can be seen3N4The spectra of the catalysts are very similar. It can be seen that g-C3N4At 810cm-1Has a characteristic peak which represents the out-of-plane bending of a heptaphenyl ring and is 900-1800 cm-1The characteristic peak between N and C in the catalyst frame is N hybridized and is 3000-3500 cm-1A plurality of peaks in between correspond to stretching vibration of the N — H bond. For the modified carbon nitride series samples, two significant changes in the FT-IR spectrum were observed. With the in-situ doping of B, O elements, the first change is 3000-3300 cm-1With a rightward shift of the N-H stretch peak in between. Another variation is in situ doping with B, O element at 810cm-1A similar shift occurs. The results show that in the synthesis of g-C3N4In the series of samples, the B, O element is doped in situ, so that the electronic structural arrangement of the material is changed.
FIG. 3 is a graph showing the effect of different reaction temperatures on the photocatalytic oxidation of glucose by modified carbon nitride to synthesize lactic acid in example 9. The reaction temperature is an important parameter for the conversion of carbohydrates. It was found that as the reaction temperature increased, the conversion of glucose gradually increased and the yield of lactic acid gradually increased, with the yield of lactic acid reaching a maximum when the temperature was increased to 60.0 ℃ and decreasing when the temperature was increased again, probably due to the conversion of part of the lactic acid to other by-products during the reaction.
FIG. 4 is a graph showing the effect of different KOH concentrations on the synthesis of lactic acid by the photocatalytic oxidation of glucose with modified carbon nitride in examples 10 and 9, wherein the concentrations of KOH solutions in examples 10 and 9 are 0.1mol/L, 1.0mol/L, 2.0mol/L, 4.0mol/L and 5.0mol/L, respectively, the reaction temperature in example 9 is 60.0 ℃ and the concentration of KOH solution is 3.0 mol/L. The concentration of KOH also affects the yield of lactic acid, which is hardly detectable under neutral conditions. When the concentration of KOH was increased to 2.0mol/L, the yield of lactic acid reached the maximum and then showed a tendency to decrease again. Therefore, 2.0mol/L KOH solution was selected as the optimum reaction condition.
FIG. 5 is a graph showing the effect of different catalyst dosages in examples 11 and 10 on the synthesis of lactic acid by the photocatalytic oxidation of glucose by modified carbon nitride, wherein the dosages of the modified carbon nitride photocatalyst in example 11 are set to 5.0mg, 10.0mg, 20.0mg, 30.0mg, 40.0mg, 60.0mg and 70.0mg, respectively, and the concentration of KOH solution in example 10 is 2.0mol/L and the dosage of the modified carbon nitride photocatalyst is 50.0 mg. The amount of catalyst used is also an important parameter affecting the conversion of glucose. The influence of the amount of the modified carbon nitride on the conversion of photocatalytic oxidation of glucose into lactic acid was studied. It was found that the lactic acid yield increased with increasing catalyst amount. When the amount of the catalyst is more than 30.0mg, the yield of the lactic acid is reduced to some extent. This is probably due to the fact that the reactants form intermediates on the catalyst surface, reducing the activation energy of the reaction. Therefore, the amount of the catalyst used is preferably 30.0mg as the optimum condition for further investigating the catalytic process.
FIG. 6 is a graph showing the effect of different reaction times on the photocatalytic oxidation of glucose to lactic acid by modified carbon nitride in examples 12 and 11, wherein the irradiation reaction times in example 12 are 30.0min, 90.0min, 120.0min, 150.0min and 180.0min, respectively, the amount of the modified carbon nitride photocatalyst in example 11 is 30.0mg, and the irradiation reaction time in example 11 is 60 min. The influence of different reaction times on the synthesis of lactic acid by the photocatalytic oxidation of glucose by modified carbon nitride is explored. It was found that the yield of lactic acid tended to increase and then decrease. The lactic acid yield reached a maximum at a reaction time of 90.0 min. This is probably due to the fact that under the same conditions, the lactic acid formed is further reacted to form other by-products as the reaction time is extended.
Fig. 7 is a catalyst cycle experiment of the modified carbon nitride photocatalyst for photocatalytic oxidation of glucose to synthesize lactic acid in example 13. As can be seen from fig. 7, after 11 cycles, the conversion of glucose and the yield of lactic acid remained at high levels, and after 11 cycles, the conversion and yield were 99.9% and 99.3% of the first time, respectively, and the reaction activity was hardly changed. This indicates that the modification of g-C3N4Can still ensure higher catalytic efficiency in the process of multiple recycling, and has higher recycling capability and excellent stability.
The above embodiments are part of the implementation process of the present invention, but the implementation manner of the present invention is not limited by the above embodiments, and any other changes, substitutions, combinations, and simplifications which are made without departing from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.
Claims (10)
1. A preparation method of a modified carbon nitride photocatalyst is characterized by comprising the following steps:
(1) uniformly mixing a nitrogen-containing compound precursor with a boric acid-acetic acid solution and water, and calcining at the temperature of 300.0-450.0 ℃ for 1.0-3.0 h;
wherein the concentration of boric acid in the boric acid-acetic acid solution is 0.8mol/L, and the volume concentration of acetic acid is 0.5-7.5%; the proportion of the nitrogen-containing compound precursor, the boric acid-acetic acid solution and water is 3.0 g: 0-3.0 mL: 0-3.0 mL;
(2) and (2) calcining the product obtained in the step (1) at the temperature of 500.0-600.0 ℃ for 1.0-3.0 h to obtain the modified carbon nitride photocatalytic material.
2. The method for preparing a modified carbon nitride photocatalyst according to claim 1, wherein in the step (1), the nitrogen-containing compound precursor is urea, thiourea, dicyanodiamine or melamine.
3. The method for preparing a modified carbon nitride photocatalyst according to claim 1, wherein in the step (1), the calcination temperature is 400.0 ℃ and the calcination time is 2.0 h.
4. The method for preparing a modified carbon nitride photocatalyst according to claim 1, wherein in the step (2), the calcination temperature is 560.0 ℃ and the calcination time is 2.0 h.
5. The method for preparing a modified carbon nitride photocatalyst according to claim 1, wherein in the steps (1) and (2), the calcination is followed by grinding.
6. Use of the modified carbon nitride photocatalyst obtained by the preparation method according to any one of claims 1 to 5 for photocatalytic oxidation of glucose to lactic acid.
7. The application of claim 6, wherein the modified carbon nitride photocatalyst, glucose and alkaline solution are uniformly mixed and subjected to a photocatalytic reaction at 20.0-90.0 ℃ for 30.0-180.0 min.
8. Use according to claim 7, wherein the alkaline solution is a water-soluble alkaline solution.
9. The use according to claim 7, wherein the concentration of the alkaline solution is 0.1-5.0 mol/L.
10. The use according to claim 7, wherein the ratio of glucose, alkaline solution, modified carbon nitride photocatalyst is 0.1 g: 10.0 mL: 5.0-70.0 mg.
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