CN114917942B - Preparation method of one-dimensional nanorod-shaped carbon nitride photocatalyst and application of photocatalyst in synthesis of lactic acid by photocatalytic oxidation of monosaccharide - Google Patents
Preparation method of one-dimensional nanorod-shaped carbon nitride photocatalyst and application of photocatalyst in synthesis of lactic acid by photocatalytic oxidation of monosaccharide Download PDFInfo
- Publication number
- CN114917942B CN114917942B CN202210387296.1A CN202210387296A CN114917942B CN 114917942 B CN114917942 B CN 114917942B CN 202210387296 A CN202210387296 A CN 202210387296A CN 114917942 B CN114917942 B CN 114917942B
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- lactic acid
- photocatalyst
- dimensional
- monosaccharide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000004310 lactic acid Substances 0.000 title claims abstract description 46
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 46
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 41
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 150000002772 monosaccharides Chemical class 0.000 title claims abstract description 22
- 230000003647 oxidation Effects 0.000 title claims abstract description 22
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 title abstract description 11
- 230000015572 biosynthetic process Effects 0.000 title abstract description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 10
- -1 nitrogenous compound Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004108 freeze drying Methods 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000011363 dried mixture Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 239000002073 nanorod Substances 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 12
- 239000012670 alkaline solution Substances 0.000 abstract description 6
- 102000004190 Enzymes Human genes 0.000 abstract description 4
- 108090000790 Enzymes Proteins 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 35
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 13
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 12
- 229930091371 Fructose Natural products 0.000 description 8
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 8
- 239000005715 Fructose Substances 0.000 description 8
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 8
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 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 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000008103 glucose Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 5
- 239000002028 Biomass Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 239000004626 polylactic acid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000007787 solid Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003738 black carbon Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 229920002522 Wood fibre Polymers 0.000 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 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002025 wood fiber Substances 0.000 description 2
- 241000700605 Viruses Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 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 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/50—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- 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
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
-
- 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
Abstract
The invention belongs to the field of photocatalytic synthesis, and discloses a preparation method of a one-dimensional nanorod carbon nitride (HCN) photocatalyst and application thereof in synthesizing lactic acid by photocatalytic oxidation of monosaccharide, wherein the preparation method comprises the following steps: dispersing a soluble nitrogenous compound precursor and one-dimensional linear nanocellulose in water, freeze-drying and calcining, and finally carrying out hydro-thermal treatment on a calcined sample and hydrogen peroxide to obtain a one-dimensional nanorod-shaped carbon nitride material (HCN) material with oxygen atoms and nitrogen vacancies introduced into the structure. And mixing the prepared HCN photocatalyst, monosaccharide and alkaline solution, and synthesizing lactic acid by catalytic oxidation of the monosaccharide under visible light. The method for preparing the catalyst has the advantages of good universality, wide precursor sources, diversity of substrate selection, high activity, good thermal stability, recycling and the like, and compared with the traditional thermocatalysis and enzyme catalysis, the method can rapidly synthesize the lactic acid under the conditions of greenness and approaching normal temperature.
Description
Technical Field
The invention belongs to the field of photocatalytic synthesis, and in particular relates to a preparation method of a one-dimensional nanorod carbon nitride (HCN) photocatalyst and application thereof in synthesizing lactic acid by photocatalytic oxidation of monosaccharide.
Background
With the development of human society, the shortage of energy and resources is increasingly highlighted, and the climate and environmental problems caused by the large use of non-renewable energy sources are also becoming serious. The development of low-carbon green recycling economy is the mainstream of today's society. Biomass, which is the only renewable carbon source, has the advantages of rich sources, biodegradability and the like, and has become one of the alternatives to fossil energy. Wood fibers are the most important biomass source, and the conversion and utilization of wood fibers is of great significance for solving the current energy and environmental problems. The three components of the lignocellulose are cellulose, hemicellulose and lignin respectively, wherein the cellulose and the hemicellulose are bio-based high polymer taking monosaccharide as a structural unit, and the glucose content is first and the xylose content is second. The monosaccharide represented by xylose can be converted into various high-value platform chemicals, such as sugar acid, furfural, lactic acid and the like, and has wide application in the fields of chemical industry, medical treatment, agriculture, food and the like. Therefore, the high-valued conversion and utilization of biomass-based monosaccharides represented by xylose are important means and ways for realizing carbon peak and carbon neutralization in China.
Lactic Acid (LA) is also called alpha-hydroxy-propionic acid, is an organic acid with hydroxyl and carboxyl, is a multifunctional platform chemical product, and has wide application in chemical industry, medicine, food and daily chemical industry. Meanwhile, lactic acid is also a main raw material for synthesizing polylactic acid (PLA), which is an environment-friendly bio-based degradable material and is widely applied to the fields of packaging, medical treatment, textile and the like at present. Polylactic acid productivity is also in an explosive growth phase, and statistics of European bioplastic society show that global polylactic acid productivity is about 27.13 ten thousand tons in 2019; in 2020, the capacity has increased to 39.48 ten thousand tons. Therefore, the development of a large amount of efficient and green methods for synthesizing lactic acid has great significance.
Currently, the synthesis methods of lactic acid are mainly chemical and biological. Lactic acid is a product of certain biological metabolism, and thus biological processes mainly include enzyme catalysis and fermentation processes, in which lactic acid is obtained by catalyzing hydrolysis of carbohydrates with biological enzymes. The method has the advantages of wide raw material sources, long reaction period, low yield, high energy consumption, difficult purification of lactic acid, incapability of recycling enzyme and the like. Lactic acid is synthesized chemically, mainly by thermocatalytic method, by catalytic oxidation of saccharides. The chemical synthesis method has the advantages of easy separation of products, high reaction rate and the like, but the industrialized application of the chemical synthesis method is limited to a certain extent due to the high reaction temperature and the need of a special high-pressure container. Therefore, the development of a green and mild method for synthesizing lactic acid is one of the targets of the industrial efforts. The photocatalytic oxidation technology is a green reaction technology taking sunlight as an energy source, has the advantages of mild reaction conditions, easy recovery of a catalyst, low energy consumption, high reaction rate, high selectivity and the like, and is widely applied to the fields of organic pollutant degradation, virus killing, organic synthesis and the like. The photocatalytic oxidation technology is applied to the selective oxidation of monosaccharide to synthesize lactic acid, and a new way is provided for the green and efficient synthesis of lactic acid.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the primary purpose of the invention is to provide a preparation method of a one-dimensional nanorod-shaped carbon nitride photocatalyst.
The invention also aims to provide the one-dimensional nanorod-shaped carbon nitride photocatalyst prepared by the method.
The invention also aims to provide the application of the one-dimensional nanorod-shaped carbon nitride photocatalyst in synthesizing lactic acid by photocatalytic oxidation of monosaccharide.
The aim of the invention is achieved by the following scheme:
a preparation method of a one-dimensional nanorod-shaped carbon nitride photocatalyst comprises the following steps:
(1) Dispersing a nitrogenous compound precursor and a nanocellulose (CNF) aqueous dispersion liquid in water, then performing ultrasonic treatment to fully dissolve the nitrogenous compound precursor, and finally drying the obtained liquid to obtain a mixture;
(2) Calcining the dried mixture in the step (1), and naturally cooling to room temperature after the calcining to obtain a carbon nitride photocatalyst containing amorphous carbon;
(3) And (2) mixing the carbon nitride photocatalyst containing amorphous carbon obtained in the step (2) with hydrogen peroxide, performing hydrothermal treatment, and washing and drying the obtained product to obtain the one-dimensional nano rod-like carbon nitride photocatalyst (HCN) with oxygen atoms and nitrogen vacancies introduced into the structure.
The nitrogen-containing compound precursor in the step (1) is cyanamide, urea, thiourea or dicyandiamide (dicyandiamide);
the concentration of the nano Cellulose (CNF) aqueous dispersion liquid in the step (1) is 0.5-2wt%;
the dry weight mass ratio of the nitrogenous compound precursor to the nanocellulose (CNF) in the step (1) is 10:1-200:1;
the ultrasonic time in the step (1) is 1-4 h; the drying is freeze drying;
the calcination temperature in the step (2) is 550 ℃, the calcination time is 4 hours, and the calcination atmosphere is N 2 ， N 2 The flow is 10-30 ml/min;
the solid-to-liquid ratio of the amorphous carbon-containing carbon nitride to the hydrogen peroxide in the step (3) is 1:20-1:50 (g/ml), and the hydrogen peroxide is preferably 30wt% hydrogen peroxide;
the hydrothermal treatment in the step (3) means hydrothermal treatment at 100-180 ℃ for 8-48 hours to remove free amorphous carbon;
the washing in the step (3) means washing with water; the drying is preferably performed at 60 ℃ for 12 hours, and the obtained yellowish solid is the one-dimensional nanorod carbon nitride photocatalyst (HCN).
A one-dimensional nanorod-shaped carbon nitride photocatalyst (HCN) prepared by the method.
The application of the one-dimensional nanorod carbon nitride photocatalyst in synthesizing lactic acid by photocatalytic oxidation of monosaccharide.
A method for synthesizing lactic acid by photo-catalytic oxidation of monosaccharide, which comprises the following steps:
mixing a one-dimensional nanorod carbon nitride (HCN) photocatalyst, monosaccharide and an alkaline solution, introducing air or oxygen at a certain temperature, and reacting under visible light.
The alkaline solution is water-soluble alkaline solution such as potassium hydroxide solution, sodium hydroxide solution and the like, preferably potassium hydroxide solution; the concentration of the alkaline solution is 0.1-6.0 mol/L, preferably 2mol/L;
the monosaccharide is glucose, fructose, xylose or arabinose, preferably fructose;
the proportion of the monosaccharide, the alkaline solution and the HCN photocatalyst is 0.05-0.2 g: 5-15 g m L:5 to 80mg, preferably 0.1g:10mL:40mg;
the reaction temperature is 30-80 ℃, preferably 50 ℃; the reaction time is 30-180 min, preferably 90min;
the flow rate of the air or the oxygen is 0-10 ml/min.
Compared with the prior art, the invention has the following advantages:
(1) The raw materials for preparing the catalyst are easy to obtain, the selection is wide, the universality is realized, and the catalyst is nontoxic and pollution-free; compared with unmodified carbon nitride (BCN), the prepared one-dimensional nanorod carbon nitride material (HCN) not only has a typical one-dimensional nanorod shape, but also has stronger light absorption capacity and a large specific surface, thereby having higher photocatalytic activity. The method for synthesizing the lactic acid has the advantages of high reaction rate, reusable catalyst, easy separation of products, low equipment requirement and the like, and has certain industrial application prospect; the lactic acid synthesized by the invention is a chemical with high value, has two functional groups of carboxyl and hydroxyl, is an important chemical raw material, and has wide application prospect in the fields of medicines, foods and the like.
(2) The one-dimensional nanorod carbon nitride (HCN) photocatalyst prepared by the method is applied to the synthesis of lactic acid by photocatalytic oxidation of fructose, and experimental conditions are optimized in terms of reaction temperature, catalyst dosage, KOH concentration, reaction time and the like; under the optimal reaction conditions of 0.1g of fructose, 10ml of a 2.0mol/L KOH solution, 40mg of HCN photocatalyst, the reaction temperature was 50 ℃ and the reaction time was 90min.
(3) The one-dimensional nanorod carbon nitride (HCN) photocatalyst prepared by the method is used in the reaction of synthesizing lactic acid by photocatalytic oxidation of fructose, and has the advantages of mild conditions, low equipment requirements, easily separated products, reusability of the catalyst and the like. The lactic acid synthesized by the photocatalytic oxidation of the HCN photocatalyst can be used as a new energy source and a high-value chemical, has wide application prospect in the aspects of medicines, cosmetics, foods and the like, and particularly has the advantage that polylactic acid (PLA) taking lactic acid as a raw material is a biomass-based degradable high polymer material with wide application range, and has important significance in reducing the use of petroleum-based materials such as plastics and the like, so that the use of fossil energy sources is reduced, and the problem of environmental pollution caused by the use of fossil energy sources is also reduced.
Drawings
FIG. 1 is an SEM image of HCN prepared according to the present invention;
FIG. 2 is an XRD pattern for the preparation of HCN in accordance with the present invention;
FIG. 3 shows the preparation of HCN and N of unmodified carbon nitride (BCN) according to the present invention 2 Desorbing the attached drawing;
FIG. 4 is a UV-visible Diffuse Reflectance (DRS) spectrum of a prepared HCN and unmodified carbon nitride (BCN) according to the present invention;
FIG. 5 is a graph showing the effect of different KOH concentration, catalyst amount, illumination time and reaction temperature on the synthesis of lactic acid by photocatalytic oxidation of HCN prepared in example 1;
FIG. 6 is a graph of the cycle performance of the catalyst prepared according to the present invention;
FIG. 7 is a graph showing the photo-oxidative lactic acid production performance of different monosaccharide catalysts.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but embodiments of the present invention are not limited thereto. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The reagents used in the examples are commercially available as usual unless otherwise specified.
Example 1
(1) Accurately weighing 4g dicyandiamide, adding 4ml 1wt% nano Cellulose (CNF) aqueous dispersion into a 150ml beaker, adding 96ml deionized water, then performing ultrasonic treatment for 2 hours to fully dissolve the dicyandiamide, and finally drying the obtained liquid in a freeze drying way to obtain a mixture.
(2) Taking 2g of the dried mixture obtained in the step (1), heating to 550 ℃ under the nitrogen atmosphere (nitrogen flow rate is 10 ml/min) at the heating rate of 2.3 ℃/min, preserving heat for 4 hours, and naturally cooling to room temperature after finishing to obtain black carbon nitride solid containing amorphous carbon.
(3) Taking 1g of the product obtained by calcining the step (2), adding 20ml of 30wt% hydrogen peroxide, carrying out hydrothermal treatment at 100 ℃ for 24 hours, washing the obtained product with deionized water, and drying at 60 ℃ for 12 hours to obtain the one-dimensional nanorod carbon nitride photocatalyst (HCN).
Example 2
(1) Accurately weighing 10g of urea and 10ml of 1wt% nano Cellulose (CNF) dispersion, adding into a 50ml beaker, adding 10ml of deionized water, performing ultrasonic treatment for 2 hours to fully dissolve the urea, and finally drying the obtained liquid in a freeze drying way to obtain a mixture.
(2) Taking 5g of the mixture obtained in the step (1), heating to 550 ℃ under the nitrogen atmosphere (the nitrogen flow rate is 10 ml/min) at the heating rate of 10 ℃/min, preserving heat for 2 hours, and finally naturally cooling to room temperature to obtain black carbon nitride solid containing amorphous carbon.
(3) Taking 1g of the product obtained by calcining the step (2), adding 20ml of 30wt% hydrogen peroxide, carrying out hydrothermal treatment at 100 ℃ for 24 hours, washing the obtained product with deionized water, and drying at 60 ℃ for 12 hours to obtain the one-dimensional nanorod carbon nitride photocatalyst (HCN).
Example 3
(1) Accurately weighing 10g of cyanamide and 20ml of 1wt% nano Cellulose (CNF) dispersion, adding into a 50ml beaker, then carrying out ultrasonic treatment for 2 hours to fully dissolve the cyanamide, and finally drying the obtained liquid in a freeze drying mode.
(2) Taking 5g of the mixture obtained in the step (1), heating to 550 ℃ under nitrogen atmosphere (nitrogen flow rate 10 ml/min) at a heating rate of 2.3 ℃/min, preserving heat for 2h, and finally naturally cooling to room temperature to obtain black carbon nitride solid containing amorphous carbon.
(3) Taking 1g of the product obtained by calcining the step (2), adding 20ml of 30wt% hydrogen peroxide, carrying out hydrothermal treatment at 100 ℃ for 48 hours, washing the obtained product with deionized water, and drying at 60 ℃ for 12 hours to obtain the one-dimensional nanorod carbon nitride photocatalyst (HCN).
Example 4
(1) 0.1g of fructose and 10ml of 1mol/L KOH solution are taken and added into a pressure-resistant bottle at the temperature of 40 ℃ with the HCN photocatalyst prepared in example 1 (20 mg, 30mg, 40mg, 50mg and 60mg respectively);
(2) Sealing the system in the step (1), and carrying out illumination reaction for 60min by using a xenon lamp with the wavelength of 300W (with a 420nm cut-off filter added);
(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) KOH concentrations were set to 0.1mol/L, 0.2mol/L, 0.5mol/L, 1.0mol/L, 2.0mol/L, 6mol/L, respectively, in the same manner as in step (1) of example 4;
(2) The catalyst amount of the system was maintained at 40mg, otherwise in 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) Setting the reaction time of the system to be 30min, 60min, 90min, 120min, 150min and 180min respectively, and carrying out the same steps as in the step (1) of the embodiment 4;
(2) Maintaining the KOH concentration of the system at 2mol/L, otherwise the same as in the step (2) of example 5;
(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 7
(1) Setting the reaction temperature of the system to 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ respectively, and otherwise carrying out the step (1) of example 6;
(2) The reaction time of the system is maintained at 90min, and the step (2) of the example 6 is otherwise carried out;
(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 8
(1) Taking 0.1g of xylose and 10m L of 2mol/L of KOH solution, and adding 40mg of the HCN photocatalyst prepared in the example 1 into a pressure-resistant bottle at the temperature of 50 ℃;
(2) Sealing the system in the step (1), and carrying out illumination reaction for 90min by using a xenon lamp with the power of 300W (with a 420nm cut-off filter added);
(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 9
(1) 40mg of the HCN photocatalyst prepared in example 1 was added to a pressure-resistant bottle at 50℃from 0.1g of glucose and 10ml of 2mol/L KOH solution;
(2) Sealing the system in the step (1), and carrying out illumination reaction for 90min by using a xenon lamp with the power of 300W (with a 420nm cut-off filter added);
(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 10
(1) 40mg of the HCN photocatalyst prepared in example 1 was added to a pressure-resistant bottle at 50℃from 0.1g of glucose and 10ml of 2mol/L KOH solution;
(2) Sealing the system in the step (1), and carrying out illumination reaction for 90min by using a xenon lamp with the power of 300W (with a 420nm cut-off filter added);
(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.
The one-dimensional nanorod carbon nitride (HCN) photocatalyst prepared by the invention is applied to the synthesis of lactic acid by photocatalytic oxidation of fructose, and experimental conditions are optimized in terms of reaction temperature, catalyst dosage, KOH concentration, reaction time and the like, and the experimental result is shown in figure 5; under the optimal reaction conditions (0.1 g fructose, 10m L of 2.0mol/L KOH solution, 40mg HCN photocatalyst, reaction temperature of 50 ℃ and reaction time of 90 min), the yield of lactic acid reaches 77.5%, after five cycles, the yield of lactic acid still reaches 72.65%, and the experimental results are shown in FIG. 6. When the substrate is changed into glucose, xylose and arabinose, the yields of lactic acid are 55.49%, 41.37% and 37.62%, respectively, and the experimental results are shown in fig. 7, which shows that the method has good substrate adaptability.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. An application of a one-dimensional nano rod-shaped carbon nitride photocatalyst in synthesizing lactic acid by photocatalytic oxidation of monosaccharide is characterized in that:
the preparation method of the one-dimensional nanorod-shaped carbon nitride photocatalyst comprises the following steps:
(1) Dispersing a nitrogenous compound precursor and a nanocellulose aqueous dispersion in water, then performing ultrasonic treatment to fully dissolve the nitrogenous compound precursor, and finally drying the obtained liquid to obtain a mixture;
(2) Calcining the dried mixture in the step (1), and naturally cooling to room temperature after the calcining to obtain a carbon nitride photocatalyst containing amorphous carbon;
(3) Mixing the carbon nitride photocatalyst containing amorphous carbon obtained in the step (2) with hydrogen peroxide, performing hydrothermal treatment, and washing and drying the obtained product to obtain the one-dimensional nano rod-shaped carbon nitride photocatalyst with oxygen atoms and nitrogen vacancies introduced into the structure;
the nitrogen-containing compound precursor in the step (1) is cyanamide, urea, thiourea or dicyandiamide;
the calcination temperature in the step (2) is 550 ℃, and the calcination time is 2 hours or 4 hours;
the hydrothermal treatment in the step (3) means hydrothermal treatment for 8-48 hours at 100-180 ℃.
2. The application of the one-dimensional nanorod-shaped carbon nitride photocatalyst in synthesizing lactic acid by photocatalytic oxidation of monosaccharides, according to claim 1, characterized in that:
the concentration of the nano cellulose aqueous dispersion liquid in the step (1) is 0.5-2 wt%.
3. The application of the one-dimensional nanorod-shaped carbon nitride photocatalyst in synthesizing lactic acid by photocatalytic oxidation of monosaccharides, according to claim 1, characterized in that: the dry weight mass ratio of the nitrogenous compound precursor to the nanocellulose in the step (1) is 10:1-200:1;
the drying in step (1) is freeze drying.
4. The application of the one-dimensional nanorod-shaped carbon nitride photocatalyst in synthesizing lactic acid by photocatalytic oxidation of monosaccharides, according to claim 1, characterized in that: the calcining atmosphere in the step (2) is N 2 ，N 2 The flow rate is 10-30 mL/min.
5. The application of the one-dimensional nanorod-shaped carbon nitride photocatalyst in synthesizing lactic acid by photocatalytic oxidation of monosaccharides, according to claim 1, characterized in that: in the step (3), the solid-to-liquid ratio of the carbon nitride containing amorphous carbon to the hydrogen peroxide is 1:20-1:50, g/mL, and the hydrogen peroxide is 30wt% hydrogen peroxide;
the drying in the step (3) is drying at 60 ℃ for 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210387296.1A CN114917942B (en) | 2022-04-14 | 2022-04-14 | Preparation method of one-dimensional nanorod-shaped carbon nitride photocatalyst and application of photocatalyst in synthesis of lactic acid by photocatalytic oxidation of monosaccharide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210387296.1A CN114917942B (en) | 2022-04-14 | 2022-04-14 | Preparation method of one-dimensional nanorod-shaped carbon nitride photocatalyst and application of photocatalyst in synthesis of lactic acid by photocatalytic oxidation of monosaccharide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114917942A CN114917942A (en) | 2022-08-19 |
| CN114917942B true CN114917942B (en) | 2023-09-26 |
Family
ID=82806191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210387296.1A Active CN114917942B (en) | 2022-04-14 | 2022-04-14 | Preparation method of one-dimensional nanorod-shaped carbon nitride photocatalyst and application of photocatalyst in synthesis of lactic acid by photocatalytic oxidation of monosaccharide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114917942B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116586096A (en) * | 2023-05-26 | 2023-08-15 | 昆明理工大学 | Carbon nitride modified biochar material and preparation method thereof |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN106799250A (en) * | 2016-12-31 | 2017-06-06 | 浙江工业大学 | One species graphite-phase g C3N4/ montmorillonite composite material and its application in cellulose hydrolysis |
| CN106810436A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation glycerine prepares lactic acid |
| CN107715903A (en) * | 2017-10-11 | 2018-02-23 | 肇庆市华师大光电产业研究院 | A kind of method for being acidified assisting alcohol-hydrothermal method and preparing high-efficiency silicon nitride carbon nano rod photochemical catalyst |
| CN107983390A (en) * | 2017-12-08 | 2018-05-04 | 吉林师范大学 | A kind of surface imprinted carbonitride/composite titania material photocatalysis membrana and preparation method and purposes |
| CN108079966A (en) * | 2017-12-26 | 2018-05-29 | 肇庆市华师大光电产业研究院 | A kind of carbonitride/cellulose aerogels composite photo-catalyst and its preparation method and application |
| CN108816262A (en) * | 2018-04-25 | 2018-11-16 | 西安交通大学 | A kind of preparation method of nickel oxide-nitridation carbon composite photocatalyst |
| CN108927198A (en) * | 2018-07-09 | 2018-12-04 | 华南理工大学 | A kind of method that modified carbon nitride photocatalyst and its preparation synthesize xylonic with photochemical catalytic oxidation xylose |
| CN110327955A (en) * | 2019-06-13 | 2019-10-15 | 福建农林大学 | A kind of preparation method of the micro- hetero-junctions carbon nitride photocatalyst of carbon fiber interpenetrating |
| WO2019229255A1 (en) * | 2018-05-31 | 2019-12-05 | Cambridge Enterprise Limited | Photocatalyst and photocatalytic methods for producing hydrogen |
| CN111889129A (en) * | 2020-07-30 | 2020-11-06 | 大连工业大学 | Preparation of ultrathin porous nano carbon nitride photocatalyst and application of ultrathin porous nano carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of fructose |
| CN113509949A (en) * | 2021-03-24 | 2021-10-19 | 大连工业大学 | Preparation of porous hollow carbon nitride nanotube photocatalyst and application of photocatalyst in synthesis of lactic acid by photocatalytic oxidation of xylose |
-
2022
- 2022-04-14 CN CN202210387296.1A patent/CN114917942B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104084228A (en) * | 2014-06-25 | 2014-10-08 | 华南理工大学 | Oxygen-doped carbon nitride/zinc oxide photo-catalyst as well as preparation method and application thereof |
| CN106810436A (en) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation glycerine prepares lactic acid |
| CN106799250A (en) * | 2016-12-31 | 2017-06-06 | 浙江工业大学 | One species graphite-phase g C3N4/ montmorillonite composite material and its application in cellulose hydrolysis |
| CN107715903A (en) * | 2017-10-11 | 2018-02-23 | 肇庆市华师大光电产业研究院 | A kind of method for being acidified assisting alcohol-hydrothermal method and preparing high-efficiency silicon nitride carbon nano rod photochemical catalyst |
| CN107983390A (en) * | 2017-12-08 | 2018-05-04 | 吉林师范大学 | A kind of surface imprinted carbonitride/composite titania material photocatalysis membrana and preparation method and purposes |
| CN108079966A (en) * | 2017-12-26 | 2018-05-29 | 肇庆市华师大光电产业研究院 | A kind of carbonitride/cellulose aerogels composite photo-catalyst and its preparation method and application |
| CN108816262A (en) * | 2018-04-25 | 2018-11-16 | 西安交通大学 | A kind of preparation method of nickel oxide-nitridation carbon composite photocatalyst |
| WO2019229255A1 (en) * | 2018-05-31 | 2019-12-05 | Cambridge Enterprise Limited | Photocatalyst and photocatalytic methods for producing hydrogen |
| CN108927198A (en) * | 2018-07-09 | 2018-12-04 | 华南理工大学 | A kind of method that modified carbon nitride photocatalyst and its preparation synthesize xylonic with photochemical catalytic oxidation xylose |
| CN110327955A (en) * | 2019-06-13 | 2019-10-15 | 福建农林大学 | A kind of preparation method of the micro- hetero-junctions carbon nitride photocatalyst of carbon fiber interpenetrating |
| CN111889129A (en) * | 2020-07-30 | 2020-11-06 | 大连工业大学 | Preparation of ultrathin porous nano carbon nitride photocatalyst and application of ultrathin porous nano carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of fructose |
| WO2022021506A1 (en) * | 2020-07-30 | 2022-02-03 | 大连工业大学 | Preparation of ultrathin porous carbon nitride nano-photocatalyst and applications thereof in photocatalytically oxidizing fructose to synthesize lactic acid |
| CN113509949A (en) * | 2021-03-24 | 2021-10-19 | 大连工业大学 | Preparation of porous hollow carbon nitride nanotube photocatalyst and application of photocatalyst in synthesis of lactic acid by photocatalytic oxidation of xylose |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114917942A (en) | 2022-08-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108927198B (en) | Modified carbon nitride photocatalyst, preparation method thereof and method for synthesizing xylonic acid by photocatalytic oxidation of xylose | |
| CN111889129B (en) | Preparation of ultrathin porous nano carbon nitride photocatalyst and application of ultrathin porous nano carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of fructose | |
| CN106824226B (en) | Preparation method and application of carbon-based solid acid | |
| CN108658747B (en) | Application of tungsten-based solid acid in preparation of lactic acid and lactate from biomass saccharides | |
| CN105879902B (en) | A kind of preparation method for the molecular sieve catalyst preparing lactic acid and lactate for sugared conversion | |
| CN113509949B (en) | Preparation of porous hollow carbon nitride nanotube photocatalyst and application of photocatalyst in synthesis of lactic acid by photocatalytic oxidation of xylose | |
| CN114917942B (en) | Preparation method of one-dimensional nanorod-shaped carbon nitride photocatalyst and application of photocatalyst in synthesis of lactic acid by photocatalytic oxidation of monosaccharide | |
| CN109721631B (en) | Method for preparing fructose through selective isomerization of glucose | |
| CN103382512B (en) | Glucose preparation method by hydrolyzing cellulose through microwave heating | |
| CN113527703B (en) | Metal carbon-based coordination polymer, preparation method and application thereof in synthesis of 2,5-furandimethanol | |
| Cheng et al. | Direct conversion of corn cob to formic and acetic acids over nano oxide catalysts | |
| CN113509931B (en) | Cu (copper) alloy 2 Preparation of O/CuO@CA photocatalyst and application of O/CuO@CA photocatalyst in synthesis of lactic acid by photocatalytic oxidation of xylose | |
| CN113181891B (en) | Preparation of anatase phase titanium dioxide photocatalyst and application of anatase phase titanium dioxide photocatalyst in synthesis of xylonic acid by photocatalytic oxidation of xylose | |
| CN1046435C (en) | Catalyst for producing synthetic gas by methane selectively oxidizing | |
| CN113145169B (en) | Preparation of photocatalytic hydrogel and application of photocatalytic hydrogel in synthesis of lactic acid by photocatalytic oxidation of xylose | |
| CN112044424B (en) | Preparation of kaolin-boehmite composite catalyst and method for catalyzing cellulose hydrolysis by using kaolin-boehmite composite catalyst | |
| CN114887645B (en) | 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 | |
| CN113214072A (en) | Method for preparing lactic acid by converting cellulose in molten salt hydrate | |
| JP2013006142A (en) | Catalyst for hydrolysis of plant-base material, and method of manufacturing saccharide | |
| CN114870868B (en) | CdIn 2 S 4 Preparation of composite carbon aerogel photocatalyst and application of composite carbon aerogel photocatalyst in synthesis of xylonic acid by photocatalytic oxidation of xylose | |
| CN111498913A (en) | Preparation method and application of cobaltosic oxide nanoparticles | |
| CN115007173B (en) | CuInS 2 Preparation of quantum dot carbon aerogel photocatalyst and application of quantum dot carbon aerogel photocatalyst in synthesis of xylonic acid by photocatalytic oxidation of xylose | |
| CN107266312A (en) | A kind of method that wood fiber biomass prepares ethyl levulinate | |
| CN117160504A (en) | Preparation method of CNs@PY53 photocatalyst and application thereof in photocatalysis synchronous production of lactic acid and CO | |
| CN113385197A (en) | Zirconium dioxide and titanium dioxide doped solid acid catalyst and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |