CN117160504A - Preparation method of CNs@PY53 photocatalyst and application thereof in photocatalysis synchronous production of lactic acid and CO - Google Patents
Preparation method of CNs@PY53 photocatalyst and application thereof in photocatalysis synchronous production of lactic acid and CO Download PDFInfo
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- CN117160504A CN117160504A CN202310925745.8A CN202310925745A CN117160504A CN 117160504 A CN117160504 A CN 117160504A CN 202310925745 A CN202310925745 A CN 202310925745A CN 117160504 A CN117160504 A CN 117160504A
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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 130
- 239000004310 lactic acid Substances 0.000 title claims abstract description 65
- 235000014655 lactic acid Nutrition 0.000 title claims abstract description 65
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000001360 synchronised effect Effects 0.000 title abstract description 13
- 238000007146 photocatalysis Methods 0.000 title abstract description 11
- 239000002028 Biomass Substances 0.000 claims abstract description 38
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 238000004108 freeze drying Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- SRBFZHDQGSBBOR-IOVATXLUSA-N Xylose Natural products O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 14
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000000137 annealing Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- SHZGCJCMOBCMKK-UHFFFAOYSA-N D-mannomethylose Natural products CC1OC(O)C(O)C(O)C1O SHZGCJCMOBCMKK-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 claims description 4
- 229930091371 Fructose Natural products 0.000 claims description 4
- 239000005715 Fructose Substances 0.000 claims description 4
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- SHZGCJCMOBCMKK-JFNONXLTSA-N L-rhamnopyranose Chemical compound C[C@@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O SHZGCJCMOBCMKK-JFNONXLTSA-N 0.000 claims description 4
- PNNNRSAQSRJVSB-UHFFFAOYSA-N L-rhamnose Natural products CC(O)C(O)C(O)C(O)C=O PNNNRSAQSRJVSB-UHFFFAOYSA-N 0.000 claims description 4
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 238000013032 photocatalytic reaction Methods 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000004677 Nylon Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229920001778 nylon Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 13
- 238000004064 recycling Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 8
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 abstract description 7
- 239000002096 quantum dot Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 47
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 21
- 238000000975 co-precipitation Methods 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 238000007789 sealing Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 238000005286 illumination Methods 0.000 description 6
- 230000005418 spin wave Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 150000002972 pentoses Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalysis, and particularly discloses a preparation method of a CNs@PY53 photocatalyst and application thereof in photocatalysis synchronous production of lactic acid and CO. The preparation method of the photocatalyst comprises the following steps: (1) And calcining urea in a tube furnace at high temperature to obtain carbon nitride. (2) And dispersing carbon nitride into concentrated hydrochloric acid for stripping, and then carrying out ultrasonic treatment on the obtained solid, and freeze-drying to obtain the carbon nitride quantum dot. (3) Dispersing carbon nitride quantum dots and titanium nickel yellow in ethanol, mixing, performing ultrasonic treatment, and evaporating and drying to obtain the CNs@PY53 catalyst. The photocatalyst prepared by the invention has good recycling property, chemical stability and application universality, can efficiently and selectively oxidize different biomass-based monosaccharides into lactic acid and CO, is easy to realize industrial production, and has good application prospect.
Description
Technical Field
The invention relates to a preparation method of a CNs@PY53 photocatalyst and application thereof in the synchronous production of lactic acid and CO by selective oxidation cleavage of a C-C bond of a photocatalytic biomass-based monosaccharide, 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 the chemical industry. CO is an important component of synthesis gas and can be used for synthesizing a series of high-added-value chemicals, such as methanol, ethylene, propylene, long-chain alkane, aldehyde and the like. The traditional CO production method mainly comprises a coke-pure oxygen method, a water gas pressure swing adsorption method, a coke pure oxygen carbon dioxide gas production method and the like, but the methods are all required to be carried out under high temperature conditions, and the problems of complex operation, high energy consumption, heavy pollution and the like generally exist, so that the practical application of the method has great limitation. However, the selective oxidation of a photocatalytic biomass-based feedstock to produce CO is an emerging technology that has the advantages of mild and easily controlled reaction conditions, low cost, environmental friendliness, and the like, and has proven viable. Lactic acid is one of the three world organic acids and is also one of the important products of the selective oxidation of biomass-based feedstocks. Lactic acid has unique acidity, hydrophilicity and good biocompatibility, and has been widely used in industries such as food, medicine, chemical industry and the like. As a key resource for developing bioeconomical and biomass conversion, the market for lactic acid is growing. Thus, how to selectively oxidize biomass-based feedstock by photocatalytic techniques to produce lactic acid and CO simultaneously with achieving liquid/gas product separation is one of the key technical challenges in the art.
Disclosure of Invention
The invention aims at providing a preparation method of a CNs@PY53 photocatalyst material and an application thereof in the synchronous production of lactic acid and CO by selective oxidation cleavage of a C-C bond of a photocatalytic biomass-based monosaccharide aiming at the existing photocatalytic production of lactic acid. Aiming at the problems of high energy consumption, low yield and the like of the existing catalytic system, the invention prepares the CNs@PY53 photocatalyst by a novel and simple method, and various biomass-based monosaccharides are selectively oxidized into lactic acid and CO by a photocatalysis technology. The CNs@PY53 photocatalyst prepared by the method has good catalytic activity, recycling property, chemical stability and application universality. The synthesis method of the invention is simple and easy to control, has low cost, is green and has no pollution, and has potential of industrialized application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a CNs@PY53 photocatalyst for synchronously producing lactic acid and CO by photocatalytic biomass-based monosaccharide selective oxidation comprises the following steps:
(1) Urea in a tube furnace, N 2 Annealing (high-temperature calcination) for 2-6 hours at 400-600 ℃ in the atmosphere, and naturally cooling to obtain Carbon Nitride (CN);
(2) Dispersing CN into concentrated hydrochloric acid, heating and stirring in a water bath at 80-90 ℃ for 20-30 hours to strip, obtaining suspension, filtering and washing to obtain a solid product;
(3) Dispersing the solid product obtained in the step (2) into deionized water, and carrying out ultrasonic treatment for 20-30 h;
(4) Filtering the dispersion liquid obtained in the step (3) through a water-based filter membrane (such as a polytetrafluoroethylene filter membrane, a nylon filter membrane, a mixed cellulose filter membrane and a polyether sulfone filter membrane) with the diameter of 0.22-0.45 mu m, and freeze-drying the dispersion liquid at the temperature of-40 to-60 ℃ for 36-48 hours to obtain carbon nitride quantum dots (CNs);
(5) Dispersing CNs and titanium nickel yellow (PY 53) obtained in the step (4) into absolute ethyl alcohol, mixing and carrying out ultrasonic treatment for 0.5-3.0 h, wherein the mass ratio of CNs to PY53 is 0.005-1.0: 0.5 to 3.0;
(6) Evaporating and drying the dispersion liquid obtained in the step (5) for 2-4 hours at 75-95 ℃ to obtain the CNs@PY53 photocatalyst.
According to the above technical scheme, in the step (1), urea is preferably placed in a crucible, heated to 70-90 ℃ and dried (kept) for 1-2 hours before use.
According to the above technical solution, preferably, the heating temperature is 80 ℃ and the holding time is 1h.
According to the above technical solution, in the preferred case, in the step (1), the annealing temperature is 560 ℃, and the annealing time is 4 hours.
According to the above technical solution, in the step (2), the ratio of CN to concentrated hydrochloric acid is preferably 2.0-10.0 g:20 to 100mL, preferably 4.0g:80mL.
According to the above technical scheme, in the step (2), the heating temperature of the water bath is preferably 90 ℃ and the heating time is preferably 24 hours.
According to the above technical scheme, in the step (2), the suspension is diluted with deionized water and then filtered, and the obtained solid is washed with deionized water to be neutral.
According to the above technical solution, preferably, in the step (3), the ratio of the solid product to deionized water is 2.0 to 10.0g:50 to 500mL, preferably 2.0 to 4.0g:200mL.
According to the above technical scheme, in the step (4), the filter membrane material is preferably a polytetrafluoroethylene filter membrane with a thickness of 0.22 μm, and the freeze-drying time is preferably 48 hours.
According to the above technical solution, in the preferred case, in the step (5), the ultrasonic treatment time is 3 hours.
According to the above technical solution, in the preferred case, in the step (5), the mass ratio of CNs to PY53 is 0.005 to 0.3:0.5 to 1.0g, preferably 0.1g:1.0g.
According to the above technical solution, in the preferred case, in the step (5), the ratio of CNs to absolute ethanol is 0.005-1.0 g:2 to 80mL, preferably 0.005 to 0.3g:20-80mL, preferably 0.1g:40mL.
According to the above technical solution, in the step (6), the evaporation drying temperature is preferably 90 ℃ and the evaporation drying time is preferably 3 hours.
The CNs@PY53 material is characterized by means of X-ray diffraction and the like, and is used as a good photocatalyst to be applied to the photocatalytic biomass-based monoselective oxidation synchronous production of lactic acid and CO.
The CNs@PY53 photocatalyst prepared by the method is applied to the synchronous production of lactic acid and CO by the selective oxidation of photocatalytic biomass-based monosaccharides, and the reaction process is as follows: uniformly mixing the CNs@PY53 photocatalyst, biomass-based monosaccharide and alkaline solution, carrying out photocatalytic reaction for 0.5-8.0 h at 20-80 ℃, and detecting the content of lactic acid and CO by adopting a high performance liquid chromatograph and a gas chromatograph after the reaction is finished.
According to the above-described technical scheme, preferably, the alkaline solution is a water-soluble alkaline solution, such as potassium hydroxide solution, sodium hydroxide solution, barium hydroxide solution, sodium carbonate solution, potassium carbonate solution, sodium bicarbonate solution, and the like, and preferably potassium hydroxide solution.
According to the above-mentioned technical scheme, the concentration of the alkaline solution is preferably 0.05-3.0 mol/L, and preferably 0.5mol/L.
According to the above technical solution, preferably, the biomass-based monosaccharide is xylose, arabinose, fructose, rhamnose, mannose or glucose.
According to the above technical scheme, preferably, the ratio of the catalyst, the biomass-based monosaccharide and the alkaline solution is 0.05-30 mg:0.01 to 1.0g:20 to 100mL, preferably 25mg:0.2g:20mL.
According to the above technical scheme, preferably, the reaction temperature is 50 ℃.
According to the above technical scheme, preferably, the reaction time is 5.0h.
The preparation of the CNs@PY53 photocatalyst and the application of the photocatalytic biomass-based monosaccharide selective oxidation for synchronously producing lactic acid and CO respectively optimize experimental conditions in terms of catalyst dosage, KOH concentration, reaction temperature, reaction time and the like; and explores the recycling property of CNs@PY53 photocatalyst under the optimal reaction condition.
Compared with the prior art, the invention has the following advantages:
(1) The invention synchronously produces lactic acid and CO by selectively oxidizing biomass-based raw materials through a photocatalysis technology.
(2) The lactic acid synthesized by the invention is a chemical product with high added value, and is an important chemical intermediate;
(3) The CO obtained by the invention is a high-value energy fuel, and is one of important components of the synthesis gas;
(4) CNs@PY53 prepared by the method is used as a photocatalyst, and has excellent performances such as good catalytic activity, recycling property, application universality and the like;
(5) The method for synchronously producing lactic acid and CO by the selective oxidation of the photocatalytic biomass-based monosaccharide has the advantages of safety, no toxicity, quick response, low energy consumption and the like, and has potential of industrial production;
(6) The method can efficiently and selectively oxidize different biomass-based monosaccharides into lactic acid and CO, is easy to realize industrial production, and has good application prospect;
(7) The product of the invention provides an effective way for solving the energy crisis problem.
Drawings
Fig. 1 is an XRD spectrum of the CNs, PY53 and cns@py53 photocatalyst, wherein a is the cns@py53 catalyst obtained after step (8) in example 1, b is titanium nickel yellow, and c is the carbon nitride quantum dot obtained in step (6) in example 1.
FIG. 2 is a graph showing the effect of different amounts of catalyst on the simultaneous production of lactic acid and CO by the photocatalytic biomass-based monosaccharides of CNs@PY53 in example 2, wherein the line graph represents lactic acid yield and the bar graph represents CO precipitation rate.
FIG. 3 is a graph showing the effect of different potassium hydroxide concentrations on the synchronous production of lactic acid and CO by the CNs@PY53 photocatalyst and the photocatalytic biomass-based monosaccharide in example 2 and example 3, wherein the line graph represents the lactic acid yield and the bar graph represents the CO precipitation rate.
FIG. 4 is a graph showing the effect of different reaction temperatures on the synchronous production of lactic acid and CO by the CNs@PY53 photocatalyst and the photocatalytic biomass-based monosaccharide in example 3 and example 4, wherein the line graph represents the lactic acid yield and the bar graph represents the CO precipitation rate.
FIG. 5 is a graph showing the effect of different reaction times in example 4 and example 5 on the synchronous production of lactic acid and CO by the photocatalysis of biomass-based monosaccharides by the CNs@PY53 photocatalyst, wherein the line graph represents the lactic acid yield and the bar graph represents the CO precipitation rate.
FIG. 6 is a graph of catalyst recycling for simultaneous production of lactic acid and CO by the CNs@PY53 photocatalyst photocatalytic biomass-based monosaccharide in example 6, wherein the line graph represents lactic acid yield and the bar graph represents CO leaching rate.
FIG. 7 is a graph showing the effect of different biomass-based monosaccharides on the photocatalytic simultaneous production of lactic acid and CO by the CNs@PY53 photocatalyst in example 5 and example 7, wherein the line graph represents the lactic acid yield and the bar graph represents the CO precipitation rate.
Detailed Description
The invention will be further illustrated by the following examples for better understanding of technical features of the invention, but the scope of the invention is not limited thereto.
Example 1
(1) 20g of urea was placed in a crucible, heated to 80℃and dried for 1h;
(2) Transferring the product obtained in the step (1) into a tube furnace, and transferring the product into a furnace with a temperature of N 2 Annealing for 4 hours at 560 ℃ in the atmosphere, and naturally cooling to obtain CN;
(3) Dispersing 4.0g of the product obtained in the step (2) into 80mL of concentrated hydrochloric acid for stripping, and stirring for 24h in a water bath at 90 ℃;
(4) Adding 100mL of deionized water into the suspension obtained in the step (3), diluting, filtering, and washing the obtained powder with a large amount of deionized water to be neutral;
(5) Dispersing the product obtained in the step (4) into 200mL of deionized water, and carrying out ultrasonic treatment for 24 hours;
(6) Filtering the dispersion liquid obtained in the step (5) through a polytetrafluoroethylene filter membrane with the diameter of 0.22 mu m, and freeze-drying at the temperature of minus 53 ℃ for 48 hours to obtain CNs;
(7) Adding 0.1g of the product obtained in the step (6) and 1.0g of PY53 into 40mL of absolute ethanol, and carrying out ultrasonic treatment for 3.0h;
(8) Evaporating and drying the dispersion liquid obtained in the step (7) for 4 hours at 90 ℃ to obtain the CNs@PY53 photocatalyst.
Example 2
(1) 0.2g of xylose, 20.0mL of KOH solution with concentration of 1.0mol/L and CNs@PY53 photocatalyst (5, 10, 15, 20, 25 and 30mg respectively) prepared in example 1 with different masses are taken and added into a pressure-resistant bottle;
(2) Sealing the system in the step (1), adding a magnon, and stirring for 30min under dark conditions;
(3) Sealing the system in the step (2), and carrying out illumination reaction for 4.0h at 40 ℃ through a Perfectlight PCX 50C multichannel photocatalysis reaction system (size specification: 320 L.320 W.400H, LED light source, wavelength 420nm, power 5W, stirring speed 200rpm/min, unit switching interval 30 s);
(4) And (3) measuring the content of lactic acid and CO in the system after the reaction in the step (3) through a high performance liquid chromatograph and a gas chromatograph.
Example 3
(1) 0.2g of xylose, 20.0mL of KOH solutions of different concentrations (0.05, 0.1, 0.5, 2.0 and 3.0mol/L, respectively) and 25mg of CNs@PY53 photocatalyst prepared in example 1 were taken and added to a pressure-resistant bottle;
(2) Sealing the system in the step (1), adding a magnon, and stirring for 30min under dark conditions;
(3) Sealing the system in the step (2), and carrying out illumination reaction for 4.0h at 40 ℃ through a Perfectlight PCX 50C multichannel photocatalysis reaction system (size specification: 320 L.320 W.400H, LED light source, wavelength 420nm, power 5W, stirring speed 200rpm/min, unit switching interval 30 s);
(4) And (3) measuring the content of lactic acid and CO in the system after the reaction in the step (3) through a high performance liquid chromatograph and a gas chromatograph.
Example 4
(1) 0.2g of xylose, 20.0mL of KOH solution with the concentration of 0.5mol/L and 25mg of CNs@PY53 photocatalyst prepared in example 1 are taken and added into a pressure-resistant bottle;
(2) Sealing the system in the step (1), adding a magnon, and stirring for 30min under dark conditions;
(3) Sealing the system in the step (2), and carrying out illumination reaction for 4.0h at 30, 50, 60 and 70 ℃ through a Perfectlight PCX 50C multichannel photocatalytic reaction system (size specification: 320L. Times.320W. Times.400H, LED light source, wavelength 420nm, power 5W, stirring speed 200rpm/min and unit switching interval 30 s);
(4) And (3) measuring the content of lactic acid and CO in the system after the reaction in the step (3) through a high performance liquid chromatograph and a gas chromatograph.
Example 5
(1) 0.2g of xylose, 20.0mL of KOH solution with the concentration of 0.5mol/L and 25mg of CNs@PY53 photocatalyst prepared in example 1 are taken and added into a pressure-resistant bottle;
(2) Sealing the system in the step (1), adding a magnon, and stirring for 30min under dark conditions;
(3) Sealing the system in the step (2), and respectively carrying out illumination reaction for 0.5, 1.0, 2.0, 5.0 and 6.0 hours at 50 ℃ through a Perfectlight PCX 50℃ multichannel photocatalysis reaction system (size specification: 320L, 320W, 400H, LED light source, wavelength of 420nm, power of 5W, stirring speed of 200rpm/min and unit switching interval of 30 s);
(4) And (3) measuring the content of lactic acid and CO in the system after the reaction in the step (3) through a high performance liquid chromatograph and a gas chromatograph.
Example 6
(1) Filtering the system after the reaction for 5.0h in the embodiment 5 to obtain CNs@PY53 photocatalyst, centrifuging, washing with deionized water to be neutral, and drying overnight;
(2) Adding 0.2g of xylose, 20.0mL of KOH solution with the concentration of 0.5mol/L and 25mg of CNs@PY53 photocatalyst obtained in the step (1) into a pressure-resistant bottle;
(3) Sealing the system in the step (2), adding a magnon, and stirring for 30min under dark conditions;
(4) Carrying out illumination reaction on the system in the step (3) at 50.0 ℃ by a Perfectlight PCX 50C multichannel photocatalytic reaction system (size specification: 320 L.320 W.400H, LED light source, wavelength 420nm, power 5W, stirring speed 200rpm/min and unit switching interval 30 s) for 5.0h;
(5) Measuring the content of lactic acid and CO in the system after the reaction in the step (4) through a high performance liquid chromatograph and a gas chromatograph;
(6) Filtering the sample after the test in the step (5) to obtain a recycled CNs@PY53 photocatalyst, centrifuging, washing with deionized water to be neutral, drying overnight, and repeating the steps (2) - (5) for 5 times.
Example 7
(1) 0.2g of different biomass-based monosaccharides (arabinose, fructose, rhamnose, glucose, mannose respectively), 20.0mL of KOH solution with a concentration of 0.5mol/L and 25mg of CNs@PY53 photocatalyst prepared in example 1 were taken and added into a pressure-resistant bottle;
(2) Sealing the system in the step (1), adding a magnon, and stirring for 30min under dark conditions;
(3) Sealing the system in the step (2), and carrying out illumination reaction for 5.0h at 50 ℃ through a Perfectlight PCX 50℃ multichannel photocatalysis reaction system (size specification: 320 L.320 W.400H, LED light source, wavelength 420nm, power 5W, stirring speed 200rpm/min, unit switching interval 30 s);
(4) And (3) measuring the content of lactic acid and CO in the system after the reaction in the step (3) through a high performance liquid chromatograph and a gas chromatograph.
Fig. 1 shows an XRD spectrum of the cns@py53 catalyst, where a is the cns@py53 catalyst obtained after step (8) in example 1, b is titanium nickel yellow, and c is the carbon nitride quantum dot obtained in step (6) in example 1, and it can be seen from the figure that the spectrum of the cns@py53 photocatalyst is very similar to that of pure titanium nickel yellow, and characteristic peaks representing (110), (101), (111), (211), (220) and (301) crystal planes of titanium nickel yellow appear, which indicate that the introduction of the carbon nitride quantum dot does not affect the crystallinity of titanium nickel yellow.
FIG. 2 is a graph showing the effect of different amounts of catalyst on the simultaneous production of lactic acid and CO by the photocatalytic biomass-based monosaccharides of CNs@PY53 in example 2, wherein the line graph represents lactic acid yield and the bar graph represents CO precipitation rate. The amounts of CNs@PY53 photocatalyst used in example 2 were set to 5mg, 10mg, 15mg, 20mg, 25mg and 30mg, respectively. It was found that the lactic acid yield and the CO evolution rate increased and decreased with increasing catalyst usage and reached a maximum at 25mg. The reason why the lactic acid yield and the CO precipitation rate are lowered may be that scattering and refraction of light caused by an excessive catalyst decrease the photocatalytic efficiency of the catalyst.
FIG. 3 is a graph showing the effect of different potassium hydroxide concentrations on the synchronous production of lactic acid and CO by the CNs@PY53 photocatalyst and the photocatalytic biomass-based monosaccharide in example 2 and example 3, wherein the line graph represents the lactic acid yield and the bar graph represents the CO precipitation rate. Wherein the KOH concentration in example 3 was 0.05, 0.1, 0.5, 2.0 and 3.0M, respectively, the KOH solution in example 2 was 1.0M and the photocatalyst was used in an amount of 25mg. It can be seen that as the KOH concentration increases, the lactic acid yield gradually increases, probably because the catalyst surface adsorbs more hydroxide ions at high alkali concentrations, favoring the generation of hydroxyl radicals and thus promoting the formation of lactic acid. Meanwhile, as the concentration of KOH increases, the precipitation rate of CO increases and then decreases, and the maximum value is reached at a concentration of 0.5M KOH, probably because glyceraldehyde is first produced as an intermediate product in the process of converting xylose into CO, and an excessively high alkali concentration decreases the oxidation activity of glyceraldehyde, thus causing a decrease in the CO precipitation rate.
FIG. 4 is a graph showing the effect of different reaction temperatures on the synchronous production of lactic acid and CO by the CNs@PY53 photocatalyst and the photocatalytic biomass-based monosaccharide in example 3 and example 4, wherein the line graph represents the lactic acid yield and the bar graph represents the CO precipitation rate. Wherein the reaction temperatures in example 4 were 30, 50, 60 and 70℃respectively, the KOH solution concentration in example 3 was 0.5M and the reaction temperature was 40 ℃. It was found that as the reaction temperature increased, both the evolution rate of CO and the yield of lactic acid tended to increase and then decrease. Of these, the CO evolution rate is highest at 50℃and the lactic acid yield is highest at 60℃probably because part of the lactic acid and CO are converted into other byproducts during the reaction as the reaction temperature increases.
FIG. 5 is a graph showing the effect of different reaction times in example 4 and example 5 on the synchronous production of lactic acid and CO by the photocatalysis of biomass-based monosaccharides by the CNs@PY53 photocatalyst, wherein the line graph represents the lactic acid yield and the bar graph represents the CO precipitation rate. Wherein the reaction times in example 5 were set to 0.5, 1.0, 2.0, 5.0 and 6.0 hours, respectively, and the reaction temperature in example 4 was 50℃and the reaction time was 4.0 hours. It can be seen from fig. 5 that the lactic acid yield and CO evolution rate increased with the reaction time and gradually tended to be horizontal. It was demonstrated that appropriate extension of the reaction time was beneficial for xylose conversion.
FIG. 6 is a graph of catalyst recycling for simultaneous production of lactic acid and CO by the CNs@PY53 photocatalyst photocatalytic biomass-based monosaccharide in example 6, wherein the line graph represents lactic acid yield and the bar graph represents CO leaching rate. As can be seen from fig. 6, the yield of lactic acid and the CO precipitation rate remained at high levels after 5 cycles, and the yield of lactic acid and the CO precipitation rate after 5 cycles were 94.4% and 92.1% of the first cycle, respectively, and the reactivity was hardly changed. This shows that the CNs@PY53 photocatalyst can still ensure higher catalytic efficiency in the process of multiple recycling, and has higher recycling capability and excellent stability.
FIG. 7 is a graph showing the effect of different biomass-based monosaccharides on the photocatalytic simultaneous production of lactic acid and CO by the CNs@PY53 photocatalyst in example 5 and example 7, wherein the line graph represents the lactic acid yield and the bar graph represents the CO precipitation rate. Wherein the biomass-based monosaccharides in example 7 were arabinose, fructose, rhamnose, glucose and mannose, respectively, and the biomass-based monosaccharides in example 5 were xylose, with a reaction time of 5.0h. As can be seen from fig. 7, the yield of lactic acid and the CO precipitation rate were both kept at a high level in the different biomass-based monosaccharide systems, which suggests that the cns@py53 has good application versatility. Wherein, the lactic acid yield and the CO precipitation rate of pentose are slightly higher than those of hexose, which indicates that the production of lactic acid and CO is more favorable in a pentose system.
The foregoing examples are illustrative of part of the practice of the invention, but the invention is not limited to the embodiments, and any other changes, substitutions, combinations, and simplifications that depart from the spirit and principles of the invention are intended to be equivalent thereto and are within the scope of the invention.
Claims (10)
1. The preparation method of the CNs@PY53 photocatalyst is characterized by comprising the following steps of:
(1) Urea in a tube furnace, N 2 Annealing for 2-6 h at 400-600 ℃ in the atmosphere, and naturally cooling to obtain CN;
(2) Dispersing CN into concentrated hydrochloric acid, stirring in water bath at 80-90 ℃ for 20-30 h to obtain suspension, filtering and washing to obtain a solid product;
(3) Dispersing the solid product obtained in the step (2) into deionized water, and carrying out ultrasonic treatment for 20-30 h;
(4) Filtering the dispersion liquid obtained in the step (3) through a water-based filter membrane with the diameter of 0.22-0.45 mu m, and freeze-drying the dispersion liquid at the temperature of-40 to-60 ℃ for 36-48 hours to obtain CNs;
(5) Dispersing CNs and PY53 obtained in the step (6) into absolute ethyl alcohol, and carrying out ultrasonic treatment for 0.5-3.0 h; wherein the mass ratio of CNs to PY53 is 0.005-1.0: 0.5 to 3.0;
(6) Evaporating and drying the dispersion liquid obtained in the step (5) for 2-4 hours at 75-95 ℃ to obtain the CNs@PY53 photocatalyst.
2. The process for preparing a CNs@PY53 photocatalyst according to claim 1, wherein in step (1), urea is placed in a crucible and heated to 70-90 ℃ for 1-2 hours before use.
3. The method for preparing the CNs@PY53 photocatalyst according to claim 1, wherein in the step (2), the ratio of CN to concentrated hydrochloric acid is 2.0-10.0 g: 20-100 mL; in the step (3), the ratio of the solid product to deionized water is 2.0-10.0 g: 50-500 mL; in the step (5), the ratio of CNs to absolute ethyl alcohol is 0.005-1.0: 2-80 mL.
4. The method for preparing a cns@py53 photocatalyst according to claim 1, wherein in the step (3), the suspension is diluted with deionized water and then filtered, and the resulting solid is washed with deionized water to be neutral.
5. The method for producing a cns@py53 photocatalyst according to claim 1, wherein in the step (4), the aqueous filter membrane is a polytetrafluoroethylene filter membrane, a nylon filter membrane, a mixed cellulose filter membrane or a polyether sulfone filter membrane.
6. Use of the cns@py53 photocatalyst obtained by the preparation method of any one of claims 1-5 in the photocatalytic simultaneous production of lactic acid and CO.
7. The use according to claim 6, wherein the CNs@PY53 photocatalyst, alkaline solution and biomass-based monosaccharide are uniformly mixed and subjected to photocatalytic reaction at 20.0-80.0 ℃ for 0.5-8.0 h.
8. The use according to claim 6, wherein the alkaline solution is a water-soluble alkaline solution, and the concentration of the alkaline solution is 0.05-3.0 mol/L.
9. The use according to claim 6, wherein the biomass-based monosaccharide is xylose, arabinose, fructose, rhamnose, mannose or glucose.
10. The use according to claim 6, wherein the ratio of the CNs@PY53 photocatalyst, the biomass-based monosaccharide and the alkaline solution is 0.05-30 mg:0.01 to 1.0g: 20-100 mL.
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