CN110433793B - BiZn hydrotalcite photocatalyst and preparation method and application thereof - Google Patents
BiZn hydrotalcite photocatalyst and preparation method and application thereof Download PDFInfo
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 title claims abstract description 41
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 41
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 41
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 42
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims abstract description 40
- QXKAIJAYHKCRRA-UHFFFAOYSA-N D-lyxonic acid Natural products OCC(O)C(O)C(O)C(O)=O QXKAIJAYHKCRRA-UHFFFAOYSA-N 0.000 claims abstract description 34
- QXKAIJAYHKCRRA-FLRLBIABSA-N D-xylonic acid Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C(O)=O QXKAIJAYHKCRRA-FLRLBIABSA-N 0.000 claims abstract description 34
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 34
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims abstract description 21
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003751 zinc Chemical class 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 150000001621 bismuth Chemical class 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000002135 nanosheet Substances 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims description 13
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical group [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000013032 photocatalytic reaction Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000012265 solid product Substances 0.000 description 14
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 229920002488 Hemicellulose Polymers 0.000 description 5
- 229910052724 xenon Inorganic materials 0.000 description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
- 238000007865 diluting Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 108010009736 Protein Hydrolysates Proteins 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000037345 metabolism of vitamins Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- LXUQDZITPQYMIR-UHFFFAOYSA-N thiourea;urea Chemical compound NC(N)=O.NC(N)=S LXUQDZITPQYMIR-UHFFFAOYSA-N 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 150000003700 vitamin C derivatives Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/18—Arsenic, antimony or bismuth
-
- B01J35/39—
-
- 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 BiZn hydrotalcite photocatalyst and a preparation method and application thereof, wherein the catalyst is a two-dimensional ultrathin BiZn nanosheet, and the thickness of the nanosheet is 5-10 nm. The preparation method comprises the following steps: (1) mixing a surfactant, ethylene glycol and water, then adding n-butyl alcohol, and stirring the solution until the solution is transparent; (2) adding zinc salt and bismuth salt, stirring, adding thiourea or urea to obtain a mixed solution, and heating for reaction; (3) and cooling after heating, filtering and drying to obtain the BiZn hydrotalcite catalyst, wherein the BiZn hydrotalcite photocatalyst can be used for catalyzing xylose to be converted into xylonic acid. The method has the advantages of low requirement on reaction conditions, low cost of raw materials, simple and feasible synthesis method, reduction of production cost and industrialization potential of the reaction, and the photocatalytic reaction system is different from the traditional thermocatalytic process, and is energy-saving, green, safe and environment-friendly in process.
Description
Technical Field
The invention belongs to the cross technical field of two-dimensional materials, photocatalysis and conversion of biomass into chemicals, and particularly relates to a BiZn hydrotalcite photocatalyst and a preparation method and application thereof.
Background
Hemicellulose is a biomass resource which is quite abundant in nature. Hemicellulose is a heteromultimer composed of several different types of monosaccharides, these sugars being five-and six-carbon sugars, including xylose, arabinose, galactose, and the like. Wherein xylose is the main product of hemicellulose hydrolysate, and xylonic acid can be obtained by oxidizing xylose. Xylonic acid is one of important metabolites of vitamin C, and plays a crucial regulation role in effective circulation and metabolism of vitamin C in organisms. Therefore, xylose in hemicellulose can be used for producing the xylonic acid, so that the production cost is obviously reduced, the development of the xylonic acid industry is accelerated, the additional value of the hemicellulose is improved, and the agricultural and forestry wastes are effectively utilized. The method has important significance for the utilization of lignocellulose in agricultural and forestry waste and the problem of environmental sustainable development.
Therefore, it is of great importance to find a suitable catalyst for catalyzing the conversion of xylose into xylonic acid through a green catalytic pathway. In addition, chemical synthesis and biological synthesis are the current methods for synthesizing xylonic acid. However, the two methods have the problems of more severe reaction conditions, lower yield and the like. However, the recent development of photocatalysis has attracted attention, and almost all organic and partially inorganic substances harmful to the human body and the environment can be decomposed by photocatalysis, so that not only can the reaction be accelerated, but also the natural definition can be applied, and the waste of resources and the formation of additional pollution are avoided.
The hydrotalcite is a good photocatalyst, has unique properties of adjustable and controllable cations of the laminate, exchangeable anions between layers, acid and alkali resistance and the like, and is concerned by researchers in the fields of medicine, ion exchange, catalysis, material flame retardance and the like. In the prior art, methods for synthesizing hydrotalcite mainly comprise a low saturation coprecipitation method, a hydrothermal synthesis method, an ion exchange method, a microwave crystallization method and the like, but the methods have the problems of harsh reaction conditions, complicated manufacturing process, inconvenience for practical application and the like.
Disclosure of Invention
The invention provides a BiZn hydrotalcite photocatalyst and a preparation method and application thereof, and particularly relates to a novel method for synthesizing the BiZn hydrotalcite photocatalyst by hydrolyzing zinc salt and bismuth salt in an alkaline medium urea (or thiourea)/n-butanol aqueous solution by adopting a one-pot method, and a method for catalyzing xylose to convert xylonic acid by utilizing a two-dimensional BiZn hydrotalcite catalyst.
The invention aims to be realized by at least one of the following technical solutions.
A BiZn hydrotalcite photocatalyst is a two-dimensional ultrathin BiZn nanosheet, and the thickness of the nanosheet is 5-10 nm.
The preparation method of the BiZn hydrotalcite photocatalyst comprises the following steps:
(1) mixing a surfactant, ethylene glycol and water, then adding n-butyl alcohol, and stirring the solution until the solution is transparent;
(2) adding zinc salt and bismuth salt, stirring, adding thiourea or urea to obtain a mixed solution, and heating for reaction;
(3) and cooling after heating is finished, and filtering and drying to obtain the BiZn hydrotalcite catalyst.
Further, in the step (1), the volume ratio of the volume of the ethylene glycol and the n-butanol to the volume of the water is 15-20: 1.
Further, in the step (1), the surfactant is sodium dodecyl sulfate, and the dosage ratio of the surfactant to the water is 0.0025-0.005 mol/mL.
Further, in the step (2), the dosage ratio of the thiourea or the urea to the water in the mixed solution is 0.01-0.02 mol/mL.
Further, in the step (2), the zinc salt is zinc nitrate or zinc acetate, and the bismuth salt is bismuth nitrate.
Further, in the step (2), the molar ratio of the zinc salt to the bismuth salt is 1:1, and the dosage ratio of the zinc salt to the water is 0.1-1.0:1 mol/L.
Further, in the step (2), the reaction temperature is 80-100 ℃, and the reaction time is 20-30 h.
Further, in the step (3), the drying temperature is 50-100 ℃.
The application of the BiZn hydrotalcite photocatalyst in catalyzing the conversion of xylose into xylonic acid is characterized in that the BiZn hydrotalcite photocatalyst, xylose, water and alkali liquor are mixed, and the catalytic reaction is carried out under the irradiation of visible light to obtain the xylonic acid.
Furthermore, the concentration of the BiZn hydrotalcite photocatalyst is 1-10mg/mL, the concentration of xylose is 10-100mg/mL, the concentration of alkali liquor is 0.1-1.0mol/mL, the catalytic reaction temperature is 20-80 ℃, and the reaction time is 1-10 h.
Furthermore, the volume of the water and the alkali liquor is 5-10: 1.
The preparation method relates to the following chemical reaction formula:
the Bi element has good photocatalytic performance, thiourea or urea provides an alkaline environment for Bi and Zn metals in the hydrothermal process to form hydroxide to prepare the BiZn hydrotalcite, the photocatalytic reaction performance of the catalyst structure can be well utilized, the selectivity of the catalyst can be further improved in the subsequent production process, and the preparation method has great photocatalytic industrialization prospect.
The preparation method of the invention has the following advantages:
(1) the catalyst used in the experiment is hydrotalcite which has a typical two-dimensional sheet structure, and the hydrotalcite material belongs to an anionic layered compound. Has the following characteristics: the chemical composition of the main body laminate can be adjusted; the species and the quantity of interlayer guest anions can be adjusted; the particle size and distribution of the intercalation assembly can be regulated and controlled, so that the intercalation assembly becomes a good photocatalyst, and the reaction is efficient and clean.
(2) The method has the advantages of low requirement on reaction conditions, low cost of raw materials, simple and feasible synthesis method, reduction of production cost and industrialization potential of the reaction, and the xenon lamp light source in the reaction conditions is simulated sunlight, so that the reaction cost is greatly reduced, and outdoor operation can be carried out. The reaction system is a photocatalytic reaction system under mild conditions, is different from the traditional thermal catalysis process, and is energy-saving, green, safe and environment-friendly.
(3) In the experiment of the invention, the hydrotalcite is used for catalyzing xylose to convert the xylonic acid, the selective oxidation is realized, the selected bimetal has good photocatalysis effect, and the catalyst has better selectivity according to the experimental data and is beneficial to converting the xylose into the xylonic acid.
Drawings
FIG. 1 is an SEM image of a BiZn hydrotalcite photocatalyst prepared in example 2;
FIG. 2 is a TEM image of a BiZn hydrotalcite photocatalyst prepared in example 2;
figure 3 is an XRD pattern of the BiZn hydrotalcite photocatalyst prepared in example 2;
FIG. 4 is a graph of the yield of xylose converted to xylonic acid in example 4 with different amounts of catalyst;
FIG. 5 is a graph of the yield of xylose-converted xylonic acid from example 5 under different reaction time conditions;
FIG. 6 is a graph of the yield of xylose-converted xylonic acid catalyzed by example 6 under different reaction temperature conditions;
FIG. 7 is a graph of the yield of xylose-converted xylonic acid catalyzed by example 7 under different base concentrations.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
0.72g of sodium lauryl sulfate, 20mL of ethylene glycol and 1.1mL of water were mixed, followed by dropwise addition of 1.5mL of n-butanol solution (volume ratio of ethylene glycol and n-butanol to water 19.5:1, amount ratio of surfactant to water 0.0025:1mol/mL), and the solution was allowed to stir until clear. 0.002mol of zinc acetate and 0.002mol of bismuth nitrate pentahydrate (the ratio of the zinc salt to the water is 0.1:1mol/L) are added. After stirring for 1h, 1.35g of thiourea (thiourea to water ratio 0.017:1mol/mL) was added and the oil bath heated to 80 ℃ and heating continued for 20 h. And cooling after heating, performing suction filtration to collect a solid product, and transferring the solid product into a constant temperature box to be dried at 60 ℃ to obtain the BiZn hydrotalcite photocatalyst.
Example 2
0.72g of sodium lauryl sulfate, 20mL of ethylene glycol and 1.1mL of water are mixed, followed by dropwise addition of a solution of 1.5mL of n-butanol, and the solution is allowed to stir until clear. 0.002mol of zinc acetate and 0.002mol of bismuth nitrate pentahydrate are added. After stirring for 1h, 1.35g of thiourea (or urea of the same concentration) was added and the oil bath heated to 90 ℃ and heating continued for 26 h. And cooling after heating, performing suction filtration to collect a solid product, and transferring the solid product into a constant temperature box to be dried at 60 ℃ to obtain the BiZn hydrotalcite photocatalyst. FIG. 1 is an SEM image obtained in the present embodiment, and the SEM image has a relatively clear two-dimensional ultrathin nanosheet structure, wherein the nanosheet has a thickness of 5-10 nm. Fig. 2 shows the TEM image obtained in this example, which shows typical lattice fringes of BiZn hydrotalcite. Fig. 3 shows the XRD pattern and phase analysis in the pattern obtained under the conditions of this example, and it can be seen from fig. 3 that the XRD pattern corresponds to the BiZn hydrotalcite.
Example 3
0.72g of sodium lauryl sulfate, 20mL of ethylene glycol and 1.1mL of water are mixed, followed by dropwise addition of a solution of 1.5mL of n-butanol, and the solution is allowed to stir until clear. 0.002mol of zinc acetate and 0.002mol of bismuth nitrate pentahydrate are added. After stirring for 1h, 1.35g of thiourea was added, the oil bath heated to 100 ℃ and heating continued for 30 h. And cooling after heating, performing suction filtration to collect a solid product, and transferring the solid product into a constant temperature box to be dried at 60 ℃ to obtain the BiZn hydrotalcite photocatalyst.
Example 4
1.44g of sodium lauryl sulfate, 20mL of ethylene glycol and 1.1mL of water were mixed, followed by dropwise addition of a 1.5mL solution of n-butanol, and the solution was allowed to stir until clear. 0.002mol of zinc acetate and 0.002mol of bismuth nitrate pentahydrate are added. After stirring for 1h, 1.35g of thiourea was added, the oil bath heated to 100 ℃ and heating continued for 30 h. Cooling after heating, performing suction filtration operation to collect solid products, transferring the solid products into a constant temperature box, and drying at 60 ℃ to obtain the BiZn hydrotalcite photocatalyst
Example 5
1.08g sodium lauryl sulfate, 20mL ethylene glycol, and 1.1mL water were mixed, followed by dropwise addition of a 1.5mL solution of n-butanol, and the solution was allowed to stir until clear. 0.002mol of zinc acetate and 0.002mol of bismuth nitrate pentahydrate are added. After stirring for 1h, 1.35g of thiourea was added, the oil bath heated to 100 ℃ and heating continued for 30 h. Cooling after heating, performing suction filtration operation to collect solid products, transferring the solid products into a constant temperature box, and drying at 60 ℃ to obtain the BiZn hydrotalcite photocatalyst
Example 6
0.72g of sodium lauryl sulfate, 20mL of ethylene glycol and 1.1mL of water are mixed, followed by dropwise addition of a solution of 1.5mL of n-butanol, and the solution is allowed to stir until clear. 0.002mol of zinc acetate and 0.002mol of bismuth nitrate pentahydrate are added. After stirring for 1h, 0.79g of thiourea was added, and the oil bath was heated to 100 ℃ and heating continued for 30 h. Cooling after heating, performing suction filtration operation to collect solid products, transferring the solid products into a constant temperature box, and drying at 60 ℃ to obtain the BiZn hydrotalcite photocatalyst
Example 7
0.72g of sodium lauryl sulfate, 20mL of ethylene glycol and 1.1mL of water are mixed, followed by dropwise addition of a solution of 1.5mL of n-butanol, and the solution is allowed to stir until clear. 0.002mol of zinc acetate and 0.002mol of bismuth nitrate pentahydrate are added. After stirring for 1h, 1.59g of thiourea (urea) was added, the oil bath heated to 100 ℃ and heating continued for 30 h. Cooling after heating, performing suction filtration operation to collect solid products, transferring the solid products into a constant temperature box, and drying at 60 ℃ to obtain the BiZn hydrotalcite photocatalyst
Example 8
(1) 0.1g of xylose is weighed into a glass reactor, 9mL of ultrapure water and 1mL of KOH solution with the alkali concentration of 0.5mol/L are added, and the mixture is uniformly mixed.
(2) 10mg, 20mg, 30mg, 40mg, 50mg, 60mg, 70mg of the catalyst prepared in example 2 were weighed respectively and added to the reaction system in the step (1).
(3) And (3) placing the reaction system in a water bath condition of 40 ℃, and reacting for 3h under the irradiation of a xenon lamp to obtain the xylonic acid.
(4) Diluting the reaction solution in the step (3) by one time, and measuring the content of the xylonic acid by using a high performance liquid chromatograph.
The yields of xylonic acid were determined to be 25.57%, 29.03%, 42.34%, 43.38%, 38.28%, 37.91% and 24.15% with catalyst dosages of 10mg, 20mg, 30mg, 40mg, 50mg, 60mg, 70mg, respectively. The above results are shown in FIG. 4. It can be seen from this that in fig. 4, the yield gradually increases with increasing catalyst amount, reaches a maximum value at 40mg catalyst amount, and then the yield of xylonic acid tends to decrease with increasing catalyst amount.
Example 9
(1) 0.1g of xylose and 40mg of the catalyst prepared in example 2 were weighed into a glass reactor, and 9mL of ultrapure water and 1mL of KOH solution having an alkali concentration of 0.5mol/L were added thereto and mixed well.
(2) And (3) placing the reaction system in a water bath condition at 40 ℃, reacting for 1h, 2h, 3h, 4h, 5h, 6h and 7h respectively, and reacting under the irradiation of a xenon lamp to obtain the xylonic acid.
(3) Diluting the reaction liquid in the step (2) by one time, and measuring the content of the xylonic acid by using a high performance liquid chromatograph.
The yield of the xylonic acid under the conditions of the reactions of 1h, 2h, 3h, 4h, 5h, 6h and 7h is respectively 15.94%, 19.09%, 24.27%, 21.69%, 21.51%, 21.66% and 20.47%. The above results are shown in FIG. 5. It can be seen from this that, in fig. 5, the yield gradually increased with the increase of the reaction time, reached the maximum value at the reaction time of 3 hours, and thereafter, the yield of xylonic acid tended to decrease with the increase of the amount of the catalyst.
Example 10
(1) 0.1g of xylose and 40mg of the catalyst prepared in example 2 were weighed into a glass reactor, and 9mL of ultrapure water and 1mL of KOH solution having an alkali concentration of 0.5mol/L were added thereto and mixed well.
(2) And (3) respectively placing the reaction system in water baths of 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃, reacting for 3 hours, and reacting under the irradiation of a xenon lamp to obtain the xylonic acid.
(3) Diluting the reaction liquid in the step (2) by one time, and measuring the content of the xylonic acid by using a high performance liquid chromatograph.
The test shows that the yield of the xylonic acid is 31.89%, 32.70%, 37.87%, 32.73% and 32.28% under the water bath conditions of the reaction temperature of 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃. The above results are shown in FIG. 6. It can be seen from this that, in fig. 6, the yield gradually increased with the increase of the reaction temperature, reached the maximum value at the reaction temperature of 50 ℃, and then the yield of xylonic acid decreased with the increase of the amount of the catalyst.
Example 11
(1) 0.1g xylose and 40mg catalyst were weighed into a glass reactor (the catalyst was prepared in example 2), and 9mL ultrapure water was added and mixed well.
(2) Adding 1mL of KOH solution with alkali concentration of 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L and 1.0mol/L respectively, placing the reaction system in a water bath condition at 50 ℃, and reacting for 3 hours under the irradiation of a xenon lamp to obtain the xylonic acid.
(3) Diluting the reaction liquid in the step (2) by one time, and measuring the content of the xylonic acid by using a high performance liquid chromatograph.
The yield of xylonic acid was determined to be 13.46%, 26.06%, 30.38%, 39.32%, 42.48%, 53.04%, 59.07%, 66.63%, 55.58% and 46.19% at alkali concentrations of 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L and 1.0mol/L, respectively. The above results are shown in FIG. 7. It can be seen from this that, in fig. 7, the yield gradually increased with the increase in the alkali concentration, reached the maximum value at the alkali concentration of 0.08mol/L, and then the yield of xylonic acid decreased with the increase in the catalyst amount.
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 BiZn hydrotalcite photocatalyst is characterized in that the catalyst is a two-dimensional ultrathin BiZn nanosheet, and the thickness of the nanosheet is 5-10 nm;
the preparation process of the BiZn hydrotalcite photocatalyst comprises the following steps:
(1) mixing a surfactant, ethylene glycol and water, then adding n-butyl alcohol, and stirring the solution until the solution is transparent;
(2) adding zinc salt and bismuth salt, stirring, adding thiourea or urea to obtain a mixed solution, and heating for reaction;
(3) and cooling after heating is finished, and filtering and drying to obtain the BiZn hydrotalcite photocatalyst.
2. The method of preparing a BiZn hydrotalcite photocatalyst according to claim 1, characterized by comprising the steps of:
(1) mixing a surfactant, ethylene glycol and water, then adding n-butyl alcohol, and stirring the solution until the solution is transparent;
(2) adding zinc salt and bismuth salt, stirring, adding thiourea or urea to obtain a mixed solution, and heating for reaction;
(3) and cooling after heating is finished, and filtering and drying to obtain the BiZn hydrotalcite photocatalyst.
3. The method according to claim 2, wherein in the step (1), the volume ratio of the ethylene glycol and n-butanol to the water is 15-20: 1.
4. The method according to claim 2, wherein in the step (1), the surfactant is sodium lauryl sulfate, and the amount ratio of the surfactant to water is 0.0025 to 0.005:1 mol/mL.
5. The method according to claim 2, wherein in the step (2), the ratio of the thiourea or urea to the water in the mixed solution is 0.01-0.02:1 mol/mL.
6. The method according to claim 2, wherein in the step (2), the zinc salt is zinc nitrate or zinc acetate, and the bismuth salt is bismuth nitrate.
7. The preparation method according to claim 2, wherein in the step (2), the molar ratio of the zinc salt to the bismuth salt is 1:1, and the amount ratio of the zinc salt to the water is 0.1-1.0:1 mol/L.
8. The method according to claim 2, wherein in the step (2), the reaction temperature is 80-100 ℃ and the reaction time is 20-30 hours.
9. The use of the BiZn hydrotalcite photocatalyst as claimed in claim 1 for catalyzing the conversion of xylose to xylonic acid, wherein the BiZn hydrotalcite photocatalyst, xylose, water and alkali liquor are mixed and subjected to a catalytic reaction under irradiation of visible light to obtain xylonic acid.
10. The use of claim 9, wherein the concentration of the BiZn hydrotalcite photocatalyst is 1-10mg/mL, the concentration of xylose is 10-100mg/mL, the concentration of the alkali liquor is 0.1-1.0mol/mL, the catalytic reaction temperature is 20-80 ℃, and the reaction time is 1-10 h.
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