CN109913892B - Method for photoelectrocatalytic oxidation of xylose by indium sulfide/nickel iron hydrotalcite composite membrane - Google Patents
Method for photoelectrocatalytic oxidation of xylose by indium sulfide/nickel iron hydrotalcite composite membrane Download PDFInfo
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- CN109913892B CN109913892B CN201910211462.0A CN201910211462A CN109913892B CN 109913892 B CN109913892 B CN 109913892B CN 201910211462 A CN201910211462 A CN 201910211462A CN 109913892 B CN109913892 B CN 109913892B
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- nickel
- indium sulfide
- xylose
- indium
- iron hydrotalcite
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- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 title claims abstract description 126
- GKCNVZWZCYIBPR-UHFFFAOYSA-N sulfanylideneindium Chemical compound [In]=S GKCNVZWZCYIBPR-UHFFFAOYSA-N 0.000 title claims abstract description 82
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 65
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 title claims abstract description 63
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 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 63
- 229960001545 hydrotalcite Drugs 0.000 title claims abstract description 63
- 229910001701 hydrotalcite Inorganic materials 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000003647 oxidation Effects 0.000 title claims abstract description 29
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 29
- 239000012528 membrane Substances 0.000 title claims abstract description 19
- 239000011521 glass Substances 0.000 claims abstract description 52
- 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 42
- 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 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 22
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 238000005286 illumination Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000011259 mixed solution Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 23
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 23
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 23
- 238000007789 sealing Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- VSEUCCPAJZHJSX-UHFFFAOYSA-K 2-hydroxypropane-1,2,3-tricarboxylate;indium(3+) Chemical compound [In+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VSEUCCPAJZHJSX-UHFFFAOYSA-K 0.000 claims description 14
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 13
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000007832 Na2SO4 Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000002505 iron Chemical class 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000003115 supporting electrolyte Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 43
- 239000008367 deionised water Substances 0.000 description 25
- 229910021641 deionized water Inorganic materials 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000010409 thin film Substances 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 6
- 229960002303 citric acid monohydrate Drugs 0.000 description 6
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 6
- 229910052724 xenon Inorganic materials 0.000 description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101710088194 Dehydrogenase Proteins 0.000 description 1
- 241000589232 Gluconobacter oxydans Species 0.000 description 1
- 108010015776 Glucose oxidase Proteins 0.000 description 1
- 239000004366 Glucose oxidase Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229940116332 glucose oxidase Drugs 0.000 description 1
- 235000019420 glucose oxidase Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 description 1
Images
Abstract
The invention belongs to the field of photoelectrocatalysis, and particularly relates to a method for photoelectrocatalysis oxidation of xylose by utilizing an indium sulfide/nickel iron hydrotalcite composite membrane, which comprises the following steps: and taking the indium sulfide/nickel iron hydrotalcite composite membrane loaded on the conductive glass as a photo-anode, a platinum sheet electrode as a counter electrode and a saturated calomel electrode as a reference electrode, and carrying out photoelectrocatalytic oxidation on a xylose solution containing a supporting electrolyte in an electrolytic cell under the conditions of illumination and bias voltage application to prepare the xylonic acid. Can quickly oxidize xylose into xylonic acid under the irradiation of sunlight, ultraviolet light and visible light, has the advantages of simple process, low cost and suitability for large-scale production, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of photoelectrocatalysis, and particularly relates to a method for photoelectrocatalysis oxidation of xylose by utilizing an indium sulfide/nickel iron hydrotalcite composite membrane.
Background
Renewable biomass resources such as agricultural and forestry wastes and the like are fully utilized to produce green chemical products, so that sustainable development of the chemical industry is realized, and more attention is paid. The hemicellulose is the second major component except cellulose in the agricultural and forestry waste, the content of xylosyl in the agricultural and forestry waste can reach 18-30%, xylose can be produced by hydrolyzing the hemicellulose in the agricultural waste such as cob and straw of corn, and xylonic acid can be produced by further oxidizing the xylose. Xylonic acid is one of the most promising xylose conversion products. The compound can be used as a multifunctional platform compound, is applied to various fields such as leather, textile, medicine, building, chemistry and chemical engineering, metallurgy and the like, and has great development and application prospects.
The main methods for preparing xylonic acid by utilizing xylose oxidation at present comprise a biological oxidation method, a chemical oxidation method, an electrochemical oxidation method and a photocatalytic oxidation method. The biological oxidation method is to prepare the xylonic acid by utilizing microorganisms such as gluconobacter oxydans for fermentation and oxidation or catalyzing and oxidizing the xylose by the glucose oxidase and the xylose dehydrogenase, the production process conditions are mild, the environment is not harmed, the production conditions are strict, the production period is long, and byproducts are difficult to separate. The chemical oxidation method can be divided into a homogeneous catalytic oxidation method and a heterogeneous catalytic oxidation method, the homogeneous catalytic oxidation method is to prepare xylonic acid by using iodine to catalyze and oxidize xylose, hydroxyl in xylose molecules needs to be protected in the reaction process, and a hydroxyl protecting group is removed after the reaction is finished, so that the production process is complex, byproducts are more, the product is difficult to separate, and the problems of catalyst recovery and the like exist; the catalyst used in heterogeneous catalytic oxidation is noble metal palladium or active carbon, and although the problem of catalyst separation is solved, the process needs to be carried out under the conditions of heating and oxygen introduction, and the reaction conditions are quite complex. The electrolytic oxidation method has simple process, no byproduct, large energy consumption and difficult control of conditions. The photocatalytic oxidation method is a method for preparing xylonic acid by catalytic oxidation of xylose under the action of a photocatalyst such as modified carbon nitride and illumination, overcomes the defect of high energy consumption of electrocatalytic oxidation, and has low photocatalytic reaction efficiency due to high recombination rate of photoproduction electrons and holes. Thus, the current methods for producing xylose remain to be further improved.
Disclosure of Invention
Aiming at the defects of the existing xylose oxidation technology, the invention provides a method for preparing xylonic acid by oxidizing xylose by utilizing a photoelectrocatalysis technology, which has the advantages of an electrolytic oxidation method, overcomes the defects of high recombination rate of photogenerated electrons and holes and low reaction efficiency in photocatalysis by utilizing the photoelectrocatalysis technology, and has the advantages of simple process, low cost and suitability for large-scale production.
A method for carrying out photoelectrocatalytic oxidation on xylose by utilizing an indium sulfide/nickel-iron hydrotalcite composite membrane comprises the steps of taking the indium sulfide/nickel-iron hydrotalcite composite membrane loaded on conductive glass as a photoanode, taking a platinum sheet electrode as a counter electrode and taking a saturated calomel electrode as a reference electrode, and carrying out photoelectrocatalytic oxidation on a xylose solution containing electrolyte in an electrolytic cell under the conditions of illumination and bias voltage application to prepare xylonic acid.
Preferably, the conductive glass is fluorine-doped tin oxide (FTO) conductive glass.
Preferably, the conductive glass is washed by acetone and deionized water before use.
Preferably, the molar ratio of nickel to iron in the nickel-iron hydrotalcite is 3: 1.
preferably, the illumination is one of sunlight, ultraviolet light, visible light and near infrared light;
preferably, the bias voltage is 0.1-0.3V; preferably 0.2V.
Preferably, the electrolyte is 0.25mol/L of Na2SO4An aqueous solution.
Preferably, the concentration of the xylose solution is 0.1-2 wt%.
The indium sulfide/nickel iron hydrotalcite composite membrane photo-anode loaded on the conductive glass is a composite membrane photo-electrode formed by firstly depositing an indium sulfide thin film on the conductive glass and then depositing a nickel iron hydrotalcite thin film on the conductive glass deposited with the indium sulfide thin film.
An indium sulfide/nickel iron hydrotalcite composite membrane is prepared by the following steps:
(1) adding a thioacetamide solution into an indium citrate complex solution formed by citric acid and indium chloride, transferring the formed mixed solution into a reaction kettle, simultaneously vertically placing FTO conductive glass, sealing, and reacting at 80 +/-5 ℃ for 6-10 hours to obtain conductive glass deposited with an indium sulfide film;
(2) and (2) mixing nickel salt, ferric salt, urea and ammonium fluoride, dissolving in water to form a mixed solution, transferring to a reaction kettle, simultaneously vertically placing the conductive glass deposited with the indium sulfide film obtained in the step (1), sealing, and reacting at 120 +/-5 ℃ for 10-15 hours to obtain the indium sulfide/nickel iron hydrotalcite composite film attached to the conductive glass.
In the presence of citric acid, indium chloride is used as an indium source, thioacetamide is used as a sulfur source, and highly-crystalline indium sulfide crystals are synthesized by a low-temperature hydrothermal method and are deposited on the FTO conductive glass in situ to form the indium sulfide thin film material. In the presence of ammonium fluoride, nickel nitrate and ferric nitrate are respectively used as divalent and trivalent metal salts, urea is used as a precipitator, nickel-iron hydrotalcite is synthesized by a hydrothermal method and is deposited on an indium sulfide film on the surface of conductive glass in situ, and the indium sulfide/nickel-iron hydrotalcite composite film photo-anode electrode is formed.
Preferably, the molar ratio of the citric acid to the indium chloride in the step (1) is 4-8: 1;
preferably, the molar ratio of thioacetamide to indium chloride in step (1) is 1: 3 to 5.
Preferably, the molar ratio of the nickel salt, the iron salt, the urea and the ammonium fluoride in the step (2) is 3: 1: 6-8: 1 to 4.
Preferably, the nickel salt in step (2) is nickel nitrate.
Preferably, the iron salt in step (2) is ferric nitrate.
Preferably, the thickness of the indium sulfide thin film in the step (1) is 0.5-1.0 micron, and the indium sulfide thin film is composed of cubic phase indium sulfide crystals with the granularity of 50-500 nanometers and the granularity of 1-2 microns.
Preferably, the thickness of the nickel-iron hydrotalcite film in the step (2) is 1.0-20 microns, and the nickel-iron hydrotalcite film is composed of flaky nickel-iron hydrotalcite crystals with the thickness of 20-50 nanometers and the diameter of 300-800 nanometers.
The indium sulfide/nickel iron hydrotalcite composite membrane prepared by the invention has response capability to sunlight, ultraviolet light, visible light and near infrared light due to the existence of the full spectrum photocatalyst indium sulfide and nickel iron hydrotalcite with good absorption performance in ultraviolet, visible and near infrared light regions, and can directly oxidize xylose into xylonic acid in a water medium under the irradiation of the sunlight, the ultraviolet, the visible and the near infrared light, but the oxidation speed is slow. The prepared indium sulfide and nickel iron hydrotalcite composite film is used as a photo-anode, a platinum sheet electrode is used as a cathode, a saturated calomel electrode is used as a reference electrode, a light source and a power supply form a photoelectric catalytic system, a bias voltage of 0.2V is applied, due to the conduction of photoproduction electrons, the separation of the photoproduction electrons and cavities is promoted, the oxidation effect of the photoproduction cavities on the indium sulfide and nickel iron hydrotalcite composite film on xylose is greatly improved, and the xylose can be oxidized into xylonic acid even under the irradiation of near infrared light.
Has the advantages that:
the indium sulfide/nickel iron hydrotalcite composite film has excellent photoelectric catalytic oxidation performance. Under the condition of applying 0.2V bias voltage, ultraviolet light irradiates for 2 hours, and the ratio of xylose converted into xylonic acid is as high as 97.8%; irradiating for 2 hours under visible light, wherein the conversion rate of xylose to xylonic acid reaches 86.4%; irradiating with near infrared light for 2 hr to convert xylose into xylonic acid at a ratio of 31.4%; the ratio of xylose conversion to xylonic acid was 92.7% with simulated solar irradiation for 1 hour. Therefore, the indium sulfide/nickel iron hydrotalcite composite membrane loaded on the conductive glass is used as a photo-anode, a platinum sheet electrode is used as a cathode, and a saturated calomel electrode is used as a reference electrode, so that xylose can be rapidly oxidized into xylonic acid under the irradiation of sunlight, ultraviolet light and visible light. Has the advantages of simple process, low cost and suitability for large-scale production, and has wide application prospect.
Drawings
FIG. 1 indium sulfide (In)2S3) And indium sulfide/nickel iron hydrotalcite composite film (In)2S3The X-ray diffraction pattern of the/NiFe-LDH) material, wherein the abscissa is the diffraction angle, and the ordinate is the diffraction intensity;
fig. 2 is a scanning electron microscope image of the indium sulfide/nickel iron hydrotalcite-like composite film.
Detailed Description
The present invention is further illustrated with reference to the following specific examples, which are carried out on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are provided, but the scope of the present invention is not limited to the following examples; unless otherwise indicated, the parts described in the examples are parts by mass.
Example 1
(1) Adding 5.7 parts of citric acid monohydrate into 20 parts of deionized water, fully dissolving, adding 1 part of indium chloride, and stirring to dissolve to form an indium citrate complex solution. 1.36 parts thioacetamide was dissolved in 20 parts deionized water to form a thioacetamide solution. Slowly and dropwisely adding thioacetamide solution into the indium citrate complex solution under stirring to form mixed solution, transferring the mixed solution into a reaction kettle, simultaneously vertically adding 10 x 30 mm FTO conductive glass cleaned by acetone and deionized water, sealing, and reacting at 80 ℃ for 8 hours to obtain the conductive glass deposited with the indium sulfide film. The indium sulfide thin film is 0.8-1 micron in thickness and consists of cubic indium sulfide crystals with the granularity of 100-500 nanometers and cubic indium sulfide crystals with the granularity of 1-2 microns distributed sporadically;
(2) and (2) sequentially dissolving 2.16 parts of nickel nitrate hexahydrate, 1 part of ferric nitrate nonahydrate, 1 part of urea and 0.2 part of ammonium fluoride in 40 parts of deionized water to form a mixed solution, transferring the mixed solution into a reaction kettle, vertically placing the conductive glass deposited with the indium sulfide film obtained in the step (1), sealing, and reacting at 120 ℃ for 12 hours to obtain the indium sulfide/nickel iron hydrotalcite composite film attached to the conductive glass. Wherein the thickness of the nickel-iron hydrotalcite film is 15-20 microns, and the nickel-iron hydrotalcite film is composed of flaky nickel-iron hydrotalcite crystals with the thickness of 20-50 nanometers and the diameter of 300-800 nanometers;
(3) dissolving 1 part of xylose in 250 parts of 0.25mol/L Na2SO4Adding the aqueous solution into an electrolytic cell, taking the conductive glass attached with the indium sulfide/nickel iron hydrotalcite composite membrane prepared in the step (2) as a photo-anode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, applying 0.2V bias under the irradiation of a 40W xenon lamp, and under the condition of not adding a filter, wherein the ratio of xylose to xylonic acid is 98.5 percent within 2 hours; after visible light and near infrared light of more than 380 nm are removed by adding a filter, the ratio of xylose converted into xylonic acid in 2 hours is 97.8 percent; filtering with filter to remove violet below 380 nmAfter external light, the ratio of xylose conversion to xylonic acid was 86.4% in 2 hours; after filtering out ultraviolet light and visible light below 720 nm by adding a filter, the ratio of xylose conversion to xylonic acid in 2 hours was 31.4%.
Example 2
(1) Adding 5.7 parts of citric acid monohydrate into 20 parts of deionized water, fully dissolving, adding 1 part of indium chloride, and stirring to dissolve to form an indium citrate complex solution. 1.36 parts thioacetamide was dissolved in 20 parts deionized water to form a thioacetamide solution. Slowly and dropwisely adding thioacetamide solution into the indium citrate complex solution under stirring to form mixed solution, transferring the mixed solution into a reaction kettle, simultaneously vertically adding 10 x 30 mm FTO conductive glass cleaned by acetone and deionized water, sealing, and reacting at 80 ℃ for 8 hours to obtain the conductive glass deposited with the indium sulfide film. The indium sulfide thin film is 0.8-1 micron in thickness and consists of cubic indium sulfide crystals with the granularity of 100-500 nanometers and cubic indium sulfide crystals with the granularity of 1-2 microns distributed sporadically;
(2) and (2) sequentially dissolving 2.16 parts of nickel nitrate hexahydrate, 1 part of ferric nitrate nonahydrate, 1 part of urea and 0.2 part of ammonium fluoride in 40 parts of deionized water to form a mixed solution, transferring the mixed solution into a reaction kettle, vertically placing the conductive glass deposited with the indium sulfide film obtained in the step (1), sealing, and reacting at 120 ℃ for 12 hours to obtain the indium sulfide/nickel iron hydrotalcite composite film attached to the conductive glass. Wherein the thickness of the nickel-iron hydrotalcite film is 15-20 microns, and the nickel-iron hydrotalcite film is composed of flaky nickel-iron hydrotalcite crystals with the thickness of 20-50 nanometers and the diameter of 300-800 nanometers;
(3) dissolving 0.25 part of xylose in 250 parts of 0.25mol/L Na2SO4Adding the aqueous solution into an electrolytic cell, taking the conductive glass attached with the indium sulfide/nickel iron hydrotalcite composite membrane prepared in the step (2) as a photo-anode electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, applying 0.2V bias under the irradiation of a 40W xenon lamp, and under the condition of not adding a filter, wherein the ratio of xylose to xylonic acid is 99.2 percent within 2 hours; after visible light and near infrared light of more than 380 nm are removed by adding a filter, the ratio of xylose converted into xylonic acid in 2 hours is 98.8 percent;after filtering ultraviolet light below 380 nm by adding a filter, the ratio of xylose converted into xylonic acid within 2 hours is 89.4 percent; after filtering out ultraviolet light and visible light below 720 nm with a filter, the ratio of xylose conversion to xylonic acid was 44.5% in 2 hours.
Example 3
(1) Adding 5.7 parts of citric acid monohydrate into 20 parts of deionized water, fully dissolving, adding 1 part of indium chloride, and stirring to dissolve to form an indium citrate complex solution. 1.36 parts thioacetamide was dissolved in 20 parts deionized water to form a thioacetamide solution. Slowly and dropwisely adding thioacetamide solution into indium citrate complex solution under stirring to form mixed solution, transferring the mixed solution into a reaction kettle, simultaneously vertically adding a 10X 30 mm FTO conductive glass sheet cleaned by acetone and deionized water, sealing, and reacting at 80 ℃ for 8 hours to obtain the conductive glass deposited with the indium sulfide film. The indium sulfide thin film is 0.8-1 micron in thickness and consists of cubic indium sulfide crystals with the granularity of 100-500 nanometers and cubic indium sulfide crystals with the granularity of 1-2 microns distributed sporadically;
(2) and (2) sequentially dissolving 2.16 parts of nickel nitrate hexahydrate, 1 part of ferric nitrate nonahydrate, 1 part of urea and 0.2 part of ammonium fluoride in 40 parts of deionized water to form a mixed solution, transferring the mixed solution into a reaction kettle, vertically placing the conductive glass deposited with the indium sulfide film obtained in the step (1), sealing, and reacting at 120 ℃ for 12 hours to obtain the indium sulfide/nickel iron hydrotalcite composite film attached to the conductive glass. Wherein the thickness of the nickel-iron hydrotalcite film is 15-20 microns, and the nickel-iron hydrotalcite film is composed of flaky nickel-iron hydrotalcite crystals with the thickness of 20-50 nanometers and the diameter of 300-800 nanometers;
(3) 5 parts of xylose were dissolved in 250 parts of 0.25mol/L Na2SO4Adding the aqueous solution into an electrolytic cell, taking the conductive glass attached with the indium sulfide/nickel iron hydrotalcite composite membrane prepared in the step (2) as a photo-anode electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, applying 0.2V bias under the irradiation of a 40W xenon lamp, and under the condition of not adding a filter, wherein the ratio of xylose converted into xylonic acid is 78.9 percent within 2 hours; after the visible light and near infrared light above 380 nm are removed by adding a filter, xylose is converted into xylose within 2 hoursThe ratio of xylonic acid is 78.2%; after filtering out ultraviolet light below 380 nm by adding a filter, the ratio of xylose converted into xylonic acid in 2 hours is 56.4 percent; after filtering out ultraviolet light and visible light below 720 nm by adding a filter, the ratio of xylose conversion to xylonic acid in 2 hours was 21.1%.
Example 4
(1) Adding 3.8 parts of citric acid monohydrate into 20 parts of deionized water, fully dissolving, adding 1 part of indium chloride, and stirring to dissolve to form an indium citrate complex solution. 1.70 parts thioacetamide was dissolved in 20 parts deionized water to form a thioacetamide solution. Slowly and dropwisely adding thioacetamide solution into indium citrate complex solution under stirring to form mixed solution, transferring the mixed solution into a reaction kettle, simultaneously vertically placing 10 x 30 mm FTO conductive glass sheets cleaned by acetone and deionized water, sealing, and reacting at 80 ℃ for 6 hours to obtain the conductive glass deposited with the indium sulfide film. The indium sulfide thin film is 0.5-0.8 micron in thickness and consists of cubic indium sulfide crystals with the granularity of 100-500 nanometers and cubic indium sulfide crystals with the granularity of 1-2 microns distributed sporadically;
(2) and (2) sequentially dissolving 2.16 parts of nickel nitrate hexahydrate, 1 part of ferric nitrate nonahydrate, 0.9 part of urea and 0.4 part of ammonium fluoride in 40 parts of deionized water to form a mixed solution, transferring the mixed solution into a reaction kettle, vertically placing the conductive glass deposited with the indium sulfide film obtained in the step (1), sealing, and reacting at 120 ℃ for 15 hours to obtain the indium sulfide/nickel iron hydrotalcite composite film attached to the conductive glass. Wherein the thickness of the nickel-iron hydrotalcite film is 12-18 microns, and the nickel-iron hydrotalcite film is composed of flaky nickel-iron hydrotalcite crystals with the thickness of 20-50 nanometers and the diameter of 300-800 nanometers;
(3) dissolving 1 part of xylose in 250 parts of 0.25mol/L Na2SO4Adding the aqueous solution into an electrolytic cell, taking the conductive glass attached with the indium sulfide/nickel iron hydrotalcite composite membrane prepared in the step (2) as a photo-anode electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, applying 0.2V bias under the irradiation of a 40W xenon lamp, and under the condition of not adding a filter, wherein the ratio of xylose converted into xylonic acid is 97.3 percent within 2 hours; adding filter to remove visible light and near infrared light above 380 nmAfter light, the rate of xylose conversion to xylonic acid was 96.8% for 2 hours; after filtering out ultraviolet light below 380 nm by adding a filter, the ratio of xylose converted into xylonic acid in 2 hours is 81.7 percent; after filtering out ultraviolet light and visible light below 720 nm by adding a filter, the ratio of xylose conversion to xylonic acid in 2 hours was 29.6%.
Example 5
(1) Adding 7.6 parts of citric acid monohydrate into 20 parts of deionized water, fully dissolving, adding 1 part of indium chloride, and stirring to dissolve to form an indium citrate complex solution. 1.02 parts thioacetamide was dissolved in 20 parts deionized water to form a thioacetamide solution. Slowly and dropwisely adding thioacetamide solution into indium citrate complex solution under stirring to form mixed solution, transferring the mixed solution into a reaction kettle, simultaneously vertically adding a 10X 30 mm FTO conductive glass sheet cleaned by acetone and deionized water, sealing, and reacting at 80 ℃ for 10 hours to obtain the conductive glass deposited with the indium sulfide film. The indium sulfide thin film is 0.8-1 micron in thickness and consists of cubic indium sulfide crystals with the granularity of 100-500 nanometers and cubic indium sulfide crystals with the granularity of 1-2 microns distributed sporadically;
(2) and (2) sequentially dissolving 2.16 parts of nickel nitrate hexahydrate, 1 part of ferric nitrate nonahydrate, 1.2 parts of urea and 0.09 part of ammonium fluoride in 40 parts of deionized water to form a mixed solution, transferring the mixed solution into a reaction kettle, vertically placing the conductive glass deposited with the indium sulfide film obtained in the step (1), sealing, and reacting at 120 ℃ for 10 hours to obtain the indium sulfide/nickel iron hydrotalcite composite film attached to the conductive glass. Wherein the thickness of the nickel-iron hydrotalcite film is 10-15 microns, and the nickel-iron hydrotalcite film is composed of flaky nickel-iron hydrotalcite crystals with the thickness of 20-50 nanometers and the diameter of 300-800 nanometers;
(3) dissolving 1 part of xylose in 250 parts of 0.25mol/L Na2SO4Adding the aqueous solution into an electrolytic cell, taking the conductive glass attached with the indium sulfide/nickel iron hydrotalcite composite film prepared in the step (2) as a photo-anode electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, applying 0.2V bias under the irradiation of a 40W xenon lamp, and under the condition of not adding a filter, wherein the ratio of xylose converted into xylonic acid is 96.1 percent within 2 hours; adding a light filter to removeAfter visible light and near infrared light of more than 380 nm are removed, the ratio of xylose converted into xylonic acid in 2 hours is 94.5 percent; after filtering ultraviolet light below 380 nm by adding a filter, the ratio of xylose converted into xylonic acid in 2 hours is 79.4 percent; after filtering out ultraviolet light and visible light below 720 nm by adding a filter, the ratio of xylose conversion to xylonic acid in 2 hours was 27.9%.
Comparative example 1
(1) Adding 5.7 parts of citric acid monohydrate into 20 parts of deionized water, fully dissolving, adding 1 part of indium chloride, and stirring to dissolve to form an indium citrate complex solution. 1.36 parts thioacetamide was dissolved in 20 parts deionized water to form a thioacetamide solution. Slowly and dropwisely adding thioacetamide solution into indium citrate complex solution under stirring to form mixed solution, transferring the mixed solution into a reaction kettle, simultaneously vertically adding a 10X 30 mm FTO conductive glass sheet cleaned by acetone and deionized water, sealing, and reacting at 80 ℃ for 8 hours to obtain the conductive glass deposited with the indium sulfide film. The indium sulfide thin film is 0.8-1 micron in thickness and consists of cubic indium sulfide crystals with the granularity of 100-500 nanometers and cubic indium sulfide crystals with the granularity of 1-2 microns distributed sporadically;
(2) and (2) sequentially dissolving 2.16 parts of nickel nitrate hexahydrate, 1 part of ferric nitrate nonahydrate, 1 part of urea and 0.2 part of ammonium fluoride in 40 parts of deionized water to form a mixed solution, transferring the mixed solution into a reaction kettle, vertically placing the conductive glass deposited with the indium sulfide film obtained in the step (1), sealing, and reacting at 120 ℃ for 12 hours to obtain the indium sulfide/nickel iron hydrotalcite composite film attached to the conductive glass. Wherein the thickness of the nickel-iron hydrotalcite film is 15-20 microns, and the nickel-iron hydrotalcite film is composed of flaky nickel-iron hydrotalcite crystals with the thickness of 20-50 nanometers and the diameter of 300-800 nanometers;
(3) dissolving 1 part of xylose in 250 parts of 0.25mol/L Na2SO4And (3) adding the aqueous solution into an electrolytic cell, taking the conductive glass attached with the indium sulfide/nickel iron hydrotalcite composite membrane prepared in the step (2) as a photo-anode electrode, taking a platinum sheet electrode as a counter electrode, taking a saturated calomel electrode as a reference electrode, and under the irradiation of a 40W xenon lamp and without bias voltage and an optical filter, under the condition of 2 hours, the ratio of xylose to xylonic acid is 52.3 percent; after visible light and near infrared light of more than 380 nm are removed by adding a filter, the ratio of xylose converted into xylonic acid in 2 hours is 47.7 percent; after filtering out ultraviolet light below 380 nm by adding a filter, the ratio of xylose converted into xylonic acid within 2 hours is 24.0 percent; after filtering out ultraviolet light and visible light below 720 nm by adding a filter, the ratio of xylose conversion to xylonic acid in 2 hours was 4.8%.
Claims (8)
1. A method for photoelectrocatalytic oxidation of xylose by utilizing an indium sulfide/nickel-iron hydrotalcite composite membrane is characterized in that the indium sulfide/nickel-iron hydrotalcite composite membrane loaded on conductive glass is used as a photoanode, a platinum sheet electrode is used as a counter electrode, a saturated calomel electrode is used as a reference electrode, and under the conditions of illumination and bias voltage application, the photoelectrocatalytic oxidation is carried out on xylose solution containing electrolyte in an electrolytic cell to prepare xylonic acid;
the illumination is one of sunlight, ultraviolet light, visible light and near infrared light; the bias voltage is 0.1-0.3V;
the thickness of an indium sulfide film in the indium sulfide/nickel iron hydrotalcite composite film is 0.5-1.0 micron, the indium sulfide film is composed of cubic phase indium sulfide crystals with the granularity of 50-500 nanometers and the granularity of 1-2 microns, and the thickness of a nickel iron hydrotalcite film is 1.0-20 microns, and the nickel iron hydrotalcite film is composed of flaky nickel iron hydrotalcite crystals with the thickness of 20-50 nanometers and the diameter of 300-800 nanometers.
2. The method according to claim 1, wherein the conductive glass is fluorine-doped tin oxide conductive glass.
3. The method according to claim 1, wherein the molar ratio of nickel iron in the nickel iron hydrotalcite is 3: 1.
4. the method of claim 1, wherein the bias voltage is 0.2V.
5. The method of claim 1, wherein the electrolyte is 0.25mol/L Na2SO4An aqueous solution; the concentration of the xylose solution is 0.1-2 wt%.
6. The method according to claim 1, wherein the indium sulfide/nickel iron hydrotalcite composite film is prepared by the following steps:
(1) adding thioacetamide solution into indium citrate complex solution formed by citric acid and indium chloride, transferring the formed mixed solution into a reaction kettle, simultaneously vertically placing conductive glass, sealing, and reacting for 6-10 hours at the temperature of 80 +/-5 ℃ to obtain the conductive glass deposited with the indium sulfide film;
(2) and (2) mixing nickel salt, ferric salt, urea and ammonium fluoride, dissolving in water to form a mixed solution, transferring to a reaction kettle, simultaneously vertically placing the conductive glass deposited with the indium sulfide film obtained in the step (1), sealing, and reacting at 120 +/-5 ℃ for 10-15 hours to obtain the indium sulfide/nickel iron hydrotalcite composite film attached to the conductive glass.
7. The method according to claim 6, wherein the molar ratio of citric acid to indium chloride in the step (1) is 4-8: 1; the molar ratio of thioacetamide to indium chloride is 1: 3 to 5.
8. The method of claim 6, wherein the molar ratio of the nickel salt, the iron salt, the urea and the ammonium fluoride in step (2) is 3: 1: 6-8: 1-4; the nickel salt is nickel nitrate; the ferric salt is ferric nitrate.
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