CN116237087A - Preparation method and application of cellulose nanocrystalline bonded bismuth oxide carbonate material - Google Patents
Preparation method and application of cellulose nanocrystalline bonded bismuth oxide carbonate material Download PDFInfo
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- CN116237087A CN116237087A CN202310035594.9A CN202310035594A CN116237087A CN 116237087 A CN116237087 A CN 116237087A CN 202310035594 A CN202310035594 A CN 202310035594A CN 116237087 A CN116237087 A CN 116237087A
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- 239000001913 cellulose Substances 0.000 title claims abstract description 40
- 229920002678 cellulose Polymers 0.000 title claims abstract description 40
- 239000000463 material Substances 0.000 title claims abstract description 30
- GACUIHAEKGVEIC-UHFFFAOYSA-L [Bi+2]=O.C([O-])([O-])=O Chemical compound [Bi+2]=O.C([O-])([O-])=O GACUIHAEKGVEIC-UHFFFAOYSA-L 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000004005 microsphere Substances 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 11
- 239000002159 nanocrystal Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000001621 bismuth Chemical class 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- -1 bismuth halide Chemical class 0.000 claims description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 claims description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004729 solvothermal method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 4
- 230000035484 reaction time Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 6
- 230000031700 light absorption Effects 0.000 abstract description 6
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 229910000416 bismuth oxide Inorganic materials 0.000 abstract description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 3
- MGLUJXPJRXTKJM-UHFFFAOYSA-L bismuth subcarbonate Chemical compound O=[Bi]OC(=O)O[Bi]=O MGLUJXPJRXTKJM-UHFFFAOYSA-L 0.000 description 3
- 229940036358 bismuth subcarbonate Drugs 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000002707 nanocrystalline material Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups C07C2531/02 - C07C2531/24
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention discloses a preparation method of a cellulose nanocrystalline bonding bismuth oxide material, which adopts a one-step hydrothermal method to simply and controllably bond flower-shaped bismuth oxide carbonate microspheres with cellulose nanocrystalline to develop adjustable surface Oxygen Vacancies (OVs), and the introduction of the OVs leads the bismuth oxide carbonate bonding material (CNC#BOC) to greatly enhance the light absorption covering the whole visible light region and greatly improve the charge separation and CO 2 Adsorption capacity of CO is improved 2 Efficiency of photocatalytic reduction. And the oxygen vacancy has high stability, and the performance of the catalyst is stable after 5 times of circulation. It is expected to provide new references for developing high-efficiency photocatalytic materials for solar light driving conversion.
Description
Technical field:
the invention relates to the technical field of new nano materials, in particular to a preparation method and application of a cellulose nanocrystalline bonding bismuth subcarbonate material.
The background technology is as follows:
solar driven CO 2 Conversion to chemical fuels provides a sustainable route to renewable energy production. Due to poor photocatalyst light absorption, slow charge separation and low surface reaction sites, efficient catalysts were developed to achieve solar-driven inert CO 2 Conversion to useful fuels presents a significant challenge.
The invention comprises the following steps:
the invention aims to provide a preparation method and application of a cellulose nanocrystalline bonding bismuth oxide carbonate material, wherein a one-step hydrothermal method is adopted to bond cellulose nanocrystalline and bismuth oxide carbonate, and the surface oxygen vacancy and adsorption position are regulated and controlled, so that the photocatalytic reduction of CO is improved 2 Solves the problem of CO reduction by the photocatalysis material in the prior art 2 The problems of poor light absorption, slow charge separation and low surface reaction sites are faced.
The invention is realized by the following technical scheme:
the preparation method of the cellulose nanocrystalline bonded bismuth oxide carbonate material comprises the following steps:
a. completely dissolving bismuth salt and citric acid in an acid solvent, then adjusting the pH value of the solution to 4-9 by using a sodium hydroxide solution, and uniformly stirring to obtain a mixed solution;
b. and c, adding cellulose nanocrystals into the mixed solution obtained in the step a, stirring and mixing uniformly, carrying out solvothermal reaction, reacting for 4-48 hours at 120-220 ℃, preferably reacting for 12-24 hours at 170-200 ℃, centrifuging and separating after the reaction, freeze-drying, and collecting a powdery sample.
Preferably, the bismuth salt is one of bismuth nitrate, bismuth halide, bismuth sulfate or crystalline hydrate thereof.
Preferably, the bismuth salt is bismuth nitrate pentahydrate.
Preferably, the mass ratio of bismuth salt, citric acid and cellulose nanocrystals is 10-14.56:2-5:0.2 to 0.6, more preferably: 10:2-3:0.2-0.3.
Preferably, the acidic solvent in the step a is 1-4mol.L -1 HNO of (F) 3 A solution.
Preferably, the molar concentration of the sodium hydroxide solution in the step a is 4-12 mol.L -1 。
Preferably, said step b of centrifuging, freeze-drying and collecting a powdered sample comprises the steps of: and (3) carrying out centrifugal separation to obtain sample powder, washing the sample powder with deionized water for 3-6 times, washing the sample powder with ethanol for 1-3 times, then rapidly freezing the sample powder with liquid nitrogen, putting the sample powder into a freeze drying box, and collecting a powdery sample after freeze drying for 6-24 hours.
Bismuth salt and citric acid are added into an acid solution, then a sodium hydroxide solution is used for regulating the pH value to form a bismuth oxide carbonate precursor, then cellulose nanocrystalline is added for hydrothermal reaction, the cellulose nanocrystalline is covered on the surface of the bismuth oxide carbonate, so that interfacial bonding (stable covalent chemical bonds are formed between Bi (III) ions on the surface of the bismuth oxide and-OH groups on the surface of the cellulose) is formed between the bismuth oxide and the cellulose nanocrystalline, and Oxygen Vacancies (OVs) are formed on the surface of the bismuth oxide carbonate. The introduction of OVs greatly enhances the light absorption of bismuth subcarbonate over the entire visible region and greatly improves charge separation and CO 2 Adsorption capacity; at the same time, the cellulose nanocrystalline with a large amount of hydroxyl groups can improve the surface of the catalyst and the reactant CO 2 And H 2 Interaction of O.
The invention also protects the cellulose nanocrystalline bonding bismuth oxide carbonate material obtained by the preparation method. The material synthesized by the invention has a better nanometer flower-like microsphere structure, is rich in oxygen vacancies, has the particle size of 200-400nm, has a high visible light absorption range, quick charge separation and CO 2 The advantages of multiple surface active sites and the like are that the CO can be well adsorbed 2 Has excellent CO reduction effect 2 Is a performance of the (c). The cellulose nanocrystals with optimal OVs concentration bind bismuth oxide material to CO compared to pure phase bismuth oxide carbonate or cellulose nanocrystals 2 The yield of reduction to CO is improved by 52 times or 90 times. And the oxygen vacancy has high stability, and the performance of the catalyst is stable after 5 times of circulation. Is expected to provide a new reference for developing high-efficiency photocatalytic materials for solar light driving conversion。
Therefore, the invention also protects the application of the cellulose nanocrystalline bonded bismuth oxide carbonate material in photocatalytic reduction of CO 2 。
The beneficial effects of the invention are as follows:
1) The invention adopts a one-step hydrothermal method to simply and controllably bond flower-shaped bismuth oxide carbonate microspheres with cellulose nanocrystals to develop adjustable surface Oxygen Vacancies (OVs) and adsorption sites, and the introduction of the OVs leads the bismuth oxide carbonate bonding material (CNC#BOC) to greatly enhance the light absorption covering the whole visible light region, and greatly improve the charge separation and CO 2 Adsorption capacity, the surface cellulose nanocrystalline further enhances the catalyst and reactant CO 2 And H 2 Interaction of O, thereby increasing CO 2 Efficiency of photocatalytic reduction.
2) And the oxygen vacancy has high stability, and the performance of the catalyst is stable after 5 times of circulation. It is expected to provide new references for developing high-efficiency photocatalytic materials for solar light driving conversion.
Description of the drawings:
FIG. 1 is a scanning electron microscope image of a cellulose nanocrystalline bonded bismuth subcarbonate material obtained in example 1.
FIG. 2 is a UV-visible diffuse reflectance graph of the cellulose nanocrystalline bonded bismuth oxide carbonate material obtained in example 1
FIG. 3 is a CO of a cellulose nanocrystalline bonded bismuth oxide carbonate material obtained in example 1 2 Reduction performance diagram.
The specific embodiment is as follows:
the following is a further illustration of the invention and is not a limitation of the invention.
Example 1: preparation of cellulose nanocrystalline bonded bismuth oxide carbonate material
At room temperature, at 30mL of 1 mol.L -1 HNO of (F) 3 1.5mmol bismuth nitrate pentahydrate was added to the solution and stirred at medium-high speed for 0.5 hour with stirring to dissolve. After dissolution was completed, 0.1440g of citric acid was added to the above solution and stirred well. Then use 8 mol.L -1 The pH of the solution is adjusted to 6 by NaOH, and the milk is stirred uniformly0.0180g cellulose nanocrystalline is added into the white solution, after stirring for 4 hours at room temperature, the obtained uniform solution is added into a 50mL stainless steel autoclave for reaction at 180 ℃ for 24 hours, the sample is centrifugally separated after the reaction, then the sample is washed with deionized water for 3 times and then ethanol for 1 time, then the sample is quickly frozen into solid by liquid nitrogen, and the solid is placed into a freeze drying box for drying for 12 hours, and then the powdery sample is collected.
CO 2 Reduction photocatalytic performance determination:
at normal temperature, 10mg of the prepared bonding material and 2mL of deionized water were added to a 100mL quartz bottle with a rubber stopper, and the air in the reactor was released 3 times by a mechanical pump to ensure CO in the quartz bottle 2 Is a pure product of (a). Light catalytic reduction of CO using 12W intensity LED blue lamp to simulate sunlight 2 And (3) reacting. After 1 hour of reaction, CO, CH were analyzed using a Linghua GC-9890B gas chromatograph equipped with FID detector, TCD detector and chromatographic column (BYC-04) 4 And O 2 Is a product amount of (a). The test results are shown in FIG. 3. The material showed a CO of 16. Mu. Mol.g -1 ·h -1 CH 4 0.1 mu mol g -1 ·h -1 CO compared to pure phase bismuth oxide carbonate and cellulose nanocrystals 2 The yield of reduction to CO is respectively improved by 52 times and 90 times, and the selectivity of CO is close to 100 percent and is far stronger than that of pure-phase bismuth oxide carbonate material and cellulose nanocrystalline material.
Example 2
At room temperature, at 30mL of 1 mol.L -1 HNO of (F) 3 1.5mmol bismuth nitrate pentahydrate was added to the solution and stirred at medium-high speed for 0.5 hour with stirring to dissolve. After dissolution was completed, 0.1440g of citric acid was added to the above solution and stirred well. Then use 8 mol.L -1 The pH of the solution is regulated to 6, after stirring uniformly, 0.0108g cellulose nanocrystalline is added into the milky white solution, after stirring for 4 hours at room temperature, the obtained uniform solution is added into a 50mL stainless steel autoclave for reaction for 24 hours at 180 ℃, after the reaction, the sample is centrifugally separated, then washed 3 times with deionized water, then washed 1 time with ethanol, then quickly frozen into solid with liquid nitrogen, and then placed into a freeze drying box,after 12h of drying, a powdery sample was collected.
CO 2 Reduction photocatalytic performance determination:
at normal temperature, 10mg of the prepared bonding material and 2mL of deionized water were added to a 100mL quartz bottle with a rubber stopper, and the air in the reactor was released 3 times by a mechanical pump to ensure CO in the quartz bottle 2 Is a pure product of (a). Light catalytic reduction of CO using 12W intensity LED blue lamp to simulate sunlight 2 And (3) reacting. After 1 hour of reaction, CO, CH were analyzed using a Linghua GC-9890B gas chromatograph equipped with FID detector, TCD detector and chromatographic column (BYC-04) 4 And O 2 Is a product amount of (a). The measurement method was as described in example 1. The material showed CO of 6. Mu. Mol.g -1 ·h -1 、CH 4 0.1 mu mol g -1 ·h -1 Compared to pure phase bismuth oxide carbonate and cellulose nanocrystals, CO 2 The yield of CO is improved by 20 times and 34 times, and the CO 2 Reduction to CH 4 The yield of the preparation is improved by 4 times and 6 times, and the preparation is still stronger than pure-phase bismuth oxide carbonate and cellulose nanocrystalline.
Example 3
At room temperature, at 30mL of 1 mol.L -1 HNO of (F) 3 1.5mmol bismuth nitrate pentahydrate was added to the solution and stirred at medium-high speed for 0.5 hour with stirring to dissolve. After dissolution was completed, 0.1440g of citric acid was added to the above solution and stirred well. Then use 8 mol.L -1 The pH of the solution is adjusted to 6 by NaOH, 0.0252g of cellulose nanocrystalline is added into the milky white solution after stirring uniformly, after stirring for 4 hours at room temperature, the obtained uniform solution is added into a 50mL stainless steel autoclave for reaction for 24 hours at 180 ℃, the sample is centrifugally separated after the reaction, then the sample is washed 3 times by deionized water and 1 time by ethanol, then the sample is quickly frozen into solid by liquid nitrogen, and the solid is placed into a freeze drying box for drying for 12 hours, and then the powdery sample is collected.
CO 2 Reduction photocatalytic performance determination:
10mg of the prepared bonding material and 2mL of water deionized water were added to a 100mL quartz bottle with a rubber stopper at normal temperature, and the reactor was pumped by a mechanical pumpAir release 3 times to ensure CO in the quartz bottle 2 Is a pure product of (a). Light catalytic reduction of CO using 12W intensity LED blue lamp to simulate sunlight 2 And (3) reacting. After 1 hour of reaction, CO, CH were analyzed using a Linghua GC-9890B gas chromatograph equipped with FID detector, TCD detector and chromatographic column (BYC-04) 4 And O 2 Is a product amount of (a). The measurement method was as described in example 1. The material showed a CO of 11. Mu. Mol.g -1 ·h -1 、CH 4 0.1 mu mol g -1 ·h -1 Is a reduction yield of (a). Compared with pure-phase bismuth oxide carbonate and cellulose nanocrystals, CO 2 The yield of CO is improved by 35 times and 60 times, and the CO 2 Reduction to CH 4 The yield of the preparation is improved by 4 times and 6 times, and the preparation is still stronger than pure-phase bismuth oxide carbonate and cellulose nanocrystalline.
Claims (10)
1. The preparation method of the cellulose nanocrystalline bonding bismuth oxide carbonate material is characterized by comprising the following steps:
a. completely dissolving bismuth salt and citric acid in an acid solvent, then adjusting the pH value of the solution to 4-9 by using a sodium hydroxide solution, and uniformly stirring to obtain a mixed solution;
b. and c, adding cellulose nanocrystals into the mixed solution obtained in the step a, stirring and mixing uniformly, performing solvothermal reaction, reacting for 4-48 hours at 120-220 ℃, centrifuging and separating after the reaction, freeze-drying, and collecting a powdery sample.
2. The preparation method according to claim 1, wherein the mass ratio of bismuth salt, citric acid and cellulose nanocrystals is 10-14.56:2-5:0.2-0.6.
3. The preparation method according to claim 2, wherein the mass ratio of bismuth salt, citric acid and cellulose nanocrystals is 10:2-3:0.2-0.3.
4. The method according to claim 1 or 2, wherein the bismuth salt is one of bismuth nitrate, bismuth halide, bismuth sulfate or crystalline hydrate thereof.
5. The method of claim 1 or 2, wherein the bismuth salt is bismuth nitrate pentahydrate.
6. The process according to claim 1 or 2, wherein the acidic solvent in step a is 1-4 mol.L -1 HNO of (F) 3 A solution; the molar concentration of the sodium hydroxide solution in the step a is 4-12 mol.L -1 。
7. The preparation method according to claim 1 or 2, wherein the reaction temperature in step b is 170-200 ℃ and the reaction time is 12-24h.
8. The method of claim 1 or 2, wherein the step b of centrifuging, freeze-drying and collecting the powdered sample comprises the steps of: and (3) carrying out centrifugal separation to obtain sample powder, washing the sample powder with deionized water for 3-6 times, washing the sample powder with ethanol for 1-3 times, then rapidly freezing the sample powder with liquid nitrogen, putting the sample powder into a freeze drying box, and collecting a powdery sample after freeze drying for 6-24 hours.
9. The cellulose nanocrystalline bonding bismuth oxide carbonate material obtained by the preparation method of claim 1 is characterized by having a better nanometer flower-like microsphere structure, being rich in oxygen vacancies and having a particle size of 200-400 nm.
10. The use of the cellulose nanocrystalline bonded bismuth oxide carbonate material as claimed in claim 9, characterized in that it is used for photocatalytic reduction of CO 2 。
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| US11530160B1 (en) * | 2022-06-29 | 2022-12-20 | Prince Mohammad Bin Fahd University | Robotic multi-jet system to coat photocatalyst inside glass tube |
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