CN112958120B - Silver-loaded bismuth oxychloride nano material as well as preparation method and application thereof - Google Patents
Silver-loaded bismuth oxychloride nano material as well as preparation method and application thereof Download PDFInfo
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 113
- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 88
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 66
- 239000004332 silver Substances 0.000 title claims abstract description 65
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 12
- -1 silver ions Chemical class 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 39
- 238000003756 stirring Methods 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 18
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 14
- 229930195725 Mannitol Natural products 0.000 claims description 14
- 239000000594 mannitol Substances 0.000 claims description 14
- 235000010355 mannitol Nutrition 0.000 claims description 14
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000002244 precipitate Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 239000002064 nanoplatelet Substances 0.000 claims description 4
- 239000002135 nanosheet Substances 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
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- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
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- 239000000460 chlorine Substances 0.000 description 30
- 238000006731 degradation reaction Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002159 nanocrystal Substances 0.000 description 5
- 238000012360 testing method Methods 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
- 239000007789 gas Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 150000001621 bismuth Chemical class 0.000 description 2
- 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 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006143 cell culture medium Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000002055 nanoplate Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002577 pseudohalo group Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
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- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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Abstract
The invention discloses a silver-loaded bismuth oxychloride nano material as well as a preparation method and application thereof. The preparation method comprises the following steps: (1) providing a bismuth oxychloride nano-wafer with an exposed crystal face, wherein the exposed crystal face of the bismuth oxychloride nano-wafer is provided with chlorine atoms; (2) and chemically bonding silver ions of a silver source on the exposed crystal face of the bismuth oxychloride nano-wafer. The silver-loaded bismuth oxychloride nano material prepared by adopting the strategy provided by the invention has the advantages of regular and uniform appearance, simple process and low synthesis energy consumption, has higher photocatalytic activity, can effectively degrade gaseous pollutants such as NOx and the like, and has a good effect on treating or repairing the atmospheric environment.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic materials, and particularly relates to a silver-loaded bismuth oxychloride nano material as well as a preparation method and application thereof.
Background
The monatomic catalysis is different from the nano catalysis and the sub-nano catalysis, and when the dispersion size of the particles reaches the monatomic size, the energy level structure and the electronic structure of the particles can be fundamentally changed, such as ultrahigh atom utilization rate, sharply increased surface free energy, quantum size effect, unsaturated coordination environment and the like. The special structure makes it show more catalysis than general metal catalyst or metal oxideThe catalyst has excellent catalytic performance, and the single-atom catalysis can be widely applied to electrocatalytic hydrogen evolution and CO evolution2Reduction, synthetic ammonia, VOCs purification, nitrogen oxide removal and the like. At present, research on monatomic materials mainly surrounds noble metal monatomic catalysts such as Au, Pt, Pd, Ru and the like, however, the noble metals are generally low in loading capacity (generally less than 0.2 wt%), poor in thermal stability and easy to agglomerate and deactivate, and the cost problem and the complicated process for preparing the catalysts greatly restrict the large-batch production and application of the catalysts.
At present, supported highly dispersed noble metal catalysts can be synthesized by methods such as a coprecipitation method, an atomic layer deposition method, a mass separation-soft landing method, an anti-Ostward aging method, a photochemical reduction method and the like. However, these methods have problems that affect the performance of the catalyst. The following disadvantages generally exist:
(1) the experimental conditions are harsh, ultra-high vacuum preparation conditions are required, or defects are introduced at ultra-high temperature, the selection of the metal precursor is harsh, in addition, the yield is low, the stability is insufficient, the cost is high, and the large-scale production and application are also restricted.
(2) The metal loading is low. Multiple parameters in the catalyst preparation process need to be strictly controlled, including the addition speed of the precursor, the size of liquid drops, the stirring degree, the reaction temperature, the pH value, the reaction time and the like. In addition, some of the individual metal atoms buried in the carrier aggregation interface or bulk carrier cannot come into contact with the reacting molecules and participate in the reaction, greatly reducing the overall performance of the monatomic catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a silver-loaded bismuth oxychloride nano material, a preparation method and application thereof, which can obviously improve the metal loading capacity.
In order to achieve the purpose, the silver-loaded bismuth oxychloride nano material provided by the invention is formed by chemical bonds generated by silver atoms and chlorine atoms on the exposed crystal face of a bismuth oxychloride nano wafer with an exposed crystal face.
The bismuth oxychloride nano-chip is a nano-chip with an exposed (001) crystal face, and the thickness of the bismuth oxychloride nano-chip is 3-5 nm.
The invention also provides a preparation method of the silver-loaded bismuth oxychloride nano material, which comprises the following steps:
providing a bismuth oxychloride nano-wafer with an exposed crystal face, wherein the exposed crystal face of the bismuth oxychloride nano-wafer is provided with chlorine atoms;
and chemically bonding silver ions of a silver source on the exposed crystal face of the bismuth oxychloride nano-wafer.
Further, the preparation of the bismuth oxychloride nano-chip specifically comprises the following steps: under the environment of rich chlorine, dissolving bismuth salt and a surface end-capping reagent in a solvent, and obtaining the chlorine-exposed bismuth oxychloride nano-chip by a solvothermal method.
Further, the step of chemically bonding silver ions of a silver source on the exposed crystal face of the bismuth oxychloride nano-wafer specifically comprises: soaking the bismuth oxychloride nano-chip in the silver source solution, fully stirring, washing the obtained precipitate with distilled water and absolute ethyl alcohol, centrifuging, drying, and then carrying out heat treatment.
Further, the bismuth salt is bismuth nitrate pentahydrate; the chlorine-rich environment is provided by potassium chloride; the surface end-capping agent is polyvinylpyrrolidone; the solvent is mannitol and water.
Further, the dosage of the bismuth nitrate pentahydrate is 1-5 mmol; the dosage of the polyvinylpyrrolidone is 0.4-2 g; the dosage of the potassium chloride is 3-15 mmol; in the solvent, the dosage of mannitol is 2.5-10 mmol, and the dosage of water is 35-180 ml.
Further, the solvothermal condition was 160 ℃ for 3 h.
Further, the dosage of the bismuth oxychloride nano-chip is 0.5-3 g; the silver source is silver nitrate, the concentration is 0.8-4 g/L, and the heat treatment condition is 200 ℃ for 3 hours.
Further, the silver-loaded bismuth oxychloride nano material serving as a catalyst can be applied to photocatalytic degradation of gaseous nitrogen oxides.
The invention has the beneficial effects that:
1. the invention successfully prepares the monatomic silver-loaded bismuth oxychloride nano material by taking bismuth oxychloride as a substrate material for the first time. The strategy of synthesizing the monoatomic compound by utilizing halogen bonding coordination is expected to be popularized to a series of materials such as BiOX (= Br, I) and the like, and is expected to be popularized to a series of pseudohalogen materials.
2. The silver-loaded bismuth oxychloride nanomaterial prepared by adopting the strategy provided by the invention has the advantages of regular and uniform appearance, simple process, low synthesis energy consumption and low silver cost compared with other noble metals such as Au and Pt;
3. the silver-loaded bismuth oxychloride nanomaterial prepared by adopting the strategy provided by the invention has high photocatalytic activity, can effectively degrade gaseous pollutants such as NOx and the like, and has a good effect on treating or repairing atmospheric environment.
Drawings
FIG. 1 shows AgSAC @ in example 1ClThe XRD pattern of BiOCl identifies the tetragonal BiOCl phase (JCPDS 85-861).
FIG. 2 shows AgSAC @ -examples 1 (a) - (d)ClA transmission electron microscope photograph of the BiOCl nanosheet; FIGS. 2 (a) - (b) are global topographs of nanoplates; panel (c) is a pattern of lattice fringes of the nanoplatelets; panel (d) is the electron diffraction pattern of the nanoplatelets.
FIG. 3 shows AgSAC @ according to example 1ClA scanning projection electron microscope (STEM) image of the base plane of the BiOCl nanoplatelets; FIG. 3 (a) is a graph of a monoatomic silver distribution in ADF mode; (b) is a mapping graph of Ag, Cl, Bi and other elements; (c) is a silver monoatomic diagram of a basal plane in an ABF mode.
FIG. 4 shows AgSAC @ according to example 1ClSTEM picture of side face of BiOCl nano sheet; the monoatomic silver growth on the outer layer Cl is clearly visible in ABF mode.
FIG. 5 shows AgSAC @ according to example 1ClSTEM map of the side thickness of BiOCl nanoplates.
Fig. 6 is a graph of nitrogen oxide removal rate versus time under xenon lamp irradiation (300W) for the monatomic silver catalyst prepared in example 1.
Fig. 7 is a graph of nitrogen oxide removal rate versus time under xenon lamp irradiation (300W) for the monatomic silver catalyst prepared in example 2.
Fig. 8 is a graph of nitrogen oxide removal rate versus time under xenon lamp irradiation (300W) for the monatomic silver catalyst prepared in example 3.
Fig. 9 is a graph of nitrogen oxide removal rate versus time under xenon lamp irradiation (300W) for the monatomic silver catalyst prepared in example 4.
Fig. 10 is a graph of nitrogen oxide removal rate versus time under xenon lamp irradiation (300W) of the monatomic silver catalyst prepared in example 5.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention, and that any other changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principles of the present invention are intended to be included within the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1: the silver-loaded bismuth oxychloride nanomaterial provided by this embodiment is formed by chemical bonds between silver atoms and chlorine atoms on exposed crystal faces of a bismuth oxychloride nanocrystal wafer with exposed crystal faces, and can be expressed by AgSAC @ClBiOCl represents.
The preparation of the monatomic silver-loaded bismuth oxychloride nanomaterial in the embodiment specifically comprises the following steps:
1. preparing a bismuth oxychloride nano wafer:
1) continuously stirring mannitol, polyvinylpyrrolidone and water in a ratio of 2.5mmol:0.4g:25ml until the mannitol, the polyvinylpyrrolidone and the water are completely dissolved to obtain a solution A;
2) 1mmol of Bi (NO)3)3·5H2Grinding O under an infrared lamp to fine powder, adding the fine powder into the solution A, and uniformly stirring for 20 minutes until the fine powder is completely dissolved to obtain a solution B;
3) dissolving potassium chloride and water according to the proportion of 3mmol to 10ml, uniformly stirring to obtain a solution C, adding the solution C into the solution B, and uniformly stirring for 10min to obtain a solution D;
4) transferring the solution D into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 3 hours at 160 ℃;
5) and after the reaction is finished, washing the obtained precipitate with deionized water and absolute ethyl alcohol in sequence, and then putting the product in an oven for drying to obtain the (001) surface bismuth oxychloride nano wafer E with the exposed chlorine atom at the surface terminal, wherein as shown in fig. 2c and 2d, the (001) crystal surface of the bismuth oxychloride nano wafer E is an orthogonal surface, the crystal lattice stripes are strictly orthogonal, the spacing is 0.275nm, and the bismuth oxychloride nano wafer E belongs to a high-activity surface and has better catalytic activity compared with other crystal surfaces.
2. Preparing a silver-loaded bismuth oxychloride nano material:
dissolving 8mg of silver nitrate in 10ml of water to obtain a silver nitrate solution F, adding 0.5g of the bismuth oxychloride nano wafer E obtained in the step 1 into the solution F, soaking and stirring for 30min under dark conditions, washing obtained precipitates with deionized water and absolute ethyl alcohol in sequence, then putting products into an oven for drying, transferring the dried samples into a muffle furnace for heat treatment at 200 ℃ for 3h to obtain the silver-loaded bismuth oxychloride nano material AgSAC (accumulator ion exchange chromatography) ion exchangerClBiOCl。
Testing the monatomic silver-loaded bismuth oxychloride nanomaterial AgSAC-ClPhotocatalytic performance of BiOCl: to a sample tube containing 10mL of water was added 0.15g of AgSAC prepared in this exampleClAnd (3) carrying out ultrasonic treatment on the BiOCl sample for 30 minutes, pouring the solution into a culture dish with the diameter of 9cm, and drying at 60 ℃. And then placing the culture dishes with the uniformly distributed samples obtained by drying into a reaction box with the volume of 4.5L, and performing degradation reaction on the gaseous nitrogen oxide by utilizing visible light irradiation when the NO inlet gas concentration reaches about 600ppb at room temperature. As shown in FIG. 6, based on the resulting AgSAC +ClThe NO removal rate-time curve of the BiOCl nano material under the action of simulated sunlight shows that the NO degradation rate is stabilized at about 70% after the BiOCl nano material is irradiated for 20 minutes.
Example 2: the silver-loaded bismuth oxychloride nanomaterial provided by this embodiment is formed by chemical bonds between silver atoms and chlorine atoms on the exposed crystal faces of a bismuth oxychloride nanocrystal wafer with exposed crystal faces, and can be represented by formula AgSAC/ClBiOCl represents.
The preparation of the monatomic silver-loaded bismuth oxychloride nanomaterial in the embodiment specifically comprises the following steps:
1. preparing a bismuth oxychloride nano wafer:
1) continuously stirring mannitol, polyvinylpyrrolidone and water according to the proportion of 5mmol:0.8g:50ml until the mannitol, the polyvinylpyrrolidone and the water are completely dissolved to obtain a solution A;
2) 1mmol of Bi (NO)3)3·5H2Grinding O under an infrared lamp to fine powder, adding the fine powder into the solution A, and uniformly stirring for 20 minutes until the fine powder is completely dissolved to obtain a solution B;
3) dissolving potassium chloride and water at a ratio of 6mmol to 20ml, uniformly stirring to obtain a solution C, adding the solution C into the solution B, and uniformly stirring for 10min to obtain a solution D;
4) transferring the solution D into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 3 hours at 160 ℃;
5) washing the obtained precipitate with deionized water and absolute ethyl alcohol in sequence after the reaction is finished, and then putting the product in an oven for drying to obtain a (001) surface bismuth oxychloride nano wafer E with the exposed chlorine atom at the surface terminal;
2. preparing a silver-loaded bismuth oxychloride nano material:
dissolving 16mg of silver nitrate in 20ml of water to obtain a solution F, adding 0.5g of the bismuth oxychloride nano wafer E obtained in the step 1 into the solution F, soaking and stirring for 30min under the dark condition, washing the obtained precipitate with deionized water and absolute ethyl alcohol in turn, then putting the product into an oven for drying, transferring the dried sample into a muffle furnace for heat treatment at 200 ℃ for 3h to obtain the flaky silver loaded bismuth oxychloride nano material AgSAC & ltion exchangerClBiOCl。
Testing of the monatomic silver-loaded bismuth oxychloride nanomaterial AgSAC-ClPhotocatalytic performance of BiOCl: to a sample tube containing 10mL of water was added 0.15g of AgSAC prepared in this exampleClAnd (3) carrying out ultrasonic treatment on the BiOCl sample for 30 minutes, pouring the solution into a culture dish with the diameter of 9cm, and drying at 60 ℃. Then placing the culture dish with the sample evenly distributed obtained by drying into a culture dish with the volume of 4.5In the reaction box of the L, when the NO intake concentration reaches about 600ppb at room temperature, the degradation reaction of the gaseous nitrogen oxide is carried out by utilizing visible light irradiation. As shown in fig. 7, according to the AgSAC obtainedClThe NO removal rate-time curve of the BiOCl nano material under the action of simulated sunlight shows that the NO degradation rate is stabilized at about 70% after the BiOCl nano material is irradiated for 20 minutes.
Example 3: the silver-loaded bismuth oxychloride nanomaterial provided by this embodiment is formed by chemical bonds between silver atoms and chlorine atoms on exposed crystal faces of a bismuth oxychloride nanocrystal wafer with exposed crystal faces, and can be expressed by AgSAC @ClBiOCl represents.
The preparation of the monatomic silver-loaded bismuth oxychloride nanomaterial in the embodiment specifically comprises the following steps:
1. preparing a bismuth oxychloride nano wafer:
1) continuously stirring mannitol, polyvinylpyrrolidone and water in a ratio of 8mmol to 1g to 70ml until the mannitol, the polyvinylpyrrolidone and the water are completely dissolved to obtain a solution A;
2) 3mmol of Bi (NO)3)3·5H2Grinding O under an infrared lamp to fine powder, adding the fine powder into the solution A, and uniformly stirring for 20 minutes until the fine powder is completely dissolved to obtain a solution B;
3) dissolving potassium chloride and water according to the proportion of 10mmol to 30ml, uniformly stirring to obtain a solution C, adding the solution C into the solution B, and uniformly stirring for 10min to obtain a solution D;
4) transferring the solution D into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 3 hours at 160 ℃;
5) washing the obtained precipitate with deionized water and absolute ethyl alcohol in sequence after the reaction is finished, and then putting the product in an oven for drying to obtain a (001) surface bismuth oxychloride nano wafer E with the exposed chlorine atom at the surface terminal;
2. preparing a silver-loaded bismuth oxychloride nano material:
dissolving 20mg of silver nitrate in 25ml of water to obtain a solution F, adding 0.5g of the bismuth oxychloride nano-chip E obtained in the step 1 into the solution F, soaking and stirring for 30min under a dark condition, washing obtained precipitates with deionized water and absolute ethyl alcohol in sequence, and then putting a product into an ovenDrying, transferring the dried sample into a muffle furnace for heat treatment at 200 ℃ for 3h to obtain the sheet-shaped silver supported bismuth oxychloride nano material AgSAC-ClBiOCl。
Testing the monatomic silver-loaded bismuth oxychloride nanomaterial AgSAC-ClPhotocatalytic performance of BiOCl: to a sample tube containing 10mL of water was added 0.15g of AgSAC prepared in this exampleClAnd (3) ultrasonically treating a BiOCl sample for 30 minutes, pouring the solution into a culture dish with the diameter of 9cm, and drying at 60 ℃. And then placing the culture dishes with the uniformly distributed samples obtained by drying into a reaction box with the volume of 4.5L, and performing degradation reaction on the gaseous nitrogen oxide by utilizing visible light irradiation when the NO inlet gas concentration reaches about 600ppb at room temperature. As shown in fig. 8, according to the AgSAC obtainedClThe NO removal rate-time curve of the BiOCl nano material under the action of simulated sunlight shows that the NO degradation rate is stabilized at about 69% after the BiOCl nano material is irradiated for 20 minutes.
Example 4: the silver-loaded bismuth oxychloride nanomaterial provided by this embodiment is formed by chemical bonds between silver atoms and chlorine atoms on exposed crystal faces of a bismuth oxychloride nanocrystal wafer with exposed crystal faces, and can be expressed by AgSAC @ClBiOCl represents.
The preparation of the monatomic silver-loaded bismuth oxychloride nanomaterial in the embodiment specifically comprises the following steps:
1. preparing a bismuth oxychloride nano wafer:
1) continuously stirring mannitol, polyvinylpyrrolidone and water according to the proportion of 10mmol to 1.5g to 100ml until the mannitol, the polyvinylpyrrolidone and the water are completely dissolved to obtain a solution A;
2) 1mmol of Bi (NO)3)3·5H2Grinding the O under an infrared lamp to fine powder, adding the fine powder into the solution A, and uniformly stirring for 20 minutes until the fine powder is completely dissolved to obtain a solution B;
3) dissolving potassium chloride and water at a ratio of 12mmol to 40ml, uniformly stirring to obtain a solution C, adding the solution C into the solution B, and uniformly stirring for 10min to obtain a solution D;
4) transferring the solution D into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 3 hours at 160 ℃;
5) washing the obtained precipitate with deionized water and absolute ethyl alcohol in sequence after the reaction is finished, and then putting the product in an oven for drying to obtain a (001) surface bismuth oxychloride nano wafer E with the exposed chlorine atom at the surface terminal;
2. preparing a silver-loaded bismuth oxychloride nano material:
dissolving 20mg of silver nitrate in 40ml of water to obtain a solution F, adding 0.5g of the bismuth oxychloride nano wafer E obtained in the step 1 into the solution F, soaking and stirring for 30min under dark conditions, washing obtained precipitates with ionized water and absolute ethyl alcohol in sequence, then putting products into an oven for drying, transferring the dried samples into a muffle furnace for heat treatment at 200 ℃ for 3h to obtain the flaky silver-loaded bismuth oxychloride nano material AgSAC (agar gel plant cell culture medium) ion exchangerClBiOCl。
Testing of the monatomic silver-loaded bismuth oxychloride nanomaterial AgSAC-ClPhotocatalytic performance of BiOCl: to a sample tube containing 10mL of water was added 0.15g of AgSAC prepared in this exampleClAnd (3) ultrasonically treating a BiOCl sample for 30 minutes, pouring the solution into a culture dish with the diameter of 9cm, and drying at 60 ℃. And then placing the culture dishes with the uniformly distributed samples obtained by drying into a reaction box with the volume of 4.5L, and performing degradation reaction on the gaseous nitrogen oxide by utilizing visible light irradiation when the NO inlet gas concentration reaches about 600ppb at room temperature. As shown in FIG. 9, based on the resulting AgSAC +ClThe NO removal rate-time curve of the BiOCl nano material under the action of simulated sunlight shows that the NO degradation rate is stabilized to about 67% after the BiOCl nano material is illuminated for 20 minutes.
Example 5: the silver-loaded bismuth oxychloride nanomaterial provided by this embodiment is formed by chemical bonds between silver atoms and chlorine atoms on exposed crystal faces of a bismuth oxychloride nanocrystal wafer with exposed crystal faces, and can be expressed by AgSAC @ClBiOCl represents.
The preparation of the monatomic silver-loaded bismuth oxychloride nanomaterial in the embodiment specifically comprises the following steps:
1. preparing a bismuth oxychloride nano wafer:
1) continuously stirring mannitol, polyvinylpyrrolidone and water in a ratio of 12mmol to 4g to 200ml until the mannitol, the polyvinylpyrrolidone and the water are completely dissolved to obtain a solution A;
2) 5mmol of Bi (NO)3)3·5H2Grinding the O under an infrared lamp to fine powder, adding the fine powder into the solution A, and uniformly stirring for 20 minutes until the fine powder is completely dissolved to obtain a solution B;
3) dissolving potassium chloride and water according to the proportion of 15mmol to 50ml, uniformly stirring to obtain a solution C, adding the solution C into the solution B, and uniformly stirring for 10min to obtain a solution D;
4) transferring the solution D into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 3 hours at 160 ℃;
5) after the reaction is finished, sequentially washing the obtained precipitate with deionized water and absolute ethyl alcohol, and then putting the product in an oven for drying to obtain a (001) surface bismuth oxychloride nano wafer E with the surface terminal exposed by chlorine atoms;
2. preparing a silver-loaded bismuth oxychloride nano material:
dissolving 24mg of silver nitrate in 40ml of water to obtain a solution F, adding 0.5g of the bismuth oxychloride nano wafer E obtained in the step 1 into the solution F, soaking and stirring for 30min under dark conditions, washing obtained precipitates with ionized water and absolute ethyl alcohol in sequence, then putting products into an oven for drying, transferring the dried samples into a muffle furnace for heat treatment at 200 ℃ for 3h to obtain the flaky silver-loaded bismuth oxychloride nano material AgSAC (agar gel plant cell culture medium) ion exchangerClBiOCl。
Testing of the monatomic silver-loaded bismuth oxychloride nanomaterial AgSAC-ClPhotocatalytic performance of BiOCl: to a sample tube containing 10mL of water, 0.15g of the AgSAC/ClBiOCl sample prepared in this example was added, and after 30 minutes of sonication, the solution was poured into a petri dish having a diameter of 9cm and dried at 60 ℃. And then placing the culture dishes with the uniformly distributed samples obtained by drying into a reaction box with the volume of 4.5L, and performing degradation reaction on the gaseous nitrogen oxide by utilizing visible light irradiation when the NO inlet gas concentration reaches about 600ppb at room temperature. As shown in fig. 10, according to the AgSAC obtainedClThe NO removal rate-time curve of the BiOCl nano material under the action of simulated sunlight shows that the NO degradation rate is stabilized at about 68% after the BiOCl nano material is irradiated for 20 minutes.
The above embodiments are only described to help understanding the method of the present invention and its core idea. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, it is possible to make various improvements and modifications to the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (5)
1. A preparation method of a silver-loaded bismuth oxychloride nano material is characterized by comprising the following steps:
providing a bismuth oxychloride nano-wafer with an exposed (001) crystal face, wherein the exposed crystal face of the bismuth oxychloride nano-wafer is provided with chlorine atoms;
the preparation method of the bismuth oxychloride nano-wafer with the exposed (001) crystal face comprises the following steps: s1, continuously stirring mannitol, polyvinylpyrrolidone and water in a ratio of 2.5mmol to 0.4g to 25ml until the mannitol, the polyvinylpyrrolidone and the water are completely dissolved to obtain a solution A; s2, adding 1mmol of Bi (NO)3)3·5H2Grinding O under an infrared lamp to fine powder, adding the fine powder into the solution A, and uniformly stirring for 20 minutes until the fine powder is completely dissolved to obtain a solution B; s3, dissolving potassium chloride and water according to the proportion of 3mmol to 10ml, uniformly stirring to obtain a solution C, adding the solution C into the solution B, and uniformly stirring for 10min to obtain a solution D; s4, transferring the solution D into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 3 hours at 160 ℃; s5, after the reaction is finished, washing the obtained precipitate with deionized water and absolute ethyl alcohol in sequence, and then putting the product in a drying oven for drying to obtain the (001) surface bismuth oxychloride nano-chip with the exposed chlorine atom at the surface terminal;
chemically bonding silver ions of a silver source on the exposed crystal face of the bismuth oxychloride nano wafer, and specifically: the chemical bond is formed by silver atoms and chlorine atoms on the exposed crystal face of the bismuth oxychloride nano-wafer with the exposed crystal face.
2. The preparation method according to claim 1, characterized in that the step of chemically bonding silver ions of a silver source on the exposed crystal face of the bismuth oxychloride nano-wafer is specifically as follows: soaking the bismuth oxychloride nano-chip in the silver source solution, fully stirring, washing the obtained precipitate with distilled water and absolute ethyl alcohol, centrifuging, drying, and then carrying out heat treatment.
3. The preparation method according to claim 2, wherein the amount of the bismuth oxychloride nanoplatelets is 0.5 to 3 g; the silver source is silver nitrate, and the concentration of the silver source is 0.8-4 g/L; the heat treatment conditions are 200 ℃ and 3 h.
4. The silver-loaded bismuth oxychloride nanomaterial prepared by the method according to claim 1, wherein the bismuth oxychloride nanosheet is a nanosheet with an exposed (001) crystal face and has a thickness of 3-5 nm.
5. The application of the silver-loaded bismuth oxychloride nanomaterial prepared by the method according to claim 1, wherein the silver-loaded bismuth oxychloride nanomaterial is applied as a catalyst to photocatalytic degradation of gaseous nitrogen oxides.
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