CN110064425B - Bismuth oxycarbonate-bismuth oxychloride heterojunction and synthesis method thereof - Google Patents
Bismuth oxycarbonate-bismuth oxychloride heterojunction and synthesis method thereof Download PDFInfo
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 17
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 11
- 239000002073 nanorod Substances 0.000 claims abstract description 82
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000002135 nanosheet Substances 0.000 claims abstract description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003760 magnetic stirring Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 6
- 230000002194 synthesizing effect Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 8
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000004729 solvothermal method Methods 0.000 abstract description 4
- 239000011541 reaction mixture Substances 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 25
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000002055 nanoplate Substances 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- FWIZHMQARNODNX-UHFFFAOYSA-L dibismuth;oxygen(2-);carbonate Chemical compound [O-2].[O-2].[Bi+3].[Bi+3].[O-]C([O-])=O FWIZHMQARNODNX-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000001055 reflectance spectroscopy Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses a bismuth oxycarbonate-bismuth oxychloride heterojunction and a synthetic method thereof, wherein the synthetic method comprises the step of mixing Bi2O2CO3Nano-rod in CH2Cl2Heating the reaction mixture. The invention synthesizes and obtains the one-dimensional Bi with the structure by a simple solvothermal method2O2CO3-BiOCl heterojunction nanorod with BiOCl nanosheet vertically grown in Bi2O2CO3On the nano-rod and BiOCl nano-sheet along Bi2O2CO3The nano rods are arranged in a layered manner in the length direction, the interface bonding area is large, the interface quality is high, and the transmission and separation of the photo-generated electron-hole pairs at the interface are greatly improved. Moreover, the synthesis method is simple, easy to control and high in application value.
Description
Technical Field
The invention relates to a nano material, in particular to a bismuth oxycarbonate-bismuth oxychloride heterojunction and a synthetic method thereof.
Background
Semiconductor photocatalysis for environmental treatment for solving air purification and wastewater treatmentOne promising approach to the problem has been extensively studied. Bismuth oxycarbonate (Bi)2O2CO3) Similar to bismuth oxyhalide (BiOX), the bismuth oxyhalide is a layered structure along the C-axis2O2]2+Layer and CO3 2-The layers are grown cumulatively by alternating van der waals forces. Due to the similarity of the structures, the heterojunction formed between the two components has higher interface quality, the transmission and separation of the photo-generated electron-hole pairs at the interface are greatly improved, and the photocatalytic activity is effectively improved.
Bismuth oxycarbonate-bismuth oxychloride (Bi) has been reported2O2CO3BiOCl) heterojunction with a shape of a nano-sheet structure or a three-dimensional flower structure assembled by nano-sheets, and Bi with a one-dimensional structure2O2CO3the-BiOCl heterojunction has not been reported. The one-dimensional structure is provided with long and ordered channels in the radial direction, which is beneficial to the rapid transfer and separation of photon-generated carriers and effectively enhances the photocatalytic activity. Therefore, Bi designed to synthesize a one-dimensional structure2O2CO3The BiOCl heterojunction is a technical problem to be solved.
Disclosure of Invention
The object of the present invention is to provide a Bi2O2CO3-a BiOCl heterojunction nanorod vertically grown on Bi from BiOCl nanosheets2O2CO3Formed on the nano-rod, and BiOCl nano-sheet is along Bi2O2CO3The length direction of the nano-rods is arranged in a layered manner. Bi in the invention2O2CO3The BiOCl heterojunction has large interface combination area and higher interface quality, forms a one-dimensional hierarchical structure, greatly improves the transmission and separation of the photo-generated electron-hole pairs at the interface, and improves the photocatalytic activity in application. Furthermore, the invention uses Bi2O2CO3The rod is used as a precursor, methylene dichloride is used for providing a chlorine source, and the Bi in the invention is synthesized by a simple solvothermal method2O2CO3-BiOCl heterojunction nanorods. The synthesis method is simple and easy to controlAnd has high application value.
In order to achieve the above object, the present invention provides a method for synthesizing bismuth oxycarbonate-bismuth oxychloride heterojunction, comprising the step of adding Bi2O2CO3Nano-rod in CH2Cl2Heating the reaction mixture.
The invention also provides a bismuth oxycarbonate-bismuth oxychloride heterojunction synthesized by the synthesis method.
By the technical scheme, the invention uses Bi2O2CO3The rod is used as a precursor and is used as a bismuth source in the reaction process, an organic reagent methylene dichloride is used for providing a Cl source, and the methylene dichloride is also used as a reaction solvent. Synthesizing one-dimensional Bi by a simple solvothermal method2O2CO3-BiOCl heterojunction nanorod with BiOCl nanosheet vertically grown in Bi2O2CO3On the nano-rod, the Bi with novel structure2O2CO3the-BiOCl heterojunction has not been reported in the literature. More specifically, the heterojunction nanorod is vertically grown on Bi by using a BiOCl nanosheet2O2CO3Formed on the nano-rod, and BiOCl nano-sheet is along Bi2O2CO3The length direction of the nano-rods is arranged in a layered manner. Bi in the invention2O2CO3The BiOCl heterojunction has large interface combination area and higher interface quality, forms a one-dimensional hierarchical structure, greatly improves the transmission and separation of the photo-generated electron-hole pairs at the interface, and improves the photocatalytic activity in application. Moreover, the synthesis method is simple, easy to control and high in application value.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an XRD analysis of the product of example 1 and example 2;
FIG. 2 is an SEM photograph of the product of example 1;
FIG. 3 is an SEM photograph of the product of example 2;
FIG. 4 is an SEM photograph of the product of example 3;
FIG. 5 is an SEM photograph of the product of example 4;
FIG. 6 is an SEM photograph of the product of example 5;
FIG. 7 is an optical property analysis chart in the detection example;
FIG. 8 is an analysis diagram for evaluation of rhodamine degradation under visible light in an application example.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for synthesizing bismuth oxycarbonate-bismuth oxychloride heterojunction, which comprises the step of adding Bi2O2CO3Nano-rod in CH2Cl2Heating the reaction mixture.
By the technical scheme, the invention uses Bi2O2CO3The rod is used as a precursor and is used as a bismuth source in the reaction process, an organic reagent methylene dichloride is used for providing a Cl source, and the methylene dichloride is also used as a reaction solvent. Synthesizing to obtain the one-dimensional Bi with the structure by a simple solvothermal method2O2CO3-BiOCl heterojunction nanorod with BiOCl nanosheet vertically grown in Bi2O2CO3On the nano-rod, the Bi with novel structure2O2CO3the-BiOCl heterojunction has not been reported in the literature. More specifically, the heterojunction nanorod is vertically grown on Bi by using a BiOCl nanosheet2O2CO3Formed on the nano-rod, and BiOCl nano-sheet is along Bi2O2CO3The length direction of the nano-rods is arranged in a layered manner. Bi in the invention2O2CO3the-BiOCl heterojunction has higher interface quality, greatly improves the transmission and separation of the photo-generated electron-hole pairs at the interface, and improves the photocatalytic activity in application. Moreover, the synthesis method is simple, easy to control and high in application value.
In the above-mentioned technical means, the amount of the raw material to be added may be selected within a wide range in order to increase Bi2O2CO3Yield of BiOCl heterojunction nanorods and vertical growth of BiOCl nanoplates in Bi2O2CO3On nanorods, in a preferred embodiment of the invention, Bi2O2CO3And CH2Cl2The mass ratio of (A) is not less than 1: 260. when Bi is present2O2CO3And CH2Cl2Is less than 1: at 260 deg.C, Bi2O2CO3The framework of the nanorod is reduced, so that the support body of the BiOCl nanosheet growing on the surface of the nanorod is reduced, the structure is collapsed, and most of the product is the BiOCl nanosheet.
To increase Bi2O2CO3Yield of BiOCl heterojunction nanorods and vertical growth of BiOCl nanoplates in Bi2O2CO3On nanorods, in a preferred embodiment of the invention, Bi2O2CO3And CH2Cl2The mass ratio of (1): 130-260, in which case the majority of the product is Bi2O2CO3-BiOCl heterojunction nanorods with only a small amount of Bi2O2CO3-BiOCl heterojunction nanorods.
To increase Bi2O2CO3Yield of BiOCl heterojunction nanorods and vertical growth of BiOCl nanoplates in Bi2O2CO3On the nanorods, in a preferred embodiment of the invention, the temperature of the heating reaction is 100-160 ℃, in which case the majority of the product is Bi2O2CO3-BiOCl heterojunction nanorods. When the temperature exceeds 180 ℃, Bi in an XRD pattern2O2CO3The peak almost disappears, mainly BiOCl peak (JCPDS NO.01-0600), the product is mostly BiOCl nano-sheet, and only a small amount of Bi is present2O2CO3-BiOCl heterojunction nanorods.
To increase Bi2O2CO3Yield of BiOCl heterojunction nanorods and vertical growth of BiOCl nanoplates in Bi2O2CO3On nanorods, in a preferred embodiment of the invention, the reaction time is 6-22h, in which case the major part of the product is Bi2O2CO3-BiOCl heterojunction nanorods. When the reaction time exceeds 24h, Bi in the XRD pattern2O2CO3The peak almost disappears, mainly BiOCl peak (JCPDS NO.01-0600), the product is mostly BiOCl nano-sheet, and only a small amount of Bi is present2O2CO3-BiOCl heterojunction nanorods.
The specific reaction steps can be selected in various ways, and the invention can be realized as long as the raw materials are effectively dispersed before the reaction. In a preferred embodiment of the invention, Bi is used in order to obtain a controlled morphology2O2CO3-BiOCl heterojunction nanorods, preferably, further comprising Bi before the heating reaction is carried out2O2CO3And (3) carrying out ultrasonic dispersion and/or magnetic stirring on the nanorods.
Of course, the work-up of the reaction product can be carried out by means of conventional techniques in the art, and in a preferred embodiment of the invention, for the maintenance of Bi2O2CO3The morphology of the BiOCl heterojunction nanorod is preferable, and the method further comprises the steps of naturally cooling to room temperature after the heating reaction is finished, collecting a product, washing with water and absolute ethyl alcohol for multiple times, and drying.
Bi2O2CO3The nanorod can be obtained by any method reported in the prior art, as long as it is Bi of a rod-like structure2O2CO3The nano-material, then, according to the synthesis method of the invention, can obtain the Bi of the invention2O2CO3-a BiOCl heterojunction. In the present invention, Bi synthesized by the method reported in the prior application (application No. 201910311695.8) of the present inventors is used to save the cost of raw materials2O2CO3The nano-rod is used as a raw material. The Bi2O2CO3The nanorods were prepared by the following method: comprises mixing Bi (OHC)2O4)·2H2Precursor of O nano-rod in CO2And (3) calcining at high temperature in the atmosphere. The one-dimensional Bi2O2CO3The nano-rod has a porous one-dimensional rod-like structure, and the Bi is2O2CO3The nanorod exposes a (120) crystal face, and the (120) crystal face is along [002]And (4) directionally growing. The Bi2O2CO3The absorption band edge of the nanorods extends into the visible region. Further, said Bi2O2CO3Band gap Delta E of nano rodgIt was 2.96 eV.
In the above-mentioned Bi2O2CO3In the technical scheme of nanorod synthesis, Bi (OHC)2O4)·2H2The O nanorods can be prepared by methods of the prior art, or can be obtained by methods employed in the prior application (application No. 201910311695.8), which are not described herein.
In the examples hereinafter, Bi as a raw material is used2O2CO3The nano-rod is obtained by the following method: bi (OHC)2O4)·2H2Precursor of O nano-rod in CO2Calcining at 300 ℃ for 1h in atmosphere, and synthesizing one-dimensional porous Bi in situ2O2CO3And (4) nanorods.
The invention also provides a bismuth oxycarbonate-bismuth oxychloride heterojunction synthesized by the synthesis method.
One-dimensional Bi of the present invention2O2CO3-BiOCl heterojunction nanorod with BiOCl nanosheet vertically grown in Bi2O2CO3On the nano-rod, the Bi with novel structure2O2CO3The BiOCl heterojunction has not been reported in the literature. More specifically, the heterojunction nanorod is vertically grown on Bi by using a BiOCl nanosheet2O2CO3Formed on the nano-rod, and BiOCl nano-sheet is along Bi2O2CO3The length direction of the nano-rods is arranged in a layered manner. Bi in the invention2O2CO3the-BiOCl heterojunction has higher interface quality, greatly improves the transmission and separation of the photo-generated electron-hole pairs at the interface, and improves the photocatalytic activity in application.
The present invention will be described in detail below by way of examples.
Example 1
51mg of Bi2O2CO3The nanorods were added to 5mL of CH2Cl2After ultrasonic dispersion, magnetic stirring is carried out for 30 min. Transferring the mixed solution into a reaction kettle, and reacting for 12 hours at 160 ℃. After the reaction is finished, the reaction product is naturally cooled to room temperature, the product is collected, washed for a plurality of times by deionized water and absolute ethyl alcohol, and dried for 6 hours at the temperature of 60 ℃.
The result of XRD analysis and SEM detection of the product in this example is shown in FIGS. 1 and 2. As can be seen from FIG. 1, Bi was retrieved from the XRD pattern of the product2O2CO3And the standard peak of BiOCl standard card, indicating that the sample is Bi2O2CO3-a BiOCl heterojunction. Fig. 2 is an SEM image of the sample. Bi2O2CO3The BiOCl heterojunction is a one-dimensional hierarchical structure. BiOCl nano-sheet vertically grows in Bi2O2CO3On the nano-rod and BiOCl nano-sheet along Bi2O2CO3The length direction of the nano-rods is arranged in a layered manner. In the course of the reaction, Bi2O2CO3The nanorods provide a source of Bi, and CH2Cl2A source of Cl is provided. Thus, BiOCl sheets are grown in situ in Bi2O2CO3On the nano-rod. Bi is generated along with the continuous generation of BiOCl nano-sheets2O2CO3The nanorods will gradually decrease in diameter as they are consumed by the constant supply of the Bi source. When CH is present2Cl2At 5mL, sparse BiOCl sheets grew in Bi2O2CO3On a rod. At this time, Bi in the heterojunction2O2CO3The diameter of the nano-rod is about 0.36um, and Bi is reacted with the nano-rod before2O2CO3The rod diameter is slightly reduced compared to (0.39 um).
Example 2
51mg of Bi2O2CO3The nanorods were added to 10mL of CH2Cl2After ultrasonic dispersion, magnetic stirring is carried out for 30 min. Transferring the mixed solution into a reaction kettle, and reacting for 12 hours at 160 ℃. After the reaction is finished, the reaction product is naturally cooled to room temperature, the product is collected, washed for a plurality of times by deionized water and absolute ethyl alcohol, and dried for 6 hours at the temperature of 60 ℃.
The result of XRD analysis and SEM detection of the product in this example is shown in FIGS. 1 and 3. As can be seen from FIG. 1, Bi was retrieved from the XRD pattern of the product2O2CO3And the standard peak of BiOCl standard card, indicating that the sample is Bi2O2CO3-a BiOCl heterojunction. FIG. 3 shows Bi2O2CO3SEM picture of BiOCl heterojunction, Bi2O2CO3The BiOCl heterojunction is a one-dimensional hierarchical structure. BiOCl sheets are uniform and fine and are grown in Bi2O2CO3A rod. The heterojunction nanorod is formed by vertically growing BiOCl nanosheets on Bi2O2CO3Formed on the nano-rod, and BiOCl nano-sheet is along Bi2O2CO3The length direction of the nano-rods is arranged in a layered manner. The number of BiOCl nanoplates was significantly increased compared to example 1, but the size and thickness of the nanoplates did not change significantly. In addition, Bi2O2CO3The diameter of the nano rod becomes 0.28um, and the nano rod becomes thin obviously.
Example 3
51mg of Bi2O2CO3The nanorods were added to 10mL of CH2Cl2After ultrasonic dispersion, magnetic stirring is carried out for 30 min. Mixing the aboveTransferring the resultant liquid to a reaction kettle, and reacting for 12 hours at 120 ℃. After the reaction is finished, the reaction product is naturally cooled to room temperature, the product is collected, washed for a plurality of times by deionized water and absolute ethyl alcohol, and dried for 6 hours at the temperature of 60 ℃.
The SEM examination of the product of this example shows that the results are shown in FIG. 4. Bi2O2CO3The BiOCl heterojunction is a one-dimensional hierarchical structure. BiOCl sheet grows thinly in Bi2O2CO3On the stick, also loose BiOCl pieces. At this time Bi2O2CO3The rod was slightly tapered with a diameter of 0.37 um.
Example 4
51mg of Bi2O2CO3The nanorods were added to 10mL of CH2Cl2After ultrasonic dispersion, magnetic stirring is carried out for 30 min. Transferring the mixed solution into a reaction kettle, and reacting for 12 hours at 140 ℃. After the reaction is finished, the reaction product is naturally cooled to room temperature, the product is collected, washed for a plurality of times by deionized water and absolute ethyl alcohol, and dried for 6 hours at the temperature of 60 ℃.
The SEM examination of the product in this example shows that Bi is in FIG. 52O2CO3The BiOCl heterojunction is a one-dimensional hierarchical structure, and BiOCl sheets vertically grow on Bi2O2CO3On a rod. In comparison with example 3, Bi2O2CO3The BiOCl nanoplates on the rods began to increase, but the size and thickness of the nanoplates did not change significantly. Bi2O2CO3The diameter of the rod becomes 0.30um and becomes finer.
Example 5
51mg of Bi2O2CO3The nanorods were added to 10mL of CH2Cl2After ultrasonic dispersion, magnetic stirring is carried out for 30 min. Transferring the mixed solution into a reaction kettle, and reacting for 6 hours at 160 ℃. After the reaction is finished, the reaction product is naturally cooled to room temperature, the product is collected, washed for a plurality of times by deionized water and absolute ethyl alcohol, and dried for 6 hours at the temperature of 60 ℃.
The SEM examination of the product of this example shows that the results are shown in FIG. 6. Bi2O2CO3-BiOCl heterojunction as one dimensionHierarchical structure, BiOCl plate vertically grown in Bi2O2CO3On a rod. In comparison with example 2, due to the short reaction time, BiOCl sheets grew sparsely in Bi2O2CO3On a rod of Bi2O2CO3The rod had a diameter of 0.32um and was thinned.
Example of detection
Bi in example 2 was measured by solid UV-visible diffuse reflectance spectroscopy2O2CO3Optical properties of the BiOCl heterojunction, the results are shown in FIG. 7, where A is the sample solid UV-visible diffuse reflectance spectrum and B is the sample band diagram. B in FIG. 7 shows Bi2O2CO3And BiOCl (α hv)2/nFor the line graph of hv, the band gap (Δ E) was estimated by extrapolating the straight line to the abscissag) (ii) a Thus, Δ Eg(Bi2O2CO3) And Δ Eg(BiOC) was estimated to be 2.96eV and 3.33eV, respectively.
Application example
Bi of the present invention2O2CO3The photocatalytic performance of the BiOCl heterojunction was evaluated by degrading rhodamine (RhB) under visible light. Using an equi-weight of Bi2O2CO3-BiOCl、Bi2O2CO3And BiOCl, were run in parallel under the same conditions.
As shown in FIG. 8, (A) Bi2O2CO3(B)Bi2O2CO3BiOCl (C) BiOCl degrades the UV-VIS absorption spectrum of RhB (20mg/L) under visible light, respectively, (D) degradation curve of RhB (20 mg/L). Degradation of RhB (20mg/L), Bi under visible light2O2CO3Hardly degraded by 30min, BiOCl completely degraded at 25min, and Bi2O2CO3The BiOCl heterojunction showed the most excellent photocatalytic performance in all samples, degrading 100% at 8 min.
The reason is that the heterojunction nanorod in the invention vertically grows on Bi from the BiOCl nanosheet2O2CO3Formed on the nano-rod, and BiOCl nano-sheet is along Bi2O2CO3The length direction of the nano-rods is arranged in a layered manner. Bi in the invention2O2CO3The BiOCl heterojunction has higher interface quality, and greatly improves the transmission and separation of the photogenerated electron-hole pairs at the interface. And the one-dimensional grouping structure is also beneficial to the rapid transmission of photon-generated carriers, and the photocatalytic activity is improved in application.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (7)
1. A method for synthesizing bismuth oxycarbonate-bismuth oxychloride heterojunction is characterized by comprising the step of mixing Bi2O2CO3Nano-rod in CH2Cl2Heating for reaction; wherein the temperature of the heating reaction is 100-160 ℃; wherein, Bi2O2CO3The nanorods were prepared by the following method:
comprises mixing Bi (OHC)2O4)·2H2Precursor of O nano-rod in CO2Calcining at high temperature in the atmosphere;
wherein the BiOCl nano-sheet vertically grows in Bi2O2CO3On the nano-rod.
2. The method of synthesis of claim 1, wherein Bi2O2CO3And CH2Cl2The mass ratio of (A) is not less than 1: 260.
3. the method of claim 2, wherein Bi2O2CO3And CH2Cl2The mass ratio of (1): 130-260.
4. The synthesis method according to claim 1, wherein the heating reaction time is 6-22 h.
5. The synthesis method according to any one of claims 1 to 4, further comprising reacting Bi before the heating reaction2O2CO3And (3) carrying out ultrasonic dispersion and/or magnetic stirring on the nanorods.
6. The synthesis method according to any one of claims 1 to 4, further comprising the steps of naturally cooling to room temperature after the completion of the heating reaction, collecting the product, washing with water and absolute ethanol several times, and drying.
7. The bismuth oxycarbonate-bismuth oxychloride heterojunction synthesized according to the synthesis method of any one of claims 1 to 6.
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