CN113134376A - Cs3Bi2Cl9(PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst and preparation method thereof - Google Patents
Cs3Bi2Cl9(PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst and preparation method thereof Download PDFInfo
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- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 title claims abstract description 98
- 239000004005 microsphere Substances 0.000 title claims abstract description 94
- 239000002135 nanosheet Substances 0.000 title claims abstract description 75
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 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 title claims description 16
- 238000001338 self-assembly Methods 0.000 claims abstract description 59
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims abstract description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000012296 anti-solvent Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000001953 recrystallisation Methods 0.000 claims abstract description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229940036358 bismuth subcarbonate Drugs 0.000 claims description 3
- 239000012855 volatile organic compound Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims description 2
- 150000005323 carbonate salts Chemical class 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- VZZHAYFWMLLWGG-UHFFFAOYSA-K triazanium;bismuth;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].[NH4+].[NH4+].[Bi+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O VZZHAYFWMLLWGG-UHFFFAOYSA-K 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000000047 product Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 2
- 238000000643 oven drying Methods 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 63
- 238000006731 degradation reaction Methods 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 15
- 238000011068 loading method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000527 sonication Methods 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- -1 tungsten halogen Chemical class 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000011521 glass Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
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- 229910052760 oxygen Inorganic materials 0.000 description 2
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- 238000000746 purification Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 241001198704 Aurivillius Species 0.000 description 1
- 238000004435 EPR spectroscopy Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
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- 230000027756 respiratory electron transport chain Effects 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
- 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
-
- 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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- 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
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
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Abstract
The invention provides a Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The microsphere visible-light catalyst comprises a carrier and a carried object, wherein the carrier is Cs3Bi2Cl9(PQDs) of the supported material, which is a nanosheet self-assembly (BiO)2CO3Microspheres; the invention also provides a Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Preparation method of microsphere visible-light-driven photocatalyst, weighing CsCl and BiCl3Adding the mixture into DMSO for ultrasonic dispersion, and adding the mixture into a reactionIn a solvent, obtaining a reaction product by an anti-solvent recrystallization method, and directly centrifuging and drying to obtain Cs3Bi2Cl9(PQDs); weighing soluble carbonate in an aqueous solution, and then transferring the aqueous solution to a high-pressure hydrothermal kettle for stirring; adding a bismuth-containing precursor, stirring, heating through a hydrothermal reaction to obtain a reaction product, centrifuging, washing, and drying to obtain the nanosheet self-assembly (BiO)2CO3Microsphere powder; mixing the above products, ultrasonic stirring, centrifuging, and oven drying to obtain Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3And (3) microsphere powder. The product of the invention has high catalytic activity, and the preparation method has mild conditions and simple operation.
Description
Technical Field
The invention relates to the technical field of photocatalyst preparation, in particular to Cs3Bi2Cl9(PQDs) supported nanosheet self-assembled bismuth subcarbonate microsphere visible-light-driven photocatalyst and a preparation method thereof.
Background
Nitric Oxide (NO) released by the combustion of fossil fuel is a key factor for forming haze, participates in the formation of acid rain and harms the health of human body. Although there are some conventional techniques (SCR, absorption, adsorption) applied to treat high concentrations of NOXBut for purifying low concentrations of NO in the airXIt is not economically feasible.
With the rapid development of economy, people are aware of the importance of environmental protection, and in the face of pressure and challenges brought by environmental problems in recent years, the development of a green and efficient chemical technology is the primary task, and photocatalysis is a green and efficient technology, and has a great potential for eliminating NO at the level of parts per million (ppb) because it is environmentally friendly, has little secondary pollution, and can be directly driven by sunlight irradiation. Has become the most promising technology for solving the problem.
However, at present, many problems of unsatisfactory photocatalytic efficiency and selectivity of semiconductor materials, high recombination efficiency of electron-hole pairs, low utilization rate of visible light, innovativeness of materials and the like exist and hinder application of photocatalytic technology. Therefore, it is a primary task to find a semiconductor photocatalyst with high utilization rate of visible light.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides Cs3Bi2Cl9The (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst and the preparation method thereof solve the problem that the existing photocatalyst in the prior art is low in visible-light catalytic activity.
The technical purpose of the invention is realized by the following technical scheme:
cs (volatile organic Compounds)3Bi2Cl9The (PQDs) supported nanosheet self-assembled bismuth subcarbonate microsphere visible-light-induced photocatalyst comprises a carrier and a supported object, wherein the carrier is Cs3Bi2Cl9(PQDs) of the supported material, which is a nanosheet self-assembly (BiO)2CO3Microspheres of said Cs3Bi2Cl9(PQDs) self-Assembly with nanosheets (BiO)2CO3The microspheres form a heterojunction for accelerating carrier mobility.
The invention also provides a Cs3Bi2Cl9A preparation method of a (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-induced photocatalyst comprises the following steps:
step S1, weighing CsCl and BiCl3Adding the solution into DMSO (dimethyl sulfoxide) to form a solution, adding the solution subjected to ultrasonic dispersion into a reaction solvent, reacting for 1-30 min, obtaining a reaction product by an anti-solvent recrystallization method, directly centrifuging the reaction product, and drying at 60 ℃ to obtain Cs3Bi2Cl9(PQDs)；
S2, weighing soluble carbonate into an aqueous solution, and then transferring the aqueous solution into a high-pressure hydrothermal kettle to stir for 1-60 min; adding a bismuth-containing precursor toStirring the aqueous solution for 20-120 min, heating the aqueous solution at 120-200 ℃ for 12-48 h through a hydrothermal reaction to obtain a reaction product, centrifugally washing the reaction product (respectively using water and ethanol once), and drying the reaction product at 60 ℃ to obtain the nanosheet self-assembly (BiO)2CO3Microsphere powder;
s3, mixing the Cs3Bi2Cl9(PQDs) and nanosheet self-assembly (BiO)2CO3Adding the microsphere powder into a reaction solvent, carrying out ultrasonic treatment for 10-30 min, stirring for 3-5 h, directly centrifuging, and drying at 60 ℃ to obtain Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3And (3) microsphere powder.
The invention is further configured to: the reaction solvent is any one of ethanol, isopropanol and acetone.
The invention is further configured to: the soluble carbonate salt comprises one or more of anhydrous sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate.
The invention is further configured to: the precursor containing bismuth is one or more of bismuth nitrate pentahydrate, bismuth citrate and bismuth ammonium citrate.
The invention is further configured to: in step S3, adding the Cs3Bi2Cl9(PQDs) and (BiO)2CO3The mass ratio of the microsphere powder is (0.004-0.040): 0.8.
the invention is further configured to: in step S1, this solution dispersed with ultrasound was added to the reaction solvent for a reaction time of 1 min.
The invention is further configured to: in step S2, weighing soluble carbonate into the aqueous solution, and then transferring the aqueous solution to a high-pressure hydrothermal kettle to stir for 1 min; adding a bismuth-containing precursor into the aqueous solution, stirring for 20min, and heating for 24h at 160 ℃ through a hydrothermal reaction to obtain a reaction product b.
The invention is further configured to: in step S3, the Cs is added3Bi2Cl9(PQDs) and (BiO)2CO3The mass ratio of the microsphere powder is 0.008: 0.8.
bismuth oxycarbonate (BiO)2CO3Is an indirect band gap semiconductor with the forbidden band width of 3.1eV, belongs to an orthorhombic system, has a typical Silian structure, is a layered structure similar to Aurivillius type oxide, and consists of alternating layers of [ Bi2O2]2+And CO3 2-The groups are stacked alternately. And Cs3Bi2Cl9(PQDs) have a remarkable quantum effect, strong light absorption, and high separation efficiency of photo-generated charges.
Cs obtained by the preparation method provided by the invention3Bi2Cl9The (PQDs) load nano-sheet self-assembly bismuthyl carbonate microsphere visible-light-induced photocatalyst, wherein the numerical value of the load is the ratio of the mass ratio, the heterojunction accelerates the migration of carriers, and electrons pass through (BiO)2CO3To Cs3Bi2Cl9(PQDs) are transferred, thereby inhibiting the electron-hole recombination efficiency, improving the charge transfer performance, accelerating the formation of free radicals and further improving the visible light catalytic activity.
Drawings
FIG. 1 shows Cs in the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3A flow chart of a preparation method of the microsphere visible-light-driven photocatalyst;
FIG. 2 shows the loading of Cs in three different amounts prepared in example 1, example 2 and example 3 of the present invention3Bi2Cl9(PQDs) (0.5%, 1%, 3%) of Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Microsphere visible-light-driven photocatalyst and pure-phase Cs3Bi2Cl9(PQDs) and (BiO)2CO3XRD pattern of the microspheres (XRD is an abbreviation for X-ray diffraction, i.e. X-ray diffraction); (ii) a
FIGS. 3 and 4 are graphs of 1% loading of Cs prepared in example 2 of the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Microsphere visible-light-driven photocatalyst and pure-phase Cs3Bi2Cl9(PQDs) and (BiO)2CO3XPS (XPS is an abbreviation for X-ray photoelectron spectroscopy, namely X-ray photoelectron spectroscopy);
FIG. 5 shows 1% loading of Cs prepared in example 2 of the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3TEM image of microsphere visible light catalyst (TEM is an abbreviation of Transmission Electron Microscope, i.e. Transmission Electron Microscope);
FIG. 6 is (BiO) prepared by an example of the present invention2CO3SEM image of microspheres (SEM is abbreviation for Scanning Electron Microscope, Scanning Electron Microscope);
FIG. 7 shows the loading of Cs in three different amounts prepared in examples 1, 2 and 3 of the present invention3Bi2Cl9(PQDs) (0.5%, 1%, 3%) of Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Microsphere visible-light-driven photocatalyst and pure-phase Cs3Bi2Cl9(PQDs) and (BiO)2CO3UV-Vis DRS map of microspheres (UV-Vis DRS is UV-Visable Diffuse-reflection Spectra, i.e. UV-Visible Diffuse reflectance);
FIG. 8 shows the loading of Cs in three different amounts prepared in examples 1, 2 and 3 of the present invention3Bi2Cl9(PQDs) (0.5%, 1%, 3%) of Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Microsphere visible-light-driven photocatalyst and pure-phase Cs3Bi2Cl9(PQDs) and (BiO)2CO3A comparison graph of the degradation efficiency of the microspheres for NO purification under visible light conditions;
FIG. 9 shows the loading of 1% Cs prepared in example 2 of the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3ESR (. O) of microsphere visible light catalyst2 -) Graph (ESR is an abbreviation for Electron Spin Resonance);
FIG. 10 shows the loading of 1% Cs prepared in example 2 of the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3ESR (. OH) diagram of microsphere visible light catalyst;
FIG. 11 shows 1% loading of Cs prepared in example 2 of the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3And (3) a test chart of the degradation stability of the microsphere visible-light-driven photocatalyst under the visible light condition.
Detailed Description
The technical solution of the present invention is further explained with reference to the drawings and the embodiments.
Example 1
As shown in FIG. 1, 75.75g of CsCl and 94.6g of BiCl were weighed out3Added to 5ml of DMSO (dimethyl sulfoxide) and the solution was dispersed by sonication. Adding the solution completely dispersed by ultrasonic into 250ml of acetone solution which is stirred, reacting for 1min, then directly centrifuging the reaction solution, drying the obtained reaction product at 60 ℃ to obtain Cs3Bi2Cl9(PQDs); dissolving 0.46g of anhydrous sodium carbonate in 65mL of deionized water, transferring the solution to a 100mL high-pressure hydrothermal kettle, stirring for 10min, adding 1.6g of bismuth citrate, stirring for 30min, reacting at 160 ℃ for 24h, taking out a reaction product after the reaction is finished, centrifugally washing the reaction product, drying water and ethanol once at 60 ℃ to obtain the nanosheet self-assembly (BiO)2CO3Microsphere powder; finally 0.004g of Cs3Bi2Cl9(PQDs) with 0.8g of (BiO)2CO3Transferring the microspheres into a beaker filled with 200ml of isopropanol, performing ultrasonic treatment for 20min, stirring for 4h, directly centrifuging the solution, and drying at 60 ℃ to obtain 0.5% of Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3And (3) microsphere powder.
Example 2
As shown in FIG. 1, 75.75g of CsCl and 94.6g of BiCl were weighed out3Added to 5ml of DMSO (dimethyl sulfoxide) and the solution was dispersed by sonication. Adding the solution completely dispersed by ultrasonic into 250ml of acetone solution which is stirred, reacting for 1min, then directly centrifuging the reaction solution to obtain a reaction productDrying at 60 ℃ to obtain Cs3Bi2Cl9(PQDs); dissolving 0.46g of anhydrous sodium carbonate in 65mL of deionized water, transferring the solution to a 100mL high-pressure hydrothermal kettle, stirring for 10min, adding 1.6g of bismuth citrate, stirring for 30min, reacting at 160 ℃ for 24h, taking out a reaction product after the reaction is finished, centrifugally washing the reaction product, drying water and ethanol once at 60 ℃ to obtain the nanosheet self-assembly (BiO)2CO3Microsphere powder; finally 0.008g of Cs3Bi2Cl9(PQDs) with 0.8g of (BiO)2CO3Transferring the microspheres into a beaker filled with 200ml of isopropanol, performing ultrasonic treatment for 20min, stirring for 4h, directly centrifuging the solution, and drying at 60 ℃ to obtain 1% of Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3And (3) microsphere powder.
Example 3
As shown in FIG. 1, 75.75g of CsCl and 94.6g of BiCl were weighed out3Added to 5ml of DMSO (dimethyl sulfoxide) and the solution was dispersed by sonication. Adding the solution completely dispersed by ultrasonic into 250ml of acetone solution which is stirred, reacting for 1min, then directly centrifuging the reaction solution, drying the obtained reaction product at 60 ℃ to obtain Cs3Bi2Cl9(PQDs); dissolving 0.46g of anhydrous sodium carbonate in 65mL of deionized water, transferring the solution to a 100mL high-pressure hydrothermal kettle, stirring for 10min, adding 1.6g of bismuth citrate, stirring for 30min, reacting at 160 ℃ for 24h, taking out a reaction product after the reaction is finished, centrifugally washing the reaction product, drying water and ethanol once at 60 ℃ to obtain the nanosheet self-assembly (BiO)2CO3Microsphere powder; finally, 0.024g of Cs3Bi2Cl9(PQDs) with 0.8g of (BiO)2CO3Transferring the microspheres into a beaker filled with 200ml of isopropanol, performing ultrasonic treatment for 20min, stirring for 4h, directly centrifuging the solution, and drying at 60 ℃ to obtain Cs with the load of 3%3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3And (3) microsphere powder.
Cs prepared by the present invention in example 1, example 2 and example 33Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The microsphere visible-light-induced photocatalyst is characterized, and the Cs can be known3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The microsphere visible-light-driven photocatalyst has the following characteristics:
(1) for Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Microsphere visible-light-driven photocatalyst and pure-phase Cs3Bi2Cl9(PQDs) and (BiO)2CO3XRD analysis of the microspheres, as shown in FIG. 2, confirmed Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Microsphere visible light catalysts are integral and stable (BiO)2CO3The crystal structure of (1).
(2) For Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3XPS analysis of microspherical visible-light-driven photocatalyst, as shown in FIGS. 3 and 4, confirmed that Cs were prepared according to examples 1, 2 and 3 of the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Cs in microsphere visible-light-induced photocatalyst3Bi2Cl9(PQDs) successfully loaded and the composite and background accounted for electron transfer direction by shifts in binding energy of the same element; for Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Microsphere visible light catalyst TEM analysis and phase pure (BiO)2CO3SEM analysis of the microspheres, as shown in FIGS. 5 and 6, confirmed Cs3Bi2Cl9(PQDs) have been uniformly loaded on (BiO)2CO3The surface of the microsphere is a solid microsphere formed by self-assembling nano sheets, the diameter of the microsphere is 1.20 +/-0.40 mu m, and the thickness of the nano sheets is about 20 nm.
(3) For Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The microsphere visible-light photocatalyst was subjected to UV-Vis DRS analysis, as shown in FIG. 7, and testedRange of photoresponse, evidence of Cs3Bi2Cl9Introduction of (PQDs) energy enhancement (BiO)2CO3Absorption of light by the microspheres from the ultraviolet-visible-infrared region.
Cs provided by embodiments 1, 2, and 3 of the present invention by degrading Nitric Oxide (NO)3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3And testing the photocatalytic performance of the microsphere visible-light-driven photocatalyst. The test procedure was as follows:
1. 0.2g of Cs prepared in example3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The microsphere visible-light-induced photocatalyst is arranged on the glass disc;
2. four small fans are arranged around the reactor;
3. in the dark, when the NO concentration reaches equilibrium, Cs is irradiated with 150W tungsten halogen lamp3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The microsphere visible-light photocatalyst is used for 30 min.
The conditions of the above catalytic performance test process were: relative humidity 60%; the oxygen content is 21%; the flow rate of the NO gas flow is 3.3L/min; the initial concentration of NO was 600. mu.g/kg; before the irradiation of the halogen tungsten lamp, a cut-off filter with the wavelength of 420nm is used for filtering ultraviolet light.
Cs provided by the invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The degradation effect of the microsphere visible-light-driven photocatalyst on NO degradation is as follows:
1、Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The degradation rate of the microsphere visible-light-driven photocatalyst to NO is 30-50% (as shown in figure 8), which is higher than that of pure phase (BiO)2CO3The rate of degradation of NO by the microspheres; the degradation rate is calculated by the formula of eta (%) ═ 1-C/C0)×100％，C0C is the instantaneous concentration of NO.
2. Superoxide ion (. O)2 -) And hydroxyl ion (. OH) is Cs3Bi2Cl9(PQDs) loaded nanoparticlesSheet self-assembly (BiO)2CO3The microsphere visible photocatalyst degrades the most dominant free radicals of NO under visible light conditions (as shown in fig. 9, 10).
3、Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The microsphere visible-light-driven photocatalyst can degrade NO (shown in figure 11) more stably.
Cs prepared in example 13Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The loading capacity of the microspheres is 0.5 percent of Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The microsphere visible-light-driven photocatalyst is used for degrading NO, and the specific process is as follows: 0.2g of Cs prepared in example was mixed under conditions of 60% relative humidity, 21% oxygen content, 3.3L/min flow rate of NO stream, and 600. mu.g/kg initial concentration of NO3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The microsphere visible-light-induced photocatalyst is arranged on the glass disc; four small fans are arranged around the reactor; under dark condition, using a 420nm cut-off filter to filter out ultraviolet light, and when NO concentration reaches balance, using a 150W halogen tungsten lamp to irradiate Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Carrying out microspherical visible light catalyst for 30 min; and finally, turning off the lamp. Cs obtained in example 1 of the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The degradation rate of the microsphere visible-light-driven photocatalyst to NO is 38.6 percent, and Cs is relative to two background products3Bi2Cl9(PQDs) loaded (BiO)2CO3The degradation rate of the microspheres to NO is improved.
Cs prepared in example 23Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The loading capacity of the microspheres is 1% of Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The procedure of the degradation test of NO by the microsphere visible-light-driven photocatalyst is the same as that of example 1. Result in the practice of the inventionCs prepared in example 23Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The degradation rate of the microsphere visible-light-driven photocatalyst to NO is 47.1%, compared with Cs3Bi2Cl9(PQDs) and (BiO)2CO3The activity of visible light for degrading NO is improved.
Cs prepared in example 33Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The loading capacity of the microspheres is 3% of Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The procedure of the degradation test of NO by the microsphere visible-light-driven photocatalyst is the same as that of the example 1 and the example 2. Cs obtained in example 4 of the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The degradation rate of the microsphere visible-light-driven photocatalyst to NO is 39.9%.
It can be seen that Cs is passed through3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3Degradation of NO by microsphere visible-light-driven photocatalyst relative to pure-phase Cs3Bi2Cl9(PQDs) and (BiO)2CO3For purification of NO by the microspheres, Cs3Bi2Cl9(PQDs) load (BiO)2CO3The degradation rate of the microspheres is obviously improved.
It is to be noted that Cs provided in the examples of the present invention3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3The catalysis mechanism of the microsphere visible-light-driven photocatalyst on sulfide, volatile organic compounds, non-NO nitrogen oxides and other air pollutants is the same as that of NO, so that the microsphere visible-light-driven photocatalyst has a representative NO degradation test.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (9)
1. Cs (volatile organic Compounds)3Bi2Cl9(PQDs) supported nanosheet self-assembled bismuth subcarbonate microsphere visible light catalyst, which is characterized in that: comprises a carrier and a carried object, wherein the carrier is Cs3Bi2Cl9(PQDs) of the supported material, which is a nanosheet self-assembly (BiO)2CO3Microspheres of said Cs3Bi2Cl9(PQDs) self-Assembly with nanosheets (BiO)2CO3The microspheres form a heterojunction for accelerating carrier mobility.
2. The Cs of claim 13Bi2Cl9The preparation method of the (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst is characterized by comprising the following steps: the preparation method comprises the following steps:
step S1, weighing CsCl and BiCl3Adding the solution into DMSO (dimethyl sulfoxide) to form a solution, adding the solution subjected to ultrasonic dispersion into a reaction solvent, reacting for 1-30 min, obtaining a reaction product by an anti-solvent recrystallization method, directly centrifuging the reaction product, and drying at 60 ℃ to obtain Cs3Bi2Cl9(PQDs)；
S2, weighing soluble carbonate into an aqueous solution, and then transferring the aqueous solution into a high-pressure hydrothermal kettle to stir for 1-60 min; adding a bismuth-containing precursor into the aqueous solution, stirring for 20-120 min, heating at 120-200 ℃ for 12-48 h through hydrothermal reaction to obtain a reaction product, centrifugally washing the reaction product (respectively using water and ethanol once), and drying at 60 ℃ to obtain a nanosheet self-assembly (BiO)2CO3Microsphere powder;
s3, mixing the Cs3Bi2Cl9(PQDs) and nanosheet self-assembly (BiO)2CO3Adding the microsphere powder into a reaction solvent, carrying out ultrasonic treatment for 10-30 min, stirring for 3-5 h, directly centrifuging, and drying at 60 ℃ to obtain Cs3Bi2Cl9(PQDs) load nanosheet self-assembly (BiO)2CO3And (3) microsphere powder.
3. A Cs of claim 23Bi2Cl9The preparation method of the (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst is characterized by comprising the following steps: the reaction solvent is any one of ethanol, isopropanol and acetone.
4. A Cs of claim 23Bi2Cl9The preparation method of the (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst is characterized by comprising the following steps: the soluble carbonate salt comprises one or more of anhydrous sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate.
5. A Cs of claim 23Bi2Cl9The preparation method of the (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst is characterized by comprising the following steps: the precursor containing bismuth is one or more of bismuth nitrate pentahydrate, bismuth citrate and bismuth ammonium citrate.
6. A Cs of claim 23Bi2Cl9The preparation method of the (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst is characterized by comprising the following steps: in step S3, adding the Cs3Bi2Cl9(PQDs) and (BiO)2CO3The mass ratio of the microsphere powder is (0.004-0.040): 0.8.
7. a Cs of claim 23Bi2Cl9The preparation method of the (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst is characterized by comprising the following steps: in step S1, this solution dispersed with ultrasound was added to the reaction solvent for a reaction time of 1 min.
8. A Cs of claim 23Bi2Cl9The preparation method of the (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst is characterized by comprising the following steps: in step S2, weighing soluble carbonate into the aqueous solution, and then transferring the aqueous solution to a high-pressure hydrothermal kettle to stir for 1 min; adding a bismuth-containing precursor into the aqueous solution, stirring for 20min, and heating for 24h at 160 ℃ through a hydrothermal reaction to obtain a reaction product b.
9. A Cs of claim 23Bi2Cl9The preparation method of the (PQDs) supported nanosheet self-assembled bismuth oxycarbonate microsphere visible-light-driven photocatalyst is characterized by comprising the following steps: in step S3, the Cs is added3Bi2Cl9(PQDs) and (BiO)2CO3The mass ratio of the microsphere powder is 0.008: 0.8.
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