CN113509952B - Ytterbium and erbium co-doped Yb-Er/g-C 3 N 4 Photocatalyst and synthesis method and application thereof - Google Patents
Ytterbium and erbium co-doped Yb-Er/g-C 3 N 4 Photocatalyst and synthesis method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 52
- 229910052769 Ytterbium Inorganic materials 0.000 title claims abstract description 19
- 229910052691 Erbium Inorganic materials 0.000 title claims abstract description 18
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 title claims abstract description 17
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims abstract description 7
- 229940075624 ytterbium oxide Drugs 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical group [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 claims description 19
- 229940043267 rhodamine b Drugs 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 19
- 238000005215 recombination Methods 0.000 abstract description 6
- 230000006798 recombination Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 12
- 238000006731 degradation reaction Methods 0.000 description 12
- 239000007788 liquid Substances 0.000 description 8
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000002835 absorbance Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
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- 238000005286 illumination Methods 0.000 description 4
- 229910052755 nonmetal Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000002019 doping agent Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000004776 molecular orbital Methods 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
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- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 239000003344 environmental pollutant Substances 0.000 description 1
- KWMNWMQPPKKDII-UHFFFAOYSA-N erbium ytterbium Chemical compound [Er].[Yb] KWMNWMQPPKKDII-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- -1 ytterbium-erbium ion Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C09K11/0883—Arsenides; Nitrides; Phosphides
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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- C02F2305/10—Photocatalysts
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Abstract
The invention discloses ytterbium and erbium co-doped Yb-Er/g-C 3 N 4 Photocatalyst, and a synthesis method and application thereof. The g-C is prepared by taking melamine as a raw material and adopting a high-temperature calcination method 3 N 4 (ii) a Yb-Er/g-C is prepared from ytterbium oxide and erbium oxide by microwave-assisted heating method 3 N 4 . Ytterbium and erbium codoped Yb-Er/g-C prepared by the invention 3 N 4 The photocatalysis inhibits the recombination of photon-generated carriers, and can effectively improve the energy conversion efficiency, thereby improving the visible light and near infrared light catalysis efficiency. The organic pollutants are degraded under the irradiation of visible light and near infrared light, yb-Er/g-C 3 N 4 Has important practical application value in environmental purification and clean energy production.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic materials, and particularly relates to preparation of Yb-Er/g-C by a microwave-assisted heating method 3 N 4 A method for preparing the photocatalyst and application thereof.
Background
With the development of modern society increasingly restricted by energy and environmental problems, the photocatalytic technology is receiving increasingly wide attention. The photocatalytic material can be hydrolyzed by sunlight to produce hydrogen, and can decompose harmful substances, thereby solving the energy and environmental problems in human development. Organic graphite phase carbon nitride (g-C) 3 N 4 ) The photocatalyst consists of C and N elements only, and shows great potential of the nonmetal photocatalyst in eliminating pollutants. g-C 3 N 4 The spinel material is a stable spinel material, has proper band gap, unique performance and stable photochemical characteristics, is widely applied to the fields of pigments, fireproof materials, anode materials for photochemical water splitting hydrogen production and lithium ion batteries and the like, and is also a high-efficiency photocatalyst for degrading organic pollutants by visible light.
However, g-C prepared by conventional methods 3 N 4 Not only is the specific surface area small, but also the quantum efficiency is low due to the rapid recombination of photogenerated electrons and holes, which limits more applications. It is therefore necessary to investigate the modification of semiconductor photocatalysts, the purpose and effect of which include improved excited charge separation, suppression of carrier recombination to improve quantum efficiency.
The doping modification method is used for improving the electronic structure and the surface property of the semiconductor materialOne commonly used and effective means of doping materials is mainly classified into non-metal doping and metal doping. g-C 3 N 4 A layered structure with voids that facilitates uniform doping of the dopant. Dopants and g-C 3 N 4 The original molecular orbitals undergo orbital hybridization, and then the energy band structure, the electronic structure and the optical properties of the molecular orbitals are changed. With metal ion pairs g-C 3 N 4 After doping, the g-C is influenced by the coordination bond formed between the doped metal ion and the nitrogen atom 3 N 4 The electronic structure reduces the band gap energy, improves the absorption of visible light, and inhibits the recombination of photo-generated electron-hole pairs, thereby improving the photocatalytic efficiency.
Disclosure of Invention
The invention aims to provide a method for synthesizing Yb-Er/g-C by a microwave-assisted heating method 3 N 4 A preparation method of the photocatalyst.
The technical scheme adopted by the invention is as follows: ytterbium and erbium co-doped Yb-Er/g-C 3 N 4 A photocatalyst ytterbium and erbium co-doped Yb-Er/g-C 3 N 4 Photocatalyst in molar ratio of Yb 3+ :Er 3+ :g-C 3 N 4 ＝(0.1-0.02):(0.01-0.005):1。
Ytterbium and erbium co-doped Yb-Er/g-C 3 N 4 The preparation method of the photocatalyst comprises the following steps:
1) Calcining melamine in nitrogen atmosphere to obtain g-C 3 N 4 ；
2) G to C 3 N 4 And contains Yb 3+ Solution and Er-containing 3+ The solution is evenly mixed under the ultrasonic condition, heated, centrifuged and dried under the microwave condition to obtain Yb-Er/g-C 3 N 4 A photocatalyst.
Preferably, in the preparation method, in the step 1), the temperature rise rate is controlled to be 5 ℃/min, the temperature is raised to 500-550 ℃, and the mixture is roasted at 500-550 ℃ for 4-5h.
Preferably, the above-mentioned process for the production of Yb 3+ The preparation method of the solution comprises the following steps: dissolving appropriate amount of ytterbium oxide in concentrated hydrochloric acid, heating and stirring, evaporating to dryness, and adding appropriate amount of ytterbium oxideDeionized water to obtain Yb 3+ And (3) solution.
Preferably, the preparation method is that the Er is contained 3+ The preparation method of the solution comprises the following steps: dissolving appropriate amount of erbium oxide in concentrated hydrochloric acid, heating and stirring, evaporating to dryness, and adding appropriate amount of deionized water to obtain Er-containing solution 3+ And (3) solution.
Preferably, in the above preparation method, step 2), the heating under microwave conditions is: reacting for 3-5min under 700W.
Preferably, in the above preparation method, in step 2), the drying step is: drying for 12h at the temperature of 60-80 ℃.
The ytterbium and erbium co-doped Yb-Er/g-C provided by the invention 3 N 4 The photocatalyst is applied to the catalytic degradation of organic dye under visible light or near infrared light.
Preferably, the organic dye is rhodamine B.
The invention has the beneficial effects that:
g-C 3 N 4 the non-metal N-type semiconductor is a non-metal N-type semiconductor, is widely concerned by people due to good chemical stability, thermal stability and photoelectric characteristics, has a forbidden band width of 2.7eV, can absorb visible light with a wavelength of less than 460nm, but has low quantum efficiency, weak visible light absorption response, high charge recombination, small specific surface area and easy recombination of photo-generated electrons and holes, and thus, has low photocatalytic activity. To increase g-C 3 N 4 The invention uses ytterbium oxide and erbium oxide to modify graphite-like phase carbon nitride to prepare a photocatalytic material with near infrared light catalytic effect. Yb-Er/g-C prepared by the invention 3 N 4 The low photoluminescence intensity can effectively improve the efficiency of energy conversion. The photo-generated carriers are combined when being transported to the surface of the semiconductor photocatalyst, so that the light is emitted and the heat is generated, and the photocatalytic efficiency of the semiconductor photocatalyst is influenced. Treated g-C 3 N 4 The infrared photocatalysis can be realized under the irradiation of 980nm infrared light.
Drawings
FIG. 1 shows the preparation of different molar ratiosYb-Er/g-C of 3 N 4 XRD pattern of photocatalyst.
FIG. 2 shows g-C prepared in example 1 3 N 4 (a) And Yb2% -Er0.5%/g-C 3 N 4 (b) SEM image of (d).
FIG. 3 shows Yb2% -Er0.5%/g-C prepared in example 1 3 N 4 A graph of rhodamine B catalytic degradation by the photocatalyst under visible light.
FIG. 4 shows Yb-Er/g-C prepared in different molar ratios 3 N 4 A comparison graph of rhodamine B efficiency catalytic degradation by a photocatalyst under visible light.
FIG. 5 shows Yb2% -Er0.5%/g-C prepared in example 1 3 N 4 A graph of rhodamine B catalytic degradation of the photocatalyst under near infrared light is shown.
Detailed Description
Example 1 Yb-Er Co-doped Yb-Er/g-C 3 N 4 Photocatalytic (I) pure g-C 3 N 4 Preparation of
Melamine was placed in an alumina crucible, heated to 550 ℃ from room temperature at a heating rate of 5 ℃ per minute in a tube furnace (under a constant flow of nitrogen gas), held at 550 ℃ for 4 hours, and then naturally cooled to room temperature. The nitrogen was turned off and the pale yellow solid was taken out and ground to a powder to give pure g-C 3 N 4 A photocatalyst.
(II) Yb2% -Er0.5%/g-C 3 N 4 Preparation of
1) Dissolving 0.4925g ytterbium oxide in 10mL concentrated hydrochloric acid, heating, stirring, dissolving, evaporating, adding deionized water again to obtain Yb 3+ Yb concentration of 0.00005mol/mL 3+ And (3) solution.
2) Dissolving 0.47815g of erbium oxide in 10mL of concentrated hydrochloric acid, heating, stirring, dissolving, evaporating to dryness, and adding deionized water again to obtain Er 3+ Er with the concentration of 0.00005mol/mL 3+ And (3) solution.
3) At 0.92g (0.01 mol) of pure g-C 3 N 4 To the photocatalyst, 4ml of Yb was added 3+ Solution, 1ml Er 3+ Mixing the solution under ultrasonic condition, stirring, transferring into crucible, and standing until the solution is micro-scaleReacting in a wave furnace for 5min under the condition of 700W, centrifuging, taking the precipitate, drying in an oven at 80 ℃ for 12h to obtain the molar ratio of Yb 3+ :Er 3+ :g-C 3 N 4 Yb-Er/g-C of =0.02 3 N 4 Photocatalytic, labeled Yb2% -Er0.5%/g-C 3 N 4 A photocatalyst.
Yb2% -Er1%/g-C 3 N 4 Preparation of
1) Dissolving 0.4925g ytterbium oxide in 10mL concentrated hydrochloric acid, heating, stirring, dissolving, evaporating, adding deionized water again to obtain Yb 3+ Yb concentration of 0.00005mol/mL 3+ And (3) solution.
2) Dissolving 0.47815g of erbium oxide in 10mL of concentrated hydrochloric acid, heating, stirring, dissolving, evaporating, adding deionized water again to obtain Er 3+ Er with the concentration of 0.00005mol/mL 3+ And (3) solution.
3) At 0.92g (0.01 mol) of pure g-C 3 N 4 To the photocatalyst, 4ml of Yb was added 3+ Solution, 2ml Er 3+ Mixing the solution under ultrasonic condition, stirring, transferring into crucible, placing into microwave oven, reacting at 700W for 5min, centrifuging, oven drying the precipitate at 80 deg.C for 12 hr to obtain Yb 3+ :Er 3+ :g-C 3 N 4 Yb-Er/g-C of =0.02 3 N 4 Photocatalytic, marked Yb2% -Er1%/g-C 3 N 4 A photocatalyst.
(IV) Yb10% -Er1%/g-C 3 N 4 Preparation of
1) Dissolving 0.4925g ytterbium oxide in 10mL concentrated hydrochloric acid, heating, stirring, dissolving, evaporating, adding deionized water again to obtain Yb 3+ Yb concentration of 0.00005mol/mL 3+ And (3) solution.
2) Dissolving 0.47815g of erbium oxide in 10mL of concentrated hydrochloric acid, heating, stirring, dissolving, evaporating, adding deionized water again to obtain Er 3+ Er with concentration of 0.00005mol/mL 3+ And (3) solution.
3) At 0.92g (0.01 mol) of pure g-C 3 N 4 20ml of Yb was added to the photocatalyst 3+ Solution, 2ml Er 3+ Solution in the form of a solutionMixing and stirring uniformly under sonic condition, transferring into crucible, placing into microwave oven, reacting for 5min under 700W condition, centrifuging, collecting precipitate, oven drying at 80 deg.C for 12 hr to obtain molar ratio of Yb 3+ :Er 3+ :g-C 3 N 4 Yb-Er/g-C of =0.1 3 N 4 Photocatalytic, marked as Yb10% -Er1%/g-C 3 N 4 A photocatalyst.
(V) detection
FIG. 1 shows Yb-Er/g-C prepared in different molar ratios 3 N 4 XRD pattern of photocatalyst. Wherein (a) is unmodified g-C 3 N 4 (b) Yb2% -Er0.5%/g-C 3 N 4 (C) Yb2% -Er1%/g-C 3 N 4 ，(d)Yb10％-Er1％/g-C 3 N 4 . As can be seen from FIG. 1, the samples all exhibited g-C 3 N 4 Two characteristic peaks (13 ° and 27.3 °). One is 2 θ =13 °, which is mainly due to the characteristic diffraction of the in-plane 3 s-triazine unit structure of the material, with a miller index of (100). The other is 2 θ =27.3 °, which is mainly due to a diffraction peak formed by the interlayer periodic packing, and the miller index thereof is (002). Prepared Yb 3+ 、Er 3+ Codoped g-C 3 N 4 Catalyst and unmodified g-C 3 N 4 The positions of diffraction peaks are consistent, which shows that g-C is doped 3 N 4 The crystal structure of (2) is not changed, and is a laminar carbon nitride structure formed by stacking graphite layers. And no characteristic diffraction peak of ytterbium, erbium simple substance and oxide thereof is found in XRD spectrum, which indicates that ytterbium-erbium ion co-doped graphite phase carbon nitride Yb-Er/g-C is successfully prepared 3 N 4 。
FIG. 2 is g-C of preparation 3 N 4 (a) And Yb2% -Er0.5%/g-C 3 N 4 (b) SEM image of (d). As can be seen from fig. 2, the samples all exhibited irregular block structures.
Example 2 Yb-Er codoped Yb-Er/g-C 3 N 4 Application of photocatalyst in catalytic degradation of organic dye under visible light
The method comprises the following steps: with a xenon lamp (300W, 20A) as a light source, 0.05g of ytterbium-erbium co-doped Yb-Er/g-C 3 N 4 The photocatalyst is placed in a 100ml beaker, and 50ml of rhodamine B solution to be degraded with the concentration of 10mg/L is added into the beaker. Considering that a sample has certain adsorbability, the rhodamine B solution mixed with the photocatalytic material is stirred for 30min in a dark place, and 2ml of the rhodamine B solution is sampled before and after the dark place, so that an adsorption-desorption balance state is formed between the photocatalyst and the rhodamine B, and errors caused by adsorption are avoided. And finally, aligning the lamp cap of the xenon lamp to the photocatalytic system to be tested. Sampling 2ml at regular intervals after illumination, placing the sampled sample liquid in a centrifuge for 5min at 8000rpm, placing supernatant liquid in a cuvette, testing the concentration of residual rhodamine B in the sample liquid by uv-3600, and evaluating the catalytic performance of the catalyst sample by the absorbance of the sample liquid.
FIG. 3 is a graph of Yb2% -Er0.5%/g-C prepared in example 1 3 N 4 A graph of rhodamine B catalytic degradation by the photocatalyst under visible light. As can be seen from fig. 3, under irradiation of visible light, the absorption intensity of the characteristic absorption peak of the RhB solution at 550nm gradually decreases with time, which indicates that the molecular structure of RhB is destroyed, resulting in a decrease in its absorbance. It can be seen that Yb2% -Er0.5%/g-C 3 N 4 The photocatalyst has good visible light catalytic performance.
FIG. 4 shows Yb-Er/g-C prepared in different molar ratios 3 N 4 A comparison graph of rhodamine B efficiency catalytic degradation by a photocatalyst under visible light. Wherein A is unmodified g-C 3 N 4 B is Yb2% -Er0.5%/g-C 3 N 4 C is Yb2% -Er1%/g-C 3 N 4 D is Yb10% -Er1%/g-C 3 N 4 . As can be seen from FIG. 4, ytterbium and erbium co-doped Yb-Er/g-C of the present invention 3 N 4 The degradation efficiency of the photocatalyst is obviously higher than that of unmodified g-C 3 N 4 Wherein the sample Yb2% -Er1%/g-C 3 N 4 Most obviously, the degradation efficiency of rhodamine B is improved from 38.6 percent to 93.4 percent after 52min illumination. Yb2% -Er0.5%/g-C under the same illumination time 3 N 4 The degradation efficiency is 88.2 percent, yb10 percent to Er1 percent/g-C 3 N 4 The content was 92.7%.
Examples3 Yb-Er/g-C co-doped with Yb and Er 3 N 4 Application of photocatalyst in catalytic degradation of organic dye under near infrared light
Yb2% -Er0.5%/g-C prepared as in example 1 3 N 4 And (5) carrying out a performance test on the photocatalytic material by the photocatalyst.
The method comprises the following steps: using 980nm laser as light source, weigh 0.1g Yb2% -Er0.5%/g-C 3 N 4 The photocatalyst is placed in a condensation cup, and 30ml of rhodamine B solution to be degraded with the concentration of 10mg/L is added into the condensation cup. Considering that a sample has certain adsorbability, the rhodamine B solution mixed with the photocatalytic material is stirred for 1 hour in a dark place, and 2ml of the rhodamine B solution is sampled before and after the light is shielded, so that an adsorption-desorption balance state is formed between the photocatalyst and the rhodamine B, and errors caused by adsorption are avoided. Finally, the light source is directed at the photocatalytic system to be tested. Sampling 2ml every 2h after illumination, placing the sampled sample liquid in a centrifuge for 5min at 8000rpm, placing supernatant liquid in a cuvette, testing the concentration of residual rhodamine B in the sample liquid by uv-3600, and evaluating the catalytic performance of the catalyst sample according to the absorbance of the sample liquid.
FIG. 5 shows Yb2% -Er0.5%/g-C prepared in example 1 3 N 4 A graph of rhodamine B catalytic degradation of the photocatalyst under near infrared light is shown. As shown in fig. 5, under 980nm light irradiation, the absorption intensity of the characteristic absorption peak of the RhB solution at 550nm gradually decreases with time, which indicates that the molecular structure of RhB is destroyed, resulting in a decrease in its absorbance. It can be seen that Yb2% -Er0.5%/g-C 3 N 4 The photocatalyst has infrared light photocatalysis performance to a certain extent.
Claims (7)
1. Ytterbium and erbium co-doped Yb-Er/g-C 3 N 4 The photocatalyst is characterized in that ytterbium and erbium are codoped with Yb-Er/g-C 3 N 4 Photocatalyst in molar ratio of Yb 3+ :Er 3+ : g-C 3 N 4 =(0.1-0.02): (0.01-0.005):1；
Ytterbium and erbium co-doped Yb-Er/g-C 3 N 4 A method for preparing a photocatalyst, comprisingThe following steps:
1) Calcining melamine in nitrogen atmosphere to obtain g-C 3 N 4 ；
2) G to C 3 N 4 And contains Yb 3+ Solution and Er containing 3+ Uniformly mixing the solution under the ultrasonic condition, heating and reacting for 3-5min under the microwave condition of 700W, centrifuging and drying to obtain Yb-Er/g-C 3 N 4 A photocatalyst.
2. The ytterbium and erbium co-doped Yb-Er/g-C of claim 1 3 N 4 The photocatalyst is characterized in that in the step 1), the temperature rise rate is controlled to be 5 ℃/min, the temperature is raised to 500-550 ℃, and the photocatalyst is roasted for 4-5h at 500-550 ℃.
3. The ytterbium and erbium co-doped Yb-Er/g-C of claim 1 3 N 4 The photocatalyst is characterized in that the photocatalyst contains Yb 3+ The preparation method of the solution comprises the following steps: dissolving appropriate amount of ytterbium oxide in concentrated hydrochloric acid, heating and stirring, evaporating to dryness, and adding appropriate amount of deionized water to obtain Yb-containing material 3+ And (3) solution.
4. The method of claim 1 wherein ytterbium and erbium are codoped with Yb-Er/g-C 3 N 4 The photocatalyst is characterized in that the Er is contained 3+ The preparation method of the solution comprises the following steps: dissolving appropriate amount of erbium oxide in concentrated hydrochloric acid, heating and stirring, evaporating to dryness, and adding appropriate amount of deionized water to obtain Er-containing solution 3+ And (3) solution.
5. The ytterbium and erbium co-doped Yb-Er/g-C of claim 1 3 N 4 The photocatalyst is characterized in that in the step 2), the drying is as follows: drying at 80 deg.C for 12h.
6. The method of claim 1 wherein Yb and Er are codoped with Yb-Er/g-C 3 N 4 The application of the photocatalyst in catalyzing and degrading organic dye under visible light or near infrared light.
7. Use according to claim 6, wherein the organic dye is rhodamine B.
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| Title |
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| "Enhanced upconversion luminescence of BiOCl:Yb3+,Er3+ nanosheets via carbon dot modification and their optical temperature sensing";Taizhong Xiao et al.;《Materials Chemistry Frontiers》;20210325;第5卷;第4280-4290页 * |
| "Rare-Earth Single Erbium Atoms for Enhanced Photocatalytic CO2 Reduction";Shufang Ji et al.;《Angewandte Chemie International Edition》;20200415;第59卷;第10651-10657页 * |
| "类石墨相氮化碳光催化剂的改性研究";王佰强;《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》;20210115(第01期);第12、14和23页 * |
| "铒掺杂g-C3N4催化剂的合成及其红光催化降解活性的研究";徐启立等;《人工晶体学报》;20201231;第49卷;引言、第1.2-1.3节 * |
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