CN111715265A - Rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material and preparation method and application thereof - Google Patents
Rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material and a preparation method and application thereof. G to C3N4Placing into deionized water, ultrasonic stripping to obtain suspension, adding Ce (NO)3)3·6H2O，NH4F，Pr(NO3)3·6H2And adding O into the suspension, adjusting the pH of the adjusting system to 4-5, and magnetically stirring and uniformly mixing. Then transferring the mixture into a high-pressure hydrothermal reaction kettle with a stainless steel outer sleeve and a polytetrafluoroethylene inner containerAnd carrying out hydrothermal reaction in a hydrothermal kettle at 160-180 ℃ for 10-16 hours to obtain the rare earth ion doped cerium trifluoride/graphite phase carbon nitride up-conversion composite photocatalytic material. The material is applied to the field of photocatalytic degradation of dye wastewater, and the degradation rate of the material to methylene blue reaches 93% after visible light illumination for 60 min.
Description
Technical Field
The invention relates to the field of new chemical materials, and particularly relates to a rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material and a preparation method and application thereof.
Background
With the development of textile industry in China, a large amount of organic dye wastewater is generated. If the waste water cannot be treated properly, the environment can be seriously polluted and the human health can be threatened. The current common industrial dye wastewater treatment methods at home and abroad include biological treatment, chemical flocculation, chemical oxidation, adsorption, electrochemical methods and the like. But all have the problems of certain secondary pollution, low treatment efficiency, high treatment and operation cost and the like, can not meet the sustainable development requirement, and the photocatalytic degradation technology applied to the field of environmental control has the advantages of high efficiency, greenness, economy, effective utilization of solar energy and the like.
Graphite phase carbon nitride (g-C)3N4) The organic semiconductor photocatalytic material has the advantages of simple preparation method, low cost, stable physical and chemical properties, environmental friendliness, proper forbidden bandwidth, visible light catalytic activity and the like, but has some problems in the practical application in the field of environmental photocatalysis, such as faster photoproduction electron-hole recombination, low quantum efficiency and poor absorption capacity for visible light in sunlight (the visible light with the wavelength of more than 460nm cannot be absorbed).
Disclosure of Invention
In order to fully utilize most visible light in solar energy, suppress recombination of photogenerated electrons and holes, and improve photocatalytic efficiency, it is generally one of effective methods to combine a plurality of semiconductors to form a heterostructure. Cerium trifluoride (CeF)3) The rare earth fluoride material is a functional rare earth fluoride material, has unique optical property, has good up-conversion luminescence characteristic by doping, and can be used as a photocatalyst.
In order to solve the problems of low utilization rate of sunlight, easy recombination of photoproduction electron holes, low photocatalytic activity and the like, the invention provides a rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material and a preparation method and application thereof, the composite photocatalytic material has wider spectral response characteristic, and a heterojunction structure is constructed by growing rare earth doped cerium trifluoride nanoparticles with uniform particle size on the surface of two-dimensional graphite phase carbon nitride in situ; on one hand, rare earth ions doped with cerium trifluoride are used as a photocatalytic material to form a heterojunction structure with graphite-phase carbon nitride, so that the effective separation of photoproduction electrons and cavities is promoted; on the other hand, the rare earth ion doped cerium trifluoride is used as an up-conversion luminescent material, and can up-convert near infrared light or visible light into visible light or ultraviolet light, thereby expanding the spectral response range of the composite material and improving the photocatalytic activity.
According to the invention, the rare earth ion doped cerium trifluoride and graphite phase carbon nitride form a heterojunction, so that the composition of photo-generated electrons and holes is reduced, the photoresponse range of a semiconductor material is expanded, the utilization rate of sunlight is improved, and the photocatalytic activity is greatly improved.
A composite photocatalytic material doped with rare earth ions and cerium trifluoride-graphite phase carbon nitride belongs to an enhanced wide-spectrum response material and is prepared by doping rare earth ions with cerium trifluoride (CeF)3) And graphite phase carbon nitride, wherein the rare earth ion doped cerium trifluoride accounts for 10-50% of the mass of the graphite phase carbon nitride.
The preparation method of the rare earth ion doped cerium fluoride/graphite phase carbon nitride up-conversion enhanced type broad spectral response composite photocatalytic material comprises the following steps:
step 1, putting dicyanodiamine, melamine or urea into a mortar, grinding into fine powder, putting the fine powder into an oven at 60-100 ℃, drying for 6-12 hours, then putting the fine powder into the mortar, fully grinding, putting the powder after secondary grinding into a crucible, and then putting the crucible into a muffle furnace for calcination at 520 ℃ and 550 ℃ for 2-4 hours to obtain light yellow graphite phase carbon nitride powder; step 2, dissolving faint yellow graphite phase carbon nitride powder in deionized water, carrying out ultrasonic stripping for 30-60min to obtain a suspension, and then adding Ce (NO)3)3·6H2O or CeCl3·6H2O，NH4F or NaF, Pr (NO)3)3·6H2Adding O into the suspension, stirring, adjusting pH to 4-5 with acetic acid, transferring the system into stainless steel jacket PTFEReacting for 10-16 hours in a high-pressure hydrothermal reaction kettle with an ethylene liner at 160-180 ℃ to obtain a composite photocatalytic material crude product; wherein Pr is added3+And Ce3+In a molar ratio of 1:50-100, Ce3+And F-The molar ratio of (A) to (B) is 1:3-1: 5; and 3, taking a lower layer suspension of the crude product of the composite photocatalytic material, centrifuging for 3-5 times by using a mixed solution of deionized water and ethanol, cleaning, drying a sample, and grinding to obtain the rare earth ion doped cerium fluoride/graphite phase carbon nitride up-conversion enhanced type broad-spectrum response composite photocatalytic material.
The improvement is that the temperature rise speed in the calcination in the step 1 is 2-5 ℃/min.
As an improvement, the rotating speed of the centrifugation in the step 3 is 5000-7000r/min, the time is 5-10min, and the centrifugation times are 3 times.
The improvement is that the drying temperature in the step 3 is 80-100 ℃.
The pH value is adjusted by acetic acid in the above steps to inhibit the hydrolysis of cerium salt and prevent the formation of by-product Ce (OH)3；Pr3+Can further improve the CeF3The up-conversion performance of (2). Hydrothermal method on g-C3N4Surface in situ generation of Pr3+Doping of CeF3(CeF3:Pr3+) Nanocrystals can be prepared without destroying g-C3N4In a two-dimensional layered structure, CeF3:Pr3+Nanocrystals with g-C3N4Firmly combining to form a heterojunction structure; is favorable to Pr3+Into CeF3The crystal lattice of (a) forms a solid solution, resulting in a stable hexagonal structure of CeF3:Pr3+A crystal; meanwhile, the synthesized nano-crystal has uniform distribution, small particle size and large specific surface area, and improves the photocatalytic activity.
The application of the rare earth ion doped cerium fluoride/graphite phase carbon nitride up-conversion enhanced type broad-spectrum response composite photocatalytic material in degradation of dye wastewater.
Has the advantages that:
compared with the prior art, the rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material and the preparation method and application thereof have the following advantages:
1. rare earth Pr3+Doped CeF of3The nanocrystal can enhance the up-conversion luminescence property of the solid solution. CeF with up-conversion luminescence property3:Pr3+Crystals with g-C3N4Compounding indirectly enhances g-C3N4The spectral response range improves the utilization rate of visible light; the invention does not destroy g-C3N4Using CeF under the condition of two-dimensional layered structure3:Pr3+Crystals in g-C3N4In situ growth on the surface, Ce3+And F-In g-C3N4Surface static electricity is self-contained, in-situ growth and tight combination are realized, a composite photocatalytic material is obtained, and a heterojunction is formed; the defects of mechanical mixing, untight combination and incapability of forming a heterojunction structure are avoided.
2. CeF in the invention3:Pr3+Besides being used as an up-conversion luminescent material, the crystal improves the visible light utilization rate of the composite material, and simultaneously CeF3:Pr3+The crystal is used as a semiconductor material and an organic semiconductor material g-C3N4The heterojunction is formed by compounding, so that the effective separation of photoproduction electrons and holes can be further promoted, and the efficiency of degrading the dye by photocatalysis is improved.
3. Compared with other synthesis methods, the hydrothermal synthesis method can not damage the g-C3N4The two-dimensional layered structure has more stable synthesized nano crystal structure, smaller grain diameter, more uniform distribution and larger specific surface area, and is similar to two-dimensional g-C3N4The combination is tighter, and the photocatalytic activity is better.
Drawings
FIG. 1 is an XRD pattern of various materials of the present invention;
FIG. 2 is a TEM image of the composite photocatalytic material prepared in example 1;
FIG. 3 is an EDS spectrum of the composite photocatalytic material prepared in example 1;
FIG. 4 is a fluorescence plot of photocatalysts prepared according to various embodiments of the present invention, wherein 1 is 525nm, 2 is 560nm, 3 is 785nm, and 4 is 810 nm.
Detailed Description
A composite photocatalytic material doped with rare earth ions and cerium trifluoride-graphite phase carbon nitride belongs to an enhanced wide-spectrum response material and is prepared by doping rare earth ions with cerium trifluoride (CeF)3) And graphite phase carbon nitride, wherein the rare earth ion doped cerium trifluoride accounts for 10-50% of the mass of the graphite phase carbon nitride.
Example 1
A preparation method of a rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material comprises the following steps:
(1) grinding 5g dicyanodiamine into fine powder in a mortar, drying at 80 ℃ for 10 hours, grinding again, putting the ground powder in a crucible, putting the crucible in a muffle furnace, heating at 5 ℃/min, calcining at 550 ℃ for 4 hours, cooling along with the furnace, and grinding to obtain light yellow graphite phase carbon nitride powder g-C3N4；
(2) Weighing 2g of g-C3N4Dissolving in deionized water, ultrasonic treating for 30min to obtain suspension, and mixing with 1.736gCe (NO)3)3·6H2O，0.0265g Pr(NO3)3·6H2O，0.45g NH4F, adding the suspension solution into the suspension solution, slowly dropwise adding acetic acid to adjust the pH value of the system to 4-5, and finally adding the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction at 160 ℃ for 10 hours;
(3) adding deionized water and ethanol into the sample obtained in the step (2) for multiple centrifugal washing, drying at 80 ℃ for 10 hours, and grinding to obtain the rare earth ion doped cerium fluoride/graphite phase carbon nitride up-conversion enhanced type broad spectrum response composite photocatalytic material, namely 40% wt CeF3:1.5％Pr3+/g-C3N4A composite material.
The obtained sample is subjected to X-ray powder diffraction to represent the structure and the composition of the sample, the fluorescence spectrum is utilized to test the upconversion luminescence property of the sample, the appearance of the sample is observed by using a transmission electron microscope, the XRD pattern of the upconversion enhanced type broad-spectrum response composite photocatalytic material prepared according to the process of the embodiment 1 is shown in figure 1, and CeF respectively appears in the composite material3And g-C3N4Characteristic peak of (B), indicating CeF3:1.5％Pr3+Success of the Crystal with g-C3N4Composite, Pr3+Successful doping into CeF3Crystal lattice, solid solution is formed.
The resulting 40% wt CeF3: 1.5% Pr3+/g-C3N4The TEM picture, EDS spectrum and fluorescence emission spectrum of (1) as shown in the TEM picture of FIG. 2, in two-dimensional lamellar graphite phase carbon nitride g-C3N4Has CeF uniformly distributed on the surface3:1.5％Pr3+The particles, shown in the EDS spectrum of FIG. 3, illustrate the presence of C, N, Ce, F, Pr elements in the composite, which all indicate successful preparation of the composite.
Example 2
40% wt CeF prepared in example 13:1.5％Pr3+/g-C3N4The application of the composite material in degrading dye wastewater comprises the following steps:
0.05g of methylene blue was weighed and dissolved in 500mL of deionized water to prepare a 100mg/L methylene blue solution, and 0.01g of 40% wt CeF was added to a photocatalytic reaction apparatus3:1.5％Pr3+/g-C3N4The method comprises the following steps of introducing visible light into a composite material after dark adsorption for 30min, taking 3mL of reaction liquid every 30min, transferring the reaction liquid into a centrifuge tube, centrifuging a sample in the centrifuge tube for 5 min at 6000r/min, collecting supernatant after centrifugation, further transferring the supernatant into a quartz cuvette, measuring the absorbance of the sample at the maximum absorption wavelength of a dye by using a spectrophotometer (the maximum absorption wavelength of methylene blue is 665 nm), and calculating the degradation rate of the methylene blue according to the following formula:
D＝(1-A/A0)×100％
wherein: d is the degradation rate (%); a. the0And A is the absorbance values before and after photocatalytic degradation. Under the condition of visible light illumination for 60min, the degradation rate of the methylene blue reaches 93 percent.
Example 3
The pale yellow graphite-phase carbon nitride powder g-C prepared in step 1 of example 1 was taken3N4And carrying out subsequent tests.
(1) Weighing 2g of g-C3N4Added to deionized water for 30 minutes by sonication, 0.434gCe (NO)3)3·6H2O，0.0066g Pr(NO3)3·6H2O，0.1125g NH4And F, adding the suspension solution into the suspension solution, slowly dropwise adding acetic acid to adjust the pH value of the system to be 4-5, and finally adding the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction at 160 ℃ for 10 hours.
(2) Adding deionized water and ethanol into the sample obtained in the step (1) for multiple centrifugal washing, drying at 80 ℃ for 10 hours, and grinding to obtain 10 wt% CeF3:1.5％Pr3+/g-C3N4A composite material.
The subsequent detection is as in example 1, and the degradation rate of methylene blue reaches 72%.
Example 4
The pale yellow graphite-phase carbon nitride powder g-C prepared in step 1 of example 1 was taken3N4And carrying out subsequent tests.
(1) Weighing 2g of g-C3N4Adding into deionized water, ultrasonic treating for 30min, adding 0.868gCe (NO)3)3·6H2O，0.0132g Pr(NO3)3·6H2O，0.225g NH4And F, adding the suspension solution into the suspension solution, slowly dropwise adding acetic acid to adjust the pH value of the system to be 4-5, and finally adding the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction at 160 ℃ for 10 hours.
(2) Adding deionized water and ethanol into the sample obtained in the step (1) for multiple times of centrifugal washing, drying at 80 ℃ for 10 hours, and grinding to obtain 20 wt% CeF3:1.5％Pr3+/g-C3N4A composite material.
The subsequent detection is as in example 1, and the degradation rate of methylene blue reaches 78%.
Example 5
The pale yellow graphite-phase carbon nitride powder g-C prepared in step 1 of example 1 was taken3N4And carrying out subsequent tests.
(1) Weighing 2g of g-C3N4Added to deionized water for 30 minutes by ultrasonic waves, and 1.302gCe (NO) was added3)3·6H2O，0.0198g Pr(NO3)3·6H2O，0.3375g NH4And F, adding the suspension solution into the suspension solution, slowly dropwise adding acetic acid to adjust the pH value of the system to be 4-5, and finally adding the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction at 160 ℃ for 10 hours.
(2) Adding deionized water and ethanol into the sample obtained in the step (1) for multiple centrifugal washing, drying at 80 ℃ for 10 hours, and grinding to obtain 30 wt% CeF3:1.5％Pr3+/g-C3N4A composite material.
The subsequent detection is as example 1, and the degradation rate of the methylene blue reaches 85%.
Example 6
The pale yellow graphite-phase carbon nitride powder g-C prepared in step 1 of example 1 was taken3N4And carrying out subsequent tests.
(1) Weighing 2g of g-C3N4Added to deionized water for 30 minutes by ultrasonic waves, and 2.17gCe (NO) was added3)3·6H2O，0.033g Pr(NO3)3·6H2O，0.5625g NH4And F, adding the suspension solution into the suspension solution, slowly dropwise adding acetic acid to adjust the pH value of the system to be 4-5, and finally adding the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction at 160 ℃ for 10 hours.
(2) Adding deionized water and ethanol into the sample obtained in the step (1) for multiple times of centrifugal washing, drying at 80 ℃ for 10 hours, and grinding to obtain 50 wt% CeF3:1.5％Pr3+/g-C3N4A composite material.
The subsequent detection is as in example 1, and the degradation rate of the methylene blue reaches 90 percent.
Comparative example 1
(1) 1.736g Ce (NO) was weighed out3)3·6H2O，0.0265g Pr(NO3)3·6H2O，0.45g NH4And F, adding the suspension solution into the suspension solution, slowly dropwise adding acetic acid to adjust the pH value of the system to be 4-5, and finally adding the mixed solution into a hydrothermal reaction kettle for hydrothermal reaction at 160 ℃ for 10 hours.
(2) And (2) adding deionized water and ethanol into the sample obtained in the step (1) for centrifugal washing for multiple times, drying at 80 ℃ for 10 hours, and grinding to obtain the rare earth doped cerium trifluoride.
The resulting sample was subjected to X-ray powder diffraction to characterize its structure and composition, and prepared according to the procedure of comparative example 1
CeF of3:1.5％Pr3+The XRD pattern of (A) is shown in figure 1; FIG. 4 is a fluorescence spectrum showing a wavelength of 525 nm. The near infrared light or visible light excitation material with the wavelength of 560nm, 780nm and 810nm can emit ultraviolet light with the wavelength of 300-350nm, which shows that the CeF3:1.5％Pr3+The material has obvious up-conversion luminescence property.
CeF prepared in this comparative example was exposed to 60min of light3The degradation rate of (2) was only 45% because only the rare earth fluoride up-conversion material was present in this comparative example and no heterojunction was formed.
Claims (6)
1. The composite photocatalytic material belongs to an enhanced wide-spectrum response material and consists of rare earth ion doped cerium trifluoride and graphite phase carbon nitride, wherein the rare earth ion doped cerium trifluoride accounts for 10% -50% of the mass of the graphite phase carbon nitride.
2. The preparation method of the rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material according to claim 1, comprising the following steps: step 1, putting dicyanodiamine, melamine or urea into a mortar, grinding into fine powder, putting the fine powder into an oven at 60-100 ℃, drying for 6-12 hours, then putting the fine powder into the mortar, fully grinding, putting the powder after secondary grinding into a crucible, and then putting the crucible into a muffle furnace for calcination at 520 ℃ and 550 ℃ for 2-4 hours to obtain light yellow graphite phase carbon nitride powder; step 2, dissolving faint yellow graphite phase carbon nitride powder in deionized water, carrying out ultrasonic stripping for 30-60min to obtain a suspension, and then adding Ce (NO)3)3·6H2O or CeCl3·6H2O，NH4F or NaF, Pr (NO)3)3·6H2Adding O into the suspension, stirring, and adjusting pH with acetic acidWhen the temperature is 4-5 ℃, transferring the system into a high-pressure hydrothermal reaction kettle with a stainless steel outer sleeve and a polytetrafluoroethylene inner container, and reacting for 10-16 hours at 160-180 ℃ to obtain a composite photocatalytic material crude product; wherein Pr is added3+And Ce3+In a molar ratio of 1:50-100, Ce3+And F-The molar ratio of (A) to (B) is 1:3-1: 5; and 3, taking a lower layer suspension of the crude product of the composite photocatalytic material, centrifuging for 3-5 times by using a mixed solution of deionized water and ethanol, cleaning, drying a sample, and grinding to obtain the rare earth ion doped cerium fluoride/graphite phase carbon nitride up-conversion enhanced type broad-spectrum response composite photocatalytic material.
3. The method for preparing a rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material according to claim 2, wherein the temperature rise rate during the calcination in the step 1 is 2-5 ℃/min.
4. The method for preparing a rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material as claimed in claim 2, wherein the centrifugation in step 3 has a rotation speed of 5000-7000r/min, a time of 5-10min, and a centrifugation frequency of 3 times.
5. The method for preparing a rare earth ion doped cerium trifluoride-graphite phase carbon nitride composite photocatalytic material according to claim 2, wherein the drying temperature in step 3 is 80-100 ℃.
6. The use of the rare earth ion doped cerium fluoride/graphite phase carbon nitride up-conversion enhanced broad-spectrum response composite photocatalytic material based on claim 1 for degrading dye wastewater.
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