CN115722264A - Titanium dioxide/PFNBr composite photocatalyst, preparation method and application thereof - Google Patents
Titanium dioxide/PFNBr composite photocatalyst, preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 41
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- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 5
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- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a titanium dioxide/PFNBr composite photocatalyst, a preparation method and application thereof, relating to the technical field of photocatalyst preparation 2 Compounding to provide a hydrophilic TiO 2 The PFNBr composite photocatalyst retains the hydrophilicity of materials, and enables conjugated polymer PFNBr to wrap TiO by using a simple process 2 Form an inorganic-organic hybrid structure, and expand the light of the materialThe response range reduces the recombination rate of photo-generated electrons and holes. The invention treats the prepared TiO under the same condition 2 PFNBr composite photocatalyst and two single phases (TiO) 2 PFNBr) photocatalytic degradation and hydrogen production performance were tested. The results show that the TiO prepared 2 the/PFNBr composite photocatalyst is obviously superior to two single phases in degradation and hydrogen production processes.
Description
Technical Field
The invention relates to the technical field of photocatalyst preparation, in particular to a titanium dioxide/PFNBr composite photocatalyst, a preparation method and application thereof.
Background
With the rapid development of society, the world is currently confronted with two crises of environmental pollution and energy shortage. The photocatalytic technology utilizes organic photocatalyst hybrid inorganic photocatalyst to generate photoproduction electrons-holes with higher oxidation reduction capability under the irradiation of a specific light source to realize the high-efficiency degradation and hydrogen production of organic pollutants, and has great prospect in the fields of environmental management and new energy exploration. TiO 2 2 Titanium dioxide, as a most representative n-type semiconductor photocatalyst, has good performances of photocatalytic degradation of pollutants and hydrogen production under ultraviolet light, and is widely concerned due to good photochemical stability, no secondary pollution and low cost. But TiO 2 2 The material is a wide-bandgap (3.2 eV) semiconductor material, has weak response to visible light, and has low utilization rate of light energy (only 5% of solar spectrum); simultaneous TiO 2 2 The easy recombination of photo-generated electrons and holes further limits the TiO 2 And (4) industrial process.
To TiO 2 2 The modification becomes a key factor for improving the photocatalytic performance of the TiO-based photocatalyst, the overall photocatalytic efficiency mainly depends on factors such as band gaps, carrier separation and transmission, energy conversion and the like, methods such as morphology regulation, metal and nonmetal doping, heterojunction formation and the like are adopted by people at present, but TiO is subjected to modification 2 The self performance regulation and control of the light source is limited, and the light response range is difficult to break through. In a number of modification processes, tiO is modified with organic polymers 2 The surface modification is a mild, low-cost and sustainable surface functionalization method and can be combined with TiO 2 And the conjugated polymer has the advantages of adjustable spectrum and controllable main side chain.
TiO is currently reported in most literatures 2 The modified conjugated polymer adopts hydrophobic polymer, for example Yang Lianli in patent CN 112588322A discloses a super-hydrophobic polymer/titanium-based photocatalytic aerogel block material and a preparation method thereof, and in-situ polymerization composite TiO is used by rain hiding et al in patent CN 112920382A 2 And conjugated microporous polymers to effectively broaden TiO 2 Band gap, which enhances the photocatalytic effect, but to some extent prevents the conjugated polymer from reacting with TiO 2 Compounding and contacting the surface of the catalyst with pollutants, active substances and the like in a reaction system; for example, patent CN 113634279A discloses an Ag/TiO 2 The preparation of the @ PANI photocatalyst effectively improves the adsorptivity and photocatalytic degradation efficiency of the material, but noble metal is introduced in the preparation process; for example, patent CN 111495343A discloses a TiO compound 2 The grafted polyacrylic acid hydrogel adsorption-degradation material endows polyacrylic acid-based hydrogel with excellent photocatalytic degradation performance, but the method has complex preparation process and high energy consumption; for example, patent CN 111589472A discloses TiO 2 Carboxyl-containing conjugated microporous polymer/TiO 2 The preparation method of the composite material has overlong reaction time and is not beneficial to popularization and application. Based on the above, the design of the photocatalytic composite material which is simple in synthesis, low in energy consumption, good in photocatalytic degradation and hydrogen production performance and free of uneconomical noble metals has research significance.
Disclosure of Invention
The invention aims at the problems that in the prior art, organic conjugated polymer and inorganic material TiO are adopted 2 Difficult compounding, difficult contact with target pollutants and active substances, complex preparation process and the like. Provides a simple preparation method of TiO 2 Titanium dioxide/PFNBr (TiO) matched with hydrophilic polymer in valence bond and energy band to widen photoresponse range material 2 PFNBr) composite photocatalyst and is applied to the photocatalytic fields of degradation, hydrogen production and the like.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a titanium dioxide/PFNBr composite photocatalyst, which comprises the following steps:
step (1) dissolution of PFNBr:
adding a hydrophilic conjugated polymer PFNBr into methanol, heating at the boiling point of the methanol, and obtaining a solution after the PFNBr is completely dissolved;
step (2) preparation of TiO 2 PFNBr photocatalyst:
adding TiO into the mixture 2 Dispersing the titanium dioxide/PFNBr composite photocatalyst into the solution obtained in the step (1), performing ultrasonic treatment, stirring, and performing reduced pressure distillation to obtain the titanium dioxide/PFNBr composite photocatalyst.
Further, the TiO 2 The preparation method of the/PFNBr composite photocatalyst comprises the following steps:
step (1) dissolution of PFNBr:
adding PFNBr into a flat-bottomed flask, pouring methanol (20-40 mL), heating at the boiling point of the methanol, and obtaining a solution after the PFNBr is completely dissolved;
step (2) preparation of TiO 2 PFNBr composite photocatalyst:
the obtained TiO will be purchased 2 Dispersing in the solution formed in (1), sealing the flat-bottomed flask with a sealing film, stirring for at least 1h after ultrasonic treatment, and distilling at 50 deg.C under reduced pressure to obtain TiO 2 the/PFNBr composite photocatalyst.
Further, tiO 2 And PFNBr at a mass ratio of 10: (0 to 10), tiO 2 The amount of (A) is not 0.
Further, in the step (1), the ultrasonic time is 10-40 min, and the stirring time is 1-3 h.
TiO prepared by the preparation method 2 the/PFNBr composite photocatalyst.
The TiO is 2 The application of the/PFNBr composite photocatalyst in pollutant degradation.
In the process of degrading pollutants, tiO is added 2 The PFNBr composite photocatalyst is placed in the water solution of the target pollutant, stirred in the dark to reach the adsorption and desorption balance, and then irradiated for a period of time under visible light to make the target pollutant reach the target pollutantAnd degrading target pollutants. The illumination time is 0.5 to 2h 2 The dosage of the/PFNBr composite photocatalyst in the aqueous solution of the target pollutant is 0.4-1g/L.
To test TiO 2 The invention relates to the degradation performance of a PFNBr composite photocatalyst on pollutants, in particular to TiO 2 Adding the PFNBr composite photocatalyst into the prepared target pollutant (RhB) wastewater solution, stirring for 30min in a dark place to ensure that the adsorption and desorption balance is achieved, irradiating for a period of time under visible light to degrade the target pollutant, and centrifuging 3mL of supernatant for 10min at certain intervals. And testing the absorbance of the pollutant stock solution and the supernatant liquid taken out in each time period by adopting a spectrophotometry method. The illumination time is 0.5 to 2 hours, and the mass concentration of the prepared wastewater solution containing the target pollutant (RhB) is 10 to 80 mg.L -1 ，TiO 2 The dosage of the/PFNBr composite photocatalyst in the aqueous solution of the target pollutant is 0.4-1g/L.
The titanium dioxide/PFNBr composite photocatalyst is applied to hydrogen production.
In the process of hydrogen production of the titanium dioxide/PFNBr composite photocatalyst, the titanium dioxide/PFNBr composite photocatalyst is placed in a photocatalytic reaction tank, 20mL of triethanolamine serving as a sacrificial agent and 80mL of water are added, a xenon lamp light source with a 360nm cut-off filter is used for limiting the illumination wavelength range to be lambda not less than 360nm, argon is used as carrier gas, a hydrogen production experiment is carried out for 5h, and hydrogen data in the system are collected every 1 h.
The invention discloses the following technical effects:
the invention combines organic conjugated polymer PFNBr and inorganic material TiO 2 Compounding to provide a hydrophilic TiO 2 The PFNBr composite photocatalyst retains the hydrophilicity of materials, and simultaneously, the conjugated polymer PFNBr wraps TiO by using a simple process 2 The inorganic-organic hybrid core-shell structure is formed, the photoresponse range of the material is expanded, and the recombination rate of photo-generated electrons and holes is reduced. The invention treats the prepared TiO under the same condition 2 PFNBr composite photocatalyst and two single phases (TiO) 2 PFNBr) photocatalytic degradation and hydrogen production performance were tested. The results show that the TiO prepared 2 PFNBr composite photocatalyst in degradation and hydrogen productionThe range is obviously superior to two single phases.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of the preparation process of the hydrophilic conjugated polymer PFNBr composite titanium dioxide based photocatalyst;
FIG. 2 shows TiO prepared in example 1 2 PFNBr and TiO 2 XRD pattern of (a);
FIG. 3 shows TiO prepared in example 2 2 N of/PFNBr 2 Adsorption isotherm curve;
FIG. 4 shows TiO prepared in example 3 2 /PFNBr、TiO 2 An infrared spectrum of PFNBr;
FIG. 5 shows TiO prepared in example 2 2 、TiO 2 The PFNBr is used for degrading target pollutants in water under an LED lamp;
FIG. 6 shows TiO prepared in example 2 2 、TiO 2 The effect diagram of the photocatalytic hydrogen production of the/PFNBr under the xenon lamp.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated value or intervening value in a stated range, and any other stated or intervening value in a stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The flow chart of the preparation process of the hydrophilic conjugated polymer PFNBr composite titanium dioxide-based photocatalyst is shown in figure 1.
The room temperature in the present invention means 25. + -. 2 ℃.
The starting materials in the examples of the present invention were all commercially available unless otherwise specified.
The PFNBr in the examples of the present invention was purchased from Ogtaike technologies, inc., beijing.
TiO in examples of the present invention 2 Available from makeln biochemical technologies, inc.
Example 1
10mg of PFNBr was added to a flask containing 20mL of methanol, dissolved by heating at the boiling point of methanol (64.5 ℃ C.), and 100mg of commercially available TiO was added 2 Ultrasonic treating for 30min, adding magneton, sealing the flask with sealing film, stirring for 1 hr at 600rpm/min, and reducing the temperature to 50 deg.CPressure distillation to obtain TiO 2 /PFNBr。TiO 2 With TiO 2 The XRD pattern of/PFNBr is shown in figure 2, and the composite photocatalyst mainly shows TiO 2 Mainly because the conjugated polymer PFNBr is in an amorphous state, tiO 2 Is anatase type.
Example 2
20mg of PFNBr was taken in a flask containing 20mL of methanol, dissolved by heating at the boiling point of methanol (64.5 ℃ C.), and 100mg of commercially available TiO was added 2 Performing ultrasonic treatment for 30min, adding magneton, sealing the flask with sealing film, stirring for 1 hr at 600rpm/min, and distilling at 50 deg.C under reduced pressure to obtain TiO 2 /PFNBr。TiO 2 N of/PFNBr 2 The adsorption isotherm graph is shown in FIG. 3, and the specific surface area of the composite material is 135.3m 2 The specific surface area of the material is large, the number of reactive sites is large, and the adsorption performance of the material on target pollutants is good.
Example 3
20mg of PFNBr was charged into a 40mL flask containing methanol, dissolved by heating at the boiling point of methanol (64.5 ℃ C.), and 100mg of commercially available TiO was added 2 Performing ultrasonic treatment for 30min, adding magnetons, sealing the flask with a sealing film, stirring for 3h (stirring speed is 600 rpm/min), and distilling at 50 deg.C under reduced pressure to obtain TiO 2 /PFNBr，TiO 2 、TiO 2 The infrared spectra of the/PFNBr and the PFNBr are shown in FIG. 4, the synthesized composite material mainly shows the peak of the functional group of the conjugated polymer PFNBr, the Fourier infrared spectrum mainly shows the functional group on the surface of the material, which indicates that the PFNBr is successfully coated on TiO 2 On the surface of (a).
Example 4
20mg of PFNBr was charged into a 20mL flask containing methanol, dissolved by heating at the boiling point of methanol (64.5 ℃ C.), and 100mg of commercially available TiO was added 2 Performing ultrasonic treatment for 30min, adding magneton, sealing the flask with sealing film, stirring for 3 hr (stirring speed of 600 rpm/min), and distilling at 50 deg.C under reduced pressure to obtain TiO 2 /PFNBr。
Example 5
20mg of PFNBr was added to a 20mL methanol-containing flask,dissolved by heating at the boiling point of methanol (64.5 ℃ C.), and 100mg of commercially available TiO was added 2 Performing ultrasonic treatment for 10min, adding magneton, sealing the flask with sealing film, stirring for 3 hr (stirring speed of 600 rpm/min), and distilling at 50 deg.C under reduced pressure to obtain TiO 2 /PFNBr。
Example 6
20mg of PFNBr was charged into a 20mL flask containing methanol, dissolved by heating at the boiling point of methanol (64.5 ℃ C.), and 100mg of commercially available TiO was added 2 Performing ultrasonic treatment for 30min, adding magneton, sealing the flask with sealing film, stirring vigorously for 1 hr at 600rpm/min, and distilling under reduced pressure at 50 deg.C to obtain TiO 2 /PFNBr。
Application example 1
TiO from example 2 2 PFNBr material, the degradation performance study was performed as follows: an LED lamp is used as a visible light source, the dosage of the catalyst is 0.4g/L, and the prepared 50mL concentration is 10 mg.L -1 After the catalyst is added into the RhB aqueous solution, stirring for 0.5h in a dark place to ensure that the adsorption and desorption are balanced. And placing the mixture under an LED for photocatalytic photoreaction. 3mL of supernatant was centrifuged for 10min at regular intervals. And testing the absorbance of the RhB stock solution and the taken supernatant by a spectrophotometry method. The result is shown in figure 5, the abscissa is time, the ordinate is the content of the RhB existing in the solution, the lower curve is the time-varying curve of the RhB degradation of the sample obtained by the method of the invention under the LED light, in the degradation experiment, the better composite catalyst is used for degrading the RhB, the degradation rate reaches 100% after 2h, and the TiO content is the same time 2 2.8 times of the total weight of the powder. The material of the invention has obvious degradation effect compared with pure titanium dioxide through comparison, and obviously the TiO provided by the invention 2 the/PFNBr photocatalyst has extremely high RhB photocatalytic degradation efficiency.
Application example 2
TiO from example 2 2 PFNBr material, hydrogen production performance study was performed as follows: using xenon lamp as hydrogen-producing light source, lambda is greater than or equal to 360nm, catalyst dosage is 0.2g/L, sacrificial agent is 20mL, water is 80mL, reaction tank is vacuumized, argon is used as carrier gas, and H produced in gas chromatography detection system is used 2 And performing a hydrogen production experiment for 5h, and collecting hydrogen data in the system every 1 h. TiO prepared in example 2 2 、TiO 2 The graph of the photocatalytic hydrogen production effect of PFNBr under a xenon lamp is shown in figure 6, the abscissa is time, the ordinate is hydrogen production, the upper curve is a curve of the change of the hydrogen production of a sample obtained by the method with the time under the xenon lamp and taking triethanolamine as a sacrificial agent, and comparison shows that pure titanium dioxide hardly produces hydrogen under near ultraviolet light of 360nm and TiO hardly produces hydrogen under near ultraviolet light of 360nm 2 The yield of the/PFNBr reaches 2037.5 mu mol/g in 5 h.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (6)
1. A preparation method of a titanium dioxide/PFNBr composite photocatalyst is characterized by comprising the following steps:
step (1) dissolution of PFNBr:
adding PFNBr into methanol, heating at the boiling point of the methanol, and obtaining a solution after the PFNBr is completely dissolved;
step (2) preparation of TiO 2 PFNBr photocatalyst:
mixing TiO with 2 Dispersing the titanium dioxide/PFNBr composite photocatalyst into the solution obtained in the step (1), performing ultrasonic treatment, stirring, and performing reduced pressure distillation to obtain the titanium dioxide/PFNBr composite photocatalyst.
2. The method according to claim 1, wherein the TiO is 2 And PFNBr at a mass ratio of 10: (0 to 10), tiO 2 The amount of (A) is not 0.
3. The preparation method according to claim 1, wherein in the step (2), the ultrasonic time is 10-40 min, and the stirring time is 1-3 h.
4. A titanium dioxide/PFNBr composite photocatalyst prepared by the preparation method according to any one of claims 1 to 3.
5. The use of the titanium dioxide/PFNBr composite photocatalyst of claim 4 to degrade contaminants.
6. The use of the titanium dioxide/PFNBr composite photocatalyst of claim 4 in the production of hydrogen.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211449479.8A CN115722264B (en) | 2022-11-18 | 2022-11-18 | Titanium dioxide/PFNBr composite photocatalyst, preparation method and application thereof |
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| CN202211449479.8A CN115722264B (en) | 2022-11-18 | 2022-11-18 | Titanium dioxide/PFNBr composite photocatalyst, preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN115722264A true CN115722264A (en) | 2023-03-03 |
| CN115722264B CN115722264B (en) | 2023-06-30 |
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