CN114471723A - Construction method of double-electron transfer channel photocatalyst - Google Patents

Construction method of double-electron transfer channel photocatalyst Download PDF

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CN114471723A
CN114471723A CN202210045901.7A CN202210045901A CN114471723A CN 114471723 A CN114471723 A CN 114471723A CN 202210045901 A CN202210045901 A CN 202210045901A CN 114471723 A CN114471723 A CN 114471723A
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cqds
electron transfer
mass
photocatalyst
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CN114471723B (en
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陈清华
张萌萌
杨国亮
尹冰杰
陈佳怡
王海洋
马东
刘国成
宋宁宁
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Qingdao Agricultural University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39Photocatalytic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22Organic complexes
    • B01J31/2204Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208Oxygen, e.g. acetylacetonates
    • B01J31/2226Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46Titanium
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents

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Abstract

The invention provides a construction method of a double-electron transfer channel photocatalyst, which comprises the steps of adding CQDs (carbon quantum dots) into absolute ethyl alcohol to form a CQDs ethyl alcohol solution, and then adding g-C3N4(graphite-like phase carbon nitride) is added into absolute ethyl alcohol, CQDs ethanol solution is added into g-C3N4Adding a product obtained by magnetic stirring, sealing, constant-temperature heating, cooling, vacuum drying and grinding and 2-amino terephthalic acid into an ethanol solution, adding the mixed solution into a polytetrafluoroethylene reaction kettle, heating, naturally cooling, centrifuging and vacuum drying to obtain the dual-electron transfer channel photocatalyst CQDs/g-C3N4/NH2-MIL-125. By constructing the composite structure, an internal electric field and van der Waals dissimilarity are establishedThe texture junction constructs a double-channel electron transfer mode, improves the electron transfer efficiency, inhibits the recombination of photo-generated electron hole pairs, and further improves the photocatalytic activity.

Description

Construction method of double-electron transfer channel photocatalyst
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a construction method of a double-electron transfer channel photocatalyst.
Background
The photocatalysis technology is one of the commonly used advanced oxidation technologies and is an effective means for solving the problem of environmental pollution. The photocatalysis technology can utilize sunlight as energy, has no selectivity to reactants, can almost generate oxidation-reduction reaction with any organic pollutant and further finally oxidize the organic pollutant into CO2And H2Therefore, the photocatalysis technology has wide application prospect in the aspect of treating environmental pollution. The recombination of photo-generated electrons and holes is an important factor for restricting the photocatalytic efficiency, so that the improvement of the transfer and separation efficiency of the photo-generated electrons is the key research point of the photocatalytic technology.
Disclosure of Invention
The invention aims to provide a construction method of a double-electron transfer channel photocatalyst, which specifically comprises the following steps:
a. weighing a certain amount of CQDs (carbon quantum dots) and adding the CQDs into absolute ethyl alcohol to form a CQDs ethyl alcohol solution;
b. a certain amount of g-C3N4Adding (graphite-like carbon nitride) into absolute ethyl alcohol, performing ultrasonic treatment for 30-60 min, and adding CQDs ethanol solution into g-C3N4Forming suspension in the ethanol solution, and magnetically stirring for 1 h;
c. b, putting the suspension liquid in the step b into a polytetrafluoroethylene reaction kettle, sealing, heating for 2 hours at the temperature of 60-100 ℃ in a thermostat, cooling to room temperature, and carrying out vacuum drying for 2 hours at the temperature of 60-100 ℃ on the obtained product;
d. grinding the dried product in the step c to obtainCQDs/g-C3N4Powder;
e. the CQDs/g-C obtained in the step d3N4Adding 2-amino terephthalic acid into the N, N-dimethylformamide and methanol solution, uniformly mixing, adding tetrabutyl titanate, and stirring at room temperature for 30-60 min;
f. putting the mixed solution into a polytetrafluoroethylene reaction kettle, heating for 24 hours at 120-180 ℃, naturally cooling, centrifugally separating, washing with N, N-dimethylformamide and methanol respectively, and vacuum drying for 6-10 hours at 80 ℃ to obtain the dual-electron transfer channel photocatalyst CQDs/g-C3N4/NH2-MIL-125。
Preferably, in step a, the ratio of the mass of CQDs to the volume of absolute ethanol may be: (5-10) mg: 10ml, and the optimal mass and volume ratio is 9 mg: 10 ml.
Preferably, in said step b, the mass of CQDs, g-C3N4The mass of (2) to the volume of the suspension can be (5-10) mg: (80-100) mg: mass of CQDs, g-C, in the range of 40ml3N4The optimal ratio of mass to suspension volume is 9 mg: 90 mg: 40 ml.
Preferably, in said step e, CQDs/g-C3N4The mass of (2-20) mg, the mass of 2-aminoterephthalic acid, and the volume ratio of the N, N-dimethylformamide and methanol solution to tetrabutyl titanate may be: (1000-2000) mg: 27 ml: (0.2-1.0) ml, and the optimal ratio is 5.4 mg: 1087 mg: 27 ml: 0.52 ml.
Preferably, in the step e, the volume ratio of the N, N-dimethylformamide to the methanol is 9: 1.
preferably, in the step f, the number of washing times with the N, N-dimethylformamide and methanol solution is 3.
Preferably, CQDs/g-C obtained3N4/NH2MIL-125 has a two-channel electron transfer through g-C3N4And NH2-electron transfer by built-in electric field of MIL-125 configuration; by CQDs with g-C3N4The van der waals heterojunction formed therebetween performs electron transfer.
Compared with the prior art, the invention has the advantages and effects that:
the invention couples g-C3N4The characteristics of proper energy band position and CQDs for promoting electron transfer, CQDs/g-C are developed3N4/NH2The MIL-125 composite photocatalyst establishes an internal electric field and a Van der Waals heterojunction through constructing a composite structure, constructs a dual-channel electron transfer mode, improves the electron transfer efficiency, inhibits the recombination of photo-generated electron hole pairs, and further improves the photocatalytic activity;
CQDs/g-C3N4/NH2degradation removal capability of MIL-125 on dye pollutant rhodamine B (RhB) in water is higher than that of NH2-MIL-125 and g-C3N4Can be improved by about 38.8 percent and 71.0 percent respectively.
Drawings
In order to clearly illustrate the embodiments or technical solutions of the present invention in the prior art, the drawings used in the description of the embodiments or prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a diagram of CQDs/g-C prepared in the examples of the present invention3N4/NH2SEM picture of MIL-125;
FIG. 2 is a diagram of CQDs/g-C prepared in the example of the present invention3N4/NH2-XPS spectrum of MIL-125, wherein graph a is the binding energy full spectrum of C, N, Ti, O elements, graph b is the binding energy spectrum of C elements, graph C is the binding energy spectrum of N elements, graph d is the binding energy spectrum of Ti elements, and graph e is the binding energy spectrum of O elements;
FIG. 3 is a diagram of CQDs/g-C obtained in the example of the present invention3N4/NH2-MIL-125 two-channel electron transfer schematic;
FIG. 4 is a diagram of CQDs/g-C obtained in example of the present invention3N4/NH2Comparison graph of effect of MIL-125 degrading rhodamine B dye in water.
Detailed Description
The drawings are for illustration purposes only and are not to be construed as limiting the invention; for a better understanding of the present embodiments, certain features of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; some well-known structures in the drawings and descriptions thereof may be omitted for those skilled in the art.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
Examples
9mg of CQDs was weighed out and added to 10mL of absolute ethanol to form an ethanol solution of CQDs. 90mg g-C3N4Adding into anhydrous ethanol, and performing ultrasonic treatment for 60 min. Adding CQDs ethanol solution to g-C3N4A40 mL suspension was formed in ethanol solution and stirred magnetically for 1 h. The suspension is put into a 100mL polytetrafluoroethylene reaction kettle, sealed and heated in a thermostat at 90 ℃ for 2 h. Cooled to room temperature and the resulting product was dried under vacuum at 90 ℃ for 2 h. Grinding to obtain CQDs/g-C3N4And (3) powder.
5.4mg of CQDs/g-C was taken3N4And 1.087g of 2-aminoterephthalic acid were added to a solution of N, N-dimethylformamide and methanol (volume ratio: 9:1) in a volume of 27mL, and after mixing, 0.52mL of tetrabutyl titanate was added and stirred at room temperature for 30 min. And (3) putting the mixed solution into a polytetrafluoroethylene reaction kettle, and heating at 150 ℃ for 24 h. Naturally cooling, centrifuging, washing with N, N-dimethylformamide and methanol for 3 times, vacuum drying at 80 deg.C for 6 hr to obtain dual electron transfer channel photocatalyst CQDs/g-C3N4/NH2MIL-125, as shown in FIG. 1, CQDs/g-C obtained for the examples3N4/NH2SEM image of MIL-125.
As shown in FIG. 2, CQDs/g-C were obtained3N4/NH2XPS spectrum of MIL-125, surface chemistry mainly C, N, O, Ti four elements. In the b diagram, the spectrum of C1s contains four peaks, and the binding energies are 284.54eV and 285.08eV respectively286.24eV and 288.79eV, wherein 284.54eV corresponds to C-C, C ═ C, C-H. The other bond energies correspond to C-N, C-O, C ═ O. In the spectrum of N1s in the c diagram, there are three bond energies of 399.3eV, 399.9eV and 402.1eV, which correspond to NH respectively2-NH of-MIL-1252-、g-C3N4N- (C)3Nitrogen (N) with positive charge+/-NH+-). In the d diagram, Ti 2p mainly has two bonding energies of 458.8eV and 464.5eV, which correspond to Ti 2p3/2And Ti 2p1/2It is shown that the Ti in the titanium clusters remains in the IV oxidation state after the titanium is combined with oxygen. In panel e, the spectrum represents O1s, where 530.1eV corresponds to NH2The bond energies of-MIL-125 ligand Ti-O, C ═ O and-OH are 531.5eV and 532.3eV, respectively.
FIG. 3 is a schematic diagram of the two-channel electron transfer obtained in the example, channel one, via g-C3N4And NH2-electron transfer by built-in electric field of MIL-125 configuration; channel two, by CQDs and g-C3N4The van der waals heterojunction formed therebetween performs electron transfer.
The obtained double electron transfer channel photocatalyst CQDs/g-C3N4/NH2-MIL-125、NH2-MIL-125、g-C3N4Respectively degrading a representative dye pollutant rhodamine B (RhB) under the same condition. Preparing the solution with the concentration of 5mg/L and the volume of 100mL, adding 20mg of photocatalyst, after dark reaction for 60min, illuminating by adopting a 35W xenon lamp, setting the distance between a light source and a reactor to be 14cm, carrying out photocatalytic treatment for 2h, extracting a small amount of liquid at the same interval time point, centrifuging (4000rpm for 10min), and collecting the supernatant. The RhB concentration in the solution was measured by uv-vis spectrophotometer.
As shown in FIG. 4, the results of the experiments showed that CQDs/g-C3N4/NH2Degradation removal capability of MIL-125 to dye contaminant RhB in water than NH2-MIL-125 and g-C3N4The improvement is about 38.8 percent and 71.0 percent respectively, which is the optimal scheme.
It should be noted that the illustrated embodiment of the present invention is the best embodiment in the experiments, and the inventors have performed experiments on the amount, volume and ratio of various raw materials one by one through a large number of single experiments to finally obtain the best scheme. Other non-optimal solutions are too numerous and will not be described in detail in this description. Some of the embodiments may be practiced using or with reference to conventional techniques.
It is to be understood that the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, and those skilled in the art may make modifications, alterations, additions or substitutions within the spirit and scope of the present invention.

Claims (10)

1. A construction method of a double-electron transfer channel photocatalyst is characterized by specifically comprising the following steps:
a. weighing a certain amount of CQDs and adding the CQDs into absolute ethyl alcohol to form CQDs ethyl alcohol solution;
b. a certain amount of g-C3N4Adding the mixture into absolute ethyl alcohol, performing ultrasonic treatment for 30-60 min, and adding a CQDs ethanol solution into g-C3N4Forming suspension in the ethanol solution, and magnetically stirring for 1 h;
c. b, putting the suspension liquid in the step b into a polytetrafluoroethylene reaction kettle, sealing, heating for 2 hours at the temperature of 60-100 ℃ in a thermostat, cooling to room temperature, and carrying out vacuum drying for 2 hours at the temperature of 60-100 ℃ on the obtained product;
d. grinding the product dried in step C to obtain CQDs/g-C3N4Powder;
e. the CQDs/g-C obtained in the step d3N4Adding 2-amino terephthalic acid into the N, N-dimethylformamide and methanol solution, uniformly mixing, adding tetrabutyl titanate, and stirring at room temperature for 30-60 min;
f. putting the mixed solution into a polytetrafluoroethylene reaction kettle, heating for 24 hours at 120-180 ℃, naturally cooling, centrifugally separating, washing with N, N-dimethylformamide and methanol respectively, and vacuum drying for 6-10 hours at 80 ℃ to obtain the dual-electron transfer channel photocatalyst CQDs/g-C3N4/NH2-MIL-125。
2. The method for constructing a photocatalyst with two electron transfer channels as claimed in claim 1, wherein in step a, the ratio of the mass of CQDs to the volume of absolute ethyl alcohol is (5-10) mg: 10 ml.
3. The method as claimed in claim 2, wherein in step a, the ratio of the mass of CQDs to the volume of absolute ethanol is 9 mg: 10 ml.
4. The method as claimed in claim 1, wherein the CQDs in step b have a mass g-C3N4The mass to volume ratio of the suspension is (5-10) mg: (80-100) mg: 40 ml.
5. The method as claimed in claim 4, wherein the CQDs mass g-C in step b3N49mg mass to volume of suspension: 90 mg: 40 ml.
6. The method as claimed in claim 1, wherein in step e, CQDs/g-C3N4The mass of the compound, the mass of the 2-aminoterephthalic acid, the volume of the N, N-dimethylformamide and methanol solution and the volume ratio of the tetrabutyl titanate are (2-20) mg: (1000-2000) mg: 27 ml: (0.2-1.0) ml.
7. The method as claimed in claim 6, wherein CQDs/g-C3N4The mass of 2-aminoterephthalic acid, the volume of the solution of N, N-dimethylformamide and methanol to the volume of tetrabutyl titanate were in a ratio of 5.4 mg: 1087 mg: 27 ml: 0.52 ml.
8. The method for constructing a dual electron transfer channel photocatalyst as claimed in claim 6, wherein in the step e, the volume ratio of N, N-dimethylformamide to methanol is 9: 1.
9. the method as claimed in claim 1, wherein the number of washing with N, N-dimethylformamide and methanol solution in step f is 3.
10. The method of claim 1, wherein the CQDs/g-C are obtained3N4/NH2MIL-125 has a two-channel electron transfer through g-C3N4And NH2-electron transfer by built-in electric field of MIL-125 configuration; by CQDs with g-C3N4The van der waals heterojunction formed therebetween performs electron transfer.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104722335A (en) * 2015-01-30 2015-06-24 湖南大学 Graphite type carbon nitride-metal organic frame composite photocatalyst as well as preparation method and application of graphite type carbon nitride-metal organic frame composite photocatalyst
CN104841470A (en) * 2015-04-17 2015-08-19 浙江工业大学 Composite titanium dioxide nano-sheet photocatalyst, preparation method and applications thereof
CN109550049A (en) * 2018-12-03 2019-04-02 浙江大学 Application of the carbon quantum dot-class graphite phase carbon nitride catalysis material in preparation sterilization and the drug for promoting skin scar healing
US20200378018A1 (en) * 2020-04-16 2020-12-03 Chinese Research Academy Of Environmental Sciences Carbon dots-based photocatalytic electrode for simultaneous organic matter degradation and heavy metal reduction and use thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104722335A (en) * 2015-01-30 2015-06-24 湖南大学 Graphite type carbon nitride-metal organic frame composite photocatalyst as well as preparation method and application of graphite type carbon nitride-metal organic frame composite photocatalyst
CN104841470A (en) * 2015-04-17 2015-08-19 浙江工业大学 Composite titanium dioxide nano-sheet photocatalyst, preparation method and applications thereof
CN109550049A (en) * 2018-12-03 2019-04-02 浙江大学 Application of the carbon quantum dot-class graphite phase carbon nitride catalysis material in preparation sterilization and the drug for promoting skin scar healing
US20200378018A1 (en) * 2020-04-16 2020-12-03 Chinese Research Academy Of Environmental Sciences Carbon dots-based photocatalytic electrode for simultaneous organic matter degradation and heavy metal reduction and use thereof

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