CN115445649A - Microwave rapid preparation method and photodegradation application of Bi-based S-type heterojunction - Google Patents

Microwave rapid preparation method and photodegradation application of Bi-based S-type heterojunction Download PDF

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CN115445649A
CN115445649A CN202211111543.1A CN202211111543A CN115445649A CN 115445649 A CN115445649 A CN 115445649A CN 202211111543 A CN202211111543 A CN 202211111543A CN 115445649 A CN115445649 A CN 115445649A
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heterojunction
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type heterojunction
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武占省
陈增跃
李云锋
田飞
杨霞
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Xian Polytechnic University
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Abstract

The invention provides a microwave rapid preparation method of a Bi-based S-type heterojunction and photodegradation application thereof, wherein the rapid preparation method comprises the following specific steps: mixing dicyandiamide and urea in a certain mass ratio of 1Preparation of pure g-C 3 N 4 (ii) a Then different Bi-based metal oxides and g-C are prepared by taking ethylene glycol-acetic acid as a synergistic solvent system under the condition of changing the microwave heating condition of an anionic ligand 3 N 4 A composite S-type heterojunction; and compounding the prepared single S-shaped heterojunction with the synchronously synthesized CdS by using a microwave method to prepare the Bi-based double S-shaped heterojunction photocatalyst. The construction of the Bi-based S-shaped heterojunction not only greatly promotes the separation rate of photon-generated carriers, improves the removal efficiency of glyphosate, but also improves the photo-corrosion phenomenon of CdS, so that the photocatalyst has good circulating stability. Therefore, the method for preparing the Bi-based S-type heterojunction by using the ethylene glycol-acetic acid synergistic system is a green, rapid and economic way.

Description

Microwave rapid preparation method and photodegradation application of Bi-based S-type heterojunction
Technical Field
The invention belongs to the technical field of photocatalysts, and relates to a microwave rapid preparation method of a Bi-based S-type heterojunction and photodegradation application thereof.
Background
Photocatalytic technology is considered to be one of the most promising technologies for treating water pollution due to its economic feasibility and environmental friendliness. Microwave-responsive Bi-based oxide BiOCl, bi 2 MoO 6 、BiVO 4 The materials all have unique layered structures, and an internal electric field is formed between layers of the layered structures, so that the transfer of charge carriers can be accelerated, and the electron-hole separation can be promoted; the S-type heterojunction can concentrate photoelectrons and holes in a semiconductor with a more negative Conduction Band (CB) position and a more positive Valence Band (VB) position respectively under the action of an internal electric field, band bending and coulomb attraction, and is an effective strategy for improving the separation rate of electron-hole pairs. g-C 3 N 4 The N-type semiconductor with good chemical reducibility and chemical stability is an excellent monomer material for constructing the Bi-based S-type heterojunction. However, the preparation methods of Bi-based photocatalysts belonging to homologous compounds are different, so that the development and application of Bi-based materials are limited; and the preparation process usually requires the use of HNO 3 The induction of the polymerization of anions and cations can cause environmental pollution and increase unsafe factors of experiments.
However, the problem of how to synthesize Bi-based S-type heterogeneity in a green manner still needs to be solved. Therefore, the innovative idea of the patent is to use an ethylene glycol-acetic acid synergistic system as a solvent to prepare different Bi-based metal oxides by changing an anionic ligandSubstance (BiOCl, bi) 2 MoO 6 、BiVO 4 ) And S-type heterojunction thereof, in microwave response type Bi-based material and g-C 3 N 4 On the basis of compounding, cadmium sulfide (CdS) semiconductor is added again to construct a double S-type heterojunction, cdS is used as a photocatalytic material with a narrow band gap, the double S-type heterojunction has good visible light absorption capacity and strong photocatalytic activity, the construction of the double S-type heterojunction can well improve the situation, and a glycol-acetic acid synergistic system is utilized to circularly prepare a Bi-based photocatalyst with high activity. Therefore, it is important to design a green, safe, fast route for microwave response to prepare photocatalysts.
Disclosure of Invention
The invention aims to provide a rapid preparation method of a Bi-based S-type heterojunction and application of the Bi-based S-type heterojunction in photocatalytic degradation of glyphosate, so as to solve the problems in the background art.
The purpose of the invention can be realized by the following technical scheme:
1. a microwave rapid preparation method of a Bi-based S-type heterojunction and photodegradation application thereof are characterized in that the rapid preparation method comprises the following specific steps:
the method comprises the following steps: preparation of pure g-C by two-step calcination method 3 N 4 The dicyandiamide and the urea with certain mass are mixed according to the proportion of 1. After cooling the sample to room temperature, a pale yellow g-C is obtained 3 N 4 ；
Step two: preparing a Bi-based composite photocatalyst by a microwave method, and sequentially adding Bi (NO) 3 ) 3 ·5H 2 O, PVP, an anion precursor and g-C accounting for 40-60% of the mass of the composite photocatalyst 3 N 4 Adding into mixed solvent composed of 40mL ethylene glycol and 10mL acetic acid solution, stirring at room temperature for 30min, transferring the suspension into a normal pressure microwave reactor, heating for 15-30min, washing with deionized water and ethanol for more than 3 times after reaction, centrifuging, and drying in a 60 deg.C oven for 12h to obtain the final product with different colorsYellow powder of KCl and Na according to the type of the added anion precursor 2 MoO 4 、NH 4 VO 3 The samples were named BCl/CN, BMo/CN, BV/CN;
step three: sequentially adding 0.7-1.0g of one of BCl/CN, BMo/CN and BV/CN and 0.308g of Cd (NO) 3 ) 3 ·4H 2 O was added to a mixed solvent composed of 40mL of ethylene glycol and 10mL of acetic acid solution (1M) and kept at 50 ℃ for 10min, and then 0.1g of PVP and 0.6204g of Na were added 2 S 2 O 3 ·5H 2 Adding O into the solution, continuously keeping the temperature at 50 ℃ for 30min, transferring the suspension into a normal-pressure microwave reactor, heating for 10-20min, washing for more than 3 times by deionized water and ethanol after reaction, centrifuging, and finally drying in an oven at 60 ℃ for 12h to obtain dark yellow powder, wherein the prepared Bi-based double S-type heterojunction products are named ClCS, moCS and VCS according to the types of the added Bi-based composite photocatalyst, namely BCl/CN, BMo/CN and BV/CN.
2. The microwave rapid preparation method and photodegradation application of the Bi-based S-type heterojunction as claimed in claim 1, wherein in the second step, bi (NO) is added 3 ) 3 ·5H 2 The content of O is 0.485 to 0.728g, and the content of PVP is 0.150 to 0.225g.
3. The microwave rapid preparation method and photodegradation application of the Bi-based S-type heterojunction as claimed in claim 1, wherein in the second step, the anion precursor is KCl and Na respectively 2 MoO 4 Or NH 4 VO 3 The content is 0.074-0.111g, 0.103-0.154g or 0.1198-0.179g respectively.
4. The microwave rapid preparation method and the photodegradation application of the Bi-based S-type heterojunction as claimed in claim 1, wherein in the second step, the suspension is heated in an atmospheric microwave reactor under the following conditions:
the heating temperature is 120-140 ℃, the heating power is 600-800W, and the stirring speed is 2000r/min.
5. The microwave rapid preparation method and the photodegradation application of the Bi-based S-type heterojunction as claimed in claim 1, wherein in the third step, the heating conditions of the suspension in the atmospheric pressure microwave reactor are as follows:
the heating temperature is 120-140 ℃, the heating power is 600-800W, and the stirring speed is 2000r/min.
Compared with the prior art, the rapid preparation method of the Bi-based double-S-shaped heterojunction and the application thereof in photocatalytic degradation of glyphosate have the advantages that:
1. the ethylene glycol-acetic acid synergistic system is combined with a microwave method to rapidly and greenly prepare BiVO 4 /g-C 3 N 4 A composite material. The acetic acid in the synergistic system can replace the original nitric acid induced Bi 3+ And VO 4 3- The nucleation of (a); the glycol in the synergistic system can be recycled, thereby saving the cost and reducing the environmental pollution. The prepared composite material can be used for removing glyphosate in simulated agriculture and urban runoff.
2. Different Bi-based metal oxides and S-type heterojunctions thereof are prepared by changing an anion ligand, the construction of the Bi-based double S-type heterojunctions not only greatly promotes the separation rate of photon-generated carriers, improves the removal efficiency of glyphosate, but also improves the photo-corrosion phenomenon of CdS, so that the photocatalyst has good circulation stability, the Bi-based double S-type heterojunctions show excellent photocatalytic performance, and the ClCS composite photocatalyst can remove more than 98% of glyphosate within 90 min.
3. The ethylene glycol-acetic acid synergistic reaction system is constructed, so that the ethylene glycol plays an important role in the preparation process of the Bi-based material, the ethylene glycol has good regeneration performance in the preparation process of the CdS, the Bi-based double S-type heterojunction photocatalyst containing the CdS can be prepared only in 10min through the ethylene glycol-acetic acid synergistic reaction system, the ethylene glycol in the preparation process can be recycled, the prepared Bi-based double S-type heterojunction still shows excellent photocatalytic performance after the ethylene glycol is recycled for 5 times, and the preparation of the Bi-based double S-type heterojunction by using the ethylene glycol-acetic acid synergistic reaction system is a green, rapid and economic way.
Drawings
FIG. 1 shows CdS, g-C 3 N 4 、BiOCl、ClCS、Bi 2 MoO 6 、MoCS、BiVO 4 An (a) XRD spectrum and an FT-IR spectrum of VCS.
FIG. 2 shows XPS spectra of (a) full spectrum, (b) Cd 3d, (c) S2 p, (d) Bi 4f, (e) O1S, (f) Cl2p, (g) Mo 3d, and (h) V2 p for photocatalyst preparation.
FIG. 3 (a) SEM images of BiOCl, (b), (c) BCl/CN samples, (d) TEM images of BiOCl, (e), (f) BCl/CN samples; (g) Bi 2 MoO 6 (h) and (i) SEM images of BMo/CN samples, (j) Bi 2 MoO 6 (k) and (l) TEM images of BMo/CN samples; (m) BiVO 4 SEM images of (n) and (o) BV/CN samples, (p) BiVO 4 (q) and (r) TEM images of BV/CN samples.
FIG. 4 (a) SEM images of CdS, (b) and (c) TEM images of CdS samples; (d) SEM images of ClCS, (e) and (f) TEM images of ClCS samples; (g) SEM images of MoCS, (h) and (i) TEM images of MoCS samples; (j) SEM images of VCS, (k) and (l) TEM images of VCS samples.
Fig. 5 (a) shows the removal performance of the photocatalyst prepared on glyphosate, (b) shows the kinetic fitting of the removal of glyphosate, (c) shows the experimental cycle of degrading glyphosate by the ClCS heterojunction, and (d) shows XRD spectra of the ClCS heterojunction before and after the experimental cycle.
Detailed Description
The following are specific examples of the present invention and further describe the technical solutions of the present invention, but the present invention is not limited to these examples.
Example one
A microwave rapid preparation method of a Bi-based S-type heterojunction and photodegradation application thereof are characterized in that the rapid preparation method comprises the following specific steps:
the method comprises the following steps: preparation of pure g-C by two-step calcination method 3 N 4 The dicyandiamide and the urea with certain mass are mixed according to the proportion of 1. After the sample was cooled to room temperature, light yellow g-C was obtained 3 N 4 ；
Step two: preparing a Bi-based composite photocatalyst by a microwave method, and sequentially adding 0.485g of Bi (NO) 3 ) 3 ·5H 2 O, 0.15g PVP, one of the anionic precursors, e.g. 0.074g KCl or 0.103g Na 2 MoO 4 Or 0.1198g NH 4 VO 3 And g-C accounting for 60% of the mass of the composite photocatalyst 3 N 4 Adding into mixed solvent composed of 40mL of ethylene glycol and 10mL of acetic acid solution, stirring at room temperature for 30min, transferring the suspension into a normal pressure microwave reactor, and heating for 15min under the following heating conditions: the heating temperature is 140 ℃, the heating power is 800W, and the stirring speed is 2000r/min. Then washing with deionized water and ethanol for more than 3 times, centrifuging, and drying in an oven at 60 deg.C for 12 hr to obtain yellow powders with different colors, wherein the Bi-based S-type heterojunction photocatalyst prepared according to the type of the added anion precursor is KCl and Na respectively 2 MoO 4 、NH 4 VO 3 The samples are named as BCl/CN, BMo/CN and BV/CN;
step three: 0.7-1.0g of BCl/CN, one of BMo/CN and BV/CN and 0.308g of Cd (NO) are sequentially mixed 3 ) 3 ·4H 2 O was added to a mixed solvent composed of 40mL of ethylene glycol and 10mL of acetic acid solution (1M) and kept at 50 ℃ for 10min, and then 0.1g of PVP and 0.6204g of Na were added 2 S 2 O 3 ·5H 2 Adding O into the solution, keeping the temperature at 50 ℃ for 30min, transferring the suspension into a normal-pressure microwave reactor, heating for 10min at the temperature of 120 ℃, the heating power of 800W and the stirring speed of 2000r/min. And then washing the obtained product for more than 3 times by using deionized water and ethanol, centrifuging the obtained product, and finally drying the obtained product in an oven at the temperature of 60 ℃ for 12 hours to obtain dark yellow powder, wherein the types of the added Bi-based composite photocatalyst are BCl/CN, BMo/CN and BV/CN respectively, and the prepared Bi-based double S type heterojunction photocatalyst samples are named as ClCS, moCS and VCS.
The crystal phase, the catalytic activity and the like of the prepared photocatalysts ClCS, moCS and VCS are analyzed through characterization technologies such as XRD, XPS, ESR, EIS and the like, and the photocatalytic activity of the prepared Bi-based double S-type heterojunction and the recovery stability of ethylene glycol on the photocatalysts are evaluated through degrading glyphosate in water.
Characterization of materials
XRD analysis was first performed to investigate the crystal phase structure, and the results are shown in FIG. 1, wherein pure Bi-based materials (BiOCl, bi) 2 MoO 6 、BiVO 4 ) And the diffraction peak of CdS and the square phase BiOCl and the square phase Bi respectively 2 MoO 6 Monoclinic phase BiVO 4 Matched with CdS, and pure g-C 3 N 4 Diffraction peaks of (100) and (002) planes composed of s-triazine ring units also appear at 12.7 DEG and 27.7 DEG, proving that BiOCl and Bi 2 MoO 6 、BiVO 4 、g-C 3 N 4 And CdS, all characteristic peaks of Bi-based materials are successfully reserved for the composite sample, and g-C also appears in BCl/CN and BV/CN composite samples 3 N 4 The characteristic (002) crystal face diffraction peak, but the Bi-based double S-type heterojunction does not have the obvious CdS diffraction peak, probably because the CdS content is lower and the CdS diffraction peak intensity is far less than that of the Bi-based material.
The molecular structure of the sample was analyzed by FT-IR spectroscopy, as shown in FIG. 1, with pure CdS at 634cm -1 And 1007cm -1 The characteristic peaks are from the stretching and bending vibration of Cd-S, the vibration peak at 1630cm-1 is due to the moisture absorption of Cd surface, and the pure g-C 3 N 4 At 1239cm -1 -1642cm -1 The vibration peak appearing in the interval is derived from the stretching vibration of C-N heterocycle, and pure Bi-based materials BiOCl and Bi 2 MoO 6 、BiVO 4 Respectively at 1040cm -1 、734cm -1 、727cm -1 The vibration peak at (B) corresponds to vibration of Bi-Cl bond, moO 6 Asymmetric stretching vibration, v 3 (VO) 4 ) The ClCS, moCS and VCS compounds well retain respective monomers and pure g-C 3 N 4 Characteristic diffraction peak of (1).
Successful preparation of Bi-based double-S-type heterojunction and Bi-based material, cdS and g-C in Bi-based double-S-type heterojunction 3 N 4 The interaction of (c) was characterized by XPS, as shown in FIGS. 2 and 3, and full spectrum analysis showed that Cd 3The characteristic peaks of d and S2 p appear not only in the pure CdS sample, but also in the ClCS, moCS and VCS complexes, which have respective characteristic peaks and g-C 3 N 4 The characteristic N1S peak, these characteristic peaks prove the successful preparation of Bi-based double S heterojunction ClCS, moCS and VCS, there is a clear electron transfer between CdS and Bi-based material, the characteristic peaks belonging to Cd 3d3/2 and Cd 3d5/2 spin orbitals have binding energy positions of 404.39eV and 411.13eV respectively in pure CdS, while in Bi-based double S heterojunction a clear red shift occurs, with an approximate red shift of 0.61eV in the ClCS sample, this trend is also applicable to the S element, in the high resolution spectrogram of S2 p orbit, the characteristic peaks of pure CdS at 158.50eV and 163.91eV correspond to 2p1/2 and S2 p3/2 spin orbitals respectively, while in the ClCS composite sample, these two peaks are shifted by about 0.34eV towards the high binding energy direction. It can be seen that the characteristic peaks corresponding to the Bi 4f7/2 and Bi 4f5/2 spin orbitals have binding energy positions of 158.80eV and 164.13eV in pure BiOCl, while the binding energy positions in ClCS are shifted to 158.38eV and 163.64eV, respectively, by 0.42eV. Similarly, a significant shift in O element was observed, the binding energy of ClCS was reduced by about 0.66eV relative to that of pure BiOCl, the Cl2p spectrum characteristic of ClCS, the Mo 3d spectrum characteristic of MoCS, and the V2 p spectrum characteristic of VCS all exhibited similar shifts in binding energy, i.e., the binding energy of the complex was reduced relative to that of the Bi-based monomer, and the same results apply to Bi in CdS complexed with Bi 2 MoO 6 /g-C 3 N 4 And BiVO 4 /g-C 3 N 4 The combination energy of MoCS and VCS of the photocatalyst is increased compared with pure CdS, and compared with pure Bi 2 MoO 6 And BiVO4, moCS and VCS, XPS results show that ClCS, moCS and VCS have been successfully prepared, a heterojunction interface exists between the CdS and the Bi-based material, electrons are transferred between the CdS and the Bi-based material at the heterojunction interface, the CdS is used as a donor of electrons in the heterojunction, and the Bi-based monomer material is used as an acceptor of electrons in the heterojunction.
The morphology and structural information of the material was studied by SEM, TEM and HRTEM, as shown in fig. 3. From the SEM (FIG. 3 a) and TEM images (FIG. 3 d), it can be seen that pure BiOCl appears to be measured by diameterA microsphere structure consisting of nano-sheets of about 2 μm. FIGS. 3b and 3C show that BiOCl microspheres were successfully deposited on lamellar g-C of BCl/CN composites 3 N 4 Surface, and the recombination of the material did not disrupt the microsphere structure of BiOCl (fig. 3 e). HRTEM (FIG. 3 f) indicates BiOCl and g-C 3 N 4 The BiOCl has lattice spacing of 0.256nm corresponding to (111) crystal face and complete crystal lattice, which provides guarantee for good photocatalytic performance. EDX spectroscopy (FIG. 3 s) shows that the BCl/CN composite consists of Bi, O, cl, C, and N elements, consistent with XRD and XPS results. Pure Bi 2 MoO 6 Is an amorphous particle with a diameter of about tens of nanometers (fig. 3g, j). FIG. 3h, FIG. 3i and FIG. 3k show Bi in granular form 2 MoO 6 Deposited on g-C 3 N 4 On a nano-chip, and Bi 2 MoO 6 The agglomeration condition is obviously improved. In BMO/CN composites, bi 2 MoO 6 Has a complete lattice with a lattice spacing of 0.256nm, and Bi 2 MoO 6 Is (200) crystal plane matched (FIG. 3 l), and Bi 2 MoO 6 And g-C 3 N 4 With the formation of a heterojunction therebetween. Pure BiVO 4 The appearance of the structure is a rice grain-shaped structure (figure 3m, p) of about 800nm, and BiVO is not changed by increasing the temperature and shortening the microwave time 4 Further analysis showed (FIG. 3n, o, q) rice-grain-shaped BiVO 4 Well deposited on flaky g-C 3 N 4 And HRTEM fig. 4-4 r) can see that both are tightly bound and BiVO 4 (121) The lattice fringes corresponding to the crystal faces are complete.
Meanwhile, the ethylene glycol-acetic acid synergistic system still plays an important role in the preparation process of the microwave response type Bi-based material. Acetic acid can well induce the anion and cation polymerization of the Bi-based material, ethylene glycol has good lamellar guiding effect, biOCl microspheres are formed by lamellar intercalation (figure 3 a), and granular Bi 2 MoO 6 Exhibits a very pronounced short floccus (FIG. 3 j), while BiVO 4 It is a rice grain formed by a stack of sheets (fig. 3 m). The above results indicate that the excellent crystal structure of the microwave responsive bismuth-based oxide, ethylene glycol-acetic acidThe synergistic system provides possibility for the adjustment of morphology and the formation of heterojunction to enhance photocatalytic activity.
The formation of Bi-based double S-type heterojunctions was further confirmed by SEM, TEM, and HRTEM, and morphological and structural information of the material was studied. SEM and TEM images of CdS show (fig. 4a, b, c) that pure CdS tends to form aggregated spheres with diameters of about 200nm-500nm without a Bi-based material substrate. EDX images (figure 4 m) of ClCS show that the ClCS heterojunction is composed of Cd, S, bi, cl, O, C and N, SEM and TEM images of ClCS show (figure 4 d-f), the surface of BiOCl flower-shaped microspheres in ClCS is wrapped with a plurality of CdS small particles with the diameter of about 5nm, which shows that the agglomeration phenomenon of CdS is obviously improved, and the heterojunction is formed as proved by close contact between CdS and BiOCl. Bi in analogous MoCS 2 MoO 6 BiVO in popcorn (FIG. 4 g-i) and VCS 4 The surfaces of rice grains (figure 4 j-l) all have well-dispersed CdS small particle coatings and CdS successful deposition, which shows that heterojunction exists in Bi-based materials and g-C 3 N 4 In the meantime. Fig. 4N and 4O show that the MoCS and VCS heterojunctions consist of Cd, S, bi, mo, O, C, N elements and Cd, S, bi, V, O, C, N elements, respectively, further confirming the successful preparation of Bi-based double S-type heterojunctions.
In summary, cdS is a collection sphere with a diameter of 200nm-500nm when there is no Bi-based material substrate; when the Bi-based material exists, the particle size of CdS particles is about 5nm, and the CdS particles are dispersedly coated on the surface of the Bi-based material, which shows that the construction of the Bi-based double S-type heterojunction well improves the dispersion condition of CdS.
Photocatalytic performance and cycling stability results of the materials
In order to evaluate the photocatalytic performance of a prepared sample, a typical herbicide glyphosate is degraded under the irradiation of simulated sunlight, when the adsorption-desorption is balanced after the dark reaction is finished, the removal efficiency of the photocatalyst is less than 5 percent, the influence of the adsorption on the removal of the glyphosate can be ignored, and when the illumination reaches 90min, pure BiOCl and Bi are obtained 2 MoO 6 、BiVO 4 And g-C 3 N 4 The degradation rates for glyphosate were only 18%, 6%, 5% and 9%, respectively, compared to other samples showing increasing glyphosateThe degradation rate is increased because of the enhanced separation capability of the photogenerated carriers in the composite photocatalyst. The removal rates of the S-type heterojunction BCl/CN, BMo/CN and BV/CN to glyphosate are respectively improved to 80%, 76% and 72%, the double S-type heterojunction formed by adding CdS further improves the removal effect of glyphosate, the degradation rates of ClCS, moCS and VCS to glyphosate after xenon lamp irradiation for 90min respectively reach 98%, 90% and 87%, and the photocatalytic efficiencies of the double S-type heterojunction BCl/CN, BMo/CN and BV/CN are respectively 5.4 times, 15 times and 17.4 times of respective monomers. The removal kinetic fit of the glyphosate can be approximately regarded as a quasi-first-order process, and the rate constant of the ClCS photocatalyst is 0.0341min -1 Reaching 19 times of pure BiOCl and g-C 3 N 4 The ratio of the total weight of the raw materials is 43 times,
through continuous 4-time experiments of degrading glyphosate circularly by using the photocatalyst, the stability of the ClCS photocatalyst is evaluated, after 4-time circular tests, the photocatalytic performance is not obviously reduced and is only reduced by about 7%, XRD (X-ray diffraction) patterns of samples before and after the stability test show that the crystal phase of the ClCS is not changed after 4-time circular tests, and the results show that the activity of the photocatalyst is remarkably improved and the photo-corrosion of CdS is effectively improved by constructing the double S-shaped heterojunction.
The renewable performance of ethylene glycol during the preparation of non-Bi based materials (CdS) was further evaluated. Fig. 4e and f show that the ClCS-R5 sample prepared after 5 times of cyclic utilization of ethylene glycol still maintains the photocatalytic activity almost the same as that of the ClCS sample prepared for the first time, and the removal rate of glyphosate still reaches 97%. After 5 times of reutilization, the glycol still is transparent liquid without obvious impurities, and the volume of the regenerated glycol is more than 30mL, so that the recovery rate of over 80 percent is achieved.
Example two
A microwave rapid preparation method of a Bi-based S-type heterojunction and photodegradation application thereof are characterized in that the rapid preparation method comprises the following specific steps:
the method comprises the following steps: preparation of pure g-C by two-step calcination method 3 N 4 Mixing dicyandiamide and urea according to a certain mass ratio of 12h, the heating speed is 5 ℃/min. After the sample was cooled to room temperature, light yellow g-C was obtained 3 N 4 ；
Step two: preparing a Bi-based composite photocatalyst by a microwave method, and sequentially mixing 0.728g of Bi (NO) 3 ) 3 ·5H 2 O, 0.225g PVP, one of the anionic precursors, e.g. 0.111g KCl or 0.154g Na 2 MoO 4 Or 0.179g NH 4 VO 3 And g-C accounting for 40% of the mass of the composite photocatalyst 3 N 4 Adding into a mixed solvent composed of 40mL of ethylene glycol and 10mL of acetic acid solution, stirring at room temperature for 30min, transferring the suspension into a normal-pressure microwave reactor, and heating for 15min under the following heating conditions: the heating temperature is 140 ℃, the heating power is 600W, and the stirring speed is 2000r/min. Then washing with deionized water and ethanol for more than 3 times, centrifuging, and drying in an oven at 60 deg.C for 12 hr to obtain yellow powders with different colors, wherein the Bi-based S-type heterojunction photocatalyst prepared according to the type of the added anion precursor is KCl and Na respectively 2 MoO 4 、NH 4 VO 3 The samples were named BCl/CN, BMo/CN, BV/CN;
step three: 0.7g of BCl/CN, one of BMo/CN and BV/CN and 0.308g of Cd (NO) are sequentially added 3 ) 3 ·4H 2 O was added to a mixed solvent composed of 40mL of ethylene glycol and 10mL of acetic acid solution (1M) and kept at 50 ℃ for 10min, and then 0.1g of PVP and 0.6204g of Na were added 2 S 2 O 3 ·5H 2 Adding O into the solution, keeping the temperature at 50 ℃ for 30min, transferring the suspension into a normal-pressure microwave reactor, heating for 10min at the temperature of 140 ℃, the heating power of 800W and the stirring speed of 2000r/min. And then washing the obtained product for more than 3 times by using deionized water and ethanol, centrifuging the obtained product, and finally drying the obtained product in an oven at 60 ℃ for 12 hours to obtain dark yellow powder, wherein the types of the added Bi-based composite photocatalyst are BCl/CN, BMo/CN and BV/CN respectively, and the prepared Bi-based double S-type heterojunction photocatalyst samples are named as ClCS, moCS and VCS.
The crystal phase, the catalytic activity and the like of the prepared photocatalysts ClCS, moCS and VCS are analyzed through characterization technologies such as XRD, XPS, ESR, EIS and the like, and the photocatalytic activity of the prepared Bi-based double S-type heterojunction and the recovery stability of glycol on the photocatalysts are evaluated through degrading glyphosate in water.
Photocatalytic performance and cycling stability results of the material
In order to evaluate the photocatalytic performance of a prepared sample, a typical herbicide glyphosate is degraded under the irradiation of simulated sunlight, when the adsorption-desorption is balanced after the dark reaction is finished, the removal efficiency of the photocatalyst is less than 5 percent, the influence of the adsorption on the removal of the glyphosate can be ignored, and when the illumination reaches 90min, pure BiOCl and Bi are obtained 2 MoO 6 、BiVO 4 And g-C 3 N 4 The glyphosate degradation rates were only 18%, 6%, 5% and 9%, respectively, compared to other samples showing increasing glyphosate degradation rates due to the enhanced photogenerated carrier separation ability of the composite photocatalyst. The removal rates of the S-type heterojunction BCl/CN, BMo/CN and BV/CN to glyphosate are respectively improved to 80%, 76% and 72%, the double S-type heterojunction formed by adding CdS further improves the removal effect of glyphosate, and the degradation rates of ClCS, moCS and VCS to glyphosate after xenon lamp irradiation for 90min respectively reach 98%, 90% and 87%.
The ClCS-R5 sample prepared by recycling ethylene glycol for 5 times still keeps the photocatalytic activity almost the same as that of the ClCS sample prepared for the first time, and the removal rate of glyphosate still can reach 97%. After 5 times of reuse, the volume of the regenerated glycol is more than 30mL, and the recovery rate of over 82 percent is achieved.
EXAMPLE III
A microwave rapid preparation method of a Bi-based S-type heterojunction and photodegradation application thereof are characterized in that the rapid preparation method comprises the following specific steps:
the method comprises the following steps: preparation of pure g-C by two-step calcination method 3 N 4 The dicyandiamide and the urea with certain mass are mixed according to the proportion of 1. After the sample is cooled to room temperature, obtainLight yellow g-C 3 N 4 ；
Step two: preparing a Bi-based composite photocatalyst by a microwave method, and sequentially adding 0.485g of Bi (NO) 3 ) 3 ·5H 2 O, 0.15g PVP, one of the anionic precursors, e.g. 0.074g KCl or 0.103g Na 2 MoO 4 Or 0.1198g NH 4 VO 3 And g-C accounting for 60 percent of the mass of the composite photocatalyst 3 N 4 Adding into mixed solvent composed of 40mL of ethylene glycol and 10mL of acetic acid solution, stirring at room temperature for 30min, transferring the suspension into a normal pressure microwave reactor, and heating for 30min under the following heating conditions: the heating temperature is 120 ℃, the heating power is 600W, and the stirring speed is 2000r/min. Then washing with deionized water and ethanol for more than 3 times respectively, centrifuging, and finally drying in an oven at 60 ℃ for 12h to obtain yellow powder with different colors, wherein the Bi-based S-type heterojunction photocatalyst prepared according to the types of the added anion precursors is KCl and Na respectively 2 MoO 4 、NH 4 VO 3 The samples were named BCl/CN, BMo/CN, BV/CN;
step three: 1.0g of BCl/CN, one of BMo/CN and BV/CN and 0.308g of Cd (NO) are sequentially mixed 3 ) 3 ·4H 2 O was added to a mixed solvent composed of 40mL of ethylene glycol and 10mL of acetic acid solution (1M) and kept at 50 ℃ for 10min, and then 0.1g of PVP and 0.6204g of Na were added 2 S 2 O 3 ·5H 2 Adding O into the solution, keeping the temperature at 50 ℃ for 30min, transferring the suspension into a normal-pressure microwave reactor, heating for 20min at the temperature of 120 ℃, the heating power of 600W and the stirring speed of 2000r/min. And then washing the obtained product for more than 3 times by using deionized water and ethanol, centrifuging the obtained product, and finally drying the obtained product in an oven at 60 ℃ for 12 hours to obtain dark yellow powder, wherein the types of the added Bi-based composite photocatalyst are BCl/CN, BMo/CN and BV/CN respectively, and the prepared Bi-based double S-type heterojunction photocatalyst samples are named as ClCS, moCS and VCS.
The crystal phase, the catalytic activity and the like of the prepared photocatalysts ClCS, moCS and VCS are analyzed through characterization technologies such as XRD, XPS, ESR, EIS and the like, and the photocatalytic activity of the prepared Bi-based double S-type heterojunction and the recovery stability of glycol on the photocatalysts are evaluated through degrading glyphosate in water.
Photocatalytic performance and cycling stability results of the materials
In order to evaluate the photocatalytic performance of a prepared sample, a typical herbicide glyphosate is degraded under the irradiation of simulated sunlight, when the adsorption-desorption is balanced after the dark reaction is finished, the removal efficiency of the photocatalyst is less than 5 percent, the influence of the adsorption on the removal of the glyphosate can be ignored, and when the illumination reaches 90min, pure BiOCl and Bi are obtained 2 MoO 6 、BiVO 4 And g-C 3 N 4 The glyphosate degradation rates were only 17%, 5% and 7%, respectively, compared to other samples showing increasing glyphosate degradation rates due to the enhanced photogenerated carrier separation ability of the composite photocatalyst. The removal rates of the S-type heterojunction BCl/CN, BMo/CN and BV/CN to glyphosate are respectively improved to 84%, 76% and 75%, the double S-type heterojunction formed by adding CdS further improves the removal effect of glyphosate, and the degradation rates of ClCS, moCS and VCS to glyphosate respectively reach 99%, 93% and 91% after xenon lamp irradiation for 90 min.
After 4 times of cycle tests, the photocatalytic performance is not obviously reduced, and is only reduced by about 6%, which shows that the construction of the double S-type heterojunction not only obviously improves the activity of the photocatalyst, but also effectively improves the photo-corrosion of the CdS. The ClCS-R5 sample prepared by recycling the ethylene glycol for 5 times still maintains the photocatalytic activity almost the same as that of the ClCS sample prepared for the first time, and the glyphosate removal rate can still reach 95%. After 5 times of reutilization, the volume of the regenerated glycol is more than 30mL, and the recovery rate of more than 83 percent is achieved.
In conclusion, the construction of the Bi-based double S-type heterojunction not only greatly promotes the separation rate of photon-generated carriers, improves the removal efficiency of glyphosate, but also improves the photo-corrosion phenomenon of CdS, so that the photocatalyst has good cycling stability. The ethylene glycol-acetic acid synergistic system not only plays an important role in the preparation process of the Bi-based material, but also has good regeneration performance in the preparation process of CdS. Therefore, the method for preparing the Bi-based double-S type heterojunction by using the ethylene glycol-acetic acid synergistic system is a green, rapid and economic way.
Those not described in detail in this specification are well within the skill of the art. The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Claims (5)

1. A microwave rapid preparation method of a Bi-based S-type heterojunction and photodegradation application thereof are characterized in that the rapid preparation method comprises the following specific steps:
the method comprises the following steps: preparation of pure g-C by two-step calcination method 3 N 4 The dicyandiamide and the urea with certain mass are mixed according to the proportion of 1. After cooling the sample to room temperature, a pale yellow g-C is obtained 3 N 4 ；
Step two: preparing a Bi-based composite photocatalyst by a microwave method, and sequentially adding Bi (NO) 3 ) 3 ·5H 2 O, PVP, an anion precursor and g-C accounting for 40-60% of the mass of the composite photocatalyst 3 N 4 Adding into mixed solvent composed of 40mL of ethylene glycol and 10mL of acetic acid solution, stirring at room temperature for 30min, transferring the suspension into a normal pressure microwave reactor, heating for 15-30min, washing with deionized water and ethanol for more than 3 times after reaction, centrifuging, and drying in a 60 ℃ oven for 12h to obtain yellow powder with different colors, wherein the colors of the yellow powder are KCl and Na respectively according to the types of the added anion precursors 2 MoO 4 、NH 4 VO 3 The samples are named as BCl/CN, BMo/CN and BV/CN;
step three: 0.7-1.0g of BCl/CN, one of BMo/CN and BV/CN and 0.308g of Cd (NO) are sequentially mixed 3 ) 3 ·4H 2 O was added to a mixed solvent composed of 40mL of ethylene glycol and 10mL of acetic acid solution (1M) and kept at 50 ℃ for 10min, and then 0.1g of PVP and 0.6204g of Na were added 2 S 2 O 3 ·5H 2 Adding O into the solution, continuously keeping the temperature at 50 ℃ for 30min, transferring the suspension into a normal-pressure microwave reactor, heating for 10-20min, washing for more than 3 times by deionized water and ethanol after reaction, centrifuging, and finally drying in an oven at 60 ℃ for 12h to obtain dark yellow powder, wherein the prepared Bi-based double S type heterojunction products are named as ClCS, moCS and VCS according to the types of the added Bi-based composite photocatalyst, namely BCl/CN, BMo/CN and BV/CN.
2. The microwave rapid preparation method and photodegradation application of the Bi-based S-type heterojunction as claimed in claim 1, wherein in the second step, the Bi (NO) is 3 ) 3 ·5H 2 The content of O is 0.485 to 0.728g, and the content of PVP is 0.150 to 0.225g.
3. The microwave rapid preparation method and photodegradation application of the Bi-based S-type heterojunction of claim 1, wherein in the second step, the anion precursor is KCl and Na respectively 2 MoO 4 Or NH 4 VO 3 The content is 0.074-0.111g, 0.103-0.154g or 0.1198-0.179g respectively.
4. The microwave rapid preparation method and photodegradation application of the Bi-based S-type heterojunction of claim 1, wherein in the second step, the suspension is heated in an atmospheric microwave reactor under the following conditions:
the heating temperature is 120-140 ℃, the heating power is 600-800W, and the stirring speed is 2000r/min.
5. The microwave rapid preparation method and photodegradation application of a Bi-based S-type heterojunction of claim 1, wherein in the third step, the suspension is heated in an atmospheric pressure microwave reactor under the following conditions:
the heating temperature is 120-140 ℃, the heating power is 600-800W, and the stirring speed is 2000r/min.
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