CN113231099A - Preparation and application of Z-type polypyrrole-bismuth tungstate photocatalyst - Google Patents
Preparation and application of Z-type polypyrrole-bismuth tungstate photocatalyst Download PDFInfo
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- CN113231099A CN113231099A CN202110555342.XA CN202110555342A CN113231099A CN 113231099 A CN113231099 A CN 113231099A CN 202110555342 A CN202110555342 A CN 202110555342A CN 113231099 A CN113231099 A CN 113231099A
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- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 90
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 15
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- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910004803 Na2 WO4.2H2 O Inorganic materials 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
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- 238000003756 stirring Methods 0.000 claims description 12
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 27
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
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- B01J35/23—
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides preparation and application of a Z-type polypyrrole-bismuth tungstate photocatalyst, and relates to the field of photocatalysis. The invention is characterized in that Bi (NO3) 3.5H 2O (9mmol) and Na2WO 4.2H 2O (4.5mmol) are dissolved in ethylene glycol, subjected to solvothermal reaction, washed and dried to form a first precipitate; then transferring the mixture into a muffle furnace for calcining; after calcination, the polypyrrole/bismuth tungstate/polypyrrole composite material is dispersed in FeCl 3.6H2O solution, and pyrrole is added so that the pyrrole is polymerized in situ and deposited on the surface of the polypyrrole/bismuth tungstate/polypyrrole/bismuth tungstate composite material. The preparation method of the catalyst is simple and convenient, only uses the conventional solvothermal method, the calcining method and the in-situ polymerization deposition process, enhances the separation and migration capability of the photon-generated carriers, and also reserves the higher oxidation reduction capability of the catalyst.
Description
Technical Field
The invention relates to a preparation method of a catalyst, in particular to preparation and application of a Z-type polypyrrole-bismuth tungstate photocatalyst, and belongs to the technical field of photocatalysis.
Background
Cr (VI) is a very common industrial reagent and is widely applied to the fields of electroplating, printing and dyeing, tanning and the like. With the continuous development of the industrialization process, Cr (VI) is continuously discharged into the environment, and the concentration of Cr (VI) in the water environment ranges from 0.5 mg/L to 270.0 mg/L. However, the residue of cr (vi) in aquatic environments constitutes a potential threat to humans, animals and plants due to high toxicity, carcinogenicity and mutagenicity. At present, the commonly used cr (vi) wastewater treatment methods include membrane separation, ion exchange, adsorption, chemical reduction and other technologies. The methods have the defects of high cost, serious secondary pollution, high energy consumption and the like. Therefore, there is a strong need for an effective, economical, clean cr (vi) environmental remediation process. Therefore, it is imperative to develop an efficient and economical cr (vi) treatment process. With the development of the photocatalytic technology, people gradually apply the photocatalytic technology to the treatment of Cr (VI) sewage. The photocatalytic technology utilizes clean solar energy as an energy source to efficiently reduce Cr (VI) into Cr (III) ions which are low in toxicity and are trace elements necessary for a human body, so that the photocatalytic technology is considered to be an economic, environment-friendly, clean and effective Cr (VI) treatment strategy.
Bismuth tungstate is a perovskite type semiconductor material, and the band gap width of the bismuth tungstate is about 3.0eV, so that the bismuth tungstate can absorb and respond to visible light. Meanwhile, the bismuth tungstate has an easily controlled appearance, and the bismuth tungstate with a microsphere structure has a larger specific surface area and more reaction active sites. In addition, bismuth tungstate also has many excellent characteristics of no toxicity, high stability, simple preparation and the like, is widely concerned by people, and has great application prospect in the field of photocatalysis. However, a single material has the disadvantages of weak separation capability of photon-generated carriers, low migration efficiency, high recombination rate of electron-hole pairs and the like, and further influences the photocatalytic activity. Therefore, bismuth tungstate must be modified to improve the photocatalytic performance, so that a Z-type polypyrrole-bismuth tungstate photocatalyst (PPY/BWO) is prepared.
Disclosure of Invention
Technical problem to be solved
The invention aims to solve the problems in the prior art by providing a preparation method and application of a Z-type polypyrrole-bismuth tungstate photocatalyst.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: a preparation method of a Z-type polypyrrole-bismuth tungstate photocatalyst comprises the steps of firstly, respectively dissolving Bi (NO3) 3.5H 2O (9mmol) and Na2WO 4.2H 2O (4.5mmol) in 30mL of ethylene glycol;
step two, mixing Bi (NO3) 3.5H 2O and Na2WO 4.2H 2O dissolved in ethylene glycol, and violently stirring for 1H to form a mixture;
step three, transferring the mixture into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene inner container, putting the reaction kettle into an oven to react for 5 hours at 180 ℃, taking out and cooling to room temperature to obtain a first precipitate;
step four, washing the obtained precipitate with absolute ethyl alcohol and distilled water for three times respectively, then drying at 60 ℃, grinding the dried solid, putting the ground solid into a crucible, and then transferring the crucible to a muffle furnace;
step five, heating the mixture to 300 ℃ in a muffle furnace at the heating rate of 5 ℃/min and keeping the temperature for 3h, and recording the obtained material as BWO;
step six, adding 1.0g BWO into 150.0mL FeCl 3.6H2O solution and continuously stirring for 1H, then adding a specific amount of pyrrole into the mixture, and continuously stirring the solution for 6H to form a black second precipitate;
and step seven, washing the second precipitate for multiple times by using deionized water and ethanol, and drying at 60 ℃ to form the composite material.
Preferably, the mass percentage of the pyrrole is set to 1wt%, 2wt%, 3wt%, 4wt%, and the composite material is respectively recorded as 1% polypyrrole-bismuth tungstate, 2% polypyrrole-bismuth tungstate, 3% polypyrrole-bismuth tungstate, and 4% polypyrrole-bismuth tungstate.
A method for using a Z-type polypyrrole-bismuth tungstate photocatalyst in Cr (VI) comprises the steps of firstly, dispersing a prepared composite material (15.0mg) in 100.0mLCr (VI) aqueous solution (10.0mg/L), adding 1.0mL of citric acid solution (100.0g/L) as a hole scavenger, and adjusting the pH value of a reaction solution by using hydrochloric acid and sodium hydroxide solution to form a mixture;
step two, before the photocatalytic reaction is carried out, stirring the mixture in the step one for 20min in the dark to ensure that the mixture reaches adsorption balance;
step three, moving the stirred mixture to a 300W xenon lamp with a 420nm optical filter for irradiation;
step four, taking 1.0mL of reaction suspension every 5 minutes, immediately centrifuging, and using the centrifuged supernatant for determining Cr (VI).
The invention provides preparation and application of a Z-type polypyrrole-bismuth tungstate photocatalyst, which has the following beneficial effects:
1. the preparation method of the catalyst is simple and convenient, and only the conventional solvothermal method, the conventional calcining method and the conventional in-situ polymerization deposition process are used.
2. The two materials are compounded to form a unique direct Z-shaped carrier transmission structure, so that the absorption response of visible light is improved, the separation and migration capability of photon-generated carriers is enhanced, and the higher redox capability of the catalyst is reserved.
3. The catalyst produced by the preparation method has excellent photocatalytic activity, good treatment capacity on Cr (VI) sewage, no secondary pollution and strong recycling capacity, and lays a foundation for the application of a photocatalytic technology.
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of a BWO and polypyrrole-bismuth tungstate catalyst of the present invention;
FIG. 2 is a scanning electron microscope observation of the microscopic morphology and particle distribution of the catalyst sample according to the present invention; wherein, the upper left corner is a Scanning Electron Microscope (SEM) image of BWO; the top right corner is an SEM image of the 2% polypyrrole-bismuth tungstate nanocomposite; the lower left corner is a Transmission Electron Microscope (TEM) spectrum (the inset is an electron diffraction pattern SAED) of 2% polypyrrole-bismuth tungstate; the lower right corner is a high-resolution transmission electron microscopy (HRTEM) spectrum of the 2% polypyrrole-bismuth tungstate nanocomposite;
FIG. 3 is X Photoelectron Spectrum (XPS) of 2-polypyrrole-bismuth tungstate nanocomposite of the present invention, and (a) full spectrum; (b) bi4 f; (c) w4 f; (d) o1 s; (e) c1 s; (f) n1 s;
FIG. 4 shows the optical and optoelectronic properties of the catalyst of the present invention (a) ultraviolet-visible diffuse reflectance spectroscopy (UV-visDRS) of BWO and polypyrrole-bismuth tungstate nanocomposites; (b) is an absorption band edge diagram; (c) Mott-Schottky (M-S) curve; (d) electrochemical impedance curves (EIS);
FIG. 5 shows the photocatalytic experiment (a) and first order kinetic constants (b) for BWO and polypyrrole-bismuth tungstate (0.15g/L) nanocomposite degradation of 10mg/LCr (VI) according to the present invention;
FIG. 6 shows an Electron Paramagnetic Resonance (EPR) spectrum of a 2% polypyrrole-bismuth tungstate nanocomposite of the present invention under visible light irradiation, where (a) is a superoxide radical spectrum; (b) is a hydroxyl radical spectrogram; (c) is a mechanism schematic diagram of 2 percent polypyrrole-bismuth tungstate photocatalysis reduction Cr (VI).
Detailed Description
The embodiment of the invention provides a preparation method of a Z-type polypyrrole-bismuth tungstate photocatalyst, which comprises the following steps of firstly, respectively dissolving Bi (NO3) 3.5H 2O (9mmol) and Na2WO 4.2H 2O (4.5mmol) in 30mL of ethylene glycol;
step two, mixing Bi (NO3) 3.5H 2O and Na2WO 4.2H 2O dissolved in ethylene glycol, and violently stirring for 1H to form a mixture;
step three, transferring the mixture into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene inner container, putting the reaction kettle into an oven to react for 5 hours at 180 ℃, taking out and cooling to room temperature to obtain a first precipitate;
step four, washing the obtained precipitate with absolute ethyl alcohol and distilled water for three times respectively, then drying at 60 ℃, grinding the dried solid, putting the ground solid into a crucible, and then transferring the crucible to a muffle furnace;
step five, heating the mixture to 300 ℃ in a muffle furnace at the heating rate of 5 ℃/min and keeping the temperature for 3h, and recording the obtained material as BWO;
step six, adding 1.0g BWO into 150.0mL FeCl 3.6H2O solution and continuously stirring for 1H, then adding a specific amount of pyrrole into the mixture, and continuously stirring the solution for 6H to form a black second precipitate;
and step seven, washing the second precipitate for multiple times by using deionized water and ethanol, and drying at 60 ℃ to form the composite material.
The mass percentages of pyrrole are set as 1wt%, 2wt%, 3wt% and 4wt%, and the composite materials are respectively marked as 1% polypyrrole-bismuth tungstate, 2% polypyrrole-bismuth tungstate, 3% polypyrrole-bismuth tungstate and 4% polypyrrole-bismuth tungstate.
A method for using a Z-type polypyrrole-bismuth tungstate photocatalyst in Cr (VI) comprises the steps of firstly, dispersing a prepared composite material (15.0mg) in 100.0mLCr (VI) aqueous solution (10.0mg/L), adding 1.0mL of citric acid solution (100.0g/L) as a hole scavenger, and adjusting the pH value of a reaction solution by using hydrochloric acid and sodium hydroxide solution to form a mixture;
step two, before the photocatalytic reaction is carried out, stirring the mixture in the step one for 20min in the dark to ensure that the mixture reaches adsorption balance;
step three, moving the stirred mixture to a 300W xenon lamp with a 420nm optical filter for irradiation;
step four, taking 1.0mL of reaction suspension every 5 minutes, immediately centrifuging, and using the centrifuged supernatant for determining Cr (VI).
When the invention is used for preparation, the preparation method is simple and convenient, and only the conventional solvothermal method, the calcining method and the in-situ polymerization deposition process are used.
The combination of the two materials forms a unique direct Z-shaped carrier transmission structure, thereby not only improving the absorption response of visible light and enhancing the separation and migration capability of photon-generated carriers, but also reserving the higher oxidation reduction capability of the catalyst.
Has excellent photocatalytic activity, good treatment capacity on Cr (VI) sewage, no secondary pollution and strong recycling capacity, and lays a foundation for the application of a photocatalytic technology.
Referring to fig. 1, the polypyrrole-bismuth tungstate composite catalyst is well crystallized, and the characteristic diffraction peak is matched with the bismuth tungstate orthorhombic phase (PDF #39-0256, JCPDS). Due to the amorphous structure of PPy, no other impurity peak appears, and the position and the intensity of the diffraction peak of the bismuth tungstate after the PPy is added are not changed. Therefore, the introduction of PPy does not change the crystal structure of bismuth tungstate.
Referring to FIG. 2, the top left corner is a Scanning Electron Microscope (SEM) of BWO; the top right corner is an SEM image of the 2% polypyrrole-bismuth tungstate nanocomposite; the lower left corner is a Transmission Electron Microscope (TEM) spectrum (the inset is an electron diffraction pattern SAED) of 2% polypyrrole-bismuth tungstate; the lower right corner is a High Resolution Transmission Electron Microscopy (HRTEM) of a 2% polypyrrole-bismuth tungstate nanocomposite.
From SEM, it can be seen that after 2% PPy is compounded with bismuth tungstate, the obtained composite material presents a flower-ball-shaped structure similar to the original bismuth tungstate (shown in the upper left corner of FIG. 2 and the upper right corner of FIG. 2), and the structure has a larger surface area and can provide more catalytic active sites. TEM and HRTEM show more detailed morphology structure of the composite material. As shown in the left lower corner of FIG. 2, the 2% polypyrrole-bismuth tungstate particles have a diameter less than 10nm and are slightly agglomerated. The SAED plot (shown in the lower left corner of fig. 2) consists of several rings consisting of diffraction patterns of crystals, which are regular and bright, indicating that the composite has a polycrystalline structure and is well crystallized. The corresponding crystal planes of the ring in the diffraction pattern are respectively selected as (131), (202), (200), (391) and (133) planes, and are consistent with XRD data. The figure in the lower right hand corner of fig. 2 shows HRTEM of the sample. The lattice spacing is 0.315nm according to the measurement, and is consistent with the crystal face (131) of bismuth tungstate. And the PPy particles are also obviously adhered to the surface of the bismuth tungstate particles in the lower right corner of the figure 2.
Please refer to fig. 3, wherein (a) the full map; (b) bi4 f; (c) w4 f; (d) o1 s; (e) c1 s; (f) n1 s.
As shown in FIG. 3a, XPS of BWO and 2% polypyrrole-bismuth tungstate showed Bi, W, O, C and N on the composite surface. The high resolution spectra of the individual elements Bi, W, O, C and N are shown in FIG. 3 (b-f). The binding energies of the Bi4f7/2 and Bi4f5/2 peaks of BWO are about 159.3 and 164.6eV (FIG. 3b), indicating the Bi3+ oxidation state. The XPS spectrum of W4f (FIG. 3c) split into two peaks, located at 35.1eV (for W4f7/2) and 37.2eV (for W4f5/2), indicating that W is in the W6+ oxidation state. The binding energy of Bi4f and W4f was slightly reduced in 2% polypyrrole-bismuth tungstate compared to BWO, indicating that there was an interfacial interaction between BWO and PPy. As shown in FIG. 3d, the signal of O1s splits into three peaks at 529.7eV, 531.4eV, and 532.8eV, corresponding to lattice oxygen, -OH, and adsorbed oxygen, respectively. As shown in fig. 3e, the XPS spectrum of C1s was divided into 3 peaks with binding energies of 288.4eV, 285.9eV and 284.5eV, corresponding to N ═ C (-N)2, C-N and C-C bonds, respectively. As shown in fig. 3f, the N1s spectrum has three peaks, 401.3eV, 4001eV and 398.4eV, indicating the presence of positively charged nitrogen atoms (-N +), neutral nitrogen atoms (-N-H) and sp 2-bonded nitrogen atoms (C ═ N-C) in PPy, respectively.
Referring to FIG. 4, therein, (a) ultraviolet-visible diffuse reflectance spectroscopy (UV-visDRS) of BWO and polypyrrole-bismuth tungstate nanocomposites; (b) is an absorption band edge diagram; (c) Mott-Schottky (M-S) curve; and (d) is an electrochemical impedance curve (EIS).
The UV-visDRS of the prepared composite is shown in FIG. 4 a. After PPy is introduced into bismuth tungstate, a red shift phenomenon appears on the absorption edge of the prepared sample, which indicates that PPy successfully modifies the surface of bismuth tungstate nano particles, and the interaction between PPy and PPy enhances the response of the composite material to visible light. The band gap of the composite material prepared by the Kubelka-Munk formula is shown in figure 4 b: α hv ═ a (hv-Eg) n/2n, where α is the absorption coefficient, h is the planck constant, a is the proportionality constant, ν is the optical frequency, and Eg is the band gap width. The Eg values of BWO, 1% polypyrrole-bismuth tungstate, 2% polypyrrole-bismuth tungstate, 3% polypyrrole-bismuth tungstate and 4% polypyrrole-bismuth tungstate are calculated to be 3.01, 2.82, 2.77, 2.73 and 2.70eV respectively. This indicates that polypyrrole-bismuth tungstate exhibits a narrower band gap, contributing to exhibiting better performance under visible light.
To further understand the properties and band structure of the samples, we obtained M-S curves for pure bismuth tungstate and 2% polypyrrole-bismuth tungstate (as shown in FIG. 4 c). The slope of the fitted curve is positive indicating that the composite prepared is typically n-type. The planar band potentials were-1.13V and-1.28V (vs. Ag/AgCl), respectively. The measured potential is converted into an electrode potential opposite to a Normal Hydrogen Electrode (NHE) according to the following formula:
VNHE ═ VAg/AgCl + V0Ag/AgCl, where VNHE is the flat band potential after conversion, and V0Ag/AgCl (0.197V,298K) and VAg/AgCl are the standard potential and experimental potential, respectively, relative to the Ag/AgCl electrode. Since the n-type semiconductor flat band potential can be approximately regarded as the conduction band potential (VCB), VCBs of BWO and 2% polypyrrole-bismuth tungstate are about-0.93V and-1.08V (vs. NHE), respectively. The bandgaps of BWO and 2% polypyrrole-bismuth tungstate obtained from the UV-vis curve were 3.01eV and 2.77eV, respectively (FIG. 4b), and thus the VVB positions of BWO and 2% polypyrrole-bismuth tungstate were calculated to be 2.08V and 1.69V (vs. NHE), respectively.
To explore the separation and transfer of photogenerated carriers, we performed EIS analysis on the prepared composite material. As shown in fig. 4d, the nyquist circle diameter of the sample was R (bwo) > (4% polypyrrole-bismuth tungstate) > R (3% polypyrrole-bismuth tungstate) > R (1% polypyrrole-bismuth tungstate) > R (2% polypyrrole-bismuth tungstate). The arc radius of the polypyrrole-bismuth tungstate is smaller, which shows that the introduction of PPy improves the transfer rate of interface charges. This shows that the addition of PPy can make the transfer speed of photogenerated carriers faster, thereby achieving effective separation.
Referring to fig. 5, as shown in fig. 5a, the activity of pure bismuth tungstate for photocatalytic reduction of cr (vi) is low, and cr (vi) is reduced by only 31% after 30 minutes of visible light irradiation. After PPy is deposited on the surface, the photocatalytic reduction efficiency of all polypyrrole-bismuth tungstate composite materials is superior to that of pure bismuth tungstate. When the PPy composite proportion is 2%, the polypyrrole-bismuth tungstate catalyst has the best photocatalytic performance, and the reduction efficiency reaches 99.7% in 15 min. In addition, we also examined the stability and reusability of 2% polypyrrole-bismuth tungstate, and the results showed that the reduction capability of cr (vi) was only reduced by 7% after 5 cycles (fig. 5 b). The prepared photocatalyst has good recycling performance.
Referring to fig. 6, wherein (a) is a superoxide radical spectrum; (b) is a hydroxyl radical spectrogram; (c) is a mechanism schematic diagram of 2 percent polypyrrole-bismuth tungstate photocatalysis reduction Cr (VI).
As shown in fig. 6(a, b), no ESR signal was observed in the non-irradiated photocatalytic reaction. Upon irradiation with visible light, four-wire ESR signals with intensity ratios of 1:1:1:1 and 1:2:2:1 were observed, characteristic of DMPO-. O2-and DMPO-. OH, respectively. In addition, the ESR signal intensity increased significantly with the time of light irradiation, indicating that a large amount of OH and O2-were continuously generated in the system. Since the redox potential of O2/. O2-is-0.33V (vs. NHE) and the redox potential of H2O/. OH is 1.99V (vs. NHE), the electron transfer mechanism of the catalyst is probably Z-type system by combining the energy band structures of bismuth tungstate and PPy. Therefore, we have derived a mechanism for 2% polypyrrole-bismuth tungstate to reduce cr (vi), as shown in fig. 6 c. First, both bismuth tungstate and PPy are excited by visible light to generate photo-generated electrons and holes. Meanwhile, Cr (VI) is in surface contact with 2 percent of polypyrrole-bismuth tungstate composite material. The photogenerated electrons on CB of bismuth tungstate are then transferred to the contact interface and recombine with holes in the HOMO of PPy. Therefore, the photogenerated carriers on the LUMO of PPy and VB of bismuth tungstate are effectively separated and rapidly transferred to the catalyst surface. The rapid electron transfer of the highly conductive polypyrrole further avoids recombination of photogenerated carriers. All electron transfer processes described above contribute to the cr (vi) reduction reaction. Subsequently, an electron forms an O2-radical from O2 on the LUMO of PPy, and an OH-radical from H2O on the VB of bismuth tungstate. The redox potential of the electron on LUMO of PPy and O2-is higher than the cr (vi)/cr (iii) potential (1.15V vs. nhe, pH 3.0), indicating that the electron sum O2-can reduce cr (vi) to cr (iii). Meanwhile, organic pollutants are synchronously degraded, holes and OH are consumed, and electrons and O2-species in the system are prevented from being consumed by oxidizing species.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A preparation method of a Z-type polypyrrole-bismuth tungstate photocatalyst is characterized by comprising the following steps: step one, dissolving Bi (NO3) 3.5H 2O (9mmol) and Na2WO 4.2H 2O (4.5mmol) in 30mL of ethylene glycol respectively;
step two, mixing Bi (NO3) 3.5H 2O and Na2WO 4.2H 2O dissolved in ethylene glycol, and violently stirring for 1H to form a mixture;
step three, transferring the mixture into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene inner container, putting the reaction kettle into an oven to react for 5 hours at 180 ℃, taking out and cooling to room temperature to obtain a first precipitate;
step four, washing the obtained precipitate with absolute ethyl alcohol and distilled water for three times respectively, then drying at 60 ℃, grinding the dried solid, putting the ground solid into a crucible, and then transferring the crucible to a muffle furnace;
step five, heating the mixture to 300 ℃ in a muffle furnace at the heating rate of 5 ℃/min and keeping the temperature for 3h, and recording the obtained material as BWO;
step six, adding 1.0g BWO into 150.0mL FeCl 3.6H2O solution and continuously stirring for 1H, then adding a specific amount of pyrrole into the mixture, and continuously stirring the solution for 6H to form a black second precipitate;
and step seven, washing the second precipitate for multiple times by using deionized water and ethanol, and drying at 60 ℃ to form the composite material.
2. The preparation method of the Z-type polypyrrole-bismuth tungstate photocatalyst as claimed in claim 1, wherein the preparation method comprises the following steps: the mass percentages of the pyrrole are set as 1wt%, 2wt%, 3wt% and 4wt%, and the composite materials are respectively marked as 1% polypyrrole-bismuth tungstate, 2% polypyrrole-bismuth tungstate, 3% polypyrrole-bismuth tungstate and 4% polypyrrole-bismuth tungstate.
3. A method of using the Z-type polypyrrole-bismuth tungstate photocatalyst of any one of claims 1 to 2 in cr (vi), characterized in that: dispersing the prepared composite material (15.0mg) in 100.0mLCr (VI) aqueous solution (10.0mg/L), adding 1.0mL of citric acid solution (100.0g/L) as a hole scavenger, and adjusting the pH value of the reaction solution by using hydrochloric acid and sodium hydroxide solution to form a mixture;
step two, before the photocatalytic reaction is carried out, stirring the mixture in the step one for 20min in the dark to ensure that the mixture reaches adsorption balance;
step three, moving the stirred mixture to a 300W xenon lamp with a 420nm optical filter for irradiation;
step four, taking 1.0mL of reaction suspension every 5 minutes, immediately centrifuging, and using the centrifuged supernatant for determining Cr (VI).
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Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1951557A (en) * | 2006-11-03 | 2007-04-25 | 中国科学院上海硅酸盐研究所 | Hydrothermal method for preparing superstructure visible light responsive Bi2WO6 photcatalyst |
| CN102698739A (en) * | 2012-06-15 | 2012-10-03 | 南开大学 | Preparation method of sunlight-responding mesoporous Bi2WO6 microspheres |
| CN102764653A (en) * | 2011-05-06 | 2012-11-07 | 中国科学院合肥物质科学研究院 | Silver-modified bismuth tungstate composite photocatalyst, its preparation method and application thereof |
| CN102941124A (en) * | 2012-11-21 | 2013-02-27 | 江南大学 | Visible-light reaction polypyrrole/Bi2WO6 composite catalyst and preparation method thereof |
| CN103663562A (en) * | 2013-11-20 | 2014-03-26 | 南京邮电大学 | Method for low-temperature preparation of nano bismuth tungstate |
| CN103816939A (en) * | 2014-03-07 | 2014-05-28 | 青岛科技大学 | Preparation method for bismuth tungstate/polyaniline heterojunction photocatalyst |
| US20150090937A1 (en) * | 2013-10-02 | 2015-04-02 | Sabic Global Technologies B.V. | Hydrogen production from water by tuning the photonic band gap with the electronic band gap of a photoactive material |
| CN104722293A (en) * | 2015-02-02 | 2015-06-24 | 吉林大学 | Visible light responded load type Bi2WO6/Bi2O3 heterojunction photocatalyst and preparation method thereof |
| WO2015113114A1 (en) * | 2014-01-31 | 2015-08-06 | Newsouth Innovations Pty Limited | Process for preparing a polymer |
| CN107029786A (en) * | 2017-05-23 | 2017-08-11 | 江苏大学 | A kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4And its production and use |
| CN108479759A (en) * | 2018-04-24 | 2018-09-04 | 吉林建筑大学 | A kind of visible-light response type La doped wolframic acid bismuth catalyst and preparation method thereof |
| CN108607498A (en) * | 2018-05-23 | 2018-10-02 | 四川理工学院 | A kind of preparation method and application of the enhanced bismuth tungstate of absorption property |
| CN108704638A (en) * | 2018-05-28 | 2018-10-26 | 桂林电子科技大学 | A kind of silk ball-shaped Bi2WO6Nano material and its preparation method and application |
| CN109647539A (en) * | 2018-12-29 | 2019-04-19 | 东华大学 | A kind of preparation method of fabric/poly- nitrogen/polypyrrole/bismuth tungstate catalysis material |
| CN109663615A (en) * | 2018-11-30 | 2019-04-23 | 华纺股份有限公司 | A kind of g-C3N4/ppy/Bi2WO6Solid-state Z-type photochemical catalyst and preparation method |
| JP2019084527A (en) * | 2017-11-01 | 2019-06-06 | 株式会社豊田中央研究所 | Z scheme-type photocatalyst system |
| CN110947401A (en) * | 2019-12-30 | 2020-04-03 | 四川大学 | Bi2WO6/ZnS heterojunction photocatalyst and preparation method thereof |
| CN111482190A (en) * | 2020-04-24 | 2020-08-04 | 杜桂芳 | Bi2WO6-g-C3N4Heterojunction photocatalytic hydrogen production material and preparation method thereof |
| CN112156770A (en) * | 2020-10-31 | 2021-01-01 | 湘潭大学 | Bismuth tungstate composite photocatalyst with bismuth and oxygen double vacancies as well as preparation method and application thereof |
| WO2021142287A1 (en) * | 2020-01-08 | 2021-07-15 | The Regents Of The University Of Colorado, A Body Corporate | High triplet yield phenothiazine donor-acceptor complexes for photoredox catalysis |
| CN113145156A (en) * | 2021-03-11 | 2021-07-23 | 济南大学 | Preparation of NiO-based Z-type heterojunction photoelectric catalytic material |
| CN113333023A (en) * | 2021-05-20 | 2021-09-03 | 南通纺织丝绸产业技术研究院 | High-adsorption bismuth oxyiodide visible-light-driven photocatalyst and application thereof |
-
2021
- 2021-05-21 CN CN202110555342.XA patent/CN113231099B/en active Active
Patent Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1951557A (en) * | 2006-11-03 | 2007-04-25 | 中国科学院上海硅酸盐研究所 | Hydrothermal method for preparing superstructure visible light responsive Bi2WO6 photcatalyst |
| CN102764653A (en) * | 2011-05-06 | 2012-11-07 | 中国科学院合肥物质科学研究院 | Silver-modified bismuth tungstate composite photocatalyst, its preparation method and application thereof |
| CN102698739A (en) * | 2012-06-15 | 2012-10-03 | 南开大学 | Preparation method of sunlight-responding mesoporous Bi2WO6 microspheres |
| CN102941124A (en) * | 2012-11-21 | 2013-02-27 | 江南大学 | Visible-light reaction polypyrrole/Bi2WO6 composite catalyst and preparation method thereof |
| US20150090937A1 (en) * | 2013-10-02 | 2015-04-02 | Sabic Global Technologies B.V. | Hydrogen production from water by tuning the photonic band gap with the electronic band gap of a photoactive material |
| CN103663562A (en) * | 2013-11-20 | 2014-03-26 | 南京邮电大学 | Method for low-temperature preparation of nano bismuth tungstate |
| WO2015113114A1 (en) * | 2014-01-31 | 2015-08-06 | Newsouth Innovations Pty Limited | Process for preparing a polymer |
| CN103816939A (en) * | 2014-03-07 | 2014-05-28 | 青岛科技大学 | Preparation method for bismuth tungstate/polyaniline heterojunction photocatalyst |
| CN104722293A (en) * | 2015-02-02 | 2015-06-24 | 吉林大学 | Visible light responded load type Bi2WO6/Bi2O3 heterojunction photocatalyst and preparation method thereof |
| CN107029786A (en) * | 2017-05-23 | 2017-08-11 | 江苏大学 | A kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4And its production and use |
| JP2019084527A (en) * | 2017-11-01 | 2019-06-06 | 株式会社豊田中央研究所 | Z scheme-type photocatalyst system |
| CN108479759A (en) * | 2018-04-24 | 2018-09-04 | 吉林建筑大学 | A kind of visible-light response type La doped wolframic acid bismuth catalyst and preparation method thereof |
| CN108607498A (en) * | 2018-05-23 | 2018-10-02 | 四川理工学院 | A kind of preparation method and application of the enhanced bismuth tungstate of absorption property |
| CN108704638A (en) * | 2018-05-28 | 2018-10-26 | 桂林电子科技大学 | A kind of silk ball-shaped Bi2WO6Nano material and its preparation method and application |
| CN109663615A (en) * | 2018-11-30 | 2019-04-23 | 华纺股份有限公司 | A kind of g-C3N4/ppy/Bi2WO6Solid-state Z-type photochemical catalyst and preparation method |
| CN109647539A (en) * | 2018-12-29 | 2019-04-19 | 东华大学 | A kind of preparation method of fabric/poly- nitrogen/polypyrrole/bismuth tungstate catalysis material |
| CN110947401A (en) * | 2019-12-30 | 2020-04-03 | 四川大学 | Bi2WO6/ZnS heterojunction photocatalyst and preparation method thereof |
| WO2021142287A1 (en) * | 2020-01-08 | 2021-07-15 | The Regents Of The University Of Colorado, A Body Corporate | High triplet yield phenothiazine donor-acceptor complexes for photoredox catalysis |
| CN111482190A (en) * | 2020-04-24 | 2020-08-04 | 杜桂芳 | Bi2WO6-g-C3N4Heterojunction photocatalytic hydrogen production material and preparation method thereof |
| CN112156770A (en) * | 2020-10-31 | 2021-01-01 | 湘潭大学 | Bismuth tungstate composite photocatalyst with bismuth and oxygen double vacancies as well as preparation method and application thereof |
| CN113145156A (en) * | 2021-03-11 | 2021-07-23 | 济南大学 | Preparation of NiO-based Z-type heterojunction photoelectric catalytic material |
| CN113333023A (en) * | 2021-05-20 | 2021-09-03 | 南通纺织丝绸产业技术研究院 | High-adsorption bismuth oxyiodide visible-light-driven photocatalyst and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| FANG DUAN ET AL.: "Enhanced visible light photocatalytic activity of Bi2WO6 via modification with", 《APPLIED SURFACE SCIENCE》 * |
| NINGNING SONG ET AL.: "Synthesis and properties of Bi2WO6 coupled with SnO2 nano-microspheres", 《APPLIED SURFACE SCIENCE》 * |
| 张梦凡等: "Z- 型异质结光催化剂的设计、制备和应用研究进展", 《有色金属科学与工程》 * |
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