CN116673043B - Lead titanate-cadmium sulfide composite hierarchical structure dual-functional photocatalyst and preparation method and application thereof - Google Patents
Lead titanate-cadmium sulfide composite hierarchical structure dual-functional photocatalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a lead titanate-cadmium sulfide composite hierarchical structure dual-function photocatalyst and a preparation method and application thereof, belonging to the technical field of photocatalysts, wherein the preparation method comprises the following steps: (1) Synthesis of perovskite phase PbTiO 3 with hierarchical structure; (2) Preparing a precursor solution by taking perovskite phase PbTiO 3 with a hierarchical structure, sodium dodecyl benzene sulfonate, cadmium chloride and thiourea as raw materials; (3) And carrying out hydrothermal reaction on the precursor solution at 140-220 ℃ for 8-16h, washing and drying the reaction product, and further calcining at high temperature to obtain the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst. The bifunctional photocatalyst can catalyze and degrade 30mg/L rhodamine B aqueous solution to 93% in 60min under simulated solar illumination, and can be used for photocatalytic degradation of dye wastewater and photocatalytic water splitting hydrogen production, wherein the rate of photocatalytic water splitting hydrogen production under simulated solar illumination is up to 65.251 mu mol/h.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to a lead titanate-cadmium sulfide composite hierarchical structure dual-function photocatalyst, and a preparation method and application thereof.
Background
With the rapid development of modern industry and the excessive use of fossil fuels, many environmental and energy problems are becoming more serious, especially the water pollution caused by organic dye discharge and the energy crisis caused by energy shortage. The sustainable clean energy is sought to replace the traditional fossil energy, and meanwhile, the clean energy is utilized for environmental treatment and purification, so that the method becomes an urgent new requirement for development.
Solar energy, an ideal sustainable clean energy source, has become an important research object in the energy and environmental fields. The photocatalysis technology is an important technology for converting solar energy into clean energy which can be stored and utilized and degrading industrial wastewater containing pollutants by utilizing catalyst materials, and is an important technical route for relieving the problems of energy shortage and environmental pollution. The core of the photocatalysis technology is a high-efficiency photocatalyst material. The photocatalysis technology based on the semiconductor material provides a feasible effective path for realizing solar energy conversion utilization and popularization due to the advantages of high photocatalysis efficiency, no secondary pollution, wide application range and the like.
CdS is used as an n-type semiconductor, and has a suitable forbidden bandwidth (about 2.42 eV), high absorption capacity in the visible light band, and good conduction band position, so that it can fully utilize solar energy, and thus is widely used in the field of photocatalysis. However, the lower photo-generated electron-hole separation efficiency and the more serious photo-corrosion phenomenon of the CdS greatly limit the further optimization and application of the CdS photocatalytic performance. The prior art often increases CdS photocatalytic activity and stability by depositing elemental metal catalysts (typically noble metals such as Pt, ag, au, etc.) or building up composites with other compounds.
PbTiO 3 with a perovskite phase hierarchical structure is an oxide functional material with special surface ferroelectric chemical effect. It has strong spontaneous polarization characteristic, stable crystal structure, the appearance is easy to regulate and control, the specific surface area is large, and the unique built-in electric field and the surface electrostatic shielding effect can bring more surface reaction active sites. The Chinese patent application with publication number of CN113426403A discloses a preparation method of PbTiO 3 micron sheet-CdS nano particle composite material, firstly, a perovskite phase PbTiO 3 micron sheet is prepared by a hydrothermal method, then the perovskite phase PbTiO 3 micron sheet, cadmium chloride and thiourea are used as raw materials to perform hydrothermal reaction to prepare the PbTiO 3 micron sheet-CdS nano particle composite material, but the structure of the composite material prepared by the method needs to be further improved so as to improve the photocatalytic degradation effect of lead titanate-cadmium sulfide composite material on dye and the function of photolyzing hydrogen.
Disclosure of Invention
The invention provides a preparation method of a PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst, which has low equipment requirement and easy control of the process, and the prepared PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst has good dispersibility, has obvious photocatalysis effect under the condition of simulating sunlight, and can be used for degrading organic dye wastewater and photolyzing water to produce hydrogen.
The technical scheme adopted is as follows:
A preparation method of a PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst comprises the following steps:
(1) Adding titanium dioxide P25 into 10-20mol/L KOH solution, regulating the concentration of Ti 4+ to 0.4-0.625mol/L, uniformly mixing, adding absolute ethyl alcohol, stirring to obtain a mixed solution, and adding Pb (NO 3)2 for full mixing;
(2) The solution obtained in the step (1) is subjected to hydrothermal reaction at 120-200 ℃ for 8-20h, then naturally cooled to room temperature, and the reaction product is taken out, washed and dried to obtain perovskite phase PbTiO 3 micron sheets;
(3) Uniformly dispersing perovskite phase PbTiO 3 micron sheets into deionized water to form yellowish suspension; adding hydrofluoric acid, and uniformly stirring to obtain a first precursor solution;
(4) Carrying out hydrothermal reaction on the first precursor solution at 160-240 ℃ for 2-8h, then naturally cooling to room temperature, taking out a reaction product, washing and drying to obtain perovskite PbTiO 3 with a hierarchical structure;
(5) Uniformly dispersing perovskite phase PbTiO 3 with a hierarchical structure into deionized water, adding sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a mixed suspension; sequentially adding equimolar cadmium chloride and thiourea into the mixture, and stirring and dispersing the mixture uniformly to obtain a second precursor solution;
(6) And carrying out hydrothermal reaction on the second precursor solution at 140-220 ℃ for 8-16h, then naturally cooling to room temperature, taking out a reaction product, washing and drying to obtain orange powder, calcining the orange powder at high temperature under argon atmosphere, and cooling to obtain the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst.
The perovskite ferroelectric oxide PbTiO 3 with the micro-nano structure can bring special structure-effect relationship to the composite material due to the special morphology structure (hierarchical structure, mesostructure, porous structure and the like) and the unique size effect, and particularly, the material with the hierarchical structure can provide more reactive sites or reaction centers for the photocatalytic reaction due to the unique morphology, so that the separation and transportation of carriers are enhanced. The invention takes perovskite phase PbTiO 3 with a hierarchical structure, cadmium chloride (CdCl 2·5/2H2 O) and thiourea (CH 4N 2S) as main raw materials, takes Sodium Dodecyl Benzene Sulfonate (SDBS) as a surfactant, and prepares the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst through hydrothermal reaction and calcination; the addition of the surfactant SDBS can influence the crystal growth of CdS, regulate and control the morphology of the CdS crystal, so that the CdS crystal is easier to be compounded with the substrate material PbTiO 3, and the photocatalytic performance of the product photocatalyst is improved; the high-temperature calcination under the argon atmosphere can improve the crystallization degree of the composite material, the interface stability of the composite material and the like while ensuring that the components of the photocatalyst are unchanged.
Preferably, in the step (1), the ratio of KOH solution, absolute ethyl alcohol and Pb (NO 3)2 is 1mL:2-3mL:0.5-0.625 mmol).
Preferably, in the step (3), the mass fraction of hydrofluoric acid is 40%; the ratio of the perovskite phase PbTiO 3 micron sheet, deionized water and hydrofluoric acid is 0.2-0.5g:25mL:30-50 mu L.
Preferably, in the step (4), the hydrothermal reaction condition is 180-220 ℃ for 3-6h, the temperature and time are important parameters in the hydrothermal reaction process, and the perovskite phase PbTiO 3 with the hierarchical structure prepared under the hydrothermal reaction condition has good dispersibility, uniform morphology and good uniformity, and is more suitable for further preparing the composite photocatalyst.
Preferably, in the step (5), deionized water, perovskite phase PbTiO 3 with a hierarchical structure and sodium dodecyl benzene sulfonate are mixed according to the proportion of 30mL:0.2g: mixing 0.01-0.05g to obtain mixed suspension; in the second precursor solution, the ratio of perovskite phase PbTiO 3 with a hierarchical structure to cadmium chloride and thiourea is 0.2g:0.3-1mmol:0.3-1mmol.
The proportion of the raw materials can provide enough Cd source for the reaction process, and ensure that enough CdS is loaded on perovskite phase PbTiO 3 with a hierarchical structure. The sodium dodecyl benzene sulfonate can influence the crystal growth of CdS, and the sodium dodecyl benzene sulfonate and perovskite phase PbTiO 3 with a hierarchical structure act together to induce the CdS to grow towards a polymerized sphere, so that the condition that the CdS leaves independently grow is reduced, and compared with the leaf-shaped CdS crystal structure, the polymerized sphere CdS has larger specific surface area and is easier to respond to active sites on the surface of the perovskite phase PbTiO 3 with the hierarchical structure.
Preferably, in the step (6), the hydrothermal reaction condition is 140-200 ℃ for 12 hours, and the hydrothermal reaction can be more sufficient under the parameters, so that the crystallization of CdS is more facilitated.
Preferably, the conditions of the high temperature calcination are: heating to 350-550 deg.c at 3-7 deg.c/min and calcining for 1-4 hr.
Under the high-temperature calcination condition, the crystallization degree of the CdS nanosphere particles on the surface of the perovskite phase PbTiO 3 with the hierarchical structure can be improved while the components of the photocatalyst are unchanged, the combination of the CdS nanosphere particles and the perovskite phase PbTiO 3 with the hierarchical structure is facilitated, and the interface stability and the photocatalytic performance of the dual-function photocatalyst of the product are improved.
The washing mode is to wash with deionized water and absolute ethyl alcohol respectively.
The invention also provides the PbTiO 3 -CdS composite hierarchical structure double-function photocatalyst prepared by the preparation method of the PbTiO 3 -CdS composite hierarchical structure double-function photocatalyst.
The invention also provides application of the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst in photocatalytic degradation of dye wastewater. The PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst has good dispersibility and good photocatalytic degradation dye performance, and can be used for carrying out catalytic degradation on 30mg/L rhodamine B aqueous solution by 93% in 60min under simulated sunlight.
The invention also provides application of the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst in the field of hydrogen production by water photolysis. The PbTiO 3 -CdS composite hierarchical structure double-function photocatalyst has good photocatalysis hydrogen production effect, 0.25M Na 2 S and 0.35M Na 2SO3 mixed solution are used as sacrificial agents, 3 hours are irradiated under simulated sunlight, and the hydrogen production rate of the PbTiO 3 -CdS composite hierarchical structure double-function photocatalyst is up to 65.251 mu mol/h.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, perovskite phase PbTiO 3 with a hierarchical structure is adopted as a substrate material, and through a targeted structural design, the perovskite phase PbTiO 3 with the hierarchical structure and a surfactant SDBS regulate and control the crystal growth of CdS, the crystallization degree of CdS is further improved through high-temperature calcination, and the stability of the interface of the product dual-function photocatalyst is improved, so that the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst with excellent photocatalytic performance is prepared.
(2) The PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst prepared by the invention has good dispersibility, can be used for catalytically degrading 30mg/L rhodamine B aqueous solution by 93% under simulated sunlight in 60min, is 1.7 times of perovskite phase PbTiO 3 with a hierarchical structure, and is 3.2 times of a CdS sample.
(3) The PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst prepared by the invention has good photocatalytic activity, takes a mixed solution of 0.25M Na 2 S and 0.35M Na 2SO3 as a sacrificial agent, generates hydrogen for 3 hours under simulated sunlight irradiation, and has the hydrogen generation rate as high as 65.251 mu mol/h which is 3.96 times that of a CdS sample.
(4) The method has the advantages of simple process, low equipment requirement, mild reaction conditions and easy control.
Drawings
FIG. 1 is an SEM image of the products produced in examples and comparative examples, wherein (a) is perovskite-phase PbTiO 3 of the hierarchical structure produced in comparative example 1, (b) is a CdS sample produced in comparative example 2, (c) is a PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst produced in example 2, (d) is an uncalcined PbTiO 3 -CdS composite hierarchical structure photocatalyst produced in comparative example 3, and (e) is a product of failure of the SDBS-free PbTiO 3 -CdS composite reaction produced in comparative example 4.
FIG. 2 is an XRD pattern of the bifunctional photocatalyst of PbTiO 3 -CdS composite hierarchical structure prepared in example 2.
FIG. 3 is a graph showing the ultraviolet-visible absorption spectrum of the products prepared in examples and comparative examples for degrading rhodamine B aqueous solution in simulated sunlight, wherein (a) is perovskite-phase PbTiO 3 of the hierarchical structure prepared in comparative example 1, (B) is a CdS sample prepared in comparative example 2, (c) is a PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst prepared in example 2, and (d) is a PbTiO 3 -CdS composite hierarchical structure photocatalyst prepared in comparative example 3, which is not calcined.
FIG. 4 is a graph showing the comparative photocatalytic degradation efficiency of the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst prepared in example 2, the perovskite-phase PbTiO 3 of the hierarchical structure prepared in comparative example 1, the CdS sample prepared in comparative example 2, and the uncalcined PbTiO 3 -CdS composite hierarchical structure photocatalyst prepared in comparative example 3 in the degradation of rhodamine B aqueous solution under simulated sunlight.
FIG. 5 is a graph showing a first-order kinetic fit curve of the PbTiO 3 -CdS composite-hierarchy bifunctional photocatalyst prepared in example 2, the perovskite-phase PbTiO 3 of the hierarchy prepared in comparative example 1, the CdS sample prepared in comparative example 2, and the uncalcined PbTiO 3 -CdS composite-hierarchy photocatalyst prepared in comparative example 3 for degradation of rhodamine B aqueous solution under simulated sunlight.
FIG. 6 is a statistical graph of photocatalytic hydrogen production rate under simulated sunlight for the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst (S2) prepared in example 2, the perovskite-phase PbTiO 3 of the hierarchical structure prepared in comparative example 1, the CdS sample prepared in comparative example 2, and the uncalcined PbTiO 3 -CdS composite hierarchical structure photocatalyst (S1) prepared in comparative example 3.
Detailed Description
The invention is further elucidated below in connection with the examples and the accompanying drawing. It is to be understood that these examples are for illustration of the invention only and are not intended to limit the scope of the invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
Example 1 preparation of perovskite phase PbTiO 3 hierarchical structure
(1) Dispersing 8.4g KOH with 10mL deionized water in a reactor liner, dissolving, adding 0.4g titanium dioxide P25 to form a white suspension, adding 25mL absolute ethyl alcohol, and uniformly stirring to obtain a mixed solution; 2.07g Pb (NO 3)2 is added and stirred for 2 hours for thorough mixing;
(2) Filling the inner container of the reaction kettle into the reaction kettle, sealing, preserving heat for 12 hours at 160 ℃ to perform hydrothermal reaction, then naturally cooling to room temperature, taking out a reaction product, washing with deionized water and absolute ethyl alcohol to be neutral, and drying to obtain a light yellow powder perovskite phase PbTiO 3 micron sheet;
(3) Adding 0.2g of the pale yellow powder in the step (2) into a reaction kettle liner filled with 25mL of deionized water, uniformly dispersing, adding 50 mu L of hydrofluoric acid with the mass fraction of 40%, and continuously stirring to obtain a first precursor solution;
(4) Placing the inner container of the reaction kettle containing the first precursor solution in the reaction kettle, sealing, performing hydrothermal reaction at 200 ℃ for 3 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, taking out a reaction product, washing the reaction product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying to obtain the perovskite phase PbTiO 3 with a yellowish powdery hierarchical structure.
Example 2
(1) Adding 0.2g of perovskite phase PbTiO 3 with the hierarchical structure prepared in the example 1 into a reactor liner containing 30mL of deionized water, and then adding 0.05g of surfactant sodium dodecyl benzene sulfonate, stirring and dispersing uniformly to obtain a mixed suspension; 0.183g of cadmium chloride (0.8 mmol, cdCl 2·5/2H2 O) and 0.061g of thiourea (0.8 mmol, CH4N 2S) were added to the mixed suspension, and stirred for 30min to obtain a second precursor solution;
(2) The second precursor solution is subjected to hydrothermal reaction at 160 ℃ for 12 hours in a closed environment, the reaction product is naturally cooled to room temperature after the reaction is finished, the reaction product is taken out, washed to be neutral by deionized water and absolute ethyl alcohol, and dried to obtain orange powder; and further placing the orange-yellow powder into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and calcining for 2 hours to obtain the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst.
As shown in (c) of FIG. 1, an SEM image of the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst prepared in the embodiment shows that the perovskite phase PbTiO 3 of the hierarchical structure is loaded with CdS particles, the CdS nano particles are in a spherical shape, the size is about 50-70nm, the size of the CdS nano particles is uniform, and the CdS nano particles are uniformly and densely distributed on the surface of the perovskite phase PbTiO 3 of the hierarchical structure.
As shown in figure 2, the XRD pattern of the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst shows that all diffraction peaks of the dual-function photocatalyst correspond to the standard diffraction peaks of perovskite phase PbTiO 3 (JCPDS: 06-0452) and CdS (JCPDS: 77-2306), and the diffraction peaks are sharp in peak shape and high in crystallinity.
Example 3
(1) Adding 0.2g of perovskite phase PbTiO 3 with the hierarchical structure prepared in the example 1 into a reactor liner containing 30mL of deionized water, and then adding 0.05g of surfactant sodium dodecyl benzene sulfonate, stirring and dispersing uniformly to obtain a mixed suspension; 0.137g cadmium chloride (0.6 mmol, cdCl 2·5/2H2 O) and 0.046g thiourea (0.6 mmol, CH4N 2S) were added to the mixed suspension, respectively, and stirred for 30min, respectively, to obtain a second precursor solution;
(2) The second precursor solution is subjected to hydrothermal reaction at 160 ℃ for 12 hours in a closed environment, the reaction product is naturally cooled to room temperature after the reaction is finished, the reaction product is taken out, washed to be neutral by deionized water and absolute ethyl alcohol, and dried to obtain orange powder; and further placing the orange-yellow powder into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and calcining for 2 hours to obtain the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst.
Example 4
(1) Adding 0.2g of perovskite phase PbTiO 3 with the hierarchical structure prepared in the example 1 into a reactor liner containing 30mL of deionized water, and then adding 0.05g of surfactant sodium dodecyl benzene sulfonate, stirring and dispersing uniformly to obtain a mixed suspension; 0.228g of cadmium chloride (1 mmol, cdCl 2·5/2H2 O) and 0.076g of thiourea (1 mmol, CH4N 2S) were added to the mixed suspension, respectively, and stirred for 30min, respectively, to obtain a second precursor solution;
(2) The second precursor solution is subjected to hydrothermal reaction at 160 ℃ for 12 hours in a closed environment, the reaction product is naturally cooled to room temperature after the reaction is finished, the reaction product is taken out, washed to be neutral by deionized water and absolute ethyl alcohol, and dried to obtain orange powder; and further placing the orange-yellow powder into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and calcining for 2 hours to obtain the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst.
Example 5
(1) Adding 0.2g of perovskite phase PbTiO 3 with the hierarchical structure prepared in the example 1 into a reactor liner containing 30mL of deionized water, and then adding 0.01g of surfactant sodium dodecyl benzene sulfonate, stirring and dispersing uniformly to obtain a mixed suspension; 0.137g cadmium chloride (0.6 mmol, cdCl 2·5/2H2 O) and 0.046g thiourea (0.6 mmol, CH4N 2S) were added to the mixed suspension, respectively, and stirred for 30min, respectively, to obtain a second precursor solution;
(2) The second precursor solution is subjected to hydrothermal reaction at 160 ℃ for 12 hours in a closed environment, the reaction product is naturally cooled to room temperature after the reaction is finished, the reaction product is taken out, washed to be neutral by deionized water and absolute ethyl alcohol, and dried to obtain orange powder; and further placing the orange-yellow powder into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and calcining for 2 hours to obtain the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst.
Example 6
(1) Adding 0.2g of perovskite phase PbTiO 3 with the hierarchical structure prepared in the example 1 into a reactor liner containing 30mL of deionized water, and then adding 0.05g of surfactant sodium dodecyl benzene sulfonate, stirring and dispersing uniformly to obtain a mixed suspension; 0.183g of cadmium chloride (0.8 mmol, cdCl 2·5/2H2 O) and 0.061g of thiourea (0.8 mmol, CH4N 2S) were added to the mixed suspension, and stirred for 30min to obtain a second precursor solution;
(2) The second precursor solution is subjected to hydrothermal reaction at 180 ℃ for 12 hours under a closed environment, the reaction product is naturally cooled to room temperature after the reaction is finished, the reaction product is taken out, washed to be neutral by deionized water and absolute ethyl alcohol, and dried to obtain orange powder; and further placing the orange-yellow powder into a tube furnace, heating to 500 ℃ at a heating rate of 5 ℃/min under argon atmosphere, and calcining for 2 hours to obtain the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst.
Comparative example 1
(1) Dispersing 8.4g KOH with 10mL deionized water in a reactor liner, dissolving, adding 0.4g titanium dioxide P25 to form a white suspension, adding 25mL absolute ethyl alcohol, and uniformly stirring to obtain a mixed solution; 2.07g Pb (NO 3)2 is added and stirred for 2 hours for thorough mixing;
(2) Filling the inner container of the reaction kettle into the reaction kettle, sealing, preserving heat for 12 hours at 160 ℃ to perform hydrothermal reaction, then naturally cooling to room temperature, taking out a reaction product, washing with deionized water and absolute ethyl alcohol to be neutral, and drying to obtain a light yellow powder perovskite phase PbTiO 3 micron sheet;
(3) Adding 0.2g of the pale yellow powder in the step (2) into a reaction kettle liner filled with 25mL of deionized water, uniformly dispersing, adding 50 mu L of hydrofluoric acid with the mass fraction of 40%, and continuously stirring to obtain a first precursor solution;
(4) Placing the inner container of the reaction kettle containing the first precursor solution in the reaction kettle, sealing, performing hydrothermal reaction at 200 ℃ for 3 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, taking out a reaction product, washing the reaction product with deionized water and absolute ethyl alcohol for 3 times respectively, and drying to obtain the perovskite phase PbTiO 3 with a yellowish powdery hierarchical structure.
SEM images of perovskite phase PbTiO 3 of the hierarchical structure prepared in this comparative example are shown in (a) of fig. 1.
Comparative example 2
(1) Adding 0.05g of surfactant Sodium Dodecyl Benzene Sulfonate (SDBS) into a reactor liner containing 30mL of deionized water, and uniformly stirring and dispersing to obtain clear liquid; the molar ratio is 1:1, 0.183g of cadmium chloride (0.8 mmol, cdCl 2·5/2H2 O) and 0.061g of thiourea (0.8 mmol, CH4N 2S) were added to the clear liquid in sequence, and stirred for 30min each in sequence to obtain a precursor solution;
(3) And (3) carrying out hydrothermal reaction on the precursor solution in a closed environment at 160 ℃ for 12 hours, naturally cooling to room temperature after the reaction is finished, taking out reactants, washing with deionized water and absolute ethyl alcohol to be neutral, and drying to obtain a pure-phase CdS sample.
SEM images of the pure-phase CdS samples prepared in this comparative example are shown in (b) of fig. 1.
Comparative example 3
(1) Adding 0.2g of perovskite phase PbTiO 3 with the hierarchical structure prepared in the example 1 into a reactor liner containing 30mL of deionized water, and then adding 0.05g of surfactant sodium dodecyl benzene sulfonate, stirring and dispersing uniformly to obtain a mixed suspension; 0.183g of cadmium chloride (0.8 mmol, cdCl 2·5/2H2 O) and 0.061g of thiourea (0.8 mmol, CH4N 2S) were added to the mixed suspension, and stirred for 30min to obtain a second precursor solution;
(2) And (3) carrying out hydrothermal reaction on the second precursor solution in a closed environment at 160 ℃ for 12 hours, naturally cooling to room temperature after the reaction is finished, taking out a reaction product, washing with deionized water and absolute ethyl alcohol for several times, and drying to obtain the uncalcined PbTiO 3 -CdS composite hierarchical structure photocatalyst, wherein an SEM image of the photocatalyst is shown in (d) in FIG. 1.
Comparative example 4
(1) Adding 0.2g of perovskite phase PbTiO 3 with the hierarchical structure prepared in example 1 into a reaction kettle liner containing 30mL of deionized water, then adding 0.183g of cadmium chloride (0.8 mmol, cdCl 2·5/2H2 O) and 0.061g of thiourea (0.8 mmol, CH4N 2S) into the mixed suspension in sequence, and stirring for 30min to obtain a second precursor solution;
(2) And (3) carrying out hydrothermal reaction on the second precursor solution at 160 ℃ for 12 hours in a closed environment, naturally cooling to room temperature after the reaction is finished, taking out a reaction product, washing with deionized water and absolute ethyl alcohol for several times, and drying to obtain a PbTiO 3 -CdS composite reaction product without the SDBS in the hydrothermal reaction, wherein an SEM (scanning electron microscope) diagram is shown in (e) in FIG. 1, and under the condition without the SDBS, cdS in the hydrothermal reaction product tends to independently grow to form a monodisperse leaf-shaped micrometer structure, and the size of the CdS is about 4-5 mu m. CdS does not grow on the surface of perovskite-phase PbTiO 3 with a hierarchical structure, and a PbTiO 3 -CdS composite hierarchical structure material cannot be obtained. Therefore, under the reaction conditions related to the application, the perovskite phase PbTiO 3 -CdS composite hierarchical structure cannot be synthesized by the hydrothermal reaction without adding SDBS. Therefore, the addition of the surfactant SDBS with proper concentration is a key condition for successfully synthesizing the perovskite phase PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst.
Sample analysis
The photocatalytic performance of the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst prepared in example 2, the perovskite-phase PbTiO 3 of the hierarchical structure prepared in comparative example 1, the CdS sample prepared in comparative example 2, and the PbTiO 3 -CdS composite hierarchical structure photocatalyst prepared in comparative example 3 was tested.
As shown in FIG. 3, when the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst, the perovskite phase PbTiO 3 with the hierarchical structure, the CdS sample and the PbTiO 3 -CdS composite hierarchical structure photocatalyst without calcination are used for photocatalytic degradation of rhodamine B, the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst has the best effect of degrading organic dye, and can catalyze and degrade 30mg/L of rhodamine B aqueous solution by 93% in 60min under simulated solar illumination.
The comparative graph of the photocatalytic degradation efficiency of PbTiO 3 -CdS composite hierarchical structure double-function photocatalyst (PTO hierarchical structure/CdS), perovskite phase PbTiO 3 (PTO hierarchical structure), cdS sample and uncalcined PbTiO 3 -CdS composite hierarchical structure photocatalyst (uncalcined-PTO hierarchical structure/CdS) on rhodamine B aqueous solution under simulated sunlight is shown in FIG. 4, and the degradation effect of the PbTiO 3 -CdS composite hierarchical structure double-function photocatalyst on rhodamine B under the irradiation of the simulated sunlight is better and the efficiency is higher.
The results of the first order kinetic fits of the photocatalytic efficiency of the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst (PTO hierarchy/CdS), the perovskite phase PbTiO 3 of the hierarchical structure (PTO hierarchy), the CdS sample, and the uncalcined PbTiO 3 -CdS composite hierarchical structure photocatalyst (uncalcined-PTO hierarchy/CdS) are shown in fig. 5, where the catalytic efficiency of the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst is 2.1 times that of the PTO hierarchy, 3.8 times that of the CdS sample, and 1.2 times that of the uncalcined PbTiO 3 -CdS composite hierarchical structure photocatalyst.
Under the condition of strong ultrasonic dispersion, 0.1g of PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst (PTO hierarchical structure/CdS), perovskite phase PbTiO 3 (PTO hierarchical structure) with hierarchical structure, cdS sample and uncalcined PbTiO 3 -CdS composite hierarchical structure photocatalyst (uncalcined-PTO hierarchical structure/CdS) are respectively and ultrasonically dispersed in 50mmol/L of H 2PtCl6·6H2 O aqueous solution, and then 60mL of newly prepared NaBH 4 solution with the concentration of 20mmol/L is slowly dripped into the solution, so that a gray black turbid liquid is gradually obtained. And centrifuging the turbid liquid to obtain a black precipitate, respectively washing the black precipitate with deionized water and absolute ethyl alcohol for a plurality of times, and drying the black precipitate in a 60 ℃ oven for 12 hours to obtain a group of photolytic water test samples loaded with Pt.
40Mg of the above sample using Pt as a catalyst was dispersed in 100mL of deionized water to prepare a dispersion, and a sacrificial agent (a mixed solution of 0.25M Na 2 S and 0.35M Na 2SO3) was added to the dispersion, followed by a photolytic water hydrogen production test under irradiation conditions of simulated sunlight.
FIG. 6 is a hydrogen production rate histogram of PbTiO 3 -CdS composite-hierarchy bifunctional photocatalyst (S2), perovskite-phase PbTiO 3 of hierarchy (PTO hierarchy), cdS sample and uncalcined PbTiO 3 -CdS composite-hierarchy photocatalyst (S1) irradiated for 3h under simulated sunlight conditions. As can be seen from the graph, the hydrogen production rate of the PbTiO 3 -CdS composite hierarchical structure double-function photocatalyst is up to 65.251 mu mol/h, which is about 4 times that of a CdS sample and 1.7 times that of the uncalcined PbTiO 3 -CdS composite hierarchical structure photocatalyst, so that the photocatalytic activity of the PbTiO 3 -CdS composite hierarchical structure double-function photocatalyst is better.
While the foregoing embodiments have been described in detail in connection with the embodiments of the invention, it should be understood that the foregoing embodiments are merely illustrative of the invention and are not intended to limit the invention, and any modifications, additions, substitutions and the like made within the principles of the invention are intended to be included within the scope of the invention.
Claims (7)
1. The preparation method of the PbTiO 3 -CdS composite hierarchical structure bifunctional photocatalyst is characterized by comprising the following steps of:
(1) Adding titanium dioxide P25 into 10-20mol/L KOH solution, regulating the concentration of Ti 4+ to 0.4-0.625mol/L, uniformly mixing, adding absolute ethyl alcohol, stirring to obtain a mixed solution, and adding Pb (NO 3)2 for full mixing;
(2) The solution obtained in the step (1) is subjected to hydrothermal reaction at 120-200 ℃ for 8-20h, then naturally cooled to room temperature, and the reaction product is taken out, washed and dried to obtain perovskite phase PbTiO 3 micron sheets;
(3) Uniformly dispersing perovskite phase PbTiO 3 micron sheets into deionized water to form yellowish suspension; adding hydrofluoric acid, and uniformly stirring to obtain a first precursor solution;
(4) Carrying out hydrothermal reaction on the first precursor solution at 160-240 ℃ for 2-8h, then naturally cooling to room temperature, taking out a reaction product, washing and drying to obtain perovskite PbTiO 3 with a hierarchical structure;
(5) Uniformly dispersing perovskite phase PbTiO 3 with a hierarchical structure into deionized water, adding sodium dodecyl benzene sulfonate, and uniformly stirring to obtain a mixed suspension; sequentially adding equimolar cadmium chloride and thiourea into the mixture, and stirring and dispersing the mixture uniformly to obtain a second precursor solution;
(6) Carrying out hydrothermal reaction on the second precursor solution at 140-220 ℃ for 8-16h, then naturally cooling to room temperature, taking out a reaction product, washing and drying to obtain orange powder, calcining the orange powder at high temperature under argon atmosphere, and cooling to obtain the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst;
In the step (5), deionized water, perovskite phase PbTiO 3 with a hierarchical structure and sodium dodecyl benzene sulfonate are mixed according to the proportion of 30mL:0.2g: mixing 0.01-0.05g to obtain mixed suspension;
In the second precursor solution, the ratio of perovskite phase PbTiO 3 with a hierarchical structure to cadmium chloride and thiourea is 0.2g:0.3-1mmol:0.3-1mmol;
In the step (6), the conditions of high-temperature calcination are as follows: heating to 350-550 deg.c at 3-7 deg.c/min and calcining for 1-4 hr.
2. The method for preparing the dual-function photocatalyst with the PbTiO 3 -CdS composite hierarchical structure according to claim 1, wherein in the step (1), the ratio of KOH solution, absolute ethyl alcohol and Pb (NO 3)2 is 1mL:2-3mL:0.5-0.625 mmol).
3. The preparation method of the PbTiO 3 -CdS composite hierarchical structure dual-function photocatalyst according to claim 1, wherein in the step (3), the mass fraction of hydrofluoric acid is 40%; the ratio of the perovskite phase PbTiO 3 micron sheet, deionized water and hydrofluoric acid is 0.2-0.5g:25mL:30-50 mu L.
4. The method for preparing the dual-function photocatalyst with the PbTiO 3 -CdS composite hierarchical structure according to claim 1, wherein in the step (6), the hydrothermal reaction condition is 140-200 ℃ for 12h.
5. The dual-function photocatalyst of PbTiO 3 -CdS composite hierarchical structure prepared by the preparation method of the dual-function photocatalyst of PbTiO 3 -CdS composite hierarchical structure according to any one of claims 1-4.
6. The use of the dual-function photocatalyst with the PbTiO 3 -CdS composite hierarchical structure in photocatalytic degradation of dye wastewater according to claim 5.
7. The use of the dual-function photocatalyst with the PbTiO 3 -CdS composite hierarchical structure in the field of hydrogen production by water photolysis.
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