CN108067229B - Pd/BiVO4Composite nano photocatalyst and preparation method and application thereof - Google Patents
Pd/BiVO4Composite nano photocatalyst and preparation method and application thereof Download PDFInfo
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/648—Vanadium, niobium or tantalum or polonium
- B01J23/6482—Vanadium
-
- B01J35/39—
-
- 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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- 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
Abstract
The invention discloses Pd/BiVO4Composite nano photocatalyst, preparation method and application thereof, BiVO4Is of a coralline nano structure, and Pd is uniformly loaded on BiVO4The particle size of Pd is 10-30 nm, and the loading amount is 0.2-2.0 wt%; the load of Pd obviously reduces the recombination efficiency of photo-generated electron hole pairs, further improves the photocatalytic reaction activity, the preparation method of the photocatalyst is simple and easy to operate, the load of noble metal nano particles does not need additional protective agents, the long-time hydrothermal recombination process is also saved, meanwhile, the waste of noble metal raw materials in the hydrothermal process is reduced by adopting a one-step thermal reduction method, the efficient load of metal palladium is realized, and the preparation cost of the catalyst is reduced; the obtained photocatalyst can be used in visible light degradation wastewater reaction, and has good degradation activity and excellent reutilization efficiency; is favorable for the sustainable development of economic environment.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, and more specifically relates to Pd/BiVO4A composite nano photocatalyst and a preparation method and application thereof.
Background
In recent years, due to the strong oxidizing property, reaction universality and the advantages of direct utilization of sunlight, etc., the application of the photocatalytic technology in the aspects of environmental treatment and energy development has attracted extensive attention and has been studied in a large quantity. However, the photocatalytic technology still faces some limitations in industrial application, mainly represented by: 1. the effective utilization rate of sunlight (mainly aiming at visible light) is low; 2. the catalyst material has poor lasting stability; 3. the catalyst is poor in recovery and reutilization rate and easy to inactivate.
Bismuth vanadate (BiVO)4) Because its appropriate narrow band gap (-2.4 eV) allows for good absorption of visible light. BiVO, on the other hand, compared to other narrow-band semiconductors (e.g., CdS)4Shows extremely rare chemical stability, thereby effectively improving the service efficiency and the service life of the photocatalytic material under the irradiation of sunlight, but BiVO4The photocatalyst also has its own limitations, and particularly, the photocatalyst has a defect that photo-generated electron-hole pairs generated by photoexcitation easily recombine to reduce the efficiency of separating charge carriers, which is common to all narrow-band semiconductors. Therefore, the preparation of the composite photocatalyst for improving the photocatalytic reaction activity solves the problem of single crystal phase BiVO4An effective way of low reaction efficiency. A large number of literature reports that the loading of noble metal nanoparticles can significantly improve the activity of photocatalytic reactions, mainly due to the efficient separation of photo-generated electron-hole pairs by noble metal nanoparticles, thereby extending the lifetime of photo-generated charge carriers. In addition, the Surface Plasmon Resonance (SPR) effect of the noble metal is also beneficial to expanding the effective absorption range of the composite material to light, and the activity of the photocatalytic reaction is further enhanced.
Chinese patent with publication number CN 104084215A discloses BiVO with three-dimensional ordered macroporous structure4A preparation method of supported ferroferric oxide and precious metal is characterized in that a polymethyl methacrylate microsphere is used as a template to synthesize BiVO with a three-dimensional ordered macroporous structure4Then using an isovolumetric immersion method using isopropanol as a solvent to realize Fe3O4Finally, polyvinyl alcohol is used as a protective agent, and a low-temperature bubbling reduction method is adopted to obtain the uniform load of the noble metal; chinese patent with publication number CN 104001496A discloses a composite BiVO4Preparation method of nanosheet photocatalyst, wherein BiVO is prepared by combining wet chemical method with hydrothermal method4A ternary composite of graphene/palladium. In particular, separately prepared BiVO4The graphene and palladium compounds are dispersed and mixed uniformly by ultrasound, and then are combined together by a hydrothermal method.
The noble metal loading methods are complex to operate, a protective agent needs to be additionally added when the noble metal is loaded, a hydrothermal method is adopted, the time is long, the noble metal consumption is high, and the waste of noble metal materials is caused, so that the cost of the catalyst is increased, and the photocatalytic performance is not outstanding.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a Pd/BiVO4A composite nano photocatalyst.
The second purpose of the invention is to provide the Pd/BiVO4A preparation method of a composite nano photocatalyst.
The third purpose of the invention is to provide the Pd/BiVO4Application of composite nanometer photocatalyst.
The purpose of the invention is realized by the following technical scheme:
Pd/BiVO4The BiVO is a composite nano photocatalyst4Is of a coralline nano structure, wherein the branch length of each coralline branch is 300-600 nm, the diameter is 80-300 nm, the Pd is a nano metal particle and is uniformly loaded on the BiVO4The particle size of the Pd is 10-30 nm, and the loading amount of the Pd is 0.2-2.0 wt%.
Preferably, the branch length of each coral branch is 400-500 nm, the diameter is 150-200 nm, the particle size of the Pd is 15-25 nm, and the loading amount of the Pd is 0.5-1.0 wt%.
The photocatalyst responds with visible lightThe photocatalyst BiVO4 is used as a carrier, and active component nano metal palladium particles are loaded on the surface of the photocatalyst, so that the photocatalyst can promote the effective separation of photo-generated electron hole pairs, and simultaneously provide a large number of active reaction sites for degradation reaction, so that the prepared Pd/BiVO4The composite nano photocatalyst has good photocatalytic activity.
The invention also provides the Pd/BiVO4The preparation method of the composite nano photocatalyst is characterized by comprising the following steps:
s1, adding bismuth nitrate pentahydrate into nitric acid to dissolve to obtain a precursor acid solution A, and adding ammonium metavanadate into ammonia water to dissolve to obtain a precursor alkali solution B;
s2, respectively dissolving polyethylene glycol and block polyether F-127 in water, and respectively adding the obtained aqueous solution into the precursor acid solution A and the precursor solution B to respectively obtain a solution A and a solution B;
s3, mixing the solution A and the solution B under vigorous stirring to obtain yellow suspension, adjusting the pH of the yellow suspension to be neutral or close to neutral, and then continuing stirring for standby;
s4, transferring the yellow suspension obtained in the step S3 to a reaction kettle, reacting for 18-30 hours at 70-120 ℃, filtering and cleaning to obtain yellow powder;
s5, adding PdCl2Dispersing in deionized water by ultrasonic to obtain PdCl2Suspending the solution of PdCl2Suspension with yellow powder BiVO from S44Continuously and fully stirring to obtain brown mud;
s6, roasting the brown mud by adopting programmed temperature rise to obtain Pd/BiVO4The composite nano photocatalyst has the temperature programming roasting temperature of 400-500 ℃, the roasting time of 1-3 h and the heating rate of 1-3 ℃/min.
Preferably, the pH of the yellow suspension is adjusted to 6-8 in S3.
Preferably, the concentration of the bismuth nitrate pentahydrate of S1 is 0.1-0.5 mol/L, the concentration of the nitric acid is 2-6 mol/L, and the molar ratio of the bismuth nitrate pentahydrate to the nitric acid is 0.1-0.5: 4; the concentration of ammonium metavanadate is 0.1-0.5 mol/L, the concentration of ammonia water is 1-3 mol/L, and the molar ratio of ammonium metavanadate to ammonia water is 0.1-0.5: 2.
preferably, the stirring and dissolving time of the S1 precursor acid liquor A and the precursor alkali liquor B is 10-60 minutes.
Preferably, the concentration of the polyethylene glycol aqueous solution in the step S2 is 1-10 g/L, and the volume ratio of the added polyethylene glycol aqueous solution to the precursor acid solution A is 1: 3-6; the concentration of the F-127 polyether aqueous solution is 5-20 g/L, and the volume ratio of the F-127 polyether aqueous solution added into the precursor alkali liquor B to the precursor alkali liquor B is 1: 3 to 6.
Preferably, the solution A and the solution B are continuously stirred for 30-90 min in S2.
Preferably, the time for continuing the stirring in the step S3 is 50-70 min.
Preferably, the volume of the yellow suspension of S4 accounts for 40-60% of the total volume of the reaction kettle.
Preferably, S5 the PdCl2PdCl in suspension2The volume of (a) is 1-2 mL.
Preferably, S5 the PdCl2With yellow powder BiVO4The mass ratio of (A) to (B) is 0.004-0.04: 1.
the invention also provides the Pd/BiVO4The composite nano photocatalyst is applied to photocatalytic treatment of environmental pollution wastewater.
In particular, the Pd/BiVO is utilized4The composite nano photocatalyst degrades phenol in the wastewater.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides Pd/BiVO4The BiVO is a composite nano photocatalyst4Is of a coralline nano structure, the Pd is nano metal particles and is uniformly loaded on the BiVO4The particle size of the Pd is 10-30 nm, and the loading amount of the Pd is 0.2-2.0 wt%; compared with the industrial catalyst P25, the catalyst can greatly improve the absorption of visible light (400 nm-700 nm), the load of Pd obviously reduces the recombination efficiency of a photo-generated electron-hole pair, and the photocatalytic reaction activity is further improvedThe loading of the rice particles does not need an additional protective agent, so that a long-time hydrothermal compounding process is saved, meanwhile, the waste of precious metal raw materials in the hydrothermal process is reduced by adopting a one-step thermal reduction method, the efficient loading of metal palladium is realized, and the preparation cost of the catalyst is reduced; the obtained photocatalyst can be used in visible light degradation wastewater reaction, and has good degradation activity and excellent reutilization efficiency; is favorable for the sustainable development of economic environment.
Drawings
FIG. 1 is Pd/BiVO prepared in example 14SEM picture of composite nanometer photocatalyst.
FIG. 2 is Pd/BiVO prepared in example 14And the photocatalytic activity data of the composite nano photocatalyst.
FIG. 3 is Pd/BiVO prepared in example 24And (3) activity data of repeated tests of the composite nano photocatalyst.
Detailed Description
The invention will be further described with reference to the drawings and specific examples, which are not to be construed as limiting the invention. Modifications and substitutions of the methods, procedures, and conditions of the present invention can be made without departing from the spirit and substance of the invention. Unless otherwise indicated, the experimental procedures used in the examples are all conventional procedures and techniques well known to those skilled in the art, and reagents or materials are all commercially available.
The Pd loading amounts described in the following examples refer to Pd and BiVO4Is a percentage of half of the mass ratio of (a).
Example 1
Pd/BiVO4The preparation method of the composite nano photocatalyst comprises the following steps:
(1) adding 0.03 mol of bismuth nitrate pentahydrate into 100 mL of 4 mol/L nitric acid at 70 ℃, fully stirring to completely dissolve the solid to obtain precursor acid liquid A, adding 0.03 mol of ammonium vanadate into 100 mL of 2mol/L ammonia water, fully stirring to completely dissolve the solid to obtain precursor acid liquid B;
(2) respectively dissolving 0.23g of polyethylene glycol and 0.58g of F-127 polyether in 25mL of deionized water, respectively adding the solution into the precursor acid solution A and the precursor solution B to obtain a solution A and a solution B, and respectively continuing to stir for 30 min;
(3) under the condition of violent stirring, mixing the solution A with the solution B to obtain yellow suspension, adjusting the pH of the solution to be neutral, and continuously stirring for 1h for later use;
(4) transferring the obtained yellow suspension into a hydrothermal reaction kettle, wherein the volume of the yellow suspension accounts for half of the total volume of the hydrothermal reaction kettle, the kettle body is a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 80 ℃, taking out, performing centrifugal filtration, centrifugally cleaning the obtained yellow powder for several times by using deionized water, and drying to obtain yellow powder, namely BiVO4；
(5) About 0.004 g of PdCl2Dispersing in 1.0 mL deionized water by ultrasonic to obtain PdCl2The suspension was weighed to 1.0g of BiVO4Powder and PdCl obtained2Fully stirring the suspension to obtain brown mud;
(6) placing the brown mud in a muffle furnace, raising the temperature to 450 ℃ at the heating rate of 2.5 ℃/min, and keeping for 2h to obtain Pd/BiVO4A composite nano photocatalyst.
Pd/BiVO prepared in this example4The structure of the composite nano photocatalyst is shown in figure 1, BiVO4Has a coralline nano structure, Pd is nano metal particles and is uniformly and firmly loaded on BiVO4Wherein the particle diameter of Pd is 10-30 nm, BiVO4The length of each coral branch in the coral-shaped structure is 300-500 nm, the diameter of each coral branch is 100-300 nm, and the loading amount of Pd is 0.2 wt%.
Adopts the Pd/BiVO4The method for carrying out photocatalytic liquid phase degradation on phenol by using the composite nano photocatalyst comprises the following specific steps:
(1) Pd/BiVO prepared in the example4The composite nano photocatalyst is added into the sewage (Pd/BiVO) with the concentration of 5 ppm and containing phenol4Composite nano photocatalyst in phenol solutionThe concentration of the catalyst is 1 g/L), and the catalyst is uniformly dispersed in the solution by ultrasonic stirring for 30-60 s;
(2) taking a xenon lamp as a lamp source, blocking light with the wavelength less than 420 nm by using an optical filter, irradiating the light by visible light only to carry out reaction, and sampling at intervals;
(3) and (4) immediately performing centrifugal separation on the sample, taking supernatant, and measuring the concentration of phenol in the solution by using an ultraviolet-visible spectrophotometer.
As shown in FIG. 2, the volume of phenol-containing wastewater under irradiation of visible light (xenon lamp light source with filter) was 45mL, and Pd/BiVO was compared with that of a blank experiment (no photocatalysis) and a comparative experiment as a reference (P25, titanium dioxide)4The composite material has effective degradation effect on pollutants.
Example 2
Pd/BiVO4The preparation method of the composite nano photocatalyst comprises the following steps:
(1) adding 0.03 mol of bismuth nitrate pentahydrate into 100 mL of 4 mol/L nitric acid at 70 ℃, fully stirring to completely dissolve the solid to obtain precursor acid liquid A, adding 0.03 mol of ammonium vanadate into 100 mL of 2mol/L ammonia water, fully stirring to completely dissolve the solid to obtain precursor acid liquid B;
(2) respectively dissolving 0.23g of polyethylene glycol and 0.58g of F-127 polyether in 25mL of deionized water, respectively adding the solution into the precursor acid solution A and the precursor solution B to obtain a solution A and a solution B, and respectively continuing to stir for 30 min;
(3) under the condition of violent stirring, mixing the solution A with the solution B to obtain yellow suspension, adjusting the pH of the solution to be neutral, and continuously stirring for 1h for later use;
(4) transferring the obtained yellow suspension into a hydrothermal reaction kettle, wherein the volume of the yellow suspension accounts for half of the total volume of the hydrothermal reaction kettle, the kettle body is a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 80 ℃, taking out, performing centrifugal filtration, centrifugally cleaning the obtained yellow powder for several times by using deionized water, and drying to obtain yellow powder, namely BiVO4；
(5) 0.02 g of PdCl2Dispersing in 1.0 mL deionized water by ultrasonic to obtain PdCl2The suspension was weighed to 1.0g of BiVO4Powder with PdCl2Fully stirring the suspension to obtain brown mud;
(6) placing the brown mud in a muffle furnace, raising the temperature to 450 ℃ at the heating rate of 2.5 ℃/min, and keeping for 2h to obtain Pd/BiVO4A composite nano photocatalyst.
Pd/BiVO prepared in this example4Composite nano photocatalyst, BiVO4Has a coralline nano structure, Pd is nano metal particles and is uniformly and firmly loaded on BiVO4Wherein the particle diameter of Pd is 10-30 nm, BiVO4The length of each coral branch in the coral-shaped structure is 300-500 nm, the diameter of each coral branch is 100-300 nm, and the loading amount of Pd is 1.0 wt%.
After the activity test was completed according to the experimental conditions and steps of fig. 2, the remaining reaction solution was separated from the photocatalyst by high-speed centrifugal rotation and the catalyst was washed several times with deionized water, dried, and the above activity test was repeated, with the result that the catalyst showed excellent recyclability as shown in fig. 3.
Example 3
Pd/BiVO4The preparation method of the composite nano photocatalyst comprises the following steps:
(1) adding 0.01 mol of bismuth nitrate pentahydrate into 75 mL of 2mol/L nitric acid at the temperature of 20 ℃, fully stirring to completely dissolve the solid to obtain precursor acid liquid A, adding 0.01 mol of ammonium vanadate into 75 mL of 1 mol/L ammonia water, fully stirring to completely dissolve the solid to obtain precursor acid liquid B;
(2) respectively dissolving 0.23g of polyethylene glycol and 0.58g of F-127 polyether in 25mL of deionized water, respectively adding the solution into the precursor acid solution A and the precursor solution B to obtain a solution A and a solution B, and respectively continuing to stir for 60 min;
(3) under the condition of violent stirring, mixing the solution A with the solution B to obtain yellow suspension, adjusting the pH of the solution to 8, and continuously stirring for 70min for later use;
(4) transferring the obtained yellow suspension into a hydrothermal reaction kettle, wherein the volume of the yellow suspension accounts for half of the total volume of the hydrothermal reaction kettle, the kettle body is a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 30 hours at 70 ℃, taking out, performing centrifugal filtration, centrifugally cleaning the obtained yellow powder for several times by using deionized water, and drying to obtain yellow powder, namely BiVO4；
(5) About 0.03 g of PdCl2Dispersing in 1.0 mL deionized water by ultrasonic to obtain PdCl2The suspension was weighed to 1.0g of BiVO4Powder with PdCl2Fully stirring the suspension to obtain brown mud;
(6) placing the brown mud in a muffle furnace, raising the temperature to 400 ℃ at the heating rate of 1 ℃/min, and keeping the temperature for 1h to obtain Pd/BiVO4A composite nano photocatalyst.
Pd/BiVO prepared in this example4Composite nano photocatalyst, BiVO4Has a coralline nano structure, Pd is nano metal particles and is uniformly and firmly loaded on BiVO4Wherein the particle diameter of Pd is 10-30 nm, BiVO4The length of each coral branch in the coral-shaped structure is 300-500 nm, the diameter of each coral branch is 100-300 nm, and the loading amount of Pd is 1.5 wt%.
Example 4
Pd/BiVO4The preparation method of the composite nano photocatalyst comprises the following steps:
(1) adding 0.03 mol of bismuth nitrate pentahydrate into 100 mL of 4 mol/L nitric acid at 70 ℃, fully stirring to completely dissolve the solid to obtain precursor acid liquid A, adding 0.03 mol of ammonium vanadate into 100 mL of 2mol/L ammonia water, fully stirring to completely dissolve the solid to obtain precursor acid liquid B;
(2) respectively dissolving 0.5g of polyethylene glycol and 1.0g of F-127 polyether in 25mL of deionized water, respectively adding the solution into the precursor acid solution A and the precursor solution B to obtain a solution A and a solution B, and respectively continuing to stir for 60 min;
(3) under the condition of violent stirring, mixing the solution A with the solution B to obtain yellow suspension, adjusting the pH of the solution to be neutral, and continuously stirring for 1h for later use;
(4) transferring the obtained yellow suspension into a hydrothermal reaction kettle, wherein the volume of the yellow suspension accounts for half of the total volume of the hydrothermal reaction kettle, the kettle body is a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 24 hours at 80 ℃, taking out, performing centrifugal filtration, centrifugally cleaning the obtained yellow powder for several times by using deionized water, and drying to obtain yellow powder, namely BiVO4；
(5) About 0.004 g of PdCl2Dispersing in 1.0 mL deionized water by ultrasonic to obtain PdCl2The suspension was weighed to 1.0g of BiVO4Powder and PdCl obtained2Fully stirring the suspension to obtain brown mud;
(6) placing the brown mud in a muffle furnace, raising the temperature to 450 ℃ at the heating rate of 2.5 ℃/min, and keeping for 2h to obtain Pd/BiVO4A composite nano photocatalyst.
Pd/BiVO prepared in this example4The structure of the composite nano photocatalyst is shown in figure 1, BiVO4Has a coralline nano structure, Pd is nano metal particles and is uniformly and firmly loaded on BiVO4Wherein the particle diameter of Pd is 10-30 nm, BiVO4The length of each coral branch in the coral-shaped structure is 400-600 nm, the diameter of each coral branch is 80-200 nm, and the loading amount of Pd is 0.2 wt%.
Example 5
Pd/BiVO4The preparation method of the composite nano photocatalyst comprises the following steps:
(1) adding 0.04 mol of bismuth nitrate pentahydrate into 150 mL of 6mol/L nitric acid at 50 ℃, fully stirring to completely dissolve the solid to obtain precursor acid liquid A, adding 0.04 mol of ammonium vanadate into 150 mL of 3 mol/L ammonia water, fully stirring to completely dissolve the solid to obtain precursor acid liquid B;
(2) respectively dissolving 0.5g of polyethylene glycol and 1.0g of F-127 polyether in 25mL of deionized water, respectively adding the solution into the precursor acid solution A and the precursor solution B to obtain a solution A and a solution B, and respectively continuing to stir for 90 min;
(3) under the condition of violent stirring, mixing the solution A with the solution B to obtain yellow suspension, adjusting the pH of the solution to 6, and continuously stirring for 50min for later use;
(4) transferring the obtained yellow suspension into a hydrothermal reaction kettle, wherein the volume of the yellow suspension accounts for half of the total volume of the hydrothermal reaction kettle, the kettle body is a stainless steel hydrothermal reaction kettle with a polytetrafluoroethylene lining, reacting for 18 hours at 120 ℃, taking out, performing centrifugal filtration, centrifugally cleaning the obtained yellow powder for several times by using deionized water, and drying to obtain yellow powder, namely BiVO4；
(5) About 0.04 g of PdCl2Dispersing in 2.0 mL deionized water by ultrasonic to obtain PdCl2The suspension was weighed to 1.0g of BiVO4Powder with PdCl2Fully stirring the suspension to obtain brown paste;
(6) spreading the brown paste, placing in a muffle furnace, heating to 500 deg.C at a heating rate of 3 deg.C/min, and maintaining for 1h to obtain Pd/BiVO4A composite nano photocatalyst.
Pd/BiVO prepared in this example4Composite nano photocatalyst, BiVO4Has a coralline nano structure, Pd is nano metal particles and is uniformly and firmly loaded on BiVO4Wherein the particle diameter of Pd is 10-30 nm, BiVO4The length of each coral branch in the coral-shaped structure is 400-600 nm, the diameter of each coral branch is 80-200 nm, and the loading amount of Pd is 2.0 wt%.
Comparative example 1
The experimental procedure is as in example 1, the only difference being Pd/BiVO4In the preparation method of the composite nano photocatalyst, the step (6) is carried out according to the following operations: placing the brown mud in a muffle furnace, raising the temperature to 450 ℃, and keeping the temperature for 2 hours to obtain Pd/BiVO4A composite nano photocatalyst.
Pd/BiVO prepared by using the comparative example4Composite nano photocatalystThe photocatalytic liquid-phase degradation of phenol as described in example 1 was carried out (the degradation method was the same as in example 1), and the results show that: the composite photocatalyst is obtained by directly carrying out thermal reduction without temperature programming, and the photocatalytic reaction activity of the composite photocatalyst under the irradiation of visible light is reduced, because: the rapid increase of the thermal reduction temperature ensures that Pd is easy to agglomerate and can not be uniformly dispersed in BiVO according to the size of the nano small particles4Even detachment occurs, and no effective load can be formed, thereby causing reduction of Pd loading and the reaction active sites of the photocatalyst, and on the other hand, Pd and BiVO4The reduction of the contact probability between the two leads to the increase of the recombination efficiency of the photo-generated charge carriers, so that the reactivity is reduced.
Comparative example 2
The experimental procedure is as in example 1, the only difference being Pd/BiVO4In the preparation method of the composite nano photocatalyst, the step (5) is carried out according to the following operations: about 0.1g of PdCl2Dispersing in 1.0 mL deionized water by ultrasonic to obtain PdCl2The suspension was weighed to 1.0g of BiVO4Powder and PdCl obtained2The suspension was stirred well to give a brown paste.
Pd/BiVO prepared by using the comparative example4When the composite nano photocatalyst is used for carrying out the photocatalytic liquid-phase degradation of phenol as described in example 1 (the degradation method is the same as that in example 1), the results show that: BiVO4Is coated and covered by Pd particles, so that BiVO4The efficiency of light absorption and utilization is reduced. In the composite photocatalyst, BiVO4The photo-generated electrons with high activity are transferred to the surface of Pd through a Schottky barrier formed between the noble metal and the semiconductor, and then act on a target to complete a photocatalytic degradation reaction. However, Pd on BiVO4The amount of photo-generated charge carriers is reduced, so that a larger amount of reactive species cannot be formed, resulting in a decrease in photocatalytic reactivity.
Comparative example 3
The experimental procedure is as in example 1, the only difference being Pd/BiVO4In the preparation method of the composite nano photocatalyst, the operation of the step (2) is omitted, namely BiVO is adjusted without adding any polymer4And (4) microstructure.
Pd/BiVO prepared by using the comparative example4When the composite nano photocatalyst is used for carrying out the photocatalytic liquid-phase degradation of phenol as described in example 1 (the degradation method is the same as that in example 1), the results show that: BiVO with coral structure having high specific surface area cannot be obtained from the sample without adding the polymer4The polymer is proved to have a guiding effect on the microstructure growth of the material. Meanwhile, in the method, metal Pd does not form nano-particles and is uniformly loaded on BiVO4Surface, BiVO4The apparent morphology of the metal palladium has a decisive influence on the deposition mode of the metal palladium.
Comparative example 4
The experimental procedure is as in example 1, the only difference being Pd/BiVO4In the preparation method of the composite nano photocatalyst, in the operation of the step (2), polyethylene glycol and F-127 polyether are respectively dissolved in 25mL of deionized water, then respectively added into the precursor acid solution B and the precursor solution A, and then respectively continuously stirred for 30 min.
Pd/BiVO prepared by using the comparative example4When the composite nano photocatalyst is used for carrying out the photocatalytic liquid-phase degradation of phenol as described in example 1 (the degradation method is the same as that in example 1), the results show that: when two polymers are exchanged, BiVO having a coral-like structure with a high specific surface area cannot be obtained4. Meanwhile, in the method, metal Pd does not form nano-particles and is uniformly loaded on BiVO4Surface, BiVO4The apparent morphology of the metal palladium has a decisive influence on the deposition mode of the metal palladium.
Comparative example 5
The experimental procedure is as in example 1, the only difference being Pd/BiVO4In the preparation method of the composite nano photocatalyst, in the operation of the step (2), F-127 polyether is replaced by citric acid.
Pd/BiVO prepared by using the comparative example4The composite nano photocatalyst is used for carrying out the photocatalytic liquid phase degradation of phenol (the degradation method is the same as that of the embodiment 1) described in the embodiment 1,the results show that: by changing the structure-directing agent, BiVO having a coral-like structure with a high specific surface area cannot be obtained4. Meanwhile, in the method, metal Pd does not form nano-particles and is uniformly loaded on BiVO4Surface, BiVO4The apparent morphology of the metal palladium has a decisive influence on the deposition mode of the metal palladium.
Comparative example 6
The experimental procedure is as in example 1, the only difference being Pd/BiVO4In the preparation method of the composite nano photocatalyst, in the operation of the step (2), only one of polyethylene glycol and F-127 polyether is added, and then the stirring is continued for 30min respectively.
Pd/BiVO prepared by using the comparative example4When the composite nano photocatalyst is used for carrying out the photocatalytic liquid-phase degradation of phenol as described in example 1 (the degradation method is the same as that in example 1), the results show that: BiVO with coral-shaped structure with high specific surface area cannot be obtained by only adding one of polyethylene glycol and F-127 polyether4. Meanwhile, in the method, metal Pd does not form nano-particles and is uniformly loaded on BiVO4Surface, BiVO4The apparent morphology of the metal palladium has a decisive influence on the deposition mode of the metal palladium.
Claims (9)
1. Pd/BiVO4The composite nano photocatalyst is characterized in that the BiVO4Is of a coralline nano structure, wherein the branch length of each coralline branch is 300-600 nm, the diameter is 80-300 nm, the Pd is a nano metal particle and is uniformly loaded on the BiVO4The particle size of the Pd is 10-30 nm, and the loading amount of the Pd is 0.2-2.0 wt%;
the Pd/BiVO4The composite nano photocatalyst is prepared by the following method:
s1, adding bismuth nitrate pentahydrate into nitric acid to dissolve to obtain a precursor acid solution A, and adding ammonium metavanadate into ammonia water to dissolve to obtain a precursor alkali solution B;
s2, respectively dissolving polyethylene glycol and block polyether F-127 in water, and respectively adding the obtained aqueous solution into the precursor acid solution A and the precursor alkali solution B to respectively obtain a solution A and a solution B; the concentration of the polyethylene glycol aqueous solution is 1-10 g/L, and the volume ratio of the polyethylene glycol aqueous solution to the precursor acid liquid A is 1: 3-6; the concentration of the F-127 polyether aqueous solution is 5-20 g/L, and the volume ratio of the F-127 polyether aqueous solution added into the precursor alkali liquor B to the precursor alkali liquor B is 1: 3-6;
s3, mixing the solution A and the solution B under vigorous stirring to obtain yellow suspension, adjusting the pH of the yellow suspension to 6-8, and continuing stirring for later use;
s4, transferring the yellow suspension obtained in the step S3 to a reaction kettle, reacting for 18-30 hours at 70-120 ℃, filtering and cleaning to obtain yellow powder;
s5, adding PdCl2Dispersing in deionized water by ultrasonic to obtain PdCl2Suspending the solution of PdCl2Suspension with yellow powder BiVO from S44Continuously and fully stirring to obtain brown mud;
s6, roasting the brown mud by adopting programmed temperature rise to obtain Pd/BiVO4The composite nano photocatalyst has the temperature programming roasting temperature of 400-500 ℃, the roasting time of 1-3 h and the temperature rising rate of 1-3 ℃/min;
s5 the PdCl2PdCl in suspension2The volume of (a) is 1-2 mL, and the PdCl2With yellow powder BiVO4The mass ratio of (A) to (B) is 0.004-0.04: 1.
2. The Pd/BiVO of claim 14The composite nano photocatalyst is characterized in that: wherein the branch length of each coral branch is 400-500 nm, the diameter is 150-200 nm, the particle size of Pd is 15-25 nm, and the loading amount of Pd is 0.5-1.0 wt%.
3. The Pd/BiVO of claim 14The composite nano photocatalyst is characterized in that the concentration of S1 bismuth nitrate pentahydrate is 0.1-0.5 mol/L, the concentration of nitric acid is 2-6 mol/L, and the molar ratio of bismuth nitrate pentahydrate to nitric acid is 0.1-0.5: 4; the concentration of ammonium metavanadate is 0.1-0.5 mol/L, the concentration of ammonia water is 1-3 mol/L, and the molar ratio of ammonium metavanadate to ammonia water is 0.1-0.5: 2.
4. the Pd/BiVO of claim 14The composite nano photocatalyst is characterized in that the stirring and dissolving time of S1 precursor acid liquor A and precursor alkali liquor B is 10-60 minutes.
5. The Pd/BiVO of claim 14The composite nano photocatalyst is characterized in that the solution A and the solution B in the S3 are mixed and then continuously stirred for 30-90 min.
6. The Pd/BiVO of claim 14The composite nano photocatalyst is characterized in that the time for continuing stirring in the step S3 is 50-70 min.
7. The Pd/BiVO4 composite nano-photocatalyst as claimed in claim 1, wherein the volume of the yellow suspension S4 accounts for 40-60% of the total volume of the reaction vessel.
8. The Pd/BiVO of any one of claims 1-74The composite nano photocatalyst is applied to photocatalytic treatment of environmental pollution wastewater.
9. The use according to claim 8, characterized in that said Pd/BiVO is used4The composite nano photocatalyst degrades phenol in the wastewater.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170353A (en) * | 2013-04-17 | 2013-06-26 | 东华大学 | Preparation method of heterogeneous visible photocatalyst |
| CN104001496A (en) * | 2014-06-11 | 2014-08-27 | 福州大学 | BiVO4 nanosheet composite photocatalyst, and preparation method and application thereof |
| CN104016526A (en) * | 2014-06-30 | 2014-09-03 | 宣尧杭 | Printing and dyeing wastewater treatment method |
| CN104084215A (en) * | 2014-06-26 | 2014-10-08 | 北京工业大学 | Three-dimensional ordered macroporous BiVO4-carrier Fe2O3 and precious metal photocatalyst (M/Fe2O3/3DOM BiVO4) and preparation method of photocatalyst |
| CN104826627A (en) * | 2015-04-30 | 2015-08-12 | 中国科学院海洋研究所 | High-performance photocatalyst for water treatment and preparation method thereof |
| CN105268438A (en) * | 2015-11-17 | 2016-01-27 | 中国科学院海洋研究所 | Plasma compound photocatalyst and preparation method and application thereof |
| CN105537620A (en) * | 2016-01-05 | 2016-05-04 | 河南师范大学 | Universal preparation method of Au-modified oxide semiconductor |
-
2016
- 2016-11-17 CN CN201611011642.7A patent/CN108067229B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103170353A (en) * | 2013-04-17 | 2013-06-26 | 东华大学 | Preparation method of heterogeneous visible photocatalyst |
| CN104001496A (en) * | 2014-06-11 | 2014-08-27 | 福州大学 | BiVO4 nanosheet composite photocatalyst, and preparation method and application thereof |
| CN104084215A (en) * | 2014-06-26 | 2014-10-08 | 北京工业大学 | Three-dimensional ordered macroporous BiVO4-carrier Fe2O3 and precious metal photocatalyst (M/Fe2O3/3DOM BiVO4) and preparation method of photocatalyst |
| CN104016526A (en) * | 2014-06-30 | 2014-09-03 | 宣尧杭 | Printing and dyeing wastewater treatment method |
| CN104826627A (en) * | 2015-04-30 | 2015-08-12 | 中国科学院海洋研究所 | High-performance photocatalyst for water treatment and preparation method thereof |
| CN105268438A (en) * | 2015-11-17 | 2016-01-27 | 中国科学院海洋研究所 | Plasma compound photocatalyst and preparation method and application thereof |
| CN105537620A (en) * | 2016-01-05 | 2016-05-04 | 河南师范大学 | Universal preparation method of Au-modified oxide semiconductor |
Non-Patent Citations (3)
| Title |
|---|
| Lei Ge.Novel Pd/BiVO4 composite photocatalysts for efficient degradation of methyl orange under visible light irradiation.《Materials Chemistry and Physics》.2007, * |
| Low-temperature synthesis of BiVO4 powders by Pluronic-assisted hydrothermal method: Effect of the surfactant and temperature on the morphology and structural control;U.M. García-Pérez et al.;《Ceramics International》;20130907;第4632页第2.1节、Table 1和第4637页第4部分结论以及Fig2 * |
| Novel Pd/BiVO4 composite photocatalysts for efficient degradation of methyl orange under visible light irradiation;Lei Ge;《Materials Chemistry and Physics》;20070921;第466页第2.2节,第467页第3.2节，第469-470页第4部分结论和Fig2 * |
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