CN115121274A - Palladium-modified carbon nitrogen compound-loaded foam metal visible-light-induced photocatalyst and preparation method and application thereof - Google Patents
Palladium-modified carbon nitrogen compound-loaded foam metal visible-light-induced photocatalyst and preparation method and application thereof Download PDFInfo
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- CN115121274A CN115121274A CN202210551312.6A CN202210551312A CN115121274A CN 115121274 A CN115121274 A CN 115121274A CN 202210551312 A CN202210551312 A CN 202210551312A CN 115121274 A CN115121274 A CN 115121274A
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- nitrogen compound
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 115
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- 229910052763 palladium Inorganic materials 0.000 claims abstract description 87
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Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B01J35/56—
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- 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 a palladium modified carbon nitrogen compound supported foam metal visible light catalyst and a preparation method and application thereof 3 N 5 Is a carrier, and is loaded with a palladium simple substance. The preparation method comprises the steps of mixing the palladium modified carbon nitrogen compound with the adhesive and drippingSintering the foam metal. The catalyst has the advantages of convenient recovery, no toxic and harmful elements, good visible light absorption performance, excellent photocatalytic performance, small secondary pollution risk and the like, is a novel supported visible light catalyst with excellent performance, can be widely used for deeply treating organic pollutant wastewater, has high use value and good application prospect, has the advantages of simple process, mature technology, convenient operation, less used medicament, low cost, safety, environmental protection and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention relates to a supported visible-light-driven photocatalyst, in particular to a palladium-modified carbon nitride-supported foam metal visible-light-driven photocatalyst, and a preparation method and application thereof.
Background
With the rapid development of society, the demand of human society for water is increasing day by day, but the fresh water resource is very limited, which requires advanced treatment and reuse of waste water as much as possible. The conventional biological treatment technology has low treatment efficiency on trace pollutants in the wastewater, and the conventional physical and chemical treatment has the defect of high treatment cost. The photocatalysis technology is a green chemical treatment technology, has high treatment efficiency, no secondary pollution, energy conservation and unique advantage on the treatment of trace pollutants. Photocatalysts are the heart of photocatalytic technology. However, the photocatalytic technology is still mainly in the research stage of the laboratory, and is mainly limited by the following factors: 1) the photocatalyst developed at present is mainly in a powder state and is difficult to recycle in the actual use process; 2) the utilization rate of the currently developed catalyst for visible light is low, and an additional ultraviolet light source is often needed in the actual use process, so that the use cost is inevitably increased; 3) the current developed visible light catalyst has high carrier recombination efficiency and limited catalytic activity efficiency. In addition, the existing supported photocatalyst still has the defects of poor visible light absorption capacity, poor photocatalytic activity, environmental pollution, complex preparation process, secondary pollution possibly caused by the fact that a catalyst carrier cannot be recycled, and the like. Therefore, the supported palladium-modified carbon nitride-loaded foam metal visible-light-induced photocatalyst which is convenient to recover, does not contain toxic and harmful elements, has good visible-light absorption performance and excellent photocatalytic performance, and the matched preparation method which is mature and simple in process, convenient to operate, safe and environment-friendly are obtained, and the preparation method has very important significance for improving the application range of the supported composite photocatalyst and removing trace organic matters in wastewater.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a palladium-supported modified carbon nitride foam metal visible light catalyst which is convenient to recover, does not contain toxic and harmful elements, has good visible light absorption performance and excellent photocatalytic performance, a preparation method thereof and application of the palladium-supported modified carbon nitride foam metal visible light catalyst in treatment of organic pollutant (such as antibiotics, chlorophenols and dyes) wastewater.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst comprises a palladium-modified carbon nitrogen compound and foam metal, wherein the palladium-modified carbon nitrogen compound is inlaid in the foam metal and is supported on the surface of the foam metal; the palladium modified carbon-nitrogen compound takes a carbon-nitrogen compound as a carrier, a palladium simple substance is loaded on the carbon-nitrogen compound, and the carbon-nitrogen compound is C 3 N 5 。
The palladium modified carbon nitrogen compound supported foam metal visible light catalyst is further improved, wherein the mass ratio of the palladium modified carbon nitrogen compound to the foam metal is 0.1-0.5: 5; the foam metal is at least one of foam nickel, foam cobalt and foam titanium; the mass ratio of the palladium simple substance to the carbon nitrogen compound in the palladium modified carbon nitrogen compound is 0.001-0.01: 1.
As a general technical concept, the invention also provides a preparation method of the above supported palladium modified carbon nitrogen compound foam metal visible light photocatalyst, which comprises the following steps:
s1, mixing the palladium modified carbon nitrogen compound with a binder to obtain a palladium modified carbon nitrogen compound mixed solution;
and S2, dripping the palladium modified carbon nitrogen compound mixture on foam metal for sintering to obtain the foam metal visible light photocatalyst of the supported palladium modified carbon nitrogen compound.
In the preparation method, the ratio of the palladium modified carbon nitrogen compound to the binder is 0.01-0.05 g: 0.5-1.0 mL in step S1; the binder is at least one of a 1-methyl-2-pyrrolidone solution of polyvinylidene fluoride and a Nafion PFSA polymer solution; the concentration of the 1-methyl-2-pyrrolidone solution of the polyvinylidene fluoride is 1 g/L-5 g/L; the Nafion PFSA polymer solution is prepared by mixing Nafion PFSA polymer dispersion (commercially available) and ethanol; the mass concentration of the Nafion PFSA polymer solution is 0.5-5%.
In a further improvement of the above preparation method, in step S1, the preparation method of the palladium-modified carbon nitrogen compound includes the following steps:
(1) carrying out thermal polycondensation reaction on the 3-amino-1, 2, 4-triazole to obtain a carbon-nitrogen compound;
(2) ultrasonically dispersing the carbon-nitrogen compound obtained in the step (1) in deionized water, adding chloropalladite and excessive reducing agent under the stirring condition to perform reduction reaction, filtering, and drying under the vacuum condition to obtain the palladium modified carbon-nitrogen compound.
The preparation method is further improved, in the step (1), the heating rate is 2-10 ℃/min in the thermal polycondensation reaction process; the temperature of the thermal polycondensation reaction is 450-500 ℃; the time of the thermal polycondensation reaction is 3-4 h.
In the preparation method, the power of the ultrasonic dispersion in the step (2) is 300-800W; the frequency of the ultrasonic dispersion is 40 KHz; the ultrasonic dispersion time is 30-60 min; the stirring speed is 300rpm to 1000 rpm; the stirring time is 1-2 h; the reducing agent is at least one of sodium borohydride or potassium borohydride; the drying temperature is 40-60 ℃; the drying time is 6-10 h.
In a further improvement of the above preparation method, in step S1, the mixing is performed under ultrasonic conditions; the power of the ultrasonic wave is 300-800W; the frequency of the ultrasonic wave is 40 KHz; the ultrasonic time is 60-120 min.
In a further improvement of the above preparation method, in step S2, the sintering is performed under vacuum conditions; the sintering temperature is 120-150 ℃; the sintering time is 6-10 h.
As a general technical idea, the invention also provides an application of the palladium modified carbon nitrogen compound supported foam metal visible light catalyst or the palladium modified carbon nitrogen compound supported foam metal visible light catalyst prepared by the preparation method in treatment of organic pollutant wastewater.
The application is further improved, and comprises the following steps: mixing the palladium-modified carbon nitrogen compound-loaded foam metal visible light catalyst with organic pollutant wastewater, stirring, and carrying out photocatalytic degradation under the illumination condition to finish the degradation of the organic pollutants in the wastewater.
In the application, the addition amount of the palladium modified carbon nitrogen compound supported foam metal visible light catalyst is further improved, and 5.1 g-5.5 g of the palladium modified carbon nitrogen compound supported foam metal visible light catalyst is added in each liter of organic pollutant wastewater; the concentration of the organic pollutants in the organic pollutant wastewater is 0.5 mg/L-1.0 mg/L; the organic pollutant is at least one of antibiotics, chlorophenol and dyes; the antibiotic is tetracycline hydrochloride and/or terramycin; the chlorophenol is at least one of 2, 4-dichlorophenol, 4 chlorophenol and 2,4, 6-trichlorophenol; the dye is rhodamine B and/or Congo red.
The application is further improved, and the stirring time is 30-60 min; the photocatalysis time is 1-2.5 h.
In the above application, further improvement is that after the palladium modified carbon nitrogen compound supported foam metal visible light photocatalyst fails, the method further comprises the following steps: placing the foam metal visible-light-driven photocatalyst of the supported palladium modified carbon nitrogen compound into water for ultrasonic treatment; the power of ultrasonic treatment is 300-800W; the ultrasonic treatment frequency is 40 KHz; the ultrasonic treatment time is 30-60 s.
Compared with the prior art, the invention has the advantages that:
(1) aiming at the defects of poor visible light absorption capacity, poor photocatalytic activity, environmental pollution, difficulty in recovery, easiness in causing secondary pollution and the like of the existing supported photocatalyst, the invention creatively provides a palladium-modified carbon nitrogen compound-supported foam metal visible light photocatalyst, which comprises a palladium-modified carbon nitrogen compound and foam metal, wherein the palladium-modified carbon nitrogen compound is embedded in the foam metal and is supported on the surface of the foam metal, the palladium-modified carbon nitrogen compound takes a carbon nitrogen compound as a carrier, a palladium simple substance is supported on the carbon nitrogen compound, and the carbon nitrogen compound is C 3 N 5 . Compared with the traditional C 3 N 4 C used in the present invention 3 N 5 The absorption range of visible light is wider, more catalytic active sites are provided, and palladium modified C is loaded by palladium 3 N 5 Compared with pure C 3 N 5 The absorption range of visible light is further expanded, the separation efficiency of carriers is effectively improved, and palladium is more stable compared with other noble metals; on the basis, the foam metal is used as a carrier, and the foam metal has the advantages of large attachment area, good conductivity and low price, so that the palladium modified C can be modified 3 N 5 The catalyst is stably fixed in the foam metal and on the surface of the foam metal, so that more catalytic sites can be exposed, and the carrier transfer efficiency is high; in addition, the adopted foam metal has better mechanical strength, can be better fixed in water, is favorable for realizing the recovery of the catalyst and the reuse of the catalyst, and reduces the risk of secondary pollution possibly caused by the catalyst to the environment, so compared with other aerogel or hydrogel supported catalysts, the foam metal as a carrier can be recycled. Compared with the conventional supported photocatalyst, the foam metal of the supported palladium modified carbon nitrogen compound is visibleThe photocatalyst has the advantages of convenient recovery, no toxic or harmful elements, good visible light absorption performance, excellent photocatalytic performance, small secondary pollution risk and the like, is a novel supported visible photocatalyst with excellent performance, can be widely used for deeply treating organic pollutant (such as antibiotics, chlorophenol and dyes) wastewater, can effectively remove the organic pollutants in the wastewater, and has high use value and good application prospect.
(2) In the palladium modified carbon nitrogen compound supported foam metal visible light catalyst, the mass ratio of the palladium modified carbon nitrogen compound to the foam metal is optimized to be 0.1-0.5: 5, and the mass ratio of a palladium simple substance to a carbon nitrogen compound in the palladium modified carbon nitrogen compound is optimized to be 0.001-0.01: 1, so that the catalyst can be ensured to have higher photocatalytic activity and better visible light absorption capacity, and is more favorable for realizing the efficient degradation of the catalyst on target pollutants, because when the content of palladium is too low, the absorption capacity of the catalyst on light is insufficient, catalytic active sites are few, and the catalytic capacity of the catalyst is weak; when the content of palladium is too high, too much palladium can form a carrier recombination center, and the separation efficiency of carriers is reduced; similarly, when the amount of the palladium-modified carbon nitrogen compound is too small, the amount of the catalyst is insufficient, and the number of catalytically active sites is small, resulting in low catalytic activity; when the amount of the palladium-modified carbon nitrogen compound is too large, the excessive catalyst may produce a shielding effect to reduce the light penetration ability, thereby also causing a decrease in catalytic activity.
(3) The invention also provides a preparation method of the palladium modified carbon nitrogen compound supported foam metal visible light catalyst, which takes palladium modified carbon nitrogen compound and a binder as raw materials, adopts a dripping method to drip and coat the palladium modified carbon nitrogen compound mixture on the foam metal, so that the palladium modified carbon nitrogen compound permeates into the foam metal and is coated on the surface of the foam metal, and then the palladium modified carbon nitrogen compound is stably fixed in the foam metal and on the surface of the foam metal through a low-temperature sintering method, thereby obtaining the palladium modified carbon nitrogen compound supported foam metal visible light catalyst with stable structure. Meanwhile, the preparation method has the advantages of simple process, mature technology, convenient operation, less used medicament, low cost, safety, environmental protection and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(4) The invention also provides application of the palladium-modified carbon nitrogen compound-loaded foam metal visible light catalyst in treatment of organic pollutant wastewater, the palladium-modified carbon nitrogen compound-loaded foam metal visible light catalyst is mixed with the organic pollutant wastewater, stirred and subjected to photocatalytic degradation under the illumination condition, so that effective advanced treatment of the wastewater can be realized, and effective removal of organic pollutants (such as antibiotics, chlorophenol and dyes) in the wastewater can be realized.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a schematic representation of a palladium-modified carbon nitride compound (A) and a palladium-modified carbon nitride supported metal foam visible light photocatalyst (B) prepared in inventive example 1.
FIG. 2 is a schematic diagram of a palladium-modified carbon nitride compound (A) and a palladium-modified carbon nitride compound-supported metal foam visible light photocatalyst (B) prepared in example 1 of the present invention in water.
FIG. 3 is a scanning electron microscope image of the palladium-modified carbon nitride compound (A) and the palladium-modified carbon nitride compound-supported foam metal visible light photocatalyst (B) prepared in example 1 of the present invention.
FIG. 4 shows a carbonitride compound (C) prepared in example 1 of the present invention 3 N 5 ) Palladium-modified carbon nitride (Pb-C) 3 N 4 ) Palladium-modified carbon nitrogen compound (Pb-C) 3 N 5 ) Palladium-modified carbon nitride-supported nickel foam (Pb-C) 3 N 4 @ foamed nickel) and supported palladium modified carbon nitrogen compound (Pb-C) 3 N 5 @ foamed nickel) was used.
FIG. 5 shows an embodiment of the present invention1 Carbo-nitrogen compound (C) 3 N 5 ) Carbon nitride (C) 3 N 4 ) Palladium-modified carbon nitride (Pb-C) 3 N 4 ) Palladium-modified carbon nitrogen compound (Pb-C) 3 N 5 ) Electrochemical impedance spectroscopy.
FIG. 6 shows a palladium-modified carbon nitrogen compound supported foam metal visible light catalyst (Pb-C) in example 2 of the present invention 3 N 5 @ foamed nickel) is used for treating tetracycline hydrochloride wastewater, and the corresponding tetracycline hydrochloride removal rate is changed along with time.
FIG. 7 shows a palladium-modified carbon nitrogen compound supported foam metal visible light catalyst (Pb-C) in example 3 of the present invention 3 N 5 @ foamed nickel), palladium-modified carbon nitride-supported foamed nickel (Pd-C) 3 N 4 @ nickel foam) and carbonitride-loaded nickel foam (C) 3 N 5 @ foamed nickel) is used for treating the 2, 4-dichlorophenol wastewater, and the corresponding 2, 4-dichlorophenol removal rate is changed along with time.
FIG. 8 shows a palladium-modified carbon nitrogen compound supported foam metal visible light catalyst (Pb-C) in example 4 of the present invention 3 N 5 @ foamed nickel) is used for treating the rhodamine B wastewater, and the corresponding rhodamine B removal rate is changed along with time.
FIG. 9 is a graph showing the time-dependent change of the removal rate of 2, 4-dichlorophenol in the 2, 4-dichlorophenol wastewater treated by the foamed metal visible light catalyst supporting the palladium-modified carbon nitrogen compound in example 5 of the present invention.
FIG. 10 is a graph showing the time-dependent change of the removal rate of 2, 4-dichlorophenol from 2, 4-dichlorophenol wastewater treated by the palladium-modified carbon nitrogen compound supported foam metal visible light catalyst in example 6 of the present invention.
FIG. 11 is a graph showing the recycling effect of the photocatalyst for visible light of foamed metal supporting palladium-modified carbon nitride in example 7 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples, unless otherwise specified, the raw materials and equipment used were commercially available, the process used was a conventional one, the equipment used was conventional, and the data obtained were average values of three or more repeated experiments.
Example 1
A palladium-modified carbon nitride-loaded foam metal visible light catalyst comprises a palladium-modified carbon nitride and foam metal, wherein the palladium-modified carbon nitride is inlaid in the foam metal and loaded on the surface of the foam metal, the palladium-modified carbon nitride takes a carbon nitride as a carrier, a palladium simple substance is loaded on the carbon nitride, and the carbon nitride is C 3 N 5 。
In this example, the mass ratio of the palladium-modified carbon nitrogen compound to the metal foam was 0.03: 0.5. The foam metal is foam nickel.
In this example, elemental palladium and C 3 N 5 The mass ratio of (A) to (B) is 0.003: 1.
The preparation method of the palladium-modified carbon nitrogen compound-supported foam metal visible light photocatalyst in the embodiment of the invention comprises the following steps:
(1) weighing 1.5g of 3-amino-1, 2, 4-triazole, placing in a 100mL crucible with a cover, placing in a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 3h, naturally cooling to room temperature, grinding to obtain a carbon-nitrogen compound, which is marked as C 3 N 5 。
(2) Weighing 0.2g of the carbon-nitrogen compound obtained in the step (1), adding the carbon-nitrogen compound into 50mL of deionized water, performing ultrasonic dispersion for 30min under the conditions of 300W ultrasonic power and 40KHz ultrasonic frequency, then adding 56.232 mu L of chloropalladic acid, adsorbing for 1h under the stirring condition of 500rpm, then adding 50mL of 0.1M sodium borohydride solution at the dropping speed of 3mL/min, continuing to react for 30min after the dropping is finished, then filtering, cleaning with absolute ethyl alcohol and deionized water, and finally drying in a vacuum drying oven at 40 ℃ for 6h to obtain the palladium-modified carbon-nitrogen compound, which is marked as Pb-C 3 N 5 。
(3) 30mg of the palladium-modified carbon-nitrogen compound obtained in step (2) was weighed and placed in 0.5mL of 1 g/L1-methyl polyvinylidene fluorideAdding into 2-pyrrolidone solution, ultrasonic dispersing at 300W ultrasonic power and 40KHz ultrasonic frequency for 120min, and dripping the dispersed palladium modified carbon nitrogen compound mixture onto 2 × 3cm 2 Finally, the coated nickel foam is placed in a vacuum drying oven at 120 ℃ for drying for 6 hours to obtain the palladium modified carbon nitrogen compound supported foam metal visible light catalyst which is marked as Pb-C 3 N 5 @ foamed nickel.
In this example, carbon nitride (C) was also prepared 3 N 4 ) Palladium-modified carbon nitride (Pb-C) 3 N 4 ) Foamed nickel (C) carrying a carbon nitride compound 3 N 5 @ foamed nickel) and palladium-supported modified carbon nitride-supported foamed nickel (Pb-C) 3 N 4 @ nickel foam), in which carbon nitride (C) 3 N 4 ) The preparation method comprises the following steps: weighing 10g of melamine, placing the melamine in a ceramic crucible with a cover, heating the melamine to 550 ℃ at the heating rate of 10 ℃/min, preserving the heat for 4 hours, naturally cooling the melamine to room temperature to obtain carbon nitride, which is marked as C 3 N 4 . Palladium-modified carbon nitride (Pb-C) 3 N 4 ) The same as in step (2) in example 1, except that: using carbon nitride (C) 3 N 4 ) In place of carbon nitride (C) 3 N 5 ). Palladium-modified carbon nitride-supported nickel foam (Pb-C) 3 N 4 @ nickel foam) and nickel foam (C) loaded with carbon and nitrogen compounds 3 N 5 @ foamed nickel), the same as in step (3) of example 1, except that: modification of carbon nitride (Pb-C) with palladium 3 N 4 ) And carbon nitrogen compound (C) 3 N 5 ) Modification of carbon nitride Compound (Pb-C) in place of Palladium 3 N 5 )。
FIG. 1 is a schematic diagram of a palladium-modified carbon nitride compound (A) and a palladium-modified carbon nitride compound-supported metal foam visible-light-induced photocatalyst (B) prepared in example 1 of the present invention. As can be seen from FIG. 1, the prepared palladium-modified carbon nitride compound (Pb-C) 3 N 5 ) Is in powder form. Meanwhile, as can be seen from FIG. 1, the prepared palladium modified carbon nitrogen compound supported foam metal visible light catalyst (Pb-C) 3 N 5 @ foamed nickel) of 2X 3cm 2 Sheet-like structural materialMaterial, palladium modified C 3 N 5 Supported on foamed nickel.
FIG. 2 is a schematic view of a palladium-modified carbon nitride compound (A) and a palladium-modified carbon nitride compound-supported metal foam visible-light-induced photocatalyst (B) prepared in example 1 of the present invention in water. From FIG. 2, it can be seen that the palladium-modified carbon nitride compound (Pb-C) 3 N 5 ) The catalyst is completely dispersed in water, the solution is turbid, and the catalyst is difficult to separate; and the foam metal visible light catalyst (Pb-C) of the supported palladium modified carbon nitrogen compound 3 N 5 @ foamed nickel) is present in the form of a sheet in water, and the catalyst is easily taken out.
FIG. 3 is a scanning electron microscope image of the palladium-modified carbon nitride compound (A) and the palladium-modified carbon nitride compound-supported foam metal visible light photocatalyst (B) prepared in example 1 of the present invention. As can be seen from FIG. 3, the metal foam visible light photocatalyst (Pb-C) obtained by supporting palladium-modified carbon nitride 3 N 5 @ nickel foam) can be seen from the scanning electron microscope picture (fig. 3A) of nickel foam, the abundant pore structure can provide sufficient carriers for palladium modified carbon nitride, and meanwhile, as can be seen from fig. 3B, a large amount of palladium modified carbon nitride is attached to the nickel foam.
FIG. 4 shows a carbonitride compound (C) prepared in example 1 of the present invention 3 N 5 ) Palladium-modified carbon nitride (Pb-C) 3 N 4 ) Palladium-modified carbon nitrogen compound (Pb-C) 3 N 5 ) Palladium-modified carbon nitride-supported nickel foam (Pb-C) 3 N 4 @ foamed nickel) and supported palladium modified carbon nitrogen compound (Pb-C) 3 N 5 @ foamed nickel) was used. From FIG. 4, it can be seen that the palladium-modified carbon nitride compound (Pb-C) 3 N 5 ) The absorption range and the intensity to light are higher than those of palladium modified carbon nitride (Pb-C) 3 N 4 ) Foam metal visible light catalyst (Pb-C) simultaneously loaded with palladium modified carbon nitrogen compound 3 N 5 @ foamed nickel) has the same absorption range and strength to light as higher than that of foamed nickel (Pb-C) loaded on palladium-modified carbon nitride 3 N 4 @ nickel foam), indicating that loading of palladium in the present invention can increase C 3 N 5 Absorption range of light, i.e., a foamed metal visible light photocatalyst (Pb-C) supporting palladium-modified carbon nitride 3 N 5 @ nickel foam) has more excellent visible light absorption properties.
FIG. 5 shows a carbonitride compound (C) prepared in example 1 of the present invention 3 N 5 ) Carbon nitride (C) 3 N 4 ) Palladium-modified carbon nitride (Pb-C) 3 N 4 ) Palladium-modified carbon nitrogen compound (Pb-C) 3 N 5 ) Electrochemical impedance diagram of (1). As can be seen from fig. 5, the nyquist diagram radii of curvature (r) of the four catalysts are, in order: r (Pb-C) 3 N 5 )<r(C 3 N 5 )<r(Pb-C 3 N 4 )<r(C 3 N 4 ) This indicates Pd-C 3 N 5 The electron transfer resistance of (2) is minimal. Meanwhile, after Pd is loaded, the electron transfer resistance is reduced, which shows that the load of Pd is favorable for the transfer of photon-generated carriers.
Example 2
Application of palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst in treatment of antibiotic wastewater, in particular to the palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst (Pb-C) prepared in example 1 3 N 5 @ foamed nickel) for photocatalytic degradation treatment of antibiotic wastewater, comprising the following steps:
a piece of 2X 3cm prepared in example 1 was taken 2 The palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst (Pb-C) 3 N 5 @ foamed nickel, 0.53g), was added to 100mL tetracycline hydrochloride wastewater at a concentration of 1mg/L, placed in the dark, and stirred at 100rpm for 30min to allow the palladium-modified carbonitride-loaded foamed metal visible light photocatalyst (Pb-C) 3 N 5 @ foamed nickel) and tetracycline hydrochloride are fully contacted, then the obtained mixed solution is placed under a xenon lamp (300W, 420nm cutoff filter plate) at normal temperature and normal pressure, and a light source is turned on to carry out photocatalytic degradation, so that the treatment of the antibiotic wastewater is completed.
In the photocatalytic degradation process, 1.5mL of the solution is sampled every 30min, the concentration of the sample is analyzed by liquid chromatography after the sample passes through a 0.22-micron filter membrane, and then the removal rate alpha of the tetracycline hydrochloride is calculated by the formula (1).
In formula (1): α is the removal (%); c 0 The initial concentration of tetracycline hydrochloride in the solution before treatment (unit: mg/L); c is the tetracycline hydrochloride concentration (unit: mg/L) after the treatment.
FIG. 6 shows a palladium modified carbon nitrogen compound supported foam metal visible light catalyst (Pb-C) in example 2 of the present invention 3 N 5 @ foamed nickel) is used for treating tetracycline hydrochloride wastewater, and the corresponding tetracycline hydrochloride removal rate is changed along with time. As can be seen from FIG. 6, the metal foam visible light catalyst (Pb-C) using the supported palladium-modified carbon nitride 3 N 5 @ foamed nickel), the removal rate of tetracycline hydrochloride reaches 100% when visible light irradiates for 120 min.
Example 3
An application of a palladium-modified carbon nitrogen compound-loaded foam metal visible light catalyst in chlorophenol wastewater treatment, in particular to a Pb-C (Pb-C) foam metal visible light catalyst loaded with palladium-modified carbon nitrogen compound prepared in example 1 3 N 5 @ foamed nickel) is used for carrying out photocatalytic degradation treatment on chlorophenol wastewater, and the method comprises the following steps:
the areas obtained in example 1 were taken to be 2X 3cm 2 The palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst (Pb-C) 3 N 5 @ nickel foam, 0.53g), palladium modified carbon nitride supported nickel foam (Pd-C) 3 N 4 @ foamed Nickel, 0.53g) and Nitrogen-carbon Compound-Supported foamed Nickel (C) 3 N 5 @ 0.53g) of nickel foam, adding the mixture into 100mL of 2, 4-dichlorophenol wastewater with the concentration of 0.5mg/L, placing the wastewater in the dark, and stirring the wastewater for 30min at the rotating speed of 100rpm to enable the palladium modified carbon nitrogen compound supported foam metal visible light catalyst (Pb-C) 3 N 5 @ foamed nickel) with 2, 4-dichlorophenol, and then under normal temperature and pressureAnd placing the obtained mixed solution under a xenon lamp (a 300W and 420nm cut-off filter), and turning on a light source to carry out photocatalytic degradation to finish the treatment of the parachlorophenol wastewater.
During the photocatalytic degradation, 1.5mL of the sample is sampled every 30min, the concentration of the sample is analyzed by liquid chromatography after the sample passes through a filter head with the diameter of 0.22 μm, and then the removal rate alpha of the 2, 4-dichlorophenol is calculated by the formula (2).
In formula (2): α is the removal (%); c 0 Is the initial concentration (unit: mg/L) of 2, 4-dichlorophenol in the solution before treatment; c is the concentration of the 2, 4-dichlorophenol (unit: mg/L) after the treatment.
FIG. 7 shows a palladium-modified carbon nitrogen compound supported foam metal visible light catalyst (Pb-C) in example 3 of the present invention 3 N 5 @ foamed nickel), palladium-modified carbon nitride-supported foamed nickel (Pd-C) 3 N 4 @ nickel foam) and nickel foam (C) loaded with carbon and nitrogen compounds 3 N 5 @ foamed nickel) is used for treating the 2, 4-dichlorophenol wastewater, and the corresponding 2, 4-dichlorophenol removal rate is changed along with time. As can be seen from FIG. 7, the metal foam visible light catalyst (Pb-C) using the supported palladium-modified carbon nitride 3 N 5 @ foamed nickel) is used for treating the 2, 4-dichlorophenol, the removal rate of the 2, 4-dichlorophenol after visible light irradiation for 120min is 86.36%, and the concentration of the 2, 4-dichlorophenol after treatment is reduced to 0.067mg/L, thereby meeting the comprehensive sewage discharge standard GB 8978-1996. And adopting foamed nickel (Pb-C) loaded with palladium modified carbon nitride 3 N 4 @ nickel foam) and nickel foam (C) loaded with carbon and nitrogen compounds 3 N 5 @ foamed nickel) was used to treat 2, 4-dichlorophenol, the removal rates of 2, 4-dichlorophenol after 120min of visible light irradiation were 63.04% and 71.04%, respectively, indicating that the loading of Pd can increase the photocatalytic activity of the catalyst, while comparing to carbon nitride (C) 3 N 4 ) Carbon nitride (C) 3 N 5 ) Has better photocatalytic activity.
Example 4
An application of a palladium-modified carbon nitrogen compound-loaded foam metal visible light catalyst in treating dye wastewater, in particular to a palladium-modified carbon nitrogen compound-loaded foam metal visible light catalyst (Pb-C) prepared in example 1 3 N 5 @ foamed nickel) for carrying out photocatalytic degradation treatment on the dye wastewater, comprising the following steps of:
the area obtained in example 1 was taken to be 2X 3cm 2 The palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst (Pb-C) 3 N 5 @ 0.53g) is added into 100mL of 1.0mg/L rhodamine B wastewater, and the mixture is stirred for 30min under the condition of 100rpm in the dark condition, so that the palladium modified C 3 N 5 The supported foam nickel visible light catalyst is fully contacted with rhodamine B, then the obtained mixed solution is placed under a xenon lamp (a 300W and 420nm cut-off filter plate) at normal temperature and normal pressure, a light source is turned on to carry out photocatalytic degradation, and the treatment of the dye wastewater is completed.
In the photocatalytic degradation process, 4mL samples are taken every 30min, after the samples pass through a filter head with the diameter of 0.22 mu m, the absorbance of the samples is directly measured at 554nm by an ultraviolet-visible spectrophotometer, then the absorbance is converted into concentration according to the relation between the absorbance and the concentration (formula (3)), and the removal rate of rhodamine B (formula (4)) alpha is calculated according to the concentration.
A＝0.21989C+0.0007(3)
In formula (3): c is the concentration (unit: mg/L) of rhodamine B, A is the absorbance of the rhodamine B; in the formula (4), α represents a removal rate (%); c 0 Is the initial concentration (unit: mg/L) of rhodamine B in the solution before treatment; c is the concentration (unit: mg/L) of the treated rhodamine B.
FIG. 8 shows a palladium-modified carbon nitrogen compound supported foam metal visible light catalyst (Pb-C) in example 4 of the present invention 3 N 5 @ foamed nickel) for treating rhodamine B wastewater, and relationship that removal rate of corresponding rhodamine B changes along with timeA graph. As can be seen from FIG. 8, the metal foam visible light catalyst (Pb-C) using the supported palladium-modified carbon nitride 3 N 5 @ foamed nickel), the removal rate of rhodamine is 93.21% after being irradiated by visible light for 150min, and the concentration of the treated rhodamine B is reduced to 0.051 mg/L.
Example 5
A palladium-modified carbon nitride-supported foam metal visible light catalyst, and the palladium-modified carbon nitride-supported foam metal visible light catalyst (Pb-C) of example 1 3 N 5 @ nickel foam) are substantially identical, except that: in example 5, the mass ratio of the palladium-modified carbon nitrogen compound to the nickel foam was 0.04: 0.5.
0.54g of the area prepared in example 5 was set to 2X 3cm 2 The palladium supported carbon nitrogen compound foam metal visible light catalyst is used for treating 2, 4-dichlorophenol wastewater, and the rest conditions are the same as in example 3.
FIG. 9 is a graph showing the time-dependent change of the removal rate of 2, 4-dichlorophenol in the 2, 4-dichlorophenol wastewater treated by the foamed metal visible light catalyst supporting the palladium-modified carbon nitrogen compound in example 5 of the present invention. As can be seen from FIG. 9, when the 2, 4-dichlorophenol solution is treated by the foam metal visible light catalyst loaded with the palladium-modified carbon nitrogen compound, the removal rate of 2, 4-dichlorophenol after being irradiated for 120min under visible light is 91.78%, and the concentration of 2, 4-dichlorophenol after being treated is reduced to 0.041mg/L, which meets the comprehensive wastewater discharge standard GB 8978-1996.
Example 6
A palladium-modified carbon nitride-supported foam metal visible light catalyst, and the palladium-modified carbon nitride-supported foam metal visible light catalyst (Pb-C) of example 1 3 N 5 @ foamed nickel) are substantially the same, differing only in that: in example 6, the mass ratio of the palladium-modified carbon nitrogen compound to the nickel foam was 0.05: 0.5.
0.55g of the area prepared in example 6 was set to 2X 3cm 2 The foam metal visible light catalyst of the supported palladium modified carbon nitrogen compound is used for treating 2, 4-dichlorophenol solution, and the rest conditions and implementation areExample 3 the same.
FIG. 10 is a graph showing the time-dependent change of the removal rate of 2, 4-dichlorophenol from 2, 4-dichlorophenol wastewater treated by the palladium-modified carbon nitrogen compound supported foam metal visible light catalyst in example 6 of the present invention. As can be seen in FIG. 10, modification of C with Palladium 3 N 5 When the supported nickel foam visible light catalyst is used for treating a 2, 4-dichlorophenol solution, the removal rate of 2, 4-dichlorophenol is 88.33% after the 2, 4-dichlorophenol solution is irradiated for 120min under visible light, and the concentration of the 2, 4-dichlorophenol after the treatment is reduced to 0.059mg/L, thereby meeting the comprehensive wastewater discharge standard GB 8978-1996.
Example 7
The reusability of the foam metal visible light photocatalyst of the supported palladium modified carbon nitrogen compound is examined, and the method comprises the following steps:
(1) 0.54g of the palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst prepared in example 5 was added to 100mL of 2, 4-dichlorophenol wastewater with an initial concentration of 0.5mg/L, and the mixture was stirred in the dark at a rotation speed of 100rpm for 30min to allow the palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst to fully contact with 2, 4-dichlorophenol to achieve adsorption equilibrium, and then the resulting mixed solution was placed under a xenon lamp (300W, 420nm cutoff filter) at normal temperature and pressure, and the light source was turned on to carry out photocatalytic degradation for 120 min.
(2) And (2) directly taking out the foam metal visible light photocatalyst loaded with the palladium modified carbon nitrogen compound after the photocatalytic degradation in the step (1) is finished, cleaning the foam metal visible light photocatalyst with ultrapure water and absolute ethyl alcohol, and then continuously using the cleaned foam metal visible light photocatalyst loaded with the palladium modified carbon nitrogen compound for treating 2, 4-dichlorophenol wastewater.
(3) And (3) repeating the steps (1) and (2) to carry out photocatalytic degradation on the 2, 4-dichlorophenol wastewater.
FIG. 11 is a graph showing the recycling effect of the photocatalyst made of a foamed metal supporting a palladium-modified carbon nitride in example 7 of the present invention. As can be seen from fig. 11, the removal rate of the foamed metal visible light photocatalyst supporting the palladium-modified carbon nitrogen compound to 2, 4-dichlorophenol is not changed after 5 times of recycling, which indicates that the activity of the foamed metal visible light photocatalyst supporting the palladium-modified carbon nitrogen compound is not reduced, and thus, the foamed metal visible light photocatalyst supporting the palladium-modified carbon nitrogen compound is very stable and has very good reusability.
As can be seen from the above, phase ratio C 3 N 4 C used in the present invention 3 N 5 The catalyst has wider absorption range on visible light and larger specific surface area, thereby having higher catalytic activity; phase contrast C 3 N 5 In the invention, palladium modified C is adopted 3 N 5 Further improves the absorption range of visible light and the separation efficiency of current carriers, and simultaneously, the adopted foam nickel has the advantages of large attachment area and high mechanical strength, thereby being capable of modifying the palladium C 3 N 5 C fixed in the interior and on the surface of the foamed nickel and capable of modifying palladium to the maximum extent 3 N 5 C exposed outside and favorable for performing palladium modification 3 N 5 While palladium-modified C 3 N 5 The catalyst is loaded on the foamed nickel, which is beneficial to realizing the recovery and the reutilization of the catalyst and reducing the risk of secondary pollution to the environment caused by the loss of the catalyst.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to those skilled in the art without departing from the principles of the present invention should also be considered as within the scope of the present invention.
Claims (10)
1. The palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst is characterized by comprising a palladium-modified carbon nitrogen compound and foam metal, wherein the palladium-modified carbon nitrogen compound is embedded in the foam metal and supported on the surface of the foam metal; the palladium modified carbon-nitrogen compound takes a carbon-nitrogen compound as a carrier, a palladium simple substance is loaded on the carbon-nitrogen compound, and the carbon-nitrogen compound is C 3 N 5 。
2. The palladium-modified carbon nitrogen compound-supported foam metal visible light catalyst as claimed in claim 1, wherein the mass ratio of the palladium-modified carbon nitrogen compound to the foam metal is 0.1-0.5: 5; the foam metal is at least one of foam nickel, foam cobalt and foam titanium; the mass ratio of the palladium simple substance to the carbon nitrogen compound in the palladium modified carbon nitrogen compound is 0.001-0.01: 1.
3. A method for preparing the palladium modified carbon nitrogen compound supported foam metal visible light catalyst as claimed in claim 1 or 2, which comprises the following steps:
s1, mixing the palladium modified carbon nitrogen compound with a binder to obtain a palladium modified carbon nitrogen compound mixed solution;
and S2, dripping the palladium modified carbon nitrogen compound mixture on foam metal for sintering to obtain the foam metal visible light photocatalyst of the supported palladium modified carbon nitrogen compound.
4. The method according to claim 3, wherein in step S1, the ratio of the palladium-modified carbon nitrogen compound to the binder is 0.01-0.05 g: 0.5-1.0 mL; the binder is at least one of a 1-methyl-2-pyrrolidone solution of polyvinylidene fluoride and a Nafion PFSA polymer solution; the concentration of the 1-methyl-2-pyrrolidone solution of the polyvinylidene fluoride is 1 g/L-5 g/L; the Nafion PFSA polymer solution is prepared by mixing Nafion PFSA polymer dispersion liquid and ethanol; the mass concentration of the Nafion PFSA polymer solution is 0.5-5%.
5. The method according to claim 4, wherein the method for producing the palladium-modified carbon nitride compound in step S1 includes the steps of:
(1) carrying out thermal polycondensation reaction on the 3-amino-1, 2, 4-triazole to obtain a carbon-nitrogen compound;
(2) ultrasonically dispersing the carbon-nitrogen compound obtained in the step (1) in deionized water, adding chloropalladite and excessive reducing agent under the stirring condition to perform reduction reaction, filtering, and drying under the vacuum condition to obtain the palladium modified carbon-nitrogen compound.
6. The method according to claim 5, wherein in the step (1), the temperature rise rate during the thermal polycondensation reaction is 2 ℃/min to 10 ℃/min; the temperature of the thermal polycondensation reaction is 450-500 ℃; the time of the thermal polycondensation reaction is 3-4 h;
in the step (2), the power of ultrasonic dispersion is 300-800W; the frequency of the ultrasonic dispersion is 40 KHz; the ultrasonic dispersion time is 30-60 min; the stirring speed is 300 rpm-1000 rpm; the stirring time is 1-2 h; the reducing agent is at least one of sodium borohydride or potassium borohydride; the drying temperature is 40-60 ℃; the drying time is 6-10 h.
7. The method according to any one of claims 3 to 6, wherein in step S1, the mixing is performed under ultrasonic conditions; the power of the ultrasonic wave is 300-800W; the frequency of the ultrasonic wave is 40 KHz; the ultrasonic time is 60-120 min;
in step S2, the sintering is performed under vacuum conditions; the sintering temperature is 120-150 ℃; the sintering time is 6-10 h.
8. Application of the palladium modified carbon nitrogen compound supported foam metal visible light catalyst as claimed in claim 1 or 2 or the palladium modified carbon nitrogen compound supported foam metal visible light catalyst prepared by the preparation method as claimed in any one of claims 3 to 7 in treatment of organic pollutant wastewater.
9. Use according to claim 8, characterized in that it comprises the following steps: mixing a palladium-modified carbon nitrogen compound-loaded foam metal visible light catalyst with organic pollutant wastewater, stirring, and carrying out photocatalytic degradation under the illumination condition to finish degradation of organic pollutants in the wastewater; the addition amount of the palladium modified carbon nitrogen compound supported foam metal visible light catalyst is 5.1-5.5 g of the palladium modified carbon nitrogen compound supported foam metal visible light catalyst added in each liter of organic pollutant wastewater; the concentration of the organic pollutants in the organic pollutant wastewater is 0.5 mg/L-1.0 mg/L; the organic pollutant is at least one of antibiotics, chlorophenol and dyes; the antibiotic is tetracycline hydrochloride and/or terramycin; the chlorophenol is at least one of 2, 4-dichlorophenol, 4 chlorophenol and 2,4, 6-trichlorophenol; the dye is rhodamine B and/or Congo red; the stirring time is 30-60 min; the photocatalysis time is 1-2.5 h.
10. The use of claim 9, wherein the palladium-modified carbon nitrogen compound supported foam metal visible light photocatalyst is deactivated, and the method further comprises the following steps: placing the foam metal visible-light-driven photocatalyst of the supported palladium modified carbon nitrogen compound into water for ultrasonic treatment; the power of ultrasonic treatment is 300-800W; the ultrasonic treatment frequency is 40 KHz; the ultrasonic treatment time is 30-60 s.
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