CN116422326A - Doping method of semiconductor photocatalytic material - Google Patents
Doping method of semiconductor photocatalytic material Download PDFInfo
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- CN116422326A CN116422326A CN202111646831.2A CN202111646831A CN116422326A CN 116422326 A CN116422326 A CN 116422326A CN 202111646831 A CN202111646831 A CN 202111646831A CN 116422326 A CN116422326 A CN 116422326A
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- 229910052725 zinc Inorganic materials 0.000 claims abstract description 33
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 20
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- 238000001035 drying Methods 0.000 claims description 15
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- 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
- B01J23/66—Silver or gold
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F2101/30—Organic compounds
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a doping method of a semiconductor photocatalytic material. The design and construction of semiconductor-metal heterojunctions is considered to be an effective way to overcome the limited visible light absorption of semiconductors. The invention discloses a simple and convenient doping method for synthesizing an Ag/ZnO heterojunction by one-step electric substitution by zinc and copper solution reaction, and a semiconductor photocatalysis material containing the Ag/ZnO heterojunction structure is prepared by the one-step electric substitution method. The semiconductor photocatalytic material can utilize Ag/ZnO heterojunction with a visible light absorption effect to catalyze the degradation of rhodamine B under the irradiation of visible light, and the photocatalytic performance of the material is enhanced.
Description
Technical Field
The invention belongs to the field of photocatalytic materials, relates to a doping method of a semiconductor photocatalytic material, and in particular relates to a doping method of a heterojunction synthesized by one-step electro-displacement.
Background
How to dispose of environmental problems is a hot topic when environmental problems are becoming more serious. The material photocatalysis technology has wide development prospect and application space in the aspect of environmental sewage degradation. The environmental sewage containing dye, pesticide, organic pollutant and other matters can be subjected to photocatalytic reaction, and small molecular matters harmless to the environment are degraded through decolorization and photocatalysis. Compared with the traditional treatment method, the photocatalyst synthesized by the proper method has a plurality of remarkable advantages on degradation of dyes and organic matters, and the photocatalytic effect is mainly expressed in the aspects of structural nature, chemical performance, photocatalytic degree and the like.
Ion doping is one of the methods for modifying photocatalytic materials, and mainly comprises metal ion doping (rare earth metals, transition metals) and nonmetallic material doping. The metal ion doping utilizes the sensitivity of the d electrons of the transition metal ions to sunlight absorption, and the transition metal ions are doped in the material, so that the response wavelength range of the photocatalyst to light can be enlarged, and the ultraviolet light limitation is extended to the application range of visible light, thereby enhancing the photocatalytic capability. The doping of a certain amount of metal ions can enable the photocatalytic material to have a 'impurity level', and can be used as a springboard for electron jump, so that the energy required by the jump is reduced. Examples of the transition metal ions which are commonly used include Fe, cu, mo, re, ag, and rare earth metals are doped with Ce, la, nd, etc.
Among the numerous nanomaterials, silver has unique advantages due to its excellent conductivity and other characteristics, and becomes the main research angle of nanomaterials. Furthermore, ag can enhance photocatalytic activity by generating a local electric field, and optical vibration of Ag surface plasmon can enhance the electric field. At present, a great deal of Ag is doped on the surface of the material + The research of ions, wherein Ag doped on the surface of the metal material can play a role in modifying and improving the catalytic performance.
At present, many methods for doping metal surfaces are reported. In these preparation methods, the chemical method requires high temperature, high pressure and alkaline solution, and the subsequent separation and purification process is complex. Therefore, a more convenient doping method is needed.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a doping method of a semiconductor photocatalytic material and the semiconductor photocatalytic material prepared by the method. The method can prepare the semiconductor photocatalytic material with the Ag/ZnO heterojunction by a one-step substitution method at room temperature and atmospheric pressure. The Ag/ZnO heterojunction with the visible light absorption function is used for catalyzing the degradation of rhodamine B under the irradiation of visible light. The result shows that the photocatalytic performance of the doped material is enhanced.
The invention provides a doping method of semiconductor photocatalytic material, which comprises placing a metal substrate in a metal ion solution, and obtaining the semiconductor light by one-step replacementA catalytic material; wherein the material of the metal substrate is zinc; the metal ion is Ag + And/or Cu 2+， 。
Among them, the metal oxide photocatalytic material is preferably a metal oxide semiconductor photocatalytic material having a forbidden band width of more than 3 eV. The metal oxide photocatalytic material is one or the combination of more than two of binary metal oxides and multi-element metal oxides. Wherein the hetero-doped atomic ultrathin layer itself should have a band gap greater than 4eV to allow incident light to efficiently excite the core photocatalytic material. In addition, the reactants can spontaneously form a stable electric coupling displacement mechanism in the reaction solution.
The doping method specifically comprises the following steps:
(1) Configuration of Cu 2+ 、Ag + A solution.
(2) Immersing the metal substrate in hydrochloric acid with the concentration of 1M to remove oxide on the surface; repeatedly washing with ethanol and ultrapure water until the surface is clean;
(3) Placing the washed zinc plate into Cu 2+ 、Ag + In the solution, reacting at room temperature;
(4) Absorbing the brown-black product covered on the zinc sheet by the suction pipe, washing 3 times by deionized water and absolute ethyl alcohol respectively, centrifuging and drying to obtain the semiconductor photocatalytic material.
Wherein Cu in step (3) 2+ The ions act as an oxidizing agent and participate in the reaction by yielding the intermediate cuprous oxide.
Preferably, the metal substrate is a foam zinc sheet or zinc sheet, and the size of the metal substrate is 1 x 2cm.
Preferably, the Cu 2+ The solution is CuCl 2 、CuI 2 、CuBr 2 One of the solutions; the Ag is + The solution is one of silver oxide and silver nitrate solution.
Further preferably, the Cu 2+ The solution had a concentration of 2X10 -3 -5×10 -3 CuCl in mol/l 2 A solution; the Ag is + The solution had a concentration of 4.32X10 -5 mol/l silver oxide solution.
Preferably, the reaction time of step 3) is 3 days.
Preferably, in the step 4), the centrifugal speed is 7000 rpm, the centrifugal time is 5 minutes, the drying temperature is 40-60 ℃, and the drying time is 6 hours.
It is another object of the present invention to provide a semiconductor photocatalytic material prepared by the above method.
The material has the following composition, wherein the Zn content is 75-80%, the O content is 16-20%, and the Ag content is 0.3-0.8% by mass.
In addition, the invention also provides application of the semiconductor photocatalytic material in photocatalysis, in particular application in photocatalytic degradation of rhodamine B.
In the semiconductor photocatalytic material, the Ag/ZnO heterostructure has obvious visible light absorbance, and the photocatalytic performance of rhodamine B is enhanced.
The invention has the advantages that:
unlike conventional several methods for preparing semiconductor metals, such as sputtering, electrochemical deposition, chemical methods, and photo deposition, in these preparation methods, the chemical methods require high temperature, high pressure, and alkaline solutions, and the subsequent separation and purification processes are complicated. Chemical processes need improvement and optimization in view of cost, yield and scale. The semiconductor photocatalytic material is prepared by adopting a one-step substitution method under the condition of normal temperature and normal pressure, wherein the semiconductor photocatalytic material has an Ag/ZnO heterojunction structure. The Ag/ZnO heterojunction absorbing visible light can catalyze the degradation of rhodamine B under the irradiation of visible light, and the catalytic degradation performance is strong.
Drawings
FIG. 1 is a scanning electron microscope of a semiconductor photocatalytic material according to the present invention;
FIG. 2 is a graph of ultraviolet absorption spectrum of rhodamine B (RhB) catalyzed by decomposition;
fig. 3 is an X-ray diffraction pattern of the semiconductor photocatalytic material according to the present invention.
Detailed Description
The following will explain the embodiments of the present application in detail by way of examples, whereby the implementation process of how the present application applies technical means to solve technical problems and achieve technical effects can be fully understood and implemented accordingly.
The raw materials and equipment used in the present application are common raw materials and equipment used in the field and are commercially available products unless otherwise specified. The methods used in the present application are conventional in the art unless otherwise specified.
There are many other embodiments that can be implemented, and none of them are listed here, but the embodiments claimed in the claims of this application are all applicable.
"comprising" or "including" is intended to mean that the compositions (e.g., media) and methods include the recited elements, but not exclude other elements. When used to define compositions and methods, "consisting essentially of … …" means excluding other elements that have any significance to the combination for the purpose. Thus, a composition consisting essentially of the elements defined herein does not exclude other materials or steps that do not materially affect the basic and novel characteristics of the claimed application. "consisting of … …" means the process steps excluding trace elements and essential elements of other components. Embodiments defined by each of these transitional terms are within the scope of this application.
In a general implementation, the invention comprises the following steps:
1. zinc sheets or zinc foam metal are used as a substrate, and Cu < 2+ > and Ag < + > metal ions are used as precursors. The reaction was carried out at the appropriate temperature for 3 days.
2. And (3) washing the brown-black product covered on the zinc sheet or the foam zinc with deionized water and absolute ethyl alcohol for 3 times respectively, and centrifugally drying to obtain the product.
Wherein the size of the zinc sheet or the foam zinc is 1 x 2cm, the concentration of the precursor is not more than 1mol/L, and the temperature is between 30 ℃ and 70 ℃. The Cu < 2+ > solution is one of CuCl < 2 >, cuI < 2 > and CuBr < 2+ > solutions. The Ag+ solution is one of silver oxide and silver nitrate solution. The centrifugal speed is 7000 rpm, the centrifugal time is 5 minutes, the drying temperature is 40-60 ℃, and the drying time is 6 hours.
The invention is further illustrated by the following examples.
Example 1
(1) Configuration 4.32×10 -5 mol/L Ag 2 O,5×10 -3 mol/L CuCl 2 A solution.
(2) The 1 x 2cm zinc plate was immersed in 1M hydrochloric acid to remove surface oxides and repeatedly washed with ethanol and ultrapure water until the surface became clean.
(3) Placing the washed zinc plate into Ag 2 O,CuCl 2 In solution, the reaction was carried out at room temperature for 3 days.
(4) Absorbing the brown-black product covered on the zinc sheet by using a suction pipe, washing the product for 3 times by using deionized water and absolute ethyl alcohol respectively, and then centrifugally drying the product to obtain the semiconductor photocatalytic material which has an Ag/ZnO heterojunction structure.
The X-ray spectrum results of the semiconductor photocatalytic material of example 1 are shown in table 1, and it is seen that the material mainly comprises three elements, i.e., zn, O, and Ag. The structure and morphology of the product are shown in FIG. 1, and FIG. 1 is a scanning electron microscope characterization of the product of example 1. As shown in FIG. 1, TEM images show that the prepared samples are rod-shaped with a length of 1-2um. FIG. 1 shows the fringe spacing of the Ag/ZnO heterostructure with lattice spacing of 0.25nm and 0.247nm, corresponding to the 111 plane of Ag and the 101 plane of Zn, respectively, further indicating that the samples were ZnO and Ag. Fig. 3 is an X-ray diffraction pattern of the semiconductor photocatalytic material prepared in example 1.
TABLE 1
Example 2
(1) Configuration 4.32×10 -5 mol/L Ag 2 O，3×10 -3 mol/L CuCl 2 A solution.
(2) The 1 x 2cm zinc plate was immersed in 1M hydrochloric acid to remove surface oxides and repeatedly washed with ethanol and ultrapure water until the surface became clean.
(3) Placing the washed zinc plate into Ag 2 O,CuCl 2 In solution, the reaction was carried out at room temperature for 3 days.
(4) Absorbing the brown-black product covered on the zinc sheet by a suction pipe, washing 3 times by deionized water and absolute ethyl alcohol respectively, and drying at the temperature of 60 ℃ by centrifugation to obtain the product.
Example 3
(1) Configuration 4.32×10 -5 mol/LAg 2 O，2×10 -3 mol/LCuCl 2 A solution.
(2) 1 x 2cm zinc foam was immersed in 1M hydrochloric acid to remove surface oxides, and repeatedly washed with ethanol and ultrapure water until the surface became clean.
(3) Placing the washed foam zinc into Ag 2 O,CuCl 2 In solution, the reaction was carried out at room temperature for 3 days.
(4) Absorbing the brown-black product covered on the zinc sheet by a suction pipe, washing 3 times by deionized water and absolute ethyl alcohol respectively, centrifuging and drying at 60 ℃ to obtain the product.
Example 4
(1) Configuration 4.32×10 -5 mol/L Ag 2 O,1×10 -3 mol/L CuCl 2 A solution.
(2) 1 x 2cm zinc foam was immersed in 1M hydrochloric acid to remove surface oxides, and repeatedly washed with ethanol and ultrapure water until the surface became clean.
(3) Placing the washed foam zinc into Ag 2 O,CuCl 2 In the mixed solution, the reaction was carried out at room temperature for 3 days.
(4) Absorbing the brown-black product covered on the zinc sheet by a suction pipe, washing 3 times by deionized water and absolute ethyl alcohol respectively, and drying at the temperature of 60 ℃ by centrifugation to obtain the product.
Comparative example 1
(1) 1 x 2cm zinc foam was immersed in 1M hydrochloric acid to remove surface oxides, and repeatedly washed with ethanol and ultrapure water until the surface became clean.
(2) Put in 4.32X10 -5 Growing in a mol/L copper chloride solution for 3 days
(3) Absorbing the brown-black product covered on the zinc sheet by a suction pipe, washing 3 times by deionized water and absolute ethyl alcohol respectively, and drying at the temperature of 60 ℃ by centrifugation to obtain the product.
Comparative example 2
(1) The 1 x 2cm zinc plate was immersed in 1M hydrochloric acid to remove surface oxides and repeatedly washed with ethanol and ultrapure water until the surface became clean.
(2) Put in 4.32X10 -5 Growing in the mol/L silver oxide solution for 3 days
(3) Absorbing the brown-black product covered on the zinc sheet by a suction pipe, washing 3 times by deionized water and absolute ethyl alcohol respectively, and drying at the temperature of 60 ℃ by centrifugation to obtain the product.
Photocatalytic performance test:
test case
Accurately weighing 10mg of different catalysts prepared, adding 10mL of rhodamine B (0.02 mg, stirring in the dark for 1.5h until the solution reaches adsorption degradation equilibrium, fully contacting a xenon lamp (200W), adding 300 μl of hydrogen peroxide, sampling once every time period, centrifuging at 15000rpm for 3 minutes, then measuring the absorption intensity of RhB (rhodamine B) in the sample solution by using ultraviolet absorption spectroscopy, thereby measuring the concentration of RhB in the sample solution, FIG. 2 is an ultraviolet absorption spectrum diagram of the semiconductor photocatalytic material of example 1 when catalyzing the decomposition of rhodamine B (RhB), it can be seen that the absorbance of rhodamine B (λmax=552 nm) gradually decreases with time, at 240min, the absorbance of rhodamine B is almost 0, indicating that all rhodamine B in the solution has been degraded, the result shows that the catalytic efficiency gradually increases with the increase of the catalyst amount, and the absorbance of rhodamine B gradually decreases with 50mL of 2x10 -5 When MRhB is irradiated by sunlight, the degradation rate reaches more than 95% within 180 min. The obtained product has good photocatalytic activity.
Table 2 shows the photocatalytic decomposition rates of rhodamine B for various examples or comparative examples over a specified period of time.
TABLE 2
| Decomposition rate of rhodamine B | |
| Example 1 | 98 |
| Example 2 | 90 |
| Example 3 | 89 |
| Example 4 | 80 |
| Comparative example 1 | 70 |
| Comparative example 2 | 71 |
What is not described in detail in the present specification is common general knowledge of a person skilled in the art.
As used throughout the specification and claims, the word "comprise" is an open-ended term, and thus should be interpreted to mean "include, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that this application is not limited to the forms disclosed herein, but is not to be construed as an exclusive use of other embodiments, and is capable of many other combinations, modifications and environments, and adaptations within the scope of the inventive concept described herein, through the foregoing teachings or through the skill or knowledge of the relevant arts. And that modifications and variations which do not depart from the spirit and scope of the present invention are intended to be within the scope of the appended claims.
Claims (10)
1. A doping method of a semiconductor photocatalytic material is characterized in that a metal substrate is placed in a metal ion solution, and the semiconductor photocatalytic material is obtained by adopting a one-step replacement method;
wherein the material of the metal substrate is zinc; the metal ion is Ag + Or/and Cu 2+， 。
2. Doping method according to claim 1, comprising the steps of:
(1) Configuration of Cu 2+ 、Ag + A solution;
(2) Immersing the metal substrate in hydrochloric acid with the concentration of 1M to remove oxide on the surface; repeatedly washing with ethanol and ultrapure water until the surface is clean;
(3) Placing the washed zinc plate into Cu 2+ 、Ag + In the solution, reacting at room temperature;
(4) Absorbing the brown-black product covered on the zinc sheet by a suction pipe, washing 3 times by deionized water and absolute ethyl alcohol respectively, centrifuging and drying to obtain the semiconductor photocatalytic material.
3. A doping method according to claim 2, wherein the metal substrate is a foam zinc sheet or zinc sheet having a size of 1 x 2cm.
4. The doping method of claim 2, wherein the Cu 2+ The solution is CuCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The Ag is + The solution is silver oxide.
5. The doping method of claim 4, wherein the Cu 2+ The solution had a concentration of 2X10 -3 -5×10 -3 CuCl in mol/l 2 A solution; the Ag is + The solution had a concentration of 4.32X10 -5 mol/l silver oxide solution.
6. Doping method according to claim 2, characterized in that the reaction time of step 3) is 3 days.
7. Doping method according to claim 2, characterized in that in step 4) the centrifugation speed is 7000 rpm, the centrifugation time is 5 minutes, the drying temperature is 40-60 ℃, and the drying time is 6 hours.
8. A semiconductor photocatalytic material, characterized by being prepared according to the method of any one of claims 1-7.
9. The semiconductor photocatalytic material according to claim 8, wherein the Zn content is 75 to 80%, the O content is 16 to 20%, and the Ag content is 0.3 to 0.8%, both by mass.
10. Use of a semiconductor photocatalytic material according to claim 8 or 9 in photocatalysis for the photocatalytic degradation of rhodamine B.
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