CN111085228A - Phosphorus doped Mn0.3Cd0.7S nanorod photocatalyst and preparation method and application thereof - Google Patents
Phosphorus doped Mn0.3Cd0.7S nanorod photocatalyst and preparation method and application thereof Download PDFInfo
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
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- C01B3/042—Decomposition of water
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Abstract
The invention discloses a phosphorus doped Mn0.3Cd0.7S nanorod photocatalyst and a preparation method and application thereof. The method comprises the following steps: mixing a phosphorus source with Mn0.3Cd0.7S is mixed evenly, ball milled and calcined for 1 to 3 hours under the protection of inert atmosphere and the temperature of 200-400 ℃. Cooling to room temperature, washing, filtering and drying to obtain the phosphorus doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst. The composite photocatalyst prepared by the invention is of a rod-shaped structure, has a large length-diameter ratio, is beneficial to transfer and separation of photon-generated carriers, can remarkably improve the problem of serious photo-corrosion of sulfide catalysts, and shows a high photocatalytic hydrogen production rate. In addition, the raw materials used in the preparation method of the catalyst provided by the invention are cheap and easily available, and the method is simple and convenient to operateThe reaction condition is mild and easy to realize.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and discloses a phosphorus-doped Mn0.3Cd0.7S nanorod photocatalyst and a preparation method and application thereof.
Background
With the development of society and the increasing living standard of people, the environmental pollution and the energy crisis become more serious by the combustion of fossil fuels, and the energy shortage becomes one of the bottlenecks of sustainable development. In order to solve environmental and energy problems from the source, the development of clean and renewable new energy is urgent. The semiconductor photocatalytic water splitting hydrogen production technology is popular among people due to the advantages of simple process flow, simple and convenient operation, cleanness, no pollution and the like. The key of hydrogen production by semiconductor photocatalytic water decomposition is to find a photocatalyst with appropriate band gap, stability and high efficiency.
MnxCd1-xThe band gap of the S solid solution is narrow, and the visible light response range is large; the positions of the conduction band and the valence band are adjustable, the requirement of hydrogen production by photolysis of water is met, and the photocatalyst is considered to be one of the photocatalysts with better development prospects (Journal of materials chemistry A,2014,2(13): 4619-. The research shows that: when x is 0.3, Mn0.3Cd0.7S is in a rod shape and has the highest hydrogen production rate (Catalysis Science)&Technology,2019,9(6): 1427-. But when the sulfide solid solution photocatalyst is used alone for photocatalytic decomposition of water to produce hydrogen, e-、h+The recombination is easy to occur, and the serious photo-corrosion phenomenon exists, so that the photocatalytic hydrogen production rate is reduced. In order to overcome the problems, the methods of cocatalyst loading, semiconductor coupling, element doping and the like are commonly adopted to further improve the hydrogen production activity and stability. Huang et al used a two-step solvothermal method with Co (NO)3)2·6H2O、NH3·H2Preparation of Mn by using O and the like as raw materials0.25Cd0.75S/Co3O4The complex increases the hydrogen production rate by a factor of 5.35 (Journal of the Taiwan Institute of Chemical Engineers,2017,80: 570-. Liu et al prepared Mn by a two-step calcination-hydrothermal method0.8Cd0.2S/g-C3N4The hydrogen production rate of the photocatalyst is as high as 4000umol g-1h-1(Applied Catalysis A: General,2016,518: 150-157.). The catalyst promoter is loaded, the semiconductor coupling usually involves a plurality of raw materials to participate in the reaction, the preparation process is complex, and the cost is increased to a certain extent. While the element doping has a reactionSingle raw material, short preparation period, simple operation, easy realization and the like (CN 201711052242.5). The research shows that: phosphorus doping can introduce an impurity level energy level above a valence band of a semiconductor, increase a spectral response range, prolong the service life of a photon-generated carrier, improve the separation efficiency of electron-hole pairs and increase the photocatalytic hydrogen production rate (Nano letters,2017,17(6): 3803-. Phosphorus doping with Mn to date0.3Cd0.7The preparation of the S nanorod photocatalyst is not reported. Therefore, stable and efficient phosphorus-doped Mn can be prepared by a simple method using an inexpensive phosphorus source0.3Cd0.7The S-based photocatalyst has important significance.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a phosphorus-doped Mn0.3Cd0.7S nanorod photocatalyst and a preparation method and application thereof.
Aiming at the existing MnxCd1-xThe preparation method of the S-based catalyst has the problems of complex process flow and high cost, and the invention aims to provide a stable and efficient phosphorus-doped Mn catalyst by a method which is simple to operate and easy to realize0.3Cd0.7S nanorod photocatalyst and a preparation method and application thereof.
The phosphorus doped Mn provided by the invention0.3Cd0.7The S nanorod photocatalyst is high-efficiency MnxCd1-xS-based photocatalyst (P-Mn)0.3Cd0.7S). P doping can be in MnxCd1-xAnd an impurity level energy level is introduced above the valence band of S, so that the solar spectrum response range is enlarged, the transfer and separation efficiency of photon-generated carriers is accelerated, the occurrence of a photo-corrosion phenomenon is effectively inhibited, and the hydrogen production rate is remarkably improved. The experimental results show that: phosphorus doped Mn0.3Cd0.7The hydrogen production rate of the S photocatalyst is up to 328.11-4148.19umol g- 1h-1Relatively pure Mn0.3Cd0.7S is improved by 7.91-100.05 times; phosphorus doped Mn0.3Cd0.7The hydrogen production rate of the S photocatalyst can reach 4148.19umol g at most-1h-1Relatively pure Mn0.3Cd0.7The S is improved by 100.05 times. Meanwhile, the invention adopts a single reaction raw material as a doped phosphorus source, and P is doped into Mn by a simple calcination method0.3Cd0.7And S, realizing the purpose of large-scale production.
The purpose of the invention is realized by at least one of the following technical solutions.
The phosphorus doped Mn provided by the invention0.3Cd0.7S nanorod photocatalyst, wherein the phosphorus source and Mn0.3Cd0.7The mass ratio of S is 0.95-1.2: 1.
the invention provides phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) adding Mn0.3Cd0.7Mixing S with a phosphorus source, and then carrying out ball milling treatment to obtain a mixture;
(2) heating the mixture obtained in the step (1) in an inert atmosphere for calcining, cooling to room temperature, washing, filtering to obtain filter residue, and drying to obtain the phosphorus-doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst.
Further, the phosphorus source in the step (1) is NaH2PO2·H2O and NaH2PO4·2H2And O is one of the compounds.
Preferably, the phosphorus source in step (1) is NaH2PO2·H2O。
Further, Mn in the step (1)0.3Cd0.7S can be prepared by a solvothermal method; the Mn is0.3Cd0.7The raw material of S comprises Mn (OAc)2·4H2O、Cd(OAc)2·2H2O and thioacetamide. The Mn is0.3Cd0.7S can be prepared according to the literature (Catalysis Science)&Technology,2019,9(6):1427-1436.)。
Further, the phosphorus source of step (1) is mixed with Mn0.3Cd0.7The mass ratio of S is 0.95-1.2: 1.
further, the rotation speed of the ball milling treatment in the step (1) is 200 and 400 rpm; the ball milling time is 10-30 min.
Preferably, the rotation speed of the ball milling treatment in the step (1) is 300 rpm.
Preferably, the ball milling treatment time in the step (1) is 20 min.
Further, the inert atmosphere in the step (2) is argon or nitrogen atmosphere.
Further, the temperature rising rate of the step (2) is 1-5 ℃ min-1。
Preferably, the temperature rise rate of the step (2) is 2 ℃ min-1。
Further, the temperature of the calcination treatment in the step (2) is 200-400 ℃.
Preferably, the temperature of the calcination treatment in step (2) is 300 ℃.
Further, the time of the calcination treatment in the step (2) is 1-3 h.
Preferably, the calcination treatment time of the step (2) is 2 h.
Preferably, the washing in step (2) is washing with water and ethanol alternately.
The invention provides phosphorus-doped Mn prepared by the preparation method0.3Cd0.7And (3) an S nanorod photocatalyst.
The phosphorus doped Mn provided by the invention0.3Cd0.7The S nanorod photocatalyst can be applied to the reaction of photocatalytic decomposition of water to produce hydrogen.
The composite photocatalyst prepared by the invention is of a rod-shaped structure, has a large length-diameter ratio, is beneficial to transfer and separation of photon-generated carriers, can remarkably improve the problem of serious photo-corrosion of sulfide catalysts, and shows a high photocatalytic hydrogen production rate. In addition, the raw materials used in the preparation method of the catalyst provided by the invention are cheap and easily available, the method is simple and convenient to operate, and the reaction condition is mild and easy to realize.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the phosphorus prepared by the invention is doped with Mn0.3Cd0.7The S nanorod photocatalyst is of a rod-shaped structure, has a large length-diameter ratio, is beneficial to transfer and separation of photon-generated carriers, and is used for doping P into Mn0.3Cd0.7After S, phosphorus doping can be at MnxCd1-xThe impurity level energy level is introduced above the valence band of S, the spectral response range is increased, the separation of photon-generated carriers is facilitated, the recombination of the carriers is inhibited, the photocatalytic hydrogen production rate is obviously improved and can reach 4148.19umol g at most-1h-1；
(2) The phosphorus prepared by the invention is doped with Mn0.3Cd0.7The S nanorod photocatalyst has good photo-corrosion resistance and good stability;
(3) the preparation method provided by the invention has the characteristics of simple process, convenience in operation, low cost and the like, and the prepared phosphorus-doped Mn0.3Cd0.7The S nanorod photocatalyst can be applied to a hydrogen production system by photocatalytic decomposition of water.
Drawings
FIG. 1 is a graph showing hydrogen production rates by photocatalytic decomposition of catalysts prepared in examples and comparative examples;
FIG. 2 is an XRD pattern of catalysts prepared in examples and comparative examples;
FIG. 3 is a partial enlarged XRD pattern of catalysts prepared in examples and comparative examples;
FIG. 4 shows phosphorus-doped Mn obtained in example 40.3Cd0.7SEM picture of S nano-rod photocatalyst;
FIG. 5 shows Mn obtained in comparative example 10.3Cd0.7SEM image of S nanorod photocatalyst.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Mn used in the following examples and comparative examples0.3Cd0.7The preparation of the S catalyst comprises the following steps: taking 6mmol Mn (OAc)2·4H2O,14mmol Cd(OAc)2·2H2O dissolved in 30mL H2Mixing O and 30mL of anhydrous Ethylenediamine (EDA) mixed solution, uniformly stirring, adding 25mmol of thioacetamide, stirring (time is 1h, stirring speed is 200rpm), transferring into a polytetrafluoroethylene inner container, sealing in a stainless steel shell, heating at 200 ℃ for 24h, cooling to room temperature, washing, filtering to obtain precipitate, and drying to obtain yellow powder, namely Mn0.3Cd0.7S catalyst (see catalysis science for preparation process)&Technology,2019,9(6):1427-1436.)。
The performance tests conducted in the following examples and comparative examples were conducted in a photocatalytic hydrogen production system using a 300WXe lamp (. lamda. gtoreq.420 nm) as a light source. The test comprises the following steps: taking 10mg of the prepared catalyst, loading the catalyst into a reaction kettle with the diameter of 7cm and the height of 12cm, adding 100mL of 20 vol% lactic acid aqueous solution, stirring for 5min, performing ultrasonic treatment for 10min, vacuumizing, turning on a light source, controlling the reaction temperature at 15 ℃, and performing online detection and hydrogen production calculation by using a gas chromatography.
Example 1
Phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) 190mg of NaH2PO2·H2O, 200mg of Mn0.3Cd0.7Mixing S catalysts, and then carrying out ball milling for 20min under the condition that the rotating speed is 300rpm to obtain a mixture;
(2) transferring the mixture to a tube furnace, introducing argon, heating for 30min under the protection of argon at a heating rate of 2 ℃ for min-1And calcining for 2 hours at the temperature of 300 ℃. Cooling to room temperature, alternately washing with ethanol and water, filtering to obtain precipitate, and drying to obtain the phosphorus-doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst. Phosphorus prepared in example 1 was doped with Mn0.3Cd0.7The photocatalyst mark of the S nanorod is 190P-Mn0.3Cd0.7S。
Under the irradiation of a 300WXe lamp and the reaction temperature of 15 ℃, the phosphorus prepared in the example 1 is doped with Mn0.3Cd0.7S nanorod photocatalyst (190P-Mn)0.3Cd0.7S) hydrogen production rate of 1067.32umol g-1h-1As shown in fig. 1.
Example 2
Phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) 200mg of NaH2PO2·H2O, 200mg of Mn0.3Cd0.7Mixing S catalysts, and then performing ball milling for 20min at the rotating speed of 300rpm to obtain a mixture;
(2) transferring the mixture to a tube furnace, introducing argon, heating for 30min under the protection of argon at a heating rate of 2 ℃ for min-1And calcining for 2 hours at the temperature of 300 ℃. Cooling to room temperature, washing, filtering to obtain precipitate, and drying to obtain the phosphorus-doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst. Phosphorus prepared in example 2 was doped with Mn0.3Cd0.7The photocatalyst mark of the S nanorod is 200P-Mn0.3Cd0.7S。
Under the irradiation of a 300WXe lamp and the reaction temperature of 15 ℃, the phosphorus prepared in the example 2 is doped with Mn0.3Cd0.7S nanorod photocatalyst (i.e. 200P-Mn)0.3Cd0.7S) hydrogen production rate of 3146.54umol g-1h-1As shown in fig. 1.
Example 3
Phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) adding 210mg of NaH2PO2·H2O, 200mg of Mn0.3Cd0.7Mixing S catalysts, and then carrying out ball milling for 20min under the condition that the rotating speed is 300rpm to obtain a mixture;
(2) transferring the mixture to a tube furnace, introducing argon, heating for 30min under the protection of argon at a heating rate of 2 ℃ for min-1And calcining for 2 hours at the temperature of 300 ℃. Cooling to room temperature, washing, filtering to obtain precipitate, and drying to obtain the phosphorus-doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst. Phosphorus doping from example 3Hetero Mn0.3Cd0.7The photocatalyst mark of the S nanorod is 210P-Mn0.3Cd0.7S。
Phosphorus doped Mn prepared in example 3 under the irradiation of 300WXe lamp and at a reaction temperature of 15 DEG C0.3Cd0.7S nanorod photocatalyst (210P-Mn)0.3Cd0.7S) hydrogen production rate of 3421.16umol g-1h-1As shown in fig. 1.
Example 4
Phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) adding 220mg of NaH2PO2·H2O, 200mg of Mn0.3Cd0.7Mixing S catalysts, and then carrying out ball milling for 20min under the condition that the rotating speed is 300rpm to obtain a mixture;
(2) transferring the mixture to a tube furnace, introducing argon, heating for 30min under the protection of argon at a heating rate of 2 ℃ for min-1And calcining for 2 hours at the temperature of 300 ℃. Cooling to room temperature, washing, filtering to obtain precipitate, and drying to obtain the phosphorus-doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst. Phosphorus prepared in example 4 was doped with Mn0.3Cd0.7The photocatalyst mark of the S nanorod is 220P-Mn0.3Cd0.7S。
Phosphorus doped Mn prepared in example 4 under the irradiation of 300WXe lamp and at a reaction temperature of 15 DEG C0.3Cd0.7S nanorod photocatalyst (220P-Mn)0.3Cd0.7S) hydrogen production rate of 4148.19umol g-1h-1As shown in fig. 1.
Example 5
Phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) 230mg of NaH2PO2·H2O, 200mg of Mn0.3Cd0.7Mixing S catalysts, and then carrying out ball milling for 20min under the condition that the rotating speed is 300rpm to obtain a mixture;
(2) transferring the mixture to a tubeIntroducing argon into the furnace, heating the furnace for 30min under the protection of argon at the heating rate of 2 ℃ for min-1And calcining for 2 hours at the temperature of 300 ℃. Cooling to room temperature, washing, filtering to obtain precipitate, and drying to obtain the phosphorus-doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst. Phosphorus prepared in example 5 was doped with Mn0.3Cd0.7The photocatalyst mark of the S nanorod is 230P-Mn0.3Cd0.7S。
Phosphorus doped Mn prepared in example 5 under the irradiation of 300WXe lamp and at a reaction temperature of 15 DEG C0.3Cd0.7S nanorod photocatalyst (230P-Mn)0.3Cd0.7S) hydrogen production rate of 682.67umol g-1h-1As shown in fig. 1.
Example 6
Phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) adding 240mg of NaH2PO2·H2O, 200mg of Mn0.3Cd0.7Mixing S catalysts, and then carrying out ball milling for 20min under the condition that the rotating speed is 300rpm to obtain a mixture;
(2) transferring the mixture to a tube furnace, introducing argon, heating for 30min under the protection of argon at a heating rate of 2 ℃ for min-1And calcining for 2 hours at the temperature of 300 ℃. Cooling to room temperature, washing, filtering to obtain precipitate, and drying to obtain the phosphorus-doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst. Phosphorus prepared in example 6 was doped with Mn0.3Cd0.7The photocatalyst mark of the S nanorod is 240P-Mn0.3Cd0.7S。
Phosphorus doped Mn from example 6 under the irradiation of 300WXe lamp at a reaction temperature of 15 DEG C0.3Cd0.7S nanorod photocatalyst (240P-Mn)0.3Cd0.7S) hydrogen production rate of 471.64umol g-1h-1As shown in fig. 1.
Example 7
Phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) adding 220mg of NaH2PO2·H2O, 200mg of Mn0.3Cd0.7Mixing S catalysts, and then carrying out ball milling for 10min under the condition that the rotating speed is 200rpm to obtain a mixture;
(2) transferring the mixture to a tube furnace, introducing argon, heating for 10min under the protection of argon at the heating rate of 1 ℃ for min-1And heating to 200 ℃ and calcining for 1 h. Cooling to room temperature, washing, filtering to obtain precipitate, and drying to obtain the phosphorus-doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst.
Phosphorus doped Mn from example 7 under the irradiation of 300WXe at a reaction temperature of 15 DEG C0.3Cd0.7The S nanorod photocatalyst shows a good hydrogen production rate, and can be seen in figure 1.
Example 8
Phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) adding 220mg of NaH2PO2·H2O, 200mg of Mn0.3Cd0.7Mixing S catalysts, and then carrying out ball milling for 30min under the condition that the rotating speed is 400rpm to obtain a mixture;
(2) transferring the mixture to a tube furnace, introducing argon, heating for 60min under the protection of argon at the heating rate of 5 ℃ for min-1And calcining for 3 hours at the temperature of 400 ℃. Cooling to room temperature, washing, filtering to obtain precipitate, and drying to obtain the phosphorus-doped Mn0.3Cd0.7S nanorod photocatalyst;
phosphorus doped Mn prepared in example 8 under the irradiation of 300WXe lamp at a reaction temperature of 15 DEG C0.3Cd0.7The S nanorod photocatalyst shows an excellent hydrogen production rate, and can be referred to fig. 1.
Comparative example 1
Mn0.3Cd0.7Preparation of the S catalyst, as described above.
Mn obtained in comparative example 1 under the irradiation of 300WXe lamp and at a reaction temperature of 15 DEG C0.3Cd0.7S catalystThe hydrogen production rate of the agent was 41.46umol g-1h-1As shown in fig. 1.
Comparative example 2
Calcination of Mn with argon0.3Cd0.7The preparation method of the S nanorod photocatalyst comprises the following steps:
(1) 200mg of Mn0.3Cd0.7Transferring the S catalyst to a tubular furnace, introducing argon, heating in an argon protective atmosphere after 30min, wherein the heating rate is 2 ℃ min-1And calcining for 2 hours at the temperature of 300 ℃. Cooling to room temperature, washing, filtering, taking precipitate, and drying to obtain the Mn calcined by argon0.3Cd0.7S nanorod photocatalyst, denoted Mn0.3Cd0.7S-C；
The Mn is calcined by argon gas prepared in comparative example 2 under the irradiation of 300WXe lamp and at the reaction temperature of 15 DEG C0.3Cd0.7The hydrogen production rate of the S nanorod photocatalyst is 57.04umol g-1h-1As shown in fig. 1.
FIG. 1 is a graph showing the rate of hydrogen production by photocatalytic decomposition of the catalysts prepared in examples and comparative examples. As can be seen from FIG. 1, after doping with P, Mn0.3Cd0.7The hydrogen production rate of the S catalyst is obviously improved.
Fig. 2 is an XRD pattern of the catalyst prepared in example. 190P-Mn in FIG. 20.3Cd0.7S represents phosphorus doped Mn as obtained in example 10.3Cd0.7S nanorod photocatalyst, 200P-Mn0.3Cd0.7S represents phosphorus doped Mn obtained in example 20.3Cd0.7S nanorod photocatalyst, 210P-Mn0.3Cd0.7S represents phosphorus doped Mn as obtained in example 30.3Cd0.7S nanorod photocatalyst, 220P-Mn0.3Cd0.7S represents phosphorus doped Mn as obtained in example 40.3Cd0.7S nanorod photocatalyst, 230P-Mn0.3Cd0.7S represents phosphorus doped Mn as obtained in example 50.3Cd0.7S nanorod photocatalyst, 240P-Mn0.3Cd0.7S represents Mn as obtained in example 60.3Cd0.7And (3) an S nanorod photocatalyst.
Fig. 3 is a partial enlarged spectrum of XRD of the catalyst prepared in example.
FIG. 4 shows Mn obtained in comparative example 10.3Cd0.7SEM image of S catalyst. As can be seen from FIG. 4, Mn0.3Cd0.7S shows a good rod-like structure and is uniform in appearance.
FIG. 5 shows 220P-Mn obtained in example 40.3Cd0.7SEM image of S. As can be observed from FIG. 5, 220P-Mn0.3Cd0.7The S nanorod photocatalyst consists of shorter nanorods. Phosphorus doped Mn from other examples0.3Cd0.7The S nanorod photocatalyst is also composed of nanorods, and can be seen in FIG. 5.
The above examples are only preferred embodiments of the present invention, which are intended to be illustrative and not limiting, and those skilled in the art should understand that they can make various changes, substitutions and alterations without departing from the spirit and scope of the invention.
Claims (10)
1. Phosphorus doped Mn0.3Cd0.7The preparation method of the S nanorod photocatalyst is characterized by comprising the following steps of:
(1) adding Mn0.3Cd0.7Mixing S with a phosphorus source, and then carrying out ball milling treatment to obtain a mixture;
(2) heating the mixture obtained in the step (1) in an inert atmosphere for calcining, cooling to room temperature, washing, filtering to obtain filter residue, and drying to obtain the phosphorus-doped Mn0.3Cd0.7And (3) an S nanorod photocatalyst.
2. Phosphorus doped Mn according to claim 10.3Cd0.7The preparation method of the S nanorod photocatalyst is characterized in that the phosphorus source in the step (1) is NaH2PO2·H2O and NaH2PO4·2H2And O is one of the compounds.
3. Phosphorus doped Mn according to claim 10.3Cd0.7The preparation method of the S nanorod photocatalyst is characterized in that the phosphorus source and Mn in the step (1)0.3Cd0.7The mass ratio of S is 0.95-1.2: 1.
4. phosphorus doped Mn according to claim 10.3Cd0.7The preparation method of the S nanorod photocatalyst is characterized in that the rotation speed of the ball milling treatment in the step (1) is 200-400 rpm; the ball milling time is 10-30 min.
5. Phosphorus doped Mn according to claim 10.3Cd0.7The preparation method of the S nanorod photocatalyst is characterized in that the inert atmosphere in the step (2) is argon or nitrogen.
6. Phosphorus doped Mn according to claim 10.3Cd0.7The preparation method of the S nanorod photocatalyst is characterized in that the temperature rise rate in the step (2) is 1-5 ℃ per minute-1。
7. Phosphorus doped Mn according to claim 10.3Cd0.7The preparation method of the S nanorod photocatalyst is characterized in that the calcination treatment temperature in the step (2) is 200-400 ℃.
8. Phosphorus doped Mn according to claim 10.3Cd0.7The preparation method of the S nanorod photocatalyst is characterized in that the calcination treatment time in the step (2) is 1-3 h.
9. Phosphorus doped Mn obtainable by the process according to any one of claims 1 to 80.3Cd0.7And (3) an S nanorod photocatalyst.
10. Phosphorus doped Mn according to claim 90.3Cd0.7The application of the S nanorod photocatalyst in the reaction of photocatalytic decomposition of water to produce hydrogen.
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| CN107376944A (en) * | 2017-07-25 | 2017-11-24 | 山东大学 | Transient metal sulfide loads application of the Mn Cd S solid solution in terms of Photocatalyzed Hydrogen Production |
| CN107790160A (en) * | 2017-10-30 | 2018-03-13 | 中国科学院理化技术研究所 | A kind of method of phosphorus doping zinc-cadmium sulfide solid solution catalyst, photocatalytic system and hydrogen production by water decomposition |
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