CN115055192A - Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material and preparation method and application thereof - Google Patents
Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The preparation method of the composite material comprises the following steps: preparation of Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A powder material; zn is added 0.4 (CuGa) 0.3 Ga 2 S 4 Powder material and Al 3+ Mixing according to a molar ratio of 1:0.5-1.5, dispersing into deionized water, and ultrasonically stirring for 0.5-1 h; slowly heating the mixed solution to 30-90 ℃, and magnetically stirring for 2-10h to obtain Al 3+ With Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Zn of material surfaceAnd the elements such as Cu and the like are subjected to micro ion exchange to ensure that Al 3+ Loaded on Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A surface; performing solid-liquid separation on the magnetically stirred solution, and drying the powder obtained by separation in a constant-temperature electrothermal drying oven at 60-80 ℃ for 3-36h to obtain Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material of Al supported therein 3+ In a content of Zn 0.4 (CuGa) 0.3 Ga 2 S 4 0.3-0.8 wt% of the content. Al provided by the invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The preparation method of the composite material adopts Al ions to Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The surface of the semiconductor material is modified to improve Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The active sites of the material improve the photocatalytic activity of the material. The invention also provides Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite materials and their use.
Description
Technical Field
The invention relates to the technical field of catalyst materials, and particularly relates to Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material and its preparation method and application.
Background
With the rapid development of economy, the demand of human beings for fossil energy has sharply increased. The transitional consumption of fossil energy leads to energy crisis and CO 2 Causing a greenhouse effect. Catalytic conversion of CO by solar energy 2 Is CO, CH 4 And the fuel and the high value-added chemicals are equal, so that the fuel has the characteristics of environmental friendliness, no pollution and sustainability, and has a development prospect. Photocatalytic reduction of CO 2 The technology utilizes light energy to excite semiconductor photocatalytic material to generate electron hole pairs, thereby inducing photocatalytic oxidation reduction reaction and realizing CO 2 And (4) activating and reducing. Development of suitable CO 2 The photocatalyst for activating and converting is CO increasing 2 The key to the reduction efficiency.
Currently, oxide photocatalytic materials such as TiO are being developed 2 、Nb 2 O 5 、Zn 2 GeO 4 Iso-photocatalytic CO 2 Active but still the reduction potential of its semiconductor conduction band is not strong enough. Some sulfide photocatalytic materials such as ZnS, CdS, Zn are compared to oxide semiconductor materials 1-2x (CuGa) x Ga 2 S 4 Has visible light response and higher conduction band reduction potential, and can be used for photocatalysis of CO 2 The research and application value of reduction has prospect. Of these, Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The semiconductor material has very low conduction band potential and strong reduction capability. The forbidden band width is narrow, the visible light can be effectively absorbed, and the CO can be converted in photocatalysis 2 The aspect is receiving a great deal of attention. Based on Zn 0.3 (CuGa) 0.4 Ga 2 S 4 Material development of highly active CO 2 Reducing the material is of great significance.
At present, Zn 0.3 (CuGa) 0.4 Ga 2 S 4 The material is mainly synthesized by a solid-phase calcination method: mixing ZnS and Cu 2 S，Ga 2 S 3 Mixing the three sulfide materials according to a certain proportion, fully grinding and vacuum calcining to obtain Zn 0.3 (CuGa) 0.4 Ga 2 S 4 Solid solution materials (see article: Journal of Catalysis, Elsevier Inc.,2014,310: 31-36.). The material also makes related research in the CdS compounding aspect: under a liquid phase system, a liquid phase coprecipitation method is adopted to load CdS to Zn 0.3 (CuGa) 0.4 Ga 2 S 4 Washing surface impurities by a centrifugal method on the surface, and drying the impurities at high temperature to obtain Zn 0.3 (CuGa) 0.4 Ga 2 S 4 the/CdS composite photocatalyst (see the paper: inorganic materials bulletin, 2022, (01): 15-21).
At present pure phase Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Adsorption and activation of CO by solid-phase sintered material particles 2 Less active sites of molecules, photocatalytic activation and conversion of CO 2 Is inefficient. Some research works adopt a mode of composite CdS nano particles to construct a heterojunction, but the scheme needs to add S in a liquid phase 2- Ions and Cd 2+ The ions are subjected to coprecipitation reaction to generate CdS nano particles, the synthesis process is complex, and CdS cannot be uniformly loaded to Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The photocatalytic activity of the material is improved to a limited extent.
Therefore, a need exists for a simpler systemEasy and efficient modification mode for Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The semiconductor material is subjected to surface modification, so that the photocatalytic performance of the semiconductor material is improved.
Disclosure of Invention
The technical problem to be solved by the invention is to provide Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The composite material is prepared by using Al ion pair Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The surface of the semiconductor material is modified to improve Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The active sites of the material improve the photocatalytic activity of the material.
In order to solve the problems, the technical scheme of the invention is as follows:
al (aluminum) 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The preparation method of the composite material comprises the following steps:
step S1, preparation of Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A powder material;
step S2, adding Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Powder material and Al 3+ Mixing according to a molar ratio of 1:0.5-1.5, dispersing into deionized water, and ultrasonically stirring for 0.5-1 h;
in particular, Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Powder material and Al 3+ The molar ratio may be 1:0.5, 1:0.8, 1:1, 1:1.2, 1:1.3, or 1:1.5, or other ratios within this range;
the time of ultrasonic stirring can be 0.5h, 0.6h, 0.8h, 0.9h or 1h, and can also be other time values in the range;
step S3, slowly heating the mixed solution to 30-90 ℃, and magnetically stirring for 3-10h to obtain Al 3+ With Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The Zn and Cu elements on the surface of the material are subjected to trace ion exchange to ensure that Al 3+ Loaded on Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A surface;
specifically, the heating temperature may be 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, or may be other temperature values within the range;
step S4, performing solid-liquid separation on the magnetic stirring liquid, and drying the powder obtained by separation in a constant-temperature electric heating drying oven at 60-90 ℃ for 3-36h to obtain Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material of Al supported therein 3+ In a content of Zn 0.4 (CuGa) 0.3 Ga 2 S 4 0.3-0.8 wt% of the content;
specifically, the drying temperature may be 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ or 90 ℃, or may be other temperature values within the range; the drying time may be 3h, 6h, 9h, 12h, 15h, 18h, 20h, 24h, 28h, 32h or 36h, or may be other values within this range; al (Al) 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Al in composite material 3+ The content may be Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The content of 0.3 wt.%, 0.5 wt.% or 0.8 wt.%, which may also be other values within this range, indicates only a trace amount of Al 3+ By substitution into Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The surface of the material.
Further, in step S2, Al 3+ From AlCl 3 ·6H 2 O or Al (SO) 4 ) 2 ·18H 2 And O.
Further, in step S4, deionized water or a mixture of deionized water and ethanol is used as a dispersion, and the magnetic stirring solution is subjected to suction filtration or centrifugal separation.
Further, in step S1, Zn is prepared 0.4 (CuGa) 0.3 Ga 2 S 4 The powder material comprises the following steps:
step 11, weighing ZnS and Cu with the molar ratio of 1:0.375:2-3 2 S，Ga 2 S 3 Fully mixing the raw materials by using absolute ethyl alcohol and grinding the mixture until the ethyl alcohol is volatilized to obtain Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Front of materialDriving a body;
in particular, ZnS, Cu 2 S，Ga 2 S 3 May be 1:0.375:2, 1:0.375:2.5, 1:0.375:3, or other ratios within this range;
step 12, placing the precursor material into a quartz ampoule tube, sealing and vacuumizing, placing the quartz tube into a muffle furnace, setting the heating rate to be 5-8 ℃/min, keeping the constant temperature for 8-10h after the temperature is raised to 800 ℃ plus materials, naturally cooling to room temperature, closing the muffle furnace, and taking the prepared powder out of the quartz tube after cooling;
specifically, the heating rate can be 5 ℃/min, 6 ℃/min, 7 ℃/min or 8 ℃/min, or can be other values within the range;
the heating temperature may be 700 ℃, 720 ℃, 750 ℃, 760 ℃, 780 ℃, or 800 ℃, or may be other values within the range;
the heat preservation time can be 8h, 9h or 10h, and can also be other time values in the range;
step 13, weighing a proper amount of the powder obtained in the step S12, and dispersing the powder in deionized water to enable the concentration to reach 1-100 g/L; subjecting the suspension to ultrasonic treatment, magnetically stirring at 60-100 deg.C for 1-2h, alternately centrifuging and washing with alcohol and deionized water as dispersion at 5000-10000r/min for 2-5min each time to obtain centrifuged Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A material;
specifically, the temperature condition may be 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃, or may be other values within the range;
the rotation speed of centrifugal washing can be 5000r/min, 6000r/min, 7000r/min, 8000r/min, 9000r/min or 10000r/min, and can also be other values in the range;
step 14, centrifuging the centrifuged Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The material is dried in a constant temperature drying oven at the temperature of 80-90 ℃ to obtain pure Zn without impurities 0.4 (CuGa) 0.3 Ga 2 S 4 And (3) powder.
Specifically, the drying temperature may be 80 ℃, 85 ℃ or 90 ℃, or may be other temperature values within this range.
The invention also provides Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The composite material is prepared by the preparation method.
Based on the Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The invention also provides an Al composite material 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Photocatalytic CO treatment of composite materials 2 Application in reduction.
Compared with the prior art, the Al provided by the invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The composite material and the preparation method and the application thereof have the advantages that:
first, Al provided by the invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material and its preparation method, adopting ion exchange method to treat Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The surface of the material is modified to enable Al 3+ Loaded in Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Forming Al on the surface of the semiconductor material 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A composite material. In a specific synthesis, Al 3+ With Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The material is stirred in liquid phase to exchange trace ions with Zn, Cu and other elements on the surface of the material particles, thereby changing Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The surface electronic structure of (1). This change in surface electronic structure to CO 2 And the actions of adsorption, desorption and the like of the reduction reaction intermediate change, thereby realizing the CO desorption 2 And (4) regulating and controlling the reduction reaction. Further, Al 3+ Can also act as an active site itself, affecting the catalytic reaction behavior. Due to Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The material has visible light response and micro surface Al 3+ The ion loading does not affect its visible light absorption properties. Thus, Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The composite material can realize CO under visible light 2 The regulation and control of the efficiency of the photoreduction reaction can improve the utilization rate of sunlight and the photocatalytic CO 2 Reduction performance.
II, Al provided by the invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The preparation method of the composite material is simple and environment-friendly.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows Al according to the present invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A crystal phase structure diagram of the composite material;
FIG. 2 shows Al provided by the present invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A surface microtopography of the composite;
FIG. 3 shows Al provided by the present invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Application of composite material in photocatalysis of CO 2 Efficiency map of reduction.
Detailed Description
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
Example 1
Al (aluminum) 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The preparation method of the composite material comprises the following steps:
step S1, preparing Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A powder material;
specifically, the method comprises the following steps:
step 11, weighing ZnS and Cu with the molar ratio of 1:0.375:2.875 2 S，Ga 2 S 3 Fully mixing the raw materials by using absolute ethyl alcohol and grinding the mixture until the ethyl alcohol is volatilized to obtain Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A precursor of a material;
step 12, placing the precursor material into a quartz ampoule tube, sealing and vacuumizing, placing the quartz tube into a muffle furnace, setting the heating rate to be 5 ℃/min, keeping the constant temperature for 8 hours after the temperature is raised to 800 ℃, naturally cooling to room temperature (25 ℃), closing the muffle furnace, and taking the prepared powder out of the quartz tube after cooling;
step 13, weighing 5g of the powder obtained in the step S12, dispersing the powder in 100mL of deionized water, carrying out ultrasonic treatment, magnetically stirring the powder for 1h at the temperature of 60 ℃, alternately centrifuging and washing the powder by using alcohol and deionized water as dispersion liquid, wherein the rotating speed is 8000r/min, centrifuging the powder for 3min each time, and centrifuging the powder for 3 times respectively to obtain centrifuged Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A material;
step 14, centrifuging the centrifuged Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The material is dried in a constant temperature drying oven at 100 ℃ to obtain pure Zn without impurities 0.4 (CuGa) 0.3 Ga 2 S 4 And (3) powder.
Step S2, adding Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Powder material and AlCl 3 ·6H 2 Mixing O according to the molar ratio of 1:1, dispersing into 500ml of deionized water, and ultrasonically stirring for 0.5 h;
step S3, slowly heating the mixed solution to 60 ℃, and magnetically stirring for 5h to obtain Al 3+ With Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The Zn, Cu and other elements on the surface of the material particles are subjected to trace ion exchange to ensure that Al 3+ Loaded on Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A surface;
step S4, filtering the magnetic stirring liquid by adopting a suction filtration method, taking 1L of deionized water as a suction filtration dispersing agent, and drying the filtered powder in a constant-temperature electrothermal drying oven at 60 ℃ for 24h to obtain Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material of Al supported therein 3+ In a content of Zn 0.4 (CuGa) 0.3 Ga 2 S 4 0.5 wt% of the content.
Please refer to fig. 1 and fig. 2 in combination, wherein fig. 1 is Al provided by the present invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A crystal phase structure diagram of the composite material; FIG. 2 shows Al provided by the present invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Surface microtopography of the composite. As can be seen from FIG. 1, Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material and Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The diffraction peak positions of the materials are basically consistent, which indicates that the surface is loaded with Al 3+ Does not change Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The lattice structure of the material. Study of Al by Scanning Electron Microscopy (SEM) 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The microstructure of the surface of the material, as shown in FIG. 2, can be seen to be Al 3 + /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The material is triangular pyramid type micron-sized particles, and the shape is unchanged after the attachment.
Example 2
For Zn in a closed gas circulation system 0.4 (CuGa) 0.3 Ga 2 S 4 Material and Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Respectively carrying out photocatalysis on the materials 2 And (4) evaluating the reduction performance. 0.1g of Zn is taken out respectively 0.4 (CuGa) 0.3 Ga 2 S 4 Material and 0.1gAl 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 And (3) respectively adding the composite materials into a photocatalytic reaction container, adding 200ml of deionized water, 0.02M of sulfite sacrificial agent and 0.05M of carbonate buffer, and slowly pumping air in the reactor after the reactor is sealed so as to enable the reaction system to be in a vacuum state. After the gas extraction is finished, injecting high-purity CO into the system 2 Until the gas suspension is saturated. Using filters provided with cut-off (lambda)>420nm) was irradiated with light from a xenon lamp (300w), and CO in the reaction system was sampled and measured using a gas chromatograph, resulting in CO production efficiency, as shown in fig. 3. As can be seen from FIG. 3, Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material (0.96 mu mol h) -1 g -1 ) As untreated Zn 0.4 (CuGa) 0.3 Ga 2 S 4 (0.31μmol h - 1 g -1 ) 3 times the performance, indicating Al 3+ The composition of the material effectively improves the visible light catalytic reduction of CO of the material 2 CO production performance.
Whereas in the prior art CdS was loaded to Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Photocatalytic reduction of CO at material surface 2 Is untreated Zn 0.4 (CuGa) 0.3 Ga 2 S 4 1.6 times of the material, which indicates that Al is used in the present invention 3+ Modified Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The composite material has better photocatalytic performance.
Compared with the prior art, the Al provided by the invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The composite material and the preparation method and the application thereof have the advantages that:
first, Al provided by the invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material and method for producing the same, useIon exchange method of Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The surface of the material is modified to Al 3+ Loaded on Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Forming Al on the surface of the semiconductor material 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A composite material. In a specific synthesis, Al 3+ With Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The material is stirred in liquid phase to exchange trace ions with Zn, Cu and other elements on the surface of the material, thereby changing Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The surface electronic structure of (1). This change in surface electronic structure to CO 2 And the actions of adsorption, desorption and the like of the reduction reaction intermediate change, thereby realizing the CO desorption 2 And (4) regulating and controlling the reduction reaction. Further, Al 3+ Can also act as an active site itself, affecting the catalytic reaction behavior. Due to Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The material has visible light response and micro surface Al 3+ The ion loading does not affect its visible light absorption properties. Thus, Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The composite material can realize CO under visible light 2 The regulation and control of the efficiency of the photoreduction reaction can improve the utilization rate of sunlight and the photocatalytic CO 2 And (4) reduction performance.
II, Al provided by the invention 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The preparation method of the composite material is simple and environment-friendly.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.
Claims (6)
1. Al (aluminum) 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite materialThe preparation method is characterized by comprising the following steps:
step S1, preparation of Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A powder material;
step S2, adding Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Powder material and Al 3+ Mixing according to a molar ratio of 1:0.5-1.5, dispersing into deionized water, and ultrasonically stirring for 0.5-1 h;
step S3, slowly heating the mixed solution to 30-90 ℃, and magnetically stirring for 3-10h to obtain Al 3+ With Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The Zn and Cu elements on the surface of the material are subjected to trace ion exchange to ensure that Al 3+ Loaded on Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A surface;
step S4, performing solid-liquid separation on the magnetic stirring liquid, and drying the powder obtained by separation in a constant-temperature electric heating drying oven at 60-90 ℃ for 3-36h to obtain Al 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material of Al supported therein 3+ In a content of Zn 0.4 (CuGa) 0.3 Ga 2 S 4 0.3-0.8 wt% of the content.
2. Al according to claim 1 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The method for producing a composite material is characterized in that, in step S2, Al 3+ From AlCl 3 ·6H 2 O or Al (SO) 4 ) 2 ·18H 2 And O.
3. Al according to claim 1 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The preparation method of the composite material is characterized in that in step S4, deionized water or a mixed solution of deionized water and ethanol is used as a dispersion liquid, and the magnetic stirring liquid is subjected to suction filtration or centrifugal separation.
4. Al according to claim 1 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A method for producing a composite material, characterized in that, in step S1, Zn is produced 0.4 (CuGa) 0.3 Ga 2 S 4 The powder material comprises the following steps:
step 11, weighing ZnS and Cu with the molar ratio of 1:0.375:2-3 2 S，Ga 2 S 3 Fully mixing the raw materials by using absolute ethyl alcohol and grinding the mixture until the ethyl alcohol is volatilized to obtain Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A precursor of a material;
step 12, placing the precursor material into a quartz ampoule tube, sealing and vacuumizing, placing the quartz tube into a muffle furnace, setting the heating rate to be 5-8, raising the temperature to 700-800 ℃ at the temperature mi, keeping the constant temperature for 8-10h, naturally cooling to room temperature, closing the muffle furnace, and taking the prepared powder out of the quartz tube after cooling;
step 13, weighing a proper amount of the powder obtained in the step S12, and dispersing the powder in deionized water to enable the concentration to reach 1-100 g/L; subjecting the suspension to ultrasonic treatment, magnetically stirring at 60-100 deg.C for 1-2h, alternately centrifuging and washing with alcohol and deionized water as dispersion at 5000-10000r/min for 2-5min each time to obtain centrifuged Zn 0.4 (CuGa) 0.3 Ga 2 S 4 A material;
step 14, centrifuging the centrifuged Zn 0.4 (CuGa) 0.3 Ga 2 S 4 The material is dried in a constant temperature drying oven at 80-DEG C and 90 ℃ to obtain pure Zn without impurities 0.4 (CuGa) 0.3 Ga 2 S 4 And (3) powder.
5. Al (aluminum) 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Composite material, characterized in that it is obtained by the preparation method according to any one of claims 1 to 3.
6. Al according to claim 5 3+ /Zn 0.4 (CuGa) 0.3 Ga 2 S 4 Photocatalytic CO treatment of composite materials 2 Application in reduction.
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