CN117943058A - Z-type heterojunction Mn3O4@CdIn2S4Composite material, preparation method and application thereof - Google Patents
Z-type heterojunction Mn3O4@CdIn2S4Composite material, preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photocatalytic hydrogen production, and particularly relates to a Z-type heterojunction Mn 3O4@CdIn2S4 composite material, and a preparation method and application thereof. According to the invention, mn-MOF is used as a precursor to synthesize Mn 3O4 microspheres, cdIn 2S4 (CIS) shells are grown in situ, core-shell Mn 3O4@CdIn2S4 microspheres are prepared, and Z-type heterojunction is formed. Compared with CdIn 2S4 and Mn 3O4, the photocatalytic performance of Mn 3O4@CdIn2S4 in simulated sunlight is remarkably improved. On the one hand, the Z-type electron transfer path not only improves the electron-hole separation efficiency, but also improves the charge transfer efficiency. On the other hand, the presence of the core-shell heterojunction increases the light absorption range.
Description
Technical Field
The invention belongs to the technical field of photocatalytic hydrogen production, and particularly relates to a Z-type heterojunction Mn 3O4@CdIn2S4 composite material, and a preparation method and application thereof.
Background
Environmental pollution and energy shortage have become a hot topic. The use of sustainable, pollution-free, low-cost new energy sources instead of fossil energy sources has become one way to solve the current environmental degradation problem. Hydrogen energy is considered to be one of the environmentally friendly, efficient clean energy sources, effectively converted from renewable solar energy. Since Fujishima and Honda successfully decomposed water into hydrogen and oxygen under ultraviolet light by using a TiO 2 single crystal electrode for the first time, a photocatalytic water splitting technology has become the most environment-friendly, safer and most effective method for solving the energy crisis. However, it is not easy for most semiconductor materials to achieve efficient photocatalytic activity by themselves. Therefore, the preparation of photocatalysts with excellent performance, low cost and high quantum efficiency becomes a great challenge for the technology.
In recent years, photocatalysts that produce H 2 have been explored, and metal chalcogenides have been widely favored because of their suitable band gap and band position. Among them, the three-dimensional flower-like microsphere CdIn 2S4 belonging to the ternary compound AB 2X4 family has been applied to the field of hydrogen production due to its proper band edge position, narrow band gap and superior charge mobility. However, there are many urgent problems in the hydrogen-generating reaction process, such as rapid recombination of electron-hole pairs and severe photo-etching.
In addition, manganese oxides have been widely studied due to their novel structure and excellent physical and chemical applications. Among these oxides of manganese, mn 3O4 is an interesting material because of its extraordinary surface area and unique nanoelectronic structure, suitable for a wide range of applications, and secondly Mn 3O4 is a stable oxide with spinel structure, also with catalytic and electrochemical properties.
By constructing heterojunction, promoter modification and element doping, the photocatalytic activity can be effectively accelerated. Among other things, the rational design of the heterojunction is very helpful to promote charge separation and photocatalytic activity. Heterojunction can be classified into type I, type II, and type Z according to electron migration paths. The unique Internal Electric Field (IEF) in the Z-type heterojunction can effectively separate electron hole pairs, reduce the recombination probability, retain strong oxidation-reduction active sites, expand the photoresponse range, improve the photocatalytic activity and the like.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a Z-type heterojunction Mn 3O4@CdIn2S4 composite material with a core-shell heterostructure, and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows: a Z-type heterojunction Mn 3O4@CdIn2S4 core-shell heterostructure composite material is prepared by taking Mn-MOF as a precursor to synthesize Mn 3O4 microspheres, and growing CdIn 2S4 (CIS) shells in situ to form a Z-type heterojunction.
The preparation method of the Z-type heterojunction Mn 3O4@CdIn2S4 composite material specifically comprises the following steps:
(1) 1,3, 5-benzene tricarboxylic acid (C 6H3(CO2H)3) and MnCl 2 are dissolved in N, N-Dimethylformamide (DMF), are subjected to ultrasonic treatment and stirring until the mixture is completely dissolved, are transferred into a high-pressure reaction kettle, are taken out after being reacted for 46-48 hours at 160+/-10 ℃, are centrifuged, and are dried, so that a solid product Mn-MOF is obtained. Placing the solid product Mn-MOF in a tube furnace, oxidizing and calcining at 500+/-20 ℃ for 0.5-1.5 hours, and taking out to obtain the solid Mn 3O4.
Optionally, the molar ratio of the 1,3, 5-benzene tricarboxylic acid (C 6H3(CO2H)3) to the MnCl 2 is 1:1-2; preferably 1:2.
Optionally, the Mn-MOF vacuum drying temperature is 60-70 ℃ and the drying time is 10-24 hours.
(2) Dissolving thiourea in deionized water, performing ultrasonic treatment, and stirring until the thiourea is completely dissolved to obtain thiourea solution; dissolving soluble cadmium salt and soluble indium salt in deionized water, carrying out ultrasonic treatment and stirring until the soluble cadmium salt and the soluble indium salt are completely dissolved, adding thiourea solution, and stirring until the soluble cadmium salt and the soluble indium salt are uniformly mixed; adding Mn 3O4 obtained in the step (1) for ultrasonic dispersion, and stirring at room temperature until the Mn 3O4 is uniformly mixed to obtain a mixed solution; and carrying out hydrothermal reaction on the mixed solution at 170-190 ℃ for 18-20 hours, centrifugally washing, and drying to obtain the Z-type heterojunction Mn 3O4@CdIn2S4 composite material.
Optionally, the mole ratio of the soluble cadmium salt to the soluble indium salt to the thiourea is 1:1-3:1-4; preferably 1:2:4.
Optionally, the mass ratio of Mn 3O4 to CdIn 2S4 produced is 4:6, preparing a base material; 3:7, preparing a base material; 2:8, 8;1:9, a step of performing the process; preferably 3:7. the mass ratio of Mn 3O4 in the Mn 3O4@CdIn2S4 composite material is 10% -40%.
Optionally, the soluble cadmium salt is CdCl 2 or CdCl 2·2.5H2 O; the soluble indium salt is or InCl 3InCl3·4H2 O.
Optionally, the drying temperature of the product Mn 3O4@CdIn2S4 is 60-70 ℃ and the drying time is 10-24 hours.
The invention provides the Z-type heterojunction Mn 3O4@CdIn2S4 composite material prepared by the preparation method.
The invention also provides application of the Z-type heterojunction Mn 3O4@CdIn2S4 core-shell heterostructure composite material, which is used for photocatalytic hydrogen evolution, and particularly used for visible light catalytic hydrogen evolution.
The invention adopts a simple in-situ growth method to successfully prepare the Mn 3O4@CdIn2S4 composite material of the Z-type heterojunction, and the material is applied to photocatalysis hydrogen evolution. Mn 3O4 microspheres are synthesized by taking Mn-MOF as a precursor, a CdIn 2S4 (CIS) shell grows in situ, and the existence of a core-shell heterostructure is beneficial to increasing the light absorption range, so that the photocatalytic activity is improved. In addition, the introduction of Mn 3O4 obviously improves the separation of the CdIn 2S4 carrier and inhibits the recombination of electron holes, thereby improving the photocatalytic activity of the composite material. The photocatalysis experiment result shows that Mn 3O4@CdIn2S4 has higher photocatalysis hydrogen evolution capability than Mn 3O4 and CdIn 2S4. In addition, the existence of a Z-type heterojunction between Mn 3O4 and CdIn 2S4 is confirmed through experiments and characterization, and a possible photocatalytic reaction mechanism is proposed.
Thus, cdIn 2S4 coupled with Mn 3O4 for photocatalytic hydrogen evolution studies are feasible. On the one hand, cdIn 2S4 and Mn 3O4 have appropriate energy band structures, which are favorable for the formation of Z-type heterostructures, thereby facilitating the separation of photogenerated electron-hole pairs. On the other hand, a core-shell heterostructure is formed, so that the light absorption range is greatly increased, and the hydrogen production activity is enhanced.
Drawings
FIG. 1 is an XRD pattern for Mn 3O4、CdIn2S4、30%Mn3O4@CdIn2S4;
FIG. 2 is an SEM image of Mn 3O4、CdIn2S4、30%Mn3O4@CdIn2S4 (a-c);
FIG. 3 is a TEM image (a-f) of 30% Mn 3O4@CdIn2S4;
FIG. 4 is an XPS spectrum of 30% Mn 3O4@CdIn2S4; (a) a summary spectrum; (b) S2 p; (c) In 3d; (d) Cd 3d; (e) O1 s, (f) Mn 2p;
FIG. 5 is a graph of hydrogen evolution efficiency of Mn-MOF, mn 3O4、CdIn2S4、Mn3O4@CdIn2S4 (a-b);
FIG. 6 is a graph of 30% Mn 3O4@CdIn2S4 cycle experiments;
FIG. 7 is a fluorescence emission spectrum of Mn 3O4、CdIn2S4, mn 3O4@CdIn2S4 obtained in example 3;
FIG. 8 is an ultraviolet visible diffuse reflectance spectrum of Mn 3O4、CdIn2S4, mn 3O4@CdIn2S4 prepared in example 3;
FIG. 9 is a graph showing the photoelectric current response of Mn 3O4、CdIn2S4 and Mn 3O4@CdIn2S4 obtained in example 3;
FIG. 10 is an EIS impedance chart of Mn 3O4、CdIn2S4 and Mn 3O4@CdIn2S4 obtained in example 3.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
Example 1
Mass ratio 1: preparation of Mn 3O4@CdIn2S4 composite material of 9:
(1) Mn 3O4 is prepared by oxidative calcination, and specifically comprises the following steps:
0.21g of 1,3, 5-trimellitic acid C 6H3(CO2H)3 and 0.252g of MnCl 2 are dissolved in 10ml of DMF, sonicated and stirred until complete dissolution, transferred to a high-pressure reaction kettle, reacted in an oven at 160 ℃ for 48 hours and taken out, collected by centrifugation and washed several times with ethanol and ionized water, and the product is dried at 60 ℃ for 10 hours to give a solid product as Mn-MOF. The solid product Mn-MOF was placed in a tube furnace, oxidized and calcined at 500℃for 1 hour, and then taken out to obtain solid Mn 3O4.
(2) 0.2284G of CdCl 2·2.5H2 O and 0.587g of InCl 3·4H2 O were dissolved in 30ml of deionized water, sonicated and stirred until completely dissolved. 0.304g thiourea (CH 4N2 S) was dissolved in 20ml deionized water, sonicated and stirred until completely dissolved. The solution containing CH 4N2 S was poured into the solution containing CdCl 2·2.5H2 O and InCl 3·4H2 O and stirred for 1 hour. Adding 0.1244g Mn 3O4 to perform ultrasonic dispersion to obtain a mixed solution; the mixed solution was poured into a reaction kettle and reacted in an oven at 180℃for 18 hours. The product was collected by centrifugation and washed with ethanol and ionic water several times and dried at 60 ℃ for 10 hours. The resulting solid product was a Mn 3O4@CdIn2S4 composite with a mass ratio of 1:9, designated 10% Mn 3O4@CdIn2S4.
For comparison, a pure sample of CdIn 2S4 was also prepared, i.e. with reference to the preparation method of Mn 3O4@CdIn2S4, without addition of Mn 3O4, to give the solid product CdIn 2S4, referred to as mass 1.1196g.
Example 2
Mass ratio 2: preparation of Mn 3O4@CdIn2S4 composite material of 8:
This example differs from example 1 in that 0.27985g of Mn 3O4 was added in step (2) to give a solid product with a mass ratio of 2: mn 3O4@CdIn2S4 composite of 8, designated 20% Mn 3O4@CdIn2S4.
Example 3
Mass ratio 3: preparation of Mn 3O4@CdIn2S4 composite material of 7:
This example differs from example 1 in that 0.4797g of Mn 3O4 was added in step (2) to give a solid product with a mass ratio of 3: mn 3O4@CdIn2S4 composite of 7, designated 30% Mn 3O4@CdIn2S4.
Example 4
This example differs from example 1 in that 0.7463g of Mn 3O4 was added in step (2) to give a solid product with a mass ratio of 4:6, mn 3O4@CdIn2S4 composite, designated 40% Mn 3O4@CdIn2S4.
Further, how the embodiments of the present invention may be carried out to achieve the objects of the present invention will be described with reference to the accompanying drawings, in which:
Referring to fig. 1, XRD pattern crystalline phases of the prepared Mn 3O4 and CdIn 2S4、30%Mn3O4@CdIn2S4 were measured using X-ray diffraction spectroscopy (XRD). As shown in FIG. 1, the prepared diffraction peaks of Mn 3O4 are respectively located at 18.00 degrees, 28.88 degrees, 31.02 degrees, 32.32 degrees, 36.08 degrees, 37.98 degrees, 44.44 degrees, 50.70 degrees, 58.51 degrees, 59.84 degrees and 64.65 degrees, and are well matched with a plane (PDF#24-0734). CdIn 2S4 was located at 9 distinct diffraction peaks and planes (PDF # 27-0060) of 14.1 °, 23.2 °, 27.2 °, 28.4 °, 29.1 °, 33.0 °, 40.6 °, 43.3 ° and 47.4 °. Most notably, both Mn 3O4 and CdIn 2S4 exhibited characteristic peaks in the Mn 3O4@CdIn2S4 sample, indicating that the material was successfully prepared.
Referring to fig. 2 (a-c), the Mn 3O4、CdIn2S4、30%Mn3O4@CdIn2S4 morphology was studied using a Scanning Electron Microscope (SEM). As shown in fig. 2 (a), cdIn 2S4 was prepared consisting of irregular nanoparticles. As shown in FIG. 2 (b), mn 3O4 was prepared to have a clear layered structure. In fig. 2 (c), the Mn 3O4@CdIn2S4 produced is clearly seen to consist of nanoparticles and lamellar structures, further indicating the success of the material compounding.
Referring to fig. 3, tem image analysis shows that S, in and Cd elements are dispersed at the periphery of the core-shell structure, mn and O elements are inside the core-shell structure, and the core-shell heterostructure is successfully prepared.
Referring to fig. 4, the elemental and surface electron states of the samples were studied using X-ray photoelectron spectroscopy (XPS). As shown in fig. 4 (a), investigation of XPS spectra revealed that characteristic peaks of Mn 3O4 and CdIn 2S4 exist at the surface of Mn 3O4@CdIn2S4, including S, in, cd, O and Mn. The two characteristic peaks at 161.14 and 162.37 eV in fig. 4 (b) are attributed to S2 p 3/2 and S2 p 1/2. The signals at 451.95 and 444.35 eV In fig. 4 (c) demonstrate the presence of In 3d 3/2 and In 3d 5/2. In fig. 4 (d), two characteristic peaks Cd 3d 3/2 and Cd 3d 5/2 at 411.5 and 404.74 eV are present. In FIG. 4 (e), located at 531.36 and 529.8eV, due to O1s. The two characteristic peaks at 641.46 and 653.22 eV in fig. 4 (f) are attributed to Mn 2p 3/2 and Mn 2p 1/2. In addition, S, in and Cd peaks shift to higher binding energies and Mn and O peaks shift to lower binding energies. This represents electron migration due to the difference in binding energy, and the internal electric field is tightly bound together, again demonstrating that Mn 3O4@CdIn2S4 forms a tight heterojunction.
Photocatalytic hydrogen evolution
The hydrogen evolution rate of the samples was studied by photocatalytic experiments, performed in a photo-reactor, irradiated with a xenon lamp, with 50 mL deionized water and 50 mL sacrificial agents (0.35M Na 2 S and 0.25M Na 2SO3) added to the reactor, followed by 0.01 g catalyst with Na 2 S and Na 2SO3 as hole scavengers. A 300W xenon lamp with a 420 nm filter was used as a light source for reaction for 5h. Prior to the experiment, it was determined that H 2 was not obtained in the absence of catalyst, light or water. The evolution of H 2 of the sample in FIG. 5a increased steadily within 5H. The H 2 evolution rate of the samples, see fig. 5 (a-b), mn 3O4（1.654mmol·g−1·h−1) and CdIn 2S4（1.447mmol·g−1·h−1), were poor in photocatalytic activity, probably due to the rapid recombination of photogenerated electron-hole pairs. Notably, the composite Mn 3O4@CdIn2S4 exhibits excellent hydrogen evolution properties compared to Mn 3O4 and CdIn 2S4, which should be due to the construction of the Z-type heterojunction that promotes space charge separation. Wherein, the evolution rate of H 2 of 30% Mn 3O4@CdIn2S4 reaches 17.866 mmol.g −1·h−1, which is 10.80 times of Mn 3O4 and 12.35 times of CdIn 2S4 respectively.
Referring to fig. 6, after 5 cycle experiments, the photocatalytic hydrogen evolution activity of 30Mn 3O4@CdIn2S4 still can maintain 95% of the initial catalytic activity, suggesting that the catalyst has better stability.
Referring to fig. 7, photoluminescence (PL) spectral characterization was performed to gain a more thorough understanding of charge transfer. The higher fluorescence emission peak means higher recombination rate of electron-hole pairs. The PL emission intensities of Mn 3O4 and CdIn 2S4 indicate rapid recombination of photogenerated electron-hole pairs, which is detrimental to the precipitation of photocatalytic H 2. However, the PL emission intensity of Mn 3O4@CdIn2S4 is significantly lower than that of Mn 3O4 and CdIn 2S4, indicating that the construction of the heterojunction eases the recombination of photogenerated carriers.
Referring to fig. 8, the light capturing ability of the sample was measured by ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS). Mn 3O4@CdIn2S4 has stronger visible light absorption capacity than that of Mn 3O4@CdIn2S4, and the light absorption edge is close to 680 nm.
Referring to fig. 9, photoelectrochemical (PEC) measurements were performed in order to study interfacial charge separation. The transient photocurrent response was detected and the photo-induced potential of the 300W Xe lamp under the 420 nm filter was studied. The highest photocurrent density of Mn 3O4@CdIn2S4 is due to the interfacial interaction between Mn 3O4 and CdIn 2S4, which results in improved structural uniformity.
Referring to fig. 10, electrochemical Impedance Spectroscopy (EIS) analysis shows that the nyquist arc radius of Mn 3O4@CdIn2S4 is significantly minimized due to the improved conductivity resulting in an increased interfacial charge transfer rate due to the heterojunction construction.
The foregoing is only a preferred or exemplary embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications or adaptations can be made without departing from the principles of the present invention, and such modifications or adaptations are intended to be within the scope of the invention.
Claims (7)
1. The preparation method of the Z-type heterojunction Mn 3O4@CdIn2S4 composite material is characterized by comprising the following steps of:
(1) Preparation of Mn-MOF derived Mn 3O4: dissolving 1,3, 5-benzene tricarboxylic acid and MnCl 2 in N, N-dimethylformamide, carrying out ultrasonic treatment, stirring until the solution is completely dissolved, transferring the solution into a high-pressure reaction kettle, reacting at 150-170 ℃ for 46-48 hours, taking out the solution, centrifuging the solution, and drying the solution to obtain Mn-MOF; oxidizing and calcining the Mn-MOF at 480-520 ℃ for 0.5-1.5 hours, and taking out to obtain Mn 3O4 derived from the Mn-MOF;
(2) Dissolving thiourea in deionized water, performing ultrasonic treatment, and stirring until the thiourea is completely dissolved to obtain thiourea solution; dissolving soluble cadmium salt and soluble indium salt in deionized water, carrying out ultrasonic treatment and stirring until the soluble cadmium salt and the soluble indium salt are completely dissolved, adding thiourea solution, and stirring until the soluble cadmium salt and the soluble indium salt are uniformly mixed; adding Mn 3O4 derived from Mn-MOF, performing ultrasonic dispersion, and stirring at room temperature until the Mn-MOF is uniformly mixed to obtain a mixed solution; and carrying out hydrothermal reaction on the mixed solution at 170-190 ℃ for 18-20 hours, centrifugally washing, and drying to obtain the Z-type heterojunction Mn 3O4@CdIn2S4 composite material.
2. The method for preparing a Z heterojunction Mn 3O4@CdIn2S4 composite material according to claim 1, wherein the molar ratio of 1,3, 5-benzene tricarboxylic acid to MnCl 2 in step (1) is 1:1-2.
3. The method for preparing a Z-type heterojunction Mn 3O4@CdIn2S4 composite material according to claim 1, wherein the molar ratio of the soluble cadmium salt, the soluble indium salt and thiourea in the step (2) is 1:1-3: 1-4.
4. The method of preparing a Z-type heterojunction Mn 3O4@CdIn2S4 composite according to claim 1, wherein the soluble cadmium salt of step (2) is cadmium chloride or a hydrate thereof; the soluble indium salt is indium chloride or a hydrate thereof.
5. The method for preparing a Z-type heterojunction Mn 3O4@CdIn2S4 composite material according to claim 1, wherein the mass percentage of Mn-MOF derived Mn 3O4 in the Mn 3O4@CdIn2S4 composite material in the step (2) is 10% -40%.
6. A Z-heterojunction Mn 3O4@CdIn2S4 composite prepared by the method of any one of claims 1 to 5.
7. Use of the Z-heterojunction Mn 3O4@CdIn2S4 composite as defined in claim 6 in photocatalytic hydrogen evolution.
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