CN109908956B - Functional three-vacancy silicotungstate composite nano material and preparation method and application thereof - Google Patents
Functional three-vacancy silicotungstate composite nano material and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of preparation and application of nano materials, and particularly relates to a functional three-vacancy silicotungstate composite nano material as well as a preparation method and application thereof. The invention utilizes NiS-CdS doped silicotungstate to discuss the photocatalysis and luminescence performance, when the ratio of NiS-CdS to CuSiW9 is 1:1, the photocatalysis hydrogen production is the highest, and the degradation rate of rhodamine B is 62.7% as the highest. The nano material prepared by the method not only can be used as a photocatalyst for treating industrial wastewater, but also has wide application prospect in the aspect of preparing clean energy by photocatalytic hydrogen production.
Description
Technical Field
The invention belongs to the technical field of preparation and application of nano materials, and particularly relates to a functional three-vacancy silicotungstate composite nano material as well as a preparation method and application thereof.
Background
Polyoxometalates (POMs) are a special inorganic compound that has wide applications in catalysis, magnetics, medicine and material science. Polyoxometallate-based nanomaterials (PNMs), as a subclass of POM chemistry, have attracted considerable attention due to their unique properties compared to traditional single crystal POM compounds. The application of nanotechnology in PNM preparation is a new approach for POM development in recent years, and many researchers are working on these materials. To date, various PNMs with different morphologies and properties have been reported. In 2011, Cronin et al discovered a general method of making POM tubular structures by an osmotically driven crystal morphogenesis process (g.j.t. Cooper, a.g. Boulay, p.j. Kitson, c. ritgie, c.j. Richmond, j. Thiel, d. Gabb, r. Eadie, d.l. Long and Leroy Cronin,J. Am. Chem. Soc., 2011, 133, 5947-5954.). Two years later, ping and coworkers obtained a series of uniform rhombohedral dodecahedral nanocrystals based on phosphomolybdates, useful as effective antibacterial agents (j. He, h. ping, w. Wang, y. Zhang, b. Yan, x. Li, s. Li and j. Chen,Dalton Trans., 2013, 42, 15637-15644.). Chattopadhhyay et al prepared Mn-based heteropolytungstate microspheres (k. Bhattacharjee, k.k. chattopadhhyay, and g.c. Das,J. Phys. Chem. C, 2015, 119, 1536−1547.）。
photoluminescent properties have received increasing attention in recent years as an important property of PNMs, but the photoluminescent properties have been relatively poorly studied relative to other properties of PNMs. The photocatalyst plays an important role in the photocatalytic decomposition of organic substances harmful to human bodies and the environment, and in the processes of saving resources and avoiding environmental pollution. Therefore, the research and development of the PNMs nano material with better photocatalytic performance are of great significance.
Disclosure of Invention
The invention provides a functional three-vacancy silicotungstate nanometer material, and the nanometer composite photocatalyst NiS-CdS-POM has higher specific surface area, so that more active sites can be provided for adsorbing pollutants, and the photocatalytic reaction is facilitated.
The invention also provides a preparation method of the functional three-vacancy silicotungstate nanometer material.
The invention further provides the application of the functional triple-vacancy silicotungstate nano material in the aspect of photocatalytic hydrogen production and the application in the aspect of artificial dye degradation.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a functional three-vacancy silicotungstate composite nano material comprises the following steps:
(1) preparing three-vacancy silicotungstate: dissolving soluble salt of copper or cobalt into acetic acid-sodium acetate buffer solution, heating to 60-80 ℃, adding POMs, reacting for 1-3h, cooling to room temperature, performing suction filtration to obtain clear solution, adding polyethylene glycol (polyethylene glycol can be used as a template agent, and the long-chain structure of the polyethylene glycol is beneficial to the formation of polyacid morphology) into the clear solution, stirring for 3-9h, and obtaining precipitated precipitate, namely trisection silicotungstate (nano copper silicotungstate or cobalt silicotungstate);
(2) preparing CdS quantum dots: will be provided withNa2The S solution is added to CdCl2Mixing the solution, reacting for 3-9h, standing and storing for 6-18h to obtain a precipitate, washing with distilled water, dispersing the obtained precipitate into distilled water, transferring the distilled water into a reaction kettle, aging for 3-9 days, naturally cooling, filtering and washing, and drying at 50-70 ℃ for 1-2h to obtain CdS quantum dots;
(3) preparing a NiS-CdS doped silicotungstate composite nano material: CdS quantum dots and Na2SO3Dissolving in distilled water under inert gas atmosphere, adding Na2And S, adding a soluble nickel salt solution, stirring for 10-30 min under an inert gas atmosphere, mixing the obtained solution with the triple-vacancy silicotungstate obtained in the step (1), and performing centrifugal separation to obtain the functional triple-vacancy silicotungstate composite nano material NiS-CdS-POM.
The POMs are Na9[SiW9O34]·18H2O, Na for convenience of explanation9[SiW9O34]18H2O may also be referred to as alpha-SiW for short9The synthesis method thereof is referred to as: herve G, Teze A. Study of. alpha. -and beta. -enneaatungstosilicates and germanates [ J]. Inorganic Chemistry, 1977, 16(8): 2115-2117。
Specifically, in the step (1), soluble salt of copper and Na9[SiW9O34]·18H2The mass ratio of O is 1: (4-20); soluble salts of cobalt with Na9[SiW9O34]·18H2The mass ratio of O is 1: (4-20); preferably, the soluble salt of copper is Cu (CH)3COO)2·H2O, the soluble salt of the cobalt is C4H6CoO4·4H2O。
Further, the specific operation in the step (1) is to dissolve 0.04-0.6g of soluble salt of copper or cobalt into acetic acid-sodium acetate buffer solution, heat up to 60-80 ℃, add 1.5-2.0g of POMs, react for 1-3h, cool to room temperature, filter to obtain clear solution, take clear solution, add 0.2-0.3g of polyethylene glycol into the clear solution to obtain precipitate.
Further, in the step (1), when polyethylene glycol is added, potassium chloride with the volume of 200-.
Specifically, Na in step (2)2S and CdCl2In a molar ratio of 1: (1-2); further preferably, the specific operation of step (2) is to add Na in a volume of 120-200mL and a concentration of 0.2-0.6mol/l2The S solution is added into 240mL of 160-240mL of CdCl with the concentration of 0.2-0.6mol/l2And (3) solution.
Preferably, after aging in the step (2), the obtained precipitate is heated in an oven at 250 ℃ for 48-72h, and the heating process has good promotion effect on the crystallinity of CdS and the uniform formation morphology of CdS.
Specifically, the mass ratio of CdS to silicotungstate in the step (3) is 1 (0.5-2.5).
Specifically, the soluble nickel salt in the step (3) is Ni (NO)3)2、NiCl2Or NiSO4(ii) a Specifically, the mass percent of the soluble nickel salt solution in the step (3) is 0.1-0.2 wt%.
Further preferably, the specific operation in the step (3) is to mix 0.16-0.36g CdS quantum dots and 6-9g Na2SO3Dissolving in distilled water under inert gas atmosphere, adding 15-30g Na2And S, dropwise adding soluble nickel salt solution with the total volume of 3-5mL, stirring for 10-30 min under the inert gas atmosphere, and mixing with the triple-vacancy silicotungstate in the step (1).
Preferably, the inert gas is N2Or Ar.
According to the preparation method, the NiS-CdS is doped with the silicotungstate, so that the functional triple-vacancy silicotungstate composite nano material NiS-CdS-POM is prepared.
The application of the functional triple-vacancy silicotungstate composite nano material NiS-CdS-POM as a composite photocatalyst in the aspect of photocatalytic hydrogen production comprises the following specific steps: and (4) carrying out a photocatalytic hydrogen production experiment by using the functional triple-vacancy silicotungstate composite nano material NiS-CdS-POM prepared in the step (3) and a 500W xenon lamp with a 420nm optical filter as a light source. After being illuminated, the sample was taken to test the content of hydrogen generated.
Specifically, the artificial dye can be rhodamine B, methylene blue, alizarin red S, gardenia yellow G or Congo red, and when the functional triple-vacancy silicotungstate composite nano material is applied, 0.1-0.3G of the nano material NiS-CdS-POM is added into 40-45 mL of a solution of the artificial dye with the concentration of 10-20 mg/L.
The invention has the following beneficial effects:
the operation method is simple, the preparation conditions are easy to control, and the prepared NiS-CdS doped POM nano composite material has the application values of no pollution, good catalytic efficiency, high degradation rate and the like.
The invention synthesizes the silicotungstate nanometer material with unique appearance by using the triple-vacancy silicotungstate anion as a precursor through a water solution synthesis method, and researches the photocatalysis performance and the photodegradation performance of the nanometer composite material prepared by the NiS-loaded CdS-doped silicotungstate. The invention not only provides a new way for controlling the shape of the polyacid, but also provides a potential method for the functionalization of the polyacid nano material.
Drawings
FIG. 1 is a CuSiW prepared in example 19EDX picture and scanning electron micrograph of the nanometer material, wherein, picture a is EDX picture, picture b, c are scanning electron micrograph;
FIG. 2 shows the NiS-CdS-CuSiW prepared in example 19An X-ray powder diffraction pattern of the nanomaterial;
FIG. 3 shows the NiS-CdS-CuSiW prepared in example 19An X-ray photoelectron energy spectrum of the nano material, wherein a is W element, b is Cd element, c is Cu element, and d is S element;
FIG. 4 is a CuSiW prepared in example 19The infrared spectrogram and the thermogravimetric curve of the nano material are shown in the specification, wherein a is the infrared spectrogram, and b is the thermogravimetric curve diagram;
FIG. 5 shows the NiS-CdS-CoSiW prepared in example 59Nano materialEDX and SEM images of (1), wherein a is an EDX image and b is a SEM image;
FIG. 6 shows NiS-CdS-CuSiW prepared in examples 1 and 49Photo-catalytic water hydrogen production diagram of nano material, wherein a is CdS and CuSiW9H yield at a mass ratio of 1:2.52Amount change, b is control group CdS alone to produce H2Amount change, c is CdS and CuSiW9H yield at a mass ratio of 1:1.52Amount change, d is CdS and CuSiW9H yield at a mass ratio of 1:0.52Amount change, e is d is CdS and CuSiW9H yield at a mass ratio of 1:12(ii) a change in amount;
FIG. 7 shows the NiS-CdS-CuSiW prepared in example 19A photodegradation rhodamine B effect graph of the nano material;
FIG. 8 shows the NiS-CdS-CuSiW prepared in example 19And (3) B-time graph of photodegradation rhodamine of the nano material.
Detailed Description
The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited by the following examples.
Wherein, the model of the photoreactor: CEL-LB 70-3; polyethylene glycol 8000 is commercially available.
Example 1
Functional triple-vacancy silicotungstate composite nano material NiS-CdS-CuSiW9The preparation method comprises the following steps:
（1）CuSiW9preparing the nano-whisker: 1.335 g of CH3COONa·3H2O and 11 μ l of CH3COOH was dissolved in 20 ml of distilled water, and 0.416 g of Cu (CH) was weighed3COO)2·H2Adding O into the solution under stirring until the O is dissolved, and then heating to 70 ℃; while stirring at 70 ℃ a total of 1.926g of Na were added in portions9[SiW9O34]·18H2O, reacting for 1h, cooling to room temperature, performing suction filtration to obtain a green clear solution, adding 0.251 g of polyethylene glycol 8000 into 5ml of the green clear solution, dropwise adding 4.5 mol/L of KCl 240 mu L, and stirringThe precipitated precipitate is CuSiW after 6 hours9A nanowhisker;
(2) preparing CdS: 160ml of 0.4mol/l Na are added2S·9H2O is added dropwise to 200ml of 0.4mol/l CdCl under vigorous stirring2Stirring the solution for 6 hours, standing and storing the solution for 12 hours to obtain a precipitate, washing the precipitate with distilled water, dispersing the obtained precipitate into 80 ml of distilled water, transferring the precipitate into a 150 ml reaction kettle, aging the solution for 6 days, slowly raising the temperature of an oven to 200 ℃ after aging, heating the solution at 200 ℃ for 72 hours, naturally cooling the solution, filtering and washing the solution, and drying the solution at 60 ℃ for 2 hours to obtain CdS quantum dots;
(3) NiS-CdS doped CuSiW9Preparing a composite photocatalyst of the nano-whisker: 0.260 g CdS quantum dots and 8.174 g Na2SO3Under stirring, N2Dissolved in 100 ml of distilled water with air removed under an atmosphere, 21.798 g of Na was added2S, then 3ml of Ni (NO) with the mass percent of 0.14wt% is dropwise added3)2Solution in N2Stirring for 30min under the atmosphere, adding the obtained solution into a photoreactor, and adding 0.26g of CuSiW obtained in the step (1)9Centrifuging to obtain the functional triple-vacancy silicotungstate nano material NiS-CdS-CuSiW9。
Product properties in example 1:
a scanning electron microscope is shown in FIG. 1, which is CuSiW prepared in step (1) of example 19As can be seen from the figure, CuSiW prepared in this example9The nano crystal whisker has the advantages of single structure and good dispersibility.
NiS-CdS-CuSiW prepared in example 19The X-ray powder diffraction of (2) is shown in FIG. 2, and it can be seen that the characteristic peaks at 27.9 °,41.2 ° and 49.8 ° can be respectively directed to CuSiW9The face-centered cubic crystalline CuSiW9 (004), (511), and (415) planes. Very distinct NiS-CdS peaks are observed at 24.34 °,26.14 °,27.86 °,36.29 °,43.43 °,47.55 ° and 51.57 °, which are designated as (100), (002), (101), (102), (110), (103) and (112) crystal planes of NiS-CdS.
NiS-CdS-CuSiW prepared in example 19The X-ray photoelectron spectrum is shown in FIG. 3, from which the chemical composition and binding energy of atoms can be further determined, and the peaks of Cd 3d at 404.65 and 411.39eV can be assigned to Cd of CdS particles2+(ii) a Cu 2p peaks were observed at 932.71 and 952.63eV, corresponding to Cu for POM2+. In addition, there are two peaks of W4f5/2 and W4f7/2, with binding energies of 35.07eV and 37.20 eV, respectively.
As can be seen in FIG. 4, the distances between 450 and 4000cm in FIG. 4a-1In between, alpha-SiW was observed9，CuSiW9IR spectra of nanowhiskers. CuSiW9The nanowhisker may appear by about 1007 cm-1（W-Ot），953 cm-1（Si-Oa），910 cm-1（W-Ob) And 794 cm-1（W-Oc) And alpha-SiW9And (5) the consistency is achieved. FIG. 4b shows a Thermogram (TG) with a total weight loss of 23.17% in the range of 33-1000 ℃ and a weight loss of 4.33% from 33 to 127 ℃ in the first step corresponds to the release of adsorbed water molecules; the second weight loss of 4.38% between 127 and 258 ℃ with further heating is approximately due to the removal of structural water molecules; the third weight loss from 258 to 1000 ℃ was 14.46% due to decomposition of the POM skeleton.
Example 2
This example differs from example 1 in that CdS and CuSiW are present in the photoreactor in step (3)9The mass ratio of (1: 0.5) is adopted, namely 0.260 g CdS and 0.13g CuSiW are adopted9。
Example 3
This example differs from example 1 in that CdS and CuSiW were photo-reacted in step (3)9In a mass ratio of 1:1.5, namely, 0.260 g of CdS and 0.39g of CuSiW are adopted9。
Example 4
This example differs from example 1 in that CdS and CuSiW were photo-reacted in step (3)9The mass ratio of (1: 2.5) is that 0.260 g CdS and 0.65g CuSiW are adopted9。
Example 5
Functional three-phase separatorComposite nano NiS-CdS-CoSiW material of silicotungstate9The difference between this example and example 1 is that the specific operation steps in step (1) are as follows: 0.10 g C4H6CoO4·4H2O was dissolved in 25ml of water and heated to 70 ℃ and 1.926g of Na were added with vigorous stirring9[SiW9O34]·18H2O, reacting for 1h, cooling to room temperature, performing suction filtration to obtain a reddish brown clear solution, adding 0.251 g of polyethylene glycol into 5ml of the reddish brown clear solution, dropwise adding 4.5 mol/L KCl 240 muL, stirring for 6h, and precipitating to obtain the CoSiW9A nanocrystal ball; the subsequent steps are the same as the steps (2) and (3) of example 1.
Product properties in example 5:
when C is used in step (1)4H6CoO4·4H2O instead of Cu (CH)3COO)2·H2O, prepare CoSiW9And (4) nanocrystalline spheres. FIG. 5 shows a CoSiW9Typical SEM images of the nano-crystalline spheres, according to a statistical 150 particles, the average diameter of the nano-spheres is about 370 nm.
Test performance:
photocatalytic water hydrogen production
The nano material NiS-CdS-CuSiW prepared in the examples 1 to 49Respectively adding into a photoreactor, performing photocatalytic hydrogen production experiment with 500W xenon lamp with 420nm filter as light source, taking sample every 1 hr, testing hydrogen content, and observing H2The amount of change was produced, and the results are shown in FIG. 6. In FIG. 6, a is CdS and CuSiW9H yield at a mass ratio of 1:2.52Amount change, b is control group CdS alone to produce H2Amount change, c is CdS and CuSiW9H yield at a mass ratio of 1:1.52Amount change, d is CdS and CuSiW9H yield at a mass ratio of 1:0.52Amount change, e is d is CdS and CuSiW9H yield at a mass ratio of 1:12The amount varies. As can be seen from FIG. 6, when CuSiW9When the ratio of the addition amount of (A) to CdS is 1:1, the photocatalyst activity reaches the highest, and when CuSiW is used9At a ratio of 2.5:1 to CdS,the photocatalytic activity is not improved but is lower than that of the product without CuSiW9。
As can be seen from FIG. 6, the photocatalytic activity of pure CdS is relatively low, with CdS and CuSiW9Change in mass ratio, POM (CuSiW)9) The amount of the photocatalyst is gradually increased, the activity of the photocatalyst is obviously improved, and the CuSiW with the same quality9When the nano crystal whisker is doped with CdS quantum dots, the performance of the photocatalyst is optimal; however, with CuSiW9The activity of the material decreases with the increase of nanowhiskers. The results show that the right amount of CuSiW9The nano crystal whisker can improve the visible light catalytic activity of the high-purity CdS quantum dot, and the silicotungstate is a key catalyst promoter for promoting a photocatalytic reaction.
Photodegradation of rhodamine B
0.260 g of NiS-CdS-CuSiW prepared in example 1 was added9Adding the photocatalyst into 40ml of rhodamine B solution (10 mg/L), irradiating by using an ultraviolet visible light source 500W xenon lamp, starting timing, sampling every 1h, and performing ultraviolet test analysis. FIG. 7 is a NiS-CdS-CuSiW9Statistical plot of the effect of degrading organic compounds. The results show that the catalyst (NiS-CdS-CuSiW) is irradiated for 6h9) The degradation rate of rhodamine B is 62.7 percent, which shows that NiS-CdS-CuSiW9Has better degradation effect on rhodamine B as a photocatalyst, i.e. the prepared nano material NiS-CdS-CuSiW9Can be used as a photocatalyst and has good application prospect in industrial wastewater treatment.
Fig. 8 is a graph showing the results of the test of the number of catalyst cycles, in which the degradation rate is plotted on the Y-axis and the number of catalyst cycles is plotted on the X-axis. As can be seen from FIG. 8, the catalyst (NiS-CdS-CuSiW) used in three cycles9) Still maintaining the catalytic activity, indicating that example 1 nanocomposite NiS-CdS-CuSiW9The photocatalyst activity of (2) is very high, and also shows that the nano composite material NiS-CdS-CuSiW prepared in example 1 has high catalytic efficiency9Can be recycled and reused as a catalyst, and has higher application value in the field of industrial wastewater treatment.
The foregoing examples are illustrative of embodiments of the present invention, and although the present invention has been illustrated and described with reference to specific examples, it should be appreciated that embodiments of the present invention are not limited by the examples, and that various changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. A preparation method of a functional three-vacancy silicotungstate composite nano material is characterized by comprising the following steps:
(1) preparing three-vacancy silicotungstate: dissolving soluble salt of copper or cobalt into acetic acid-sodium acetate buffer solution, heating to 60-80 ℃, adding POMs, reacting for 1-3h, cooling to room temperature, performing suction filtration to obtain clear solution, adding polyethylene glycol, stirring for 3-9h, and obtaining precipitated precipitate, namely triple-vacancy silicotungstate;
(2) preparing CdS quantum dots: mixing Na2The S solution is added to CdCl2In the solution, mixing, reacting for 3-9h, standing and storing for 6-18h to obtain a precipitate, washing, dissolving the obtained precipitate, aging for 3-9 days, cooling, washing and drying to obtain CdS quantum dots;
(3) preparing a NiS-CdS doped silicotungstate composite nano material: CdS quantum dots and Na2SO3Dissolving in distilled water under inert gas atmosphere, adding Na2S and a soluble nickel salt solution are stirred for 10-30 min under the inert gas atmosphere, the obtained solution is mixed with the triple-vacancy silicotungstate obtained in the step (1), and centrifugal separation is carried out to obtain a functional triple-vacancy silicotungstate composite nano material NiS-CdS-POM;
the POMs are Na9[SiW9O34]·18H2O；
The mass ratio of the CdS quantum dots to the silicotungstate in the step (3) is 1:0.5, 1:1 or 1: 1.5.
2. The method according to claim 1, wherein the soluble salt of copper in the step (1) is Cu (CH)3COO)2·H2O, of said cobaltThe soluble salt is C4H6CoO4·4H2O; in the step (1), the mass ratio of the soluble salt of copper or the soluble salt of cobalt to the POMs is 1: (4-20).
3. The method according to claim 1, wherein Na is used in the step (2)2S and CdCl2In a molar ratio of 1: (1-2).
4. The preparation method according to claim 1, wherein the mass ratio of the CdS quantum dots to the silicotungstate in the step (3) is 1:1.
5. The method according to claim 1, wherein the soluble nickel salt in the step (3) is Ni (NO)3)2、NiCl2Or NiSO4(ii) a The mass percentage of the soluble nickel salt solution in the step (3) is 0.1-0.2 wt%.
6. The functional trisection silicotungstate composite nano material prepared by the method of any one of claims 1-5.
7. The use of the functional trisection silicotungstate composite nano material as recited in claim 6 in photocatalytic hydrogen production.
8. The use of the functional trisection silicotungstate composite nanomaterial of claim 6, wherein the artificial dye is rhodamine B, methylene blue, alizarin Red S, gardenia yellow G, or Congo Red.
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| CN102502845A (en) * | 2011-10-24 | 2012-06-20 | 浙江理工大学 | Preparation method of monoclinic-phase lead tungstate |
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