CN113070042A - CdS quantum dot/MIL-101 (Cr) composite material and preparation method and application thereof - Google Patents

CdS quantum dot/MIL-101 (Cr) composite material and preparation method and application thereof Download PDF

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CN113070042A
CN113070042A CN202110488917.0A CN202110488917A CN113070042A CN 113070042 A CN113070042 A CN 113070042A CN 202110488917 A CN202110488917 A CN 202110488917A CN 113070042 A CN113070042 A CN 113070042A
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mil
cds
composite material
quantum dot
mesoporous
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皮云红
肖静
刘宝玉
侯青青
李希翼
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Guangdong University of Technology
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Abstract

The application belongs to the technical field of metal organic framework materials. The application provides a CdS quantum dot/MIL-101 (Cr) composite material and a preparation method and application thereof. Introducing Cd source into pore channel of MIL-101(Cr) by isovolumetric impregnation method, and introducing pure H2S gas is introduced into Cd stably diffused in an MIL-101(Cr) pore channel at constant speed2+And at the active site, CdS semiconductor quantum dots are generated in situ in an MIL-101(Cr) pore channel. The prepared CdS quantum dot/MIL-101 (Cr) composite material couples adsorption and photocatalysis technologies, achieves a synergistic effect, maintains a certain adsorption characteristic, can promote substrate activation and catalytic conversion, improves catalytic degradation efficiency, and has strong stability.

Description

CdS quantum dot/MIL-101 (Cr) composite material and preparation method and application thereof
Technical Field
The application belongs to the technical field of metal organic framework materials, and particularly relates to a CdS quantum dot/MIL-101 (Cr) composite material and a preparation method and application thereof.
Background
The harm of indoor air pollution to human health in enclosed spaces such as homes, offices, and automobiles has attracted general attention throughout the society. Volatile Organic Contaminants (VOCs) such as formaldehyde, toluene and benzene are a major source of such contamination. The existing purification methods for the pollutants comprise adsorption, biological treatment, chemical treatment, catalytic oxidation, photocatalytic degradation and the like. Among them, adsorption and photocatalytic degradation are one of the more effective methods.
Metal-organic frameworks (MOFs) are multi-dimensional periodic porous network materials formed by the self-assembly process of Metal ions and organic ligands, and due to their ultra-high specific surface area and porosity, diverse and adjustable surface structures and synthetic methods become popular materials in the fields of adsorption and catalysis. The pollutants can be quickly enriched through adsorption to achieve the purpose of purification, but the pollutants are easily saturated and inactivated, and secondary pollution is easily generated while the adsorbent is regenerated through desorption.
Photocatalyst materials, e.g. CdS, TiO2Etc. decomposing and oxidizing pollutants into CO by utilizing clean and abundant solar energy2And other low-toxicity small molecules, but the existing particles have the advantages of cleanness and high efficiency due to the high aggregation property of the particles, light instability and easy recombination of photo-generated electron-hole pairsThe photocatalytic system is unstable to light, and photo-generated charges are easy to compound, so that the photocatalytic conversion efficiency is low, and the rapid purification is difficult.
Disclosure of Invention
In view of the above, the application provides a CdS quantum dot/MIL-101 (Cr) composite material and a preparation method and application thereof, and the CdS quantum dot/MIL-101 (Cr) composite material couples adsorption and photocatalysis technologies and has the advantages of high catalytic degradation efficiency and strong stability.
The specific technical scheme of the application is as follows:
the application provides a preparation method of a CdS quantum dot/MIL-101 (Cr) composite material, which comprises the following steps:
s1: preparing a mesoporous MIL-101(Cr) material by a solvothermal method;
s2: activating the mesoporous MIL-101(Cr) material in vacuum, dispersing the mesoporous MIL-101(Cr) material in an organic solvent, adding a saturated aqueous solution of Cd salt, fully stirring, performing solid-liquid separation, and drying the solid in vacuum to obtain solid powder, wherein the volume of the saturated aqueous solution of Cd salt is equal to the pore volume of the mesoporous MIL-101(Cr) material;
s3: spreading the solid powder in a simulated gas-solid fluidized bed glass reactor, and introducing pure H2And S, until the color of the solid powder is not changed any more, purifying and drying to obtain the CdS quantum dot/MIL-101 (Cr) composite material.
In the present application, MIL-101(Cr) is a material with a super tetrahedral crystal structure based on an inorganic trimer and terephthalic acid, and has good thermal and chemical stability even under high humidity conditions. The molecule has two cage-shaped pore structures and has coordination unsaturated metal Cr (III) sites, so that the molecule not only can be used as an adsorption site for reaction, but also can improve the packaging stability of the functional quantum dots. Introducing Cd source into pore channel of MIL-101(Cr) by isovolumetric impregnation method, and introducing pure H2S gas is introduced into Cd which is stably diffused into an MIL-101(Cr) pore channel at constant speed2+Active sites generate CdS semiconductor quantum dots in the MIL-101(Cr) pore channels, so that Cd is prevented from being generated in the conventional process of preparing CdS semiconductors by liquid phase reaction2+And S2-Waste due to misadjustment of the ratio, and CdSThe in-situ growth of the quantum dots in the MIL-101(Cr) pore channel also enhances the packaging stability of the quantum dots, and avoids the problems of uneven sites, easy light corrosion loss and the like caused by the introduction of CdS after the synthesis. The preparation method can be used for carrying out multiple continuous regeneration processes, and is low in energy consumption, stable and efficient.
Preferably, H is as described in S32The S gas is introduced in real time from a gas generating apparatus in which an equimolar amount of dilute H is introduced2SO4With Na2The S aqueous solution reacts at normal temperature.
In this application, H2S gas passing through H2SO4With Na2S is prepared by reaction and is led into a reaction system, namely preparation and use are realized, the cost is lower, the operation is simple and convenient, and the rapid adsorption and diffusion of the S in an MIL-101(Cr) pore channel to the pore channel and Cd can be ensured2+The reaction is carried out and fully contacted, so that the reaction is uniform and controllable.
Preferably, H is introduced as described in S32The velocity of S gas was 10mL/min for 15 min.
Preferably, the purified reagent in S3 is deionized water, and the drying condition is vacuum drying at room temperature.
Preferably, the Cd salt in S2 is a saturated aqueous solution of Cd salt, and the Cd salt is Cd (NO)3)2And the organic solvent is n-hexane.
Preferably, the dosage of the mesoporous MIL-101(Cr) material and the organic solvent is 100mg and 40mL respectively, and the dosage of the saturated aqueous solution of Cd salt is 0.22 mL.
Preferably, the stirring temperature in S2 is room temperature, and the time is 2 h;
the drying temperature in S2 is 150 ℃, and the drying time is 3 h.
Preferably, the preparation method of the mesoporous MIL-101(Cr) material in S1 comprises the following steps:
taking Cr (NO)3)3·9H2O and H2BDC is dissolved in deionized water, stirred and mixed for 30min at room temperature, then transferred to a polytetrafluoroethylene reaction kettle to react for 24h at 180 ℃, and then centrifuged, purified and dried to obtain the mesoporous MIL-101(Cr) material.
The application also provides a CdS quantum dot/MIL-101 (Cr) composite material prepared by the preparation method.
In the application, the CdS semiconductor quantum dots are grown in situ in the pore channels of MIL-101(Cr), the characteristics of the pore channel confinement of MOF and the advantages of the CdS semiconductor quantum dots can be fully exerted, and the composite material has the characteristics of high fluorescence quantum yield, strong visible light capturing capability and easy regulation and control of current carriers. The prepared composite material couples adsorption and photocatalysis technologies, can accelerate the local enrichment of Volatile Organic Compounds (VOCs) and promote the activation and catalytic conversion of a substrate; the efficient transfer of the photo-generated charges on the composite material interface also promotes light capture and light utilization, improves the catalytic degradation efficiency, has strong stability and can achieve the aim of environmental purification.
In summary, the application provides a CdS quantum dot/MIL-101 (Cr) composite material and a preparation method and application thereof. Introducing Cd source into pore channel of MIL-101(Cr) by isovolumetric impregnation method, and introducing pure H2S gas is introduced into Cd stably diffused in an MIL-101(Cr) pore channel at constant speed2+Active sites generate CdS semiconductor quantum dots in situ in MIL-101(Cr) pore channels, so that Cd is prevented from being generated in the conventional process for preparing CdS semiconductors by liquid phase reaction2+And S2-The waste caused by the imbalance of the proportion is avoided, the encapsulation stability of the CdS quantum dots is enhanced due to the in-situ growth of the CdS quantum dots in an MIL-101(Cr) pore channel, and the problems that the CdS quantum dots are not uniform in position points, easy to corrode and run off and the like caused by the introduction of the CdS quantum dots after synthesis are solved. The prepared CdS quantum dot/MIL-101 (Cr) composite material couples adsorption and photocatalysis technologies, achieves a synergistic effect, maintains a certain adsorption characteristic, can promote substrate activation and catalytic conversion, improves catalytic degradation efficiency, and has strong stability.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without inventive exercise.
FIG. 1 is a schematic view of a production apparatus in example 2 of the present application;
FIG. 2 is a PXRD spectrum of a test example of the present application;
FIG. 3 is a Raman spectrum of a test example of the present application;
FIG. 4 shows N in the test example of the present application2Adsorption isotherms and pore size distribution maps;
FIG. 5 is a graph of the UVDRS spectrum of a test example of the present application;
FIG. 6 is an XPS spectrum of a test example of the present application;
FIG. 7 is a graph comparing the performance of adsorption-photocatalytic removal of toluene in test examples of the present application;
FIG. 8 is a graph comparing TOC with toluene removal for test examples of the present application;
FIG. 9 is a graph comparing the cycle experiments for the adsorption-photocatalytic removal of toluene in the test examples of the present application.
Detailed Description
In order to make the objects, features and advantages of the present application more obvious and understandable, the technical solutions in the embodiments of the present application are clearly and completely described, and it is obvious that the embodiments described below are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The raw materials and reagents used in the examples of the present application are commercially available or self-made.
Example 1
Preparation of metal organic framework material MIL-101 (Cr):
0.078g of Cr (NO)3)3·9H2O and 0.18g H2BDC is dissolved in 20mL deionized water, stirred vigorously for 30min at room temperature, and transferred to a 25mL polytetrafluoroethylene reaction kettle after being fully mixed, and then kept stand and reacted for 24h in a constant temperature blowing dry box at 180 ℃. And after the reaction is finished, taking out the reaction kettle and naturally cooling to room temperature. Then theCentrifuging at 10000r/min for 10min, washing with deionized water to obtain supernatant. The solid product was then purified by dispersion in 25mL of DMF and stirred overnight at 60 ℃ before purification in ethanol under the same conditions as for DMF. Finally, the solid product obtained by centrifugation was dried overnight at 60 ℃ to obtain a dark green powder of MIL-101 (Cr).
Example 2
Referring to fig. 1, preparation of CdS quantum dot/MIL-101 (Cr) composite material:
(1) the MIL-101(Cr) material prepared in the example 1 is dried in vacuum for 8 hours at the temperature of 150 ℃, 100mg of MIL-101(Cr) is placed in a round-bottom flask, 40mL of n-hexane is added, and the mixture is uniformly mixed under the condition of room temperature and uniform stirring;
(2) adding Cd (NO) with the volume equal to the pore volume of MIL-101(Cr) under stirring at room temperature3)20.22mL of saturated aqueous solution is added into the solution in the step (1) dropwise, and stirring is continued for 2h after 10min of ultrasonic treatment, so that Cd (NO)3)2The saturated aqueous solution was fully immersed in the pores of MIL-101 (Cr). Then putting the solid obtained after the solid-liquid separation of the mixed solution into a vacuum oven at 150 ℃ for drying for 3h to obtain Cd2+MIL-101(Cr) solid powder; (3) uniformly spreading the solid powder obtained in the step (2) in a simulated gas-solid phase fluidized bed glass reactor, and passing through H2S gas generator (equimolar amount of Na)2S and rare H2SO4Reaction at room temperature) was slowly fed with H at a rate of 10mL/min2And (2) fully contacting the S gas (shown in figure 1) with the solid powder, continuously ventilating for about 15min until the color of the solid powder is not changed, collecting the obtained yellow-green solid powder, purifying the yellow-green solid powder for three times by using 20mL of deionized water, and then drying the yellow-green solid powder in vacuum at room temperature to obtain the CdS quantum dot/MIL-101 (Cr) composite material.
Comparative example 1
Preparing a traditional CdS semiconductor:
adding Cd (NO)3)2Saturated aqueous solution (25 ℃ C.) was placed in a flask and passed through H2S gas generator (equimolar amount of Na)2S and rare H2SO4Reaction at room temperature) was slowly passed through at a rate of 10mL/minIn excess of H2And (5) continuously ventilating the S gas for about 15min until the color of the solid powder does not change any more. And collecting the obtained yellow solid powder, purifying the yellow solid powder with 20mL of deionized water for three times, and drying the yellow solid powder at a low temperature to obtain the traditional CdS semiconductor material.
Test example
(1) Product X-ray diffraction (PXRD) analysis
X-ray diffraction analysis is carried out on the products prepared in examples 1-2 and comparative example 1, and PXRD spectrograms are shown in figure 2. FIG. 2 shows that the MIL-101(Cr) product of example 1 has good crystallinity, and the CdS QDs @ MIL-101(Cr) product of example 2 and the CdS semiconductor product of comparative example 1 have three diffraction peaks at 26.5 °, 44.0 ° and 52.1 °, which are respectively attributed to the (111), (220) and (311) crystal planes diffraction of cubic CdS, which indicates that CdS semiconductor quantum dots in the product of example 2 have been successfully introduced into the MIL-101(Cr), and the half-peak width of the diffraction peak indicates that the introduced CdS particles have small sizes. There was a slight decrease in the crystalline strength of MIL-101(Cr) in the product of example 2 compared to the product of example 1, probably due to impregnation of CdS.
(2) Raman spectroscopy (Raman) analysis
Raman spectrum analysis is carried out on the products prepared in examples 1-2 and comparative example 1 respectively, and a Raman spectrum is shown in figure 3. FIG. 3a shows that the CdS QDs @ MIL-101(Cr) product of example 2 has all the characteristic peaks of both MIL-101(Cr) and CdS semiconductors. FIG. 3b shows the CdS semiconductor product of comparative example 1 at 304.48 and 600.90cm-1The Raman bands at (A) belong to the first and second order longitudinal optical phonon (LO) modes of CdS, whereas in the LO phonon mode of CdS in the product of example 2, a slight shift in wavenumber occurred with peak centers at 299.66 and 595.63cm, respectively-1This may be related to atomic oscillations or size effects, indicating that there is an interaction between CdS and MIL-101(Cr) confined in the pore channels. At the same time, 214cm of the product of comparative example 1 can be seen-1A characteristic peak is formed, which is attributed to the multi-phonon scattering existing in the CdS, and shows that a large amount of CdS has good crystallinity; whereas no multiphoton scattering peak was observed in the raman spectrum of the product of example 2, indicating that the CdS nanoparticles confined in the MIL-101(Cr) channels have a smaller particle size. FIG. 3c showsThe characteristic peak attributed to MIL-101(Cr) in the product of example 2 almost completely matched that of MIL-101(Cr) in the product of example 1, indicating that there was no significant defect or change in the structure of MIL-101(Cr) after loading CdS nanoparticles, which is consistent with the result of PXRD.
(3) Specific surface area and pore size structure analysis
The products prepared in examples 1-2 and comparative example 1 are respectively taken for pore structure and specific surface analysis, and the products in examples 1-2 are compared with N2The adsorption-desorption curve is shown in fig. 4. FIG. 4a shows, in the low-pressure phase, the N of the MIL-101(Cr) product of example 1 and of the CdS QDs @ MIL-101(Cr) product of example 22The adsorption characteristic is very similar to that of the I-type microporous material, namely P/PoThe secondary absorptions at approximately 0.1 and 0.2 indicate the presence of two different micropores in MIL-101 (Cr). FIG. 4b shows that the pore size of MIL-101(Cr) is about 1.5nm and 2.5nm, and its N increases with increasing pressure2The adsorption also presents a hysteresis loop which is common in the mesoporous material, and the MIL-101(Cr) is a hierarchical porous material and has two pore structures of micropores and mesopores. The specific surface area and pore volume of the product of example 2 were significantly reduced compared to the product MIL-101(Cr) of example 1 (see fig. 4b and table 1 below), indicating that CdS quantum dots were successfully incorporated into MIL-101(Cr) and occupied a portion of the pore space of MIL-101 (Cr).
TABLE 1 specific surface area and pore volume of the products of examples 1-2
Figure BDA0003044175760000071
(4) Ultraviolet diffuse reflectance spectroscopy (UVDRS) analysis
And (3) respectively taking the products prepared in the examples 1-2 and the comparative example 1 for ultraviolet visible diffuse reflection spectrum analysis, wherein the UVDRS spectrogram is shown in figure 5. FIG. 5 shows that the MIL-101(Cr) product of example 1 shows strong absorption in both the UV and visible region, with two characteristic absorption bands at 450nm and 600nm, where the absorption band in the UV region is assigned to the pi-pi transition of the ligand and the Cr-O cluster, and the absorption band in the visible region is assigned to the Cr-O cluster. Comparative example 1 the product CdS semiconductor showed strong absorption only up to 500 nm. While the product CdS QDs @ MIL-101(Cr) of example 2 shows stronger light absorption in both the ultraviolet and visible regions, maintaining a certain sunlight capturing capacity, but the absorption peak at 450nm attributed to MIL-101(Cr) disappears, probably due to the overlap of the strong light absorption of CdS and the typical absorption peak of MIL-101 (Cr). In addition, the absorption edge of the product of example 2 is between that of the traditional CdS (580nm) and MIL-101(Cr) (630nm), and is about 600nm, which shows that the band gap of the composite material has certain change, and the utilization rate of visible light and the catalytic conversion efficiency are probably improved.
(5) X-ray photoelectron spectroscopy (XPS) analysis
The products prepared in examples 1-2 and comparative example 1 were respectively taken for characterization and analysis by X-ray photoelectron spectroscopy (XPS), and the UVDRS spectrogram is shown in FIG. 6. FIG. 6a shows that the binding energy of the example 2 product CdS QDs @ MIL-101(Cr) changes from 577.52eV and 587.24eV to 577.34eV and 587.06eV, respectively, with a negative shift of 0.18eV, as compared to the example 1 product MIL-101 (Cr). FIG. 6b shows that the binding energy of S2 p in the product of example 2 exhibits a positive shift of 0.11eV from 161.43eV and 162.59eV to 161.53eV and 162.68eV, respectively, as compared to CdS semiconductor as the product of comparative example 1. FIG. 6c shows that the binding energy (405.28eV and 412.0eV) of the product of example 2 is reduced by 0.08eV compared to pure CdS (405.36eV and 412.11 eV). The above results show that in the product of example 2, strong interaction exists between CdS QDs and MIL-101(Cr), and the electron density of CdS is reduced, and the CdS can be easily transferred to Cr-O clusters of MIL-101(Cr), which can greatly improve the separation efficiency of photo-generated charges in CdS quantum dots, thereby enhancing the photocatalytic activity of the composite material.
(6) Evaluation of efficiency of adsorption-photocatalysis synergistic removal of toluene
A. The toluene concentration was calibrated by gas chromatography to establish a standard curve: respectively taking 1000ppm toluene standard samples with the volumes of 0.1mL, 0.2mL, 0.5mL, 0.8mL and 1mL, testing to obtain toluene concentration data with different peak areas, measuring each sample for three times, and taking an average value to finally obtain a standard curve;
B. the product obtained in example 1-2 and the product obtained in comparative example 1, and a physical mixture [ CdS + MIL-101(Cr) ] (the mixed product of comparative example 1 and example 1, wherein the mass fraction of the product of comparative example 1 is 0.14 wt%) 10mg are placed in a glass reactor, and 50 μ L of deionized water is added (so that the deionized water is hung on the wall to avoid wetting the catalyst). Exhausting and ventilating by using a vacuum pump to fill 1000ppm of toluene gas in the closed reactor;
C. the method comprises the steps of testing the adsorption performance of a catalyst material on toluene under a dark condition, carrying out sampling test every 1h (a miniature sample injector absorbs 1mL of gaseous sample), carrying out photocatalytic test (a xenon lamp, 300W, PLS-SXE300/300UV) after adsorption for 5h reaches adsorption equilibrium, and carrying out sampling test every 2h, wherein the adsorption and photocatalytic environments are room temperature.
The comparison of the adsorption-photocatalytic removal of toluene performance is shown in fig. 7. FIG. 7 shows that the initial concentrations of gaseous toluene were 1000ppm, and the adsorption equilibrium of each product was reached in the adsorption process 5h before the light irradiation, and that both the product MIL-101(Cr) of example 1, the product CdS QDs @ MIL-101(Cr) of example 2, and the physical mixture product [ CdS + MIL-101(Cr) ] showed strong adsorption to toluene. The toluene adsorption rate of example 2 and the mixed product is slightly lower than that of the MIL-101(Cr) (58%) of the product in example 1, which is caused by the fact that CdS QDs are introduced into MIL-101(Cr) pore channels to occupy partial pore spaces, so that the adsorption amount is reduced. But the adsorption rate of the product of example 2 reached 49%, which is improved compared with the physical mixed sample (44%). After adsorption equilibrium, under visible light (lambda is more than or equal to 400nm), MIL-101(Cr) of the product of the example 1 has almost no degradation activity on toluene, the CdS semiconductor of the product of the comparative example 1 has a degradation rate of 32% in 8h, while the product of the example 2 shows the highest and fastest toluene degradation rate (up to 43%) and the total removal rate of the adsorption-photocatalytic coupling on toluene is 92%, which are respectively increased by 56%, 119% and 31% compared with MIL-101(Cr) (59%) of the product of the example 1, 42% of the product of the comparative example 1 and 70%, and show that the coupling product of the example 2 realizes synergistic effect.
The degree of mineralization of toluene was analyzed by TOC test for toluene removal (as shown in FIG. 8) and found to be 37% for the example 2 product CdS QDs @ MIL-101(Cr) versus toluene, 2 times and 1.5 times respectively for the comparative example 1 product CdS semiconductor and the physically mixed sample [ CdS + MIL-101(Cr) ] and much higher (< 1%) than for the example 1 product MIL-101 (Cr). The application of the product of example 2 in removing VOCs by adsorption-photocatalysis coupling is feasible, and the total removal rate of the adsorption-photocatalysis synergy is far higher than that of a single MIL-101(Cr) material, a CdS material and a physical mixed product of the two.
(7) Post-desorption regeneration cycle test
The materials obtained by respectively taking the products prepared in the examples 1-2 and the comparative example 1 and carrying out the toluene adsorption-photocatalytic degradation performance evaluation are placed in a vacuum oven at 100 ℃ for 12 hours, and are subjected to 3 times of cyclic experiments through desorption regeneration, and the cyclic experiments for removing toluene through adsorption-photocatalysis are shown in a comparison graph in fig. 9. FIG. 9 shows that the removal rate of toluene of MIL-101(Cr) of the product of example 1 is gradually reduced (59% is reduced to 46%), and the reduction rate of CdS semiconductor of the product of comparative example 1 is larger (42% is reduced to 20%), while the removal rate of the CdS QDs @ MIL-101(Cr) of the product of example 2 to toluene is slightly reduced (92% is reduced to 87%), but the reduction rate is not large, and is much higher than the removal rate of single MIL-101(Cr) or CdS material, and the reduction rate gradually becomes stable after three cycle experiments, which indicates that the overall stability of the composite material obtained after the CdS quantum dots are wrapped by the MIL-101(Cr) is also obviously enhanced.
The experimental results show that in the preparation method, the Cd source is introduced into the pore channel of the MIL-101(Cr) by an isometric impregnation method and then passes through the simple H2S gas instant generating device for preparing pure H2S gas is introduced into Cd which is stably diffused into an MIL-101(Cr) pore channel at constant speed2+Active sites immediately form CdS semiconductor quantum dots in situ in MIL-101(Cr) pore channels, and the prepared CdS quantum dot/MIL-101 (Cr) composite material is coupled by utilizing adsorption and photocatalysis technologies, so that a synergistic effect is realized, a certain adsorption characteristic is maintained, simultaneously, the activation and catalytic conversion of a substrate can be promoted, the catalytic degradation efficiency is improved, and the composite material has strong stability.
The above embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions in the embodiments of the present application.

Claims (10)

1. A preparation method of a CdS quantum dot/MIL-101 (Cr) composite material is characterized by comprising the following steps:
s1: preparing a mesoporous MIL-101(Cr) material by a solvothermal method;
s2: activating the mesoporous MIL-101(Cr) material in vacuum, dispersing the mesoporous MIL-101(Cr) material in an organic solvent, adding a saturated aqueous solution of Cd salt, fully stirring, performing solid-liquid separation, and drying the solid in vacuum to obtain solid powder, wherein the volume of the saturated aqueous solution of Cd salt is equal to the pore volume of the mesoporous MIL-101(Cr) material;
s3: spreading the solid powder in a simulated gas-solid fluidized bed glass reactor, and introducing pure H2And S, until the color of the solid powder is not changed any more, purifying and drying to obtain the CdS quantum dot/MIL-101 (Cr) composite material.
2. The method according to claim 1, wherein the H in S32The S gas is introduced in real time from a gas generating apparatus in which an equimolar amount of dilute H is introduced2SO4With Na2The S aqueous solution reacts at normal temperature.
3. The method according to claim 1, wherein the H is introduced into S32The velocity of S gas was 10mL/min for 15 min.
4. The method according to claim 1, wherein the purified reagent in S3 is deionized water, and the drying condition is vacuum drying at room temperature.
5. The method as claimed in claim 1, wherein the Cd salt in S2 is Cd (NO)3)2And the organic solvent is n-hexane.
6. The method of claim 1, wherein the mesoporous MIL-101(Cr) material and the organic solvent are used in an amount of 100mg and 40mL, respectively, and the saturated aqueous solution of the Cd salt is used in an amount of 0.22 mL.
7. The method according to claim 1, wherein the stirring in S2 is performed at room temperature for 2 hours;
the drying temperature in S2 is 150 ℃, and the drying time is 3 h.
8. The method according to claim 1, wherein the mesoporous MIL-101(Cr) material in S1 is prepared by:
taking Cr (NO)3)3·9H2O and H2BDC is dissolved in deionized water, stirred and mixed for 30min at room temperature, then transferred to a polytetrafluoroethylene reaction kettle to react for 24h at 180 ℃, and then centrifuged, purified and dried to obtain the mesoporous MIL-101(Cr) material.
9. A CdS quantum dot/MIL-101 (Cr) composite material, which is prepared by the preparation method of any one of claims 1-8.
10. The CdS quantum dot/MIL-101 (Cr) composite material prepared by the preparation method of any one of claims 1-8 or the application of the CdS quantum dot/MIL-101 (Cr) composite material of claim 9 in removing volatile organic compounds.
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Application publication date: 20210706