CN113600211A - High specific surface area fine framework ZnS photocatalytic material and preparation method thereof - Google Patents
High specific surface area fine framework ZnS photocatalytic material and preparation method thereof Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract
The invention relates to a high specific surface area fine framework ZnS photocatalytic material and a preparation method thereof. The method is characterized in that: is formed by cubic periodic arrangement of ZnS spiral nano wires. The ZnS photocatalytic material of the invention has the advantages that: 1) the material is unique, the ordered mesoporous ZnS is a mesoscopic structure which takes a large mesopore with the aperture of about 11nm as a main part, the large mesopore is favorable for the transmission of molecules, a fine skeleton with the diameter of 4-8nm is favorable for the migration of photo-generated electrons and holes, and the high specific surface area can provide more surface active sites. 2) The thermal stability is enhanced: the material provided by the invention has a three-dimensional self-supporting structure, large mesopores of about 11nm are formed among the nanowires, so that the mutual contact among the nanowires is reduced, the sensitivity reduction caused by sintering phenomenon at high temperature and specific surface area loss can be reduced, and the thermal stability is enhanced; 3) the photocatalytic performance is improved.
Description
Technical Field
The invention relates to a high specific surface area fine framework ZnS photocatalytic material and a preparation method thereof.
Background
With the development of the global society and the acceleration of the industrialization process, people can cause serious pollution to the environment while making wealth, a large amount of toxic, harmful and difficult-to-degrade pollutants are discharged into the environment, water body pollution is directly or indirectly caused, and the ecological environment and the human body health are seriously threatened. Therefore, the search for a method for treating wastewater with high efficiency is receiving wide attention from various scholars. Besides adsorption, the photocatalytic degradation technology can also effectively remove organic pollutants in the wastewater. Has the advantages of no secondary pollution and low energy consumption, and can fundamentally remove organic pollutants.
In the catalysis process of the semiconductor photocatalyst, when the energy irradiated on the material is higher than the band gap energy of the forbidden band width of the semiconductor photocatalyst, electrons on the valence band can be excited to jump into the conduction band to generate corresponding electron-hole pairs, wherein the holes have extremely strong electron capturing capacity, can form strong oxidizing OH free radicals under the action of water and dissolved oxygen, have enough capacity to destroy C-N, C-O, C-S bonds and the like in organic pollutants, decompose macromolecular organic matters such as antibiotics (such as tetracycline, ofloxacin, norfloxacin, ciprofloxacin and the like), organic dyes (MB, RhB) and the like into small molecular substances, and further convert the small molecular substances into CO2And H2O, and the like. Among numerous semiconductor photocatalysts, the speed of generating photo-generated electrons and holes by photo-excitation of nano ZnS is high, the excited electrons have strong reducing capability when jumping from a conduction band to a valence band of the ZnS, and the strong oxidizing capability of the photo-generated holes enables the photo-generated holes to be shown in the aspect of photo-catalytic oxidation of pollutantsThe ZnS is an important metal chalcogenide semiconductor material and has the advantages of safety, no toxicity, low price, easy obtainment, excellent photocatalytic performance and the like. The performance of the ZnS nano material is related to the mesostructure of the ZnS nano material, the ZnS nano material with excellent performance can be obtained by controlling the structure and the shape, and the relation among the shape, the structure and the performance of the ZnS nano material is explored, so that the ZnS nano material has important significance for further development of the ZnS nano material.
Disclosure of Invention
One of the purposes of the invention is to provide a ZnS photocatalytic material with a high specific surface area and a fine framework, which can enhance the thermal stability and remarkably improve the photocatalytic degradation performance of the material.
The second purpose of the present invention is to provide a method for preparing the above material.
A ZnS photocatalytic material with high specific surface area and fine skeleton is characterized in that: is formed by cubic periodic arrangement of ZnS spiral nano wires.
The thin framework of 4-8nm in the ZnS spiral nanowire has a three-dimensional self-supporting structure.
The ZnS spiral nanowires have large mesopores of 10-12 nm.
The specific surface area of the material is 204-154m2Per g, pore diameter of 10-12nm and pore volume of 1.2-0.9cm3g-1The size of the skeleton is 4-8 nm.
A preparation method of a ZnS photocatalytic material with a high specific surface area and a fine framework is characterized by comprising the following steps:
(a) mixing 72g of surfactant P123, 2.6L of deionized water and 120ml of concentrated hydrochloric acid at 35 ℃, stirring for 12 hours until the surfactant P123 is completely dissolved and uniformly dispersed, then adding 72g of n-butyl alcohol, stirring for 2 hours, adding 154.8g of tetraethoxysilane TEOS, stirring for 24 hours, transferring to a polytetrafluoroethylene bottle, carrying out hydrothermal reaction for 24 hours at 40 ℃, naturally cooling, carrying out suction filtration, washing with deionized water to be neutral, and naturally drying at room temperature to obtain mesoporous silicon oxide containing the surfactant;
(b) calcining the mesoporous silica containing the surfactant obtained in the step (a) for 6 hours at 550 ℃ in the air to remove the surfactant P123, thus obtaining a mesoporous silica template without the surfactant, namely a KIT-6-40 template;
(c) weighing 0.454g of ZnSO4·7H2Adding O precursor into polytetrafluoroethylene lining, adding 2g deionized water to the O precursor to obtain ZnSO4·7H2Completely dissolving the O precursor, adding 2g of KIT-6-40 template obtained in the step (b), and uniformly mixing, so that the KIT-6-40 template is completely ZnSO4·7H2Soaking the O precursor mixed solution, transferring the mixture of the precursor and the template into a blast oven at the temperature of 80 ℃ for drying for 12h, transferring into a quartz crucible, heating to 300-500 ℃ at the speed of 1-2.5 ℃/min under the condition of hydrogen for calcining, preserving heat for 2-5h, switching hydrogen into nitrogen after heat preservation, and naturally cooling;
(d) adding 200ml of NaOH into the obtained product, reacting for 1h, centrifuging, pouring out supernatant, adding 150ml of NaOH, reacting for 12h, finally adding 100ml of NaOH, reacting for 1h, washing with deionized water to be neutral, and drying at 70 ℃.
The ratio of the volume of the zinc sulfate precursor to the pore volume of the mesoporous silica in the step (c) is 0.2-0.8:1, the calcining temperature of the sulfate is 500 ℃, the heating rate is 2 ℃/min, and the heat preservation is carried out for 3 h.
The concentration of all NaOH solutions in step (d) was 2M.
The ZnS photocatalytic material of the invention has the advantages that:
1) the material is unique, the ordered mesoporous ZnS is a mesoscopic structure which takes a large mesopore with the aperture of about 11nm as a main part, the large mesopore is favorable for the transmission of molecules, a fine skeleton with the diameter of 4-8nm is favorable for the migration of photo-generated electrons and holes, and the high specific surface area can provide more surface active sites.
2) The thermal stability is enhanced: the material provided by the invention has a three-dimensional self-supporting structure, large mesopores of about 11nm are formed among the nanowires, so that the mutual contact among the nanowires is reduced, the sensitivity reduction caused by sintering phenomenon at high temperature and specific surface area loss can be reduced, and the thermal stability is enhanced;
3) the photocatalytic performance is improved: the invention realizes the regulation and control of the mesostructure of the material by regulating and controlling the filling proportion of the precursor, improves the photocatalytic degradation performance of the material, and achieves the degradation of norfloxacin up to 99 percent.
Drawings
FIG. 1 is a wide-angle XRD spectrum of ordered mesoporous ZnS-40-20% obtained in example 1;
FIG. 2 is a small-angle XRD pattern of the ordered mesoporous ZnS-40-20% obtained in example 1;
FIG. 3 shows that the N content of the ordered mesoporous ZnS-40-20% obtained in example 12A physical adsorption-desorption curve;
FIG. 4 is a graph showing the pore size distribution of the ordered mesoporous ZnS-40-20% obtained in example 1;
FIG. 5 is a transmission electron microscope of the ordered mesoporous ZnS-40-20% obtained in example 1;
FIG. 6 is a graph showing the performance of the ordered mesoporous ZnS-40-20% adsorption degradation norfloxacin obtained in example 1;
FIG. 1 shows that the diffraction peak position and intensity of the wide-angle XRD pattern of the ordered mesoporous ZnS-40-20% obtained in example 1 are consistent with those of the standard pattern of ZnS, which indicates that the prepared sample is pure phase ZnS and has no impurities. FIG. 2 shows that the small-angle XRD patterns of the ordered mesoporous ZnS-40-20% obtained in example 1 have diffraction peaks (110) and (211), which indicate that the material well replicates the highly ordered mesoporous structure Ia3d of KIT-6-40 template, and is a highly ordered mesoporous material. FIG. 3 shows that the N content of the ordered mesoporous ZnS-40-20% obtained in example 12The physical adsorption-desorption curve shows that ZnS-40-20% relative pressure P/P0Capillary coagulation occurs in the range of 0.8-1.0, with hysteresis rings of the H1 type (IUPAC classification) being typical of mesoporous materials. FIG. 4 is a graph of the pore size distribution of the ordered mesoporous ZnS-40-20% obtained in example 1, and it can be seen that the pore size distribution of the material is mainly concentrated around 11 nm. FIG. 5 is a transmission electron microscope of the ordered mesoporous ZnS-40-20% obtained in example 1, from which it can be clearly seen that the material has ordered large mesopores with a pore diameter of about 11 nm; FIG. 6 is a graph showing the performance curve of the ordered mesoporous ZnS-40-20% adsorption degradation norfloxacin obtained in example 1, wherein ZnS-40-20% has a large specific surface area (204 m)2Per gram) and more catalytic active sites, has certain adsorption effect on norfloxacin molecules, the adsorption rate reaches 20.7 percent, and the pore volume is large (1.063 cm)3The/g) and the pore diameter (11.6nm) are favorable for the catalysis of norfloxacin moleculesThe transportation in the agent and the framework size (4nm) are favorable for the migration of photoproduction electrons and holes, the performance of ZnS-40-20% of norfloxacin solution photocatalytic degradation is improved, and the degradation rate of 100ml of norfloxacin solution with 20mg/l can reach 99% after the norfloxacin solution is catalytically degraded for 60min under ultraviolet light.
Detailed Description
The invention relates to a preparation method of a high-specific surface area and fine skeleton ordered mesoporous ZnS material, which takes mesoporous silica as a template and firstly prepares the mesoporous silica template by a soft template method at 40 ℃; then ZnSO is caused to flow by capillary action4·7H2The O precursor enters a pore channel of the mesoporous template and is calcined at high temperature under the atmosphere of hydrogen to form sulfide; and finally, removing the silica template by using a NaOH solution with a certain concentration, and washing the silica template by using deionized water until the silica template is neutral to obtain the ordered mesoporous ZnS. By taking the material as a photocatalyst and carrying out a norfloxacin photocatalytic degradation experiment under ultraviolet light, the degradation rate can reach 99%.
The invention provides a preparation method of a mesoporous ZnS material with high specific surface area, fine skeleton and three-dimensional order.
The invention is realized by the following modes:
a high specific surface area, thin skeleton order big mesopore ZnS photocatalysis material, the photocatalysis material is formed by ZnS spiral nano wire cubic periodicity arrangement, ZnS thin skeleton (4-8nm) forms three-dimensional self-supporting structure, big mesopore about 10-12nm is between the nano wires; specific surface area 204-2/g。
A preparation method of a ZnS photocatalytic material with high specific surface area, fine skeleton and ordered large mesopores comprises the following steps:
a) mixing 72g of surfactant P123, 2.6L of deionized water and 120ml (37%) of concentrated hydrochloric acid at 35 ℃, stirring for 12 hours until the surfactant is completely dissolved and uniformly dispersed, then adding 72g of n-butyl alcohol, stirring for 2 hours, adding 154.8g of tetraethoxysilane TEOS, stirring for 24 hours, transferring to a polytetrafluoroethylene bottle, carrying out hydrothermal reaction at 40 ℃ for 24 hours, naturally cooling, carrying out suction filtration, washing with deionized water to be neutral, and naturally drying at room temperature to obtain the mesoporous silica containing the surfactant;
b) removing the obtained sample surfactant P123 by calcining at 550 ℃ in the air for 6 hours to obtain a mesoporous silica template KIT-6-40 without the surfactant;
c) respectively weighing 0.454g of ZnSO4·7H2And (3) putting the O precursor into a polytetrafluoroethylene lining, adding 2g of deionized water to completely dissolve the precursor, adding 2g of KIT-6-40 template, and uniformly mixing to enable the KIT-6-40 template to be completely soaked by the precursor mixed solution. The mixture of precursor and template was transferred to a forced air oven for drying at 80 ℃ for 12 h. Transferring the dried sample into a quartz crucible, heating to 500 ℃ at the speed of 2 ℃/min under the condition of hydrogen, calcining at high temperature, preserving heat for 3h, and switching hydrogen into nitrogen to naturally cool after heat preservation is finished.
d) Adding 200ml NaOH into the calcined product, reacting for 1h, centrifuging, pouring out the supernatant, reacting for 12h with 150ml NaOH, and finally reacting for 1h with 100ml NaOH. Washing the obtained product with deionized water to neutrality, and drying the product at 70 ℃ to obtain the ordered mesoporous ZnS material of the invention. The NaOH concentration was 2M. The specific surface area of the material is 204m2G, pore volume 1.063cm3G, pore diameter of 11.6 nm.
The ratio of the volume of the zinc sulfate precursor in the steps c) and d) to the pore volume of the mesoporous silica is 0.2-0.8:1, the calcining temperature of the sulfate is 300-500 ℃, the heating rate is 1-2.5 ℃/min, and the calcining time is 2-5 h;
the invention is further illustrated by the following examples:
example 1:
mixing 72g of surfactant P123, 2.6L of deionized water and 120ml (37%) of concentrated hydrochloric acid at 35 ℃, stirring for 12 hours until the surfactant P123 is completely dissolved and uniformly dispersed, then adding 72g of n-butyl alcohol, stirring for 2 hours, adding 154.8g of tetraethoxysilane TEOS, stirring for 24 hours, transferring to a polytetrafluoroethylene bottle, carrying out hydrothermal reaction at 40 ℃ for 24 hours, naturally cooling, carrying out suction filtration, washing with deionized water to be neutral, and naturally drying at room temperature to obtain mesoporous silica containing the surfactant; removing the surfactant P123 in the sample by calcining at 550 ℃ in the air for 6h to obtain a mesoporous silica template without the surfactant, namely a KIT-6-40 template. The specific surface area of the obtained ordered mesoporous silica is 687m2Per g, pore volume 0.65cm3Per g, pore size is about 4.4 nm.
Weighing 0.454g of ZnSO4·7H2And (3) putting the O precursor into a polytetrafluoroethylene lining, adding 2g of deionized water to completely dissolve the precursor, adding 2g of the KIT-6-40 template, and uniformly mixing to enable the KIT-6-40 template to be completely soaked by the precursor mixed solution. The mixture of precursor and template was transferred to a forced air oven for drying at 80 ℃ for 12 h. Transferring the dried sample into a quartz crucible, heating to 500 ℃ at the speed of 2 ℃/min under the condition of hydrogen, calcining at high temperature, keeping the temperature for 3h, and switching hydrogen into nitrogen to naturally cool after the heat preservation is finished.
200ml of 2M NaOH is added into the calcined product to react for 1 hour, the supernatant is removed by centrifugation, 150ml of 2M NaOH is used for reaction for 12 hours, and finally 100ml of 2M NaOH is used for reaction for 1 hour. Washing the obtained product with deionized water to neutrality, and drying the product at 70 ℃ to obtain the ordered mesoporous ZnS material of the invention. The specific surface area of the material is 204m2G, pore volume 1.063cm3G, framework size of 4nm and pore diameter of 11.6 nm.
Example 2:
72g of surfactant P123, 2.6L of deionized water and 120ml (37%) of concentrated hydrochloric acid are mixed at 35 ℃, stirred for 12 hours until the surfactant is completely dissolved and uniformly dispersed, then 72g of n-butyl alcohol is added, after stirring for 2 hours, 154.8g of tetraethoxysilane TEOS is added, after stirring for 24 hours, the mixture is transferred into a polytetrafluoroethylene bottle, then hydrothermal reaction is carried out for 24 hours at 40 ℃, after natural cooling, the mixture is filtered, washed by deionized water to be neutral, and naturally dried at room temperature, thus obtaining the mesoporous silica containing the surfactant; and (3) removing the surfactant P123 of the sample by calcining at 550 ℃ in the air for 6h to obtain the mesoporous silica template KIT-6-40 without the surfactant. The specific surface area of the obtained ordered mesoporous silica is 687m2Per g, pore volume 0.65cm3Per g, pore size is about 4.4 nm.
Weighing 1.3620g of ZnSO4·7H2Putting the precursor O into the polytetrafluoroethylene lining, adding 2g of deionized water to completely dissolve the precursor, adding 2g of KIT-6-40 template, and uniformly mixing to ensure that the KIT-6-40 template is completely mixed by the precursorAnd soaking the mixed solution. The mixture of precursor and template was transferred to a forced air oven for drying at 80 ℃ for 12 h. Transferring the dried sample into a quartz crucible, heating to 500 ℃ at the speed of 2 ℃/min under the condition of hydrogen, calcining at high temperature, preserving heat for 3h, and switching hydrogen into nitrogen to naturally cool after heat preservation is finished.
200ml of 2M NaOH is added into the calcined product to react for 1 hour, the supernatant is centrifuged off, 150ml of 2M NaOH is used for reaction for 12 hours, and finally 100ml of 2M NaOH is used for reaction for 1 hour. Washing the obtained product with deionized water to neutrality, and drying the product at 70 ℃ to obtain the ordered mesoporous ZnS material of the invention. The specific surface area of the material is 189m2G, pore volume 1.17cm3G, the size of the framework is 5nm, and the pore diameter is 11.2 nm.
Example 3:
72g of surfactant P123, 2.6L of deionized water and 120ml (37%) of concentrated hydrochloric acid are mixed at 35 ℃, stirred for 12 hours until the surfactant is completely dissolved and uniformly dispersed, then 72g of n-butyl alcohol is added, after stirring for 2 hours, 154.8g of tetraethoxysilane TEOS is added, after stirring for 24 hours, the mixture is transferred into a polytetrafluoroethylene bottle, then hydrothermal reaction is carried out for 24 hours at 40 ℃, after natural cooling, the mixture is filtered, washed by deionized water to be neutral, and naturally dried at room temperature, thus obtaining the mesoporous silica containing the surfactant; and (3) removing the surfactant P123 of the sample by calcining at 550 ℃ in the air for 6h to obtain the mesoporous silica template KIT-6-40 without the surfactant. The specific surface area of the obtained ordered mesoporous silica is 687m2Per g, pore volume 0.65cm3Per g, pore size is about 4.4 nm.
Weighing 1.816g of ZnSO4·7H2And (3) putting the O precursor into a polytetrafluoroethylene lining, adding 2g of deionized water to completely dissolve the precursor, adding 2g of KIT-6-40 template, and uniformly mixing to enable the KIT-6-40 template to be completely soaked by the precursor mixed solution. The mixture of precursor and template was transferred to a forced air oven for drying at 80 ℃ for 12 h. Transferring the dried sample into a quartz crucible, heating to 500 ℃ at the speed of 2 ℃/min under the condition of hydrogen, calcining at high temperature, preserving heat for 3h, and switching hydrogen into nitrogen to naturally cool after heat preservation is finished.
Adding 200ml 2M NaOH into the calcined product seed, reacting for 1h, centrifuging to remove supernatant, reacting with 150ml2M NaOH for 12h, and reactingThe reaction was carried out with 100ml of 2M NaOH for 1 h. Washing the obtained product with deionized water to neutrality, and drying the product at 70 ℃ to obtain the ordered mesoporous ZnS material of the invention. The specific surface area of the material is 154m2G, pore volume 0.99cm3G, framework size 7nm, pore diameter 11.7 nm.
Claims (7)
1. A high specific surface area fine skeleton ZnS photocatalytic material is characterized in that: is formed by cubic periodic arrangement of ZnS spiral nano wires.
2. The high specific surface area fine framework ZnS photocatalytic material as claimed in claim 1, characterized by: the thin framework of 4-8nm in the ZnS spiral nanowire has a three-dimensional self-supporting structure.
3. The high specific surface area fine framework ZnS photocatalytic material as claimed in claim 1, characterized by: the ZnS spiral nanowires have large mesopores of 10-12 nm.
4. The high specific surface area fine framework ZnS photocatalytic material as claimed in claim 1, characterized by: the specific surface area of the material is 204-154m2Per g, pore diameter of 10-12nm and pore volume of 1.2-0.9cm3g-1The size of the skeleton is 4-8 nm.
5. A preparation method of a ZnS photocatalytic material with a high specific surface area and a fine framework is characterized by comprising the following steps:
(a) mixing 72g of surfactant P123, 2.6L of deionized water and 120ml of concentrated hydrochloric acid at 35 ℃, stirring for 12 hours until the surfactant P123 is completely dissolved and uniformly dispersed, then adding 72g of n-butyl alcohol, stirring for 2 hours, adding 154.8g of tetraethoxysilane TEOS, stirring for 24 hours, transferring to a polytetrafluoroethylene bottle, carrying out hydrothermal reaction for 24 hours at 40 ℃, naturally cooling, carrying out suction filtration, washing with deionized water to be neutral, and naturally drying at room temperature to obtain mesoporous silicon oxide containing the surfactant;
(b) calcining the mesoporous silica containing the surfactant obtained in the step (a) for 6 hours at 550 ℃ in the air to remove the surfactant P123, thus obtaining a mesoporous silica template without the surfactant, namely a KIT-6-40 template;
(c) weighing 0.454g of ZnSO4·7H2Adding O precursor into polytetrafluoroethylene lining, adding 2g deionized water to the O precursor to obtain ZnSO4·7H2Completely dissolving the O precursor, adding 2g of KIT-6-40 template obtained in the step (b), and uniformly mixing, so that the KIT-6-40 template is completely ZnSO4·7H2Soaking the O precursor mixed solution, transferring the mixture of the precursor and the template into a blast oven at the temperature of 80 ℃ for drying for 12h, transferring into a quartz crucible, heating to 300-500 ℃ at the speed of 1-2.5 ℃/min under the condition of hydrogen for calcining, preserving heat for 2-5h, switching hydrogen into nitrogen after heat preservation, and naturally cooling;
(d) adding 200ml of NaOH into the obtained product, reacting for 1h, centrifuging, pouring out supernatant, adding 150ml of NaOH, reacting for 12h, finally adding 100ml of NaOH, reacting for 1h, washing with deionized water to be neutral, and drying at 70 ℃.
6. The method for preparing the high specific surface area fine-skeleton ZnS photocatalytic material as claimed in claim 5, wherein: the ratio of the volume of the zinc sulfate precursor to the pore volume of the mesoporous silica in the step (c) is 0.2-0.8:1, the calcining temperature of the sulfate is 500 ℃, the heating rate is 2 ℃/min, and the heat preservation is carried out for 3 h.
7. The method for preparing the high specific surface area fine-skeleton ZnS photocatalytic material as claimed in claim 5, wherein: the concentration of all NaOH solutions in step (d) was 2M.
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