CN113600220B - High-load dispersion NiS photocatalytic degradation material of carbon nitride and preparation method thereof - Google Patents
High-load dispersion NiS photocatalytic degradation material of carbon nitride and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 82
- 238000013033 photocatalytic degradation reaction Methods 0.000 title claims abstract description 43
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000006185 dispersion Substances 0.000 title abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000011068 loading method Methods 0.000 claims abstract description 10
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 80
- 239000000203 mixture Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000377 silicon dioxide Substances 0.000 claims description 40
- 239000004094 surface-active agent Substances 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 31
- 229910021641 deionized water Inorganic materials 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 31
- 239000011148 porous material Substances 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 16
- -1 polytetrafluoroethylene Polymers 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 11
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 9
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims description 9
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 4
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- 238000000034 method Methods 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 16
- 238000006731 degradation reaction Methods 0.000 description 16
- 230000007935 neutral effect Effects 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 4
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- 231100000719 pollutant Toxicity 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- 238000003912 environmental pollution Methods 0.000 description 2
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- 238000001179 sorption measurement Methods 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
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- 150000004687 hexahydrates Chemical class 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01J35/39—
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- B01J35/394—
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- B01J35/615—
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention relates to a carbon nitride high-load dispersed NiS photocatalytic degradation material and a preparation method thereof. The method is characterized in that: is obtained by taking S-doped ordered mesoporous carbon nitride as a base and loading nickel sulfide with different mass fractions. According to the invention, the NiS promoter is further loaded on the basis of the S-doped carbon nitride material, so that not only can the separation of carriers be improved by doping, but also the high loading capacity of the NiS promoter can be ensured by utilizing a larger specific surface area, and the photocatalytic degradation performance of the material is further improved by a high-dispersion loading and ordered three-dimensional structure.
Description
Technical Field
The invention relates to a carbon nitride high-load dispersed NiS photocatalytic degradation material and a preparation method thereof.
Background
The long-term use of fossil energy causes irreparable damage to natural environment, such as ozone void occurrence, greenhouse effect, etc. Fossil energy is a non-renewable energy source, and thus new, clean energy forms that can replace fossil energy are developed, reducing damage to the environment, and realizing sustainable development is urgent (Service R f.is It Time to Shoot forthe Sun. Environmental pollution is not only limited to atmospheric pollution, but also water pollution is increasingly serious. The degradation problem of antibiotics and other medical components with the content exceeding the standard in the water body is needed to be solved. For this reason, we propose to eliminate organic pollutants in the water body in a photocatalytic degradation way. Solar energy plays a vital role in the survival and development of terrestrial organisms, is abundant in resources and easy to obtain, and provides a new idea for solving the problem of environmental pollution. The photocatalysis is energy-saving and environment-friendly, has mild reaction conditions, high efficiency and simple and convenient operation method, and has wide application in the aspects of energy storage, degradation, medical treatment and the like. The single semiconductor photocatalyst has the defects of poor visible light response, easiness in recombination of photo-generated electron-hole pairs and the like, and has low efficiency in photocatalytic degradation of pollutants, so that the development of a novel composite nano material is important for photocatalytic degradation of pollutants.
Disclosure of Invention
The invention aims to provide a high-load dispersed NiS photocatalytic degradation material for carbon nitride, which can further improve the photocatalytic degradation performance of the material, and particularly greatly improves the photocatalytic performance of graphite-phase carbon nitride;
the second object of the present invention is to provide a method for preparing the above material.
A carbon nitride high-load dispersed NiS photocatalytic degradation material is characterized in that: is obtained by taking S-doped ordered mesoporous carbon nitride as a base and loading nickel sulfide with different mass fractions.
Wherein the nickel sulfide with different mass fractions is specifically 0.3%, 1%, 3%, 5% or 10% nickel sulfide.
The preparation method of the carbon nitride high-load dispersed NiS photocatalytic degradation material is characterized by comprising the following steps of:
(a) Mixing 7.2g of surfactant P123, 260mL of water and 1.2mL of concentrated hydrochloric acid at 35 ℃, stirring for 12 hours until the surfactant P123 is completely dissolved and uniformly dispersed, then adding 7.2g of n-butanol, stirring for 2 hours, adding 15.48g of tetraethyl orthosilicate TEOS, stirring for 24 hours, transferring to a polytetrafluoroethylene bottle after suction filtration, carrying out hydrothermal reaction for 24 hours at 40 ℃ in a baking oven, carrying out suction filtration and washing to neutrality by deionized water after natural cooling, and drying at 70 ℃ overnight to obtain mesoporous silica containing the surfactant;
(b) Calcining the mesoporous silica containing the surfactant obtained in the step (a) in a muffle furnace at 550 ℃ for 6 hours, and removing the surfactant P123 to obtain the mesoporous silica without the surfactant;
(c) Adding 2.3794g of 50% aqueous solution of cyanamide into a polytetrafluoroethylene lining, adding 2g of mesoporous silica without a surfactant obtained in the step (b) as a hard template, adding 30mL of absolute ethyl alcohol, stirring at 40 ℃ until the mixture is dried, capping, calcining at 550 ℃ for 4 hours in air, and controlling the calcining heating rate to be 2 ℃/min;
(d) To the calcined product was added 100mL of 2M NH 4 HF 2 Stirring the solution for 2 hours, centrifuging, washing with deionized water to neutrality so as to remove the mesoporous silica template, and obtaining the ordered mesoporous carbon nitride material;
(e) Adding 10mL of triethanolamine, 100mL of deionized water and 0.0062g of sodium sulfide nonahydrate into a photocatalytic degradation reactor, uniformly stirring, adding 50mg of the ordered mesoporous carbon nitride material obtained in the step (d), adding 256.7uL of 0.1mol/L nickel chloride hexahydrate after uniformly mixing, finally vacuumizing, illuminating for 20min, taking out the reactor, centrifuging, and washing with water.
The specific surface area 292m of the ordered mesoporous carbon nitride material obtained in the step (d) 2 Per gram, pore volume 0.48cm 3 /g。
The volume ratio of the total volume of the cyanamide and the thiourea to the mesoporous silica in the step (c) is 0.8:1.
In the step (e), the mass ratio of the NiS to the ordered mesoporous carbon nitride is 0.3-10 percent to 1.
According to the invention, the NiS promoter is further loaded on the basis of the S-doped carbon nitride material, so that not only can the separation of carriers be improved by doping, but also the high loading capacity of the NiS promoter can be ensured by utilizing a larger specific surface area, and the photocatalytic degradation performance of the material is further improved by a high-dispersion loading and ordered three-dimensional structure.
The NiS photocatalytic degradation material has the following advantages:
1) The material is unique, the S-doped ordered mesoporous carbon nitride loaded by the NiS has a mesoscopic structure mainly comprising small mesopores with the pore diameter of about 3.5nm, and the high specific surface area can provide more sites to load more NiS.
2) The high-load dispersed NiS photocatalytic degradation material with the large specific surface area S doped with the carbon nitride increases the absorption wavelength of the S doped ordered mesoporous carbon nitride from about 600nm to about 720nm due to the load of the NiS, and the material has the effect of enhancing the response to visible light, thereby promoting the photocatalytic degradation reaction.
3) The material provided by the invention can still maintain the ordered structure and the high specific surface area when the amount of the NiS load reaches 10% due to the high specific surface area;
4) The high-load dispersed NiS material with the large specific surface area S doped with the carbon nitride has the advantages that due to the high specific surface area and high dispersion of the cocatalyst NiS, the photocatalytic performance of the graphite-phase carbon nitride is greatly improved, the degradation rate of the graphite-phase carbon nitride can reach 91% after 30min illumination, and the degradation rate of the graphite-phase carbon nitride can reach 98.90% after 1h illumination.
Drawings
FIG. 1 is an X-ray diffraction chart of a high-load dispersed NiS material with a large specific surface area S doped with carbon nitride obtained in example 3;
FIG. 2 is a graph of pore distribution of the high specific surface area S-doped carbon nitride high load dispersed NiS material obtained in example 3;
FIG. 3 is a TEM image of the large specific surface area S-doped carbon nitride high load dispersed NiS material obtained in example 3, with a scale of 500nm;
FIG. 4 is a graph showing the photocatalytic degradation performance of the S-doped carbon nitride high-load dispersed NiS material with a large specific surface area obtained in example 3;
fig. 5 is a schematic diagram showing degradation of rhodamine B by photocatalytic degradation of S-doped carbon nitride and bulk carbon nitride after loading NiS.
As can be seen from fig. 1, diffraction peaks occur at about 13 ° and 27 ° of the wide-angle XRD diffraction pattern of the inventive material, which is a characteristic peak of graphite-phase carbon nitride; whereas the diffraction peaks of NiS are not shown in fig. 1, i.e. the NiS loaded by the present method is amorphous or undetected due to a low NiS loading. FIG. 2 is a graph showing pore size distribution of the material of the present invention. From the graph, the pore diameter of the material is mainly distributed at about 3.5nm, and a set of large mesopores at about 10nm are arranged. FIG. 3 is a transmission electron microscope image of the material of the present invention, and can be seen to show the regular ordered mesoporous structure of the material at a scale of 500 nm. Fig. 4 is a degradation curve of rhodamine B in the photocatalytic degradation of the material, and it can be seen that the concentration of rhodamine B in the dark adsorption stage is slow, and after entering the photocatalytic stage, the absorbance of the pollutant is fast reduced to finally reach 98.90%, which indicates that the material of the invention has good effect and fast degradation rate on rhodamine, and is a good material for photocatalytic degradation of rhodamine B. Fig. 5 shows degradation conditions of the S-doped carbon nitride and bulk carbon nitride photocatalytic degradation rhodamine B after NiS loading, and the figure shows that the material has better performance than bulk carbon nitride in both dark adsorption and photodegradation stages, the degradation degree is advanced compared with bulk carbon nitride, and the degradation rate is obviously due to bulk carbon nitride (bulk carbon nitride 1h degradation 25% and material 1h degradation 98.90%).
Detailed Description
The invention relates to a preparation method of a high-load dispersed NiS photocatalytic degradation material with a large specific surface S-doped carbon nitride, which comprises the steps of taking mesoporous silica as a template, and firstly preparing the mesoporous silica template at 40 ℃ by using a soft template method; then, fully and uniformly stirring a cyanamide aqueous solution (50 percent), a thiourea precursor and mesoporous silica at a certain temperature; secondly, calcining in an air atmosphere; and removing the silicon dioxide template by using ammonium bifluoride solution with a certain concentration to obtain the required ordered mesoporous carbon nitride. And then on a photocatalytic degradation performance evaluation device, adding sodium sulfide nonahydrate and nickel chloride hexahydrate, and performing photo-deposition to synthesize the S-doped carbon nitride high-load dispersed NiS photocatalytic degradation material with a large specific surface.
The invention provides a high-load dispersed NiS photocatalytic degradation material with a large specific surface area S-doped carbon nitride and a preparation method thereof. The material still maintains the high specific surface area and structural order under high load, and has excellent performance in photocatalytic degradation, the degradation rate of light irradiation for 30min can reach 91%, and the degradation rate of light irradiation for 1h can reach 98.90%. I.e. the material can reach a high degradation level rapidly.
The high-load dispersed NiS photocatalytic degradation material with the large specific surface area S doped with the carbon nitride and the preparation method thereof are characterized by comprising the following steps:
a) 7.2g of surfactant P123, 260mL of water and 1.2mL of concentrated hydrochloric acid (37%) are mixed at 35 ℃ and stirred for 12 hours until the surfactant is completely dissolved and uniformly dispersed, then 7.2g of n-butanol is added, after stirring for 2 hours, 15.48g of tetraethyl orthosilicate TEOS is added, after stirring for 24 hours, the mixture is filtered by suction and transferred to a polytetrafluoroethylene bottle, subjected to hydrothermal reaction at 40 ℃ in an oven for 24 hours, and after natural cooling, filtered by suction and washed to be neutral by deionized water. Drying overnight at 70 ℃ to obtain mesoporous silica containing surfactant;
b) Calcining the sample obtained in the last step in a muffle furnace at 550 ℃ for 6 hours to remove the surfactant P123, thereby obtaining mesoporous silica without the surfactant;
c) 2.3794g of cyanamide aqueous solution (50%) and 1.3085g of thiourea are taken and put in a polytetrafluoroethylene lining, 4g of mesoporous silica is added as a hard template, 40mL of absolute ethyl alcohol is added, stirring is carried out at 40 ℃ until the mixture is dried, the mixture is covered by a crucible cover and then calcined at 550 ℃ for 4 hours in air, and the calcining heating rate is 2 ℃/min;
d) 200mL of 2M NH was added to the calcined product 4 HF 2 The solution was stirred at 400r/min for 2h and centrifuged and washed with deionized water to neutrality to remove mesoporous silica template. Thus obtaining the ordered mesoporous carbon nitride material. The specific surface area of the material 292m 2 Per gram, pore volume 0.48cm 3 /g。
e) Adding 10mL of triethanolamine, 100mL of deionized water and 0.0062g of sodium sulfide nonahydrate into a photocatalytic degradation reactor, stirring uniformly, adding 50mg of the S-doped ordered mesoporous carbon nitride material into the mixture, and rapidly adding 256.7uL of nickel chloride hexahydrate (0.1)mol/L). And vacuumizing the system, illuminating for 20min, taking down the reactor, centrifuging, washing with deionized water to remove the sacrificial agent on the surface of the material, and thus obtaining the high-load dispersed NiS ordered mesoporous carbon nitride photocatalytic degradation material. The specific surface area of the material is 271m 2 Per gram, pore volume 0.36cm 3 /g。
The ratio of the total volume of the precursor to the pore volume of the mesoporous silica in the step c is 0.8:1, the ratio of the volume of the precursor to the pore volume of the mesoporous silica is too small, the conversion rate after calcination is very low, and the obtained ordered mesoporous carbon nitride has poor order; the volume ratio is too large to obtain the S-doped ordered mesoporous carbon nitride with high specific surface area. The calcination temperature is 550 ℃, the temperature rising rate is 2 ℃/min, and the calcination time is 4 hours.
The concentration of the ammonium bifluoride solution in step d is 2M.
The concentration of the nickel chloride hexahydrate solution in the step e is 0.1M.
The invention is further illustrated by the following examples:
example 1:
7.2g of surfactant P123 and 260mL of water are taken and mixed with 1.2mL of concentrated hydrochloric acid (37%), the mixture is stirred for 12 hours at 35 ℃ until the surfactant P123 is completely dissolved and uniformly dispersed, then 7.2g of n-butanol is added, after stirring for 2 hours, 15.48g of tetraethyl orthosilicate TEOS is added, after stirring for 24 hours, the mixture is filtered by suction and then transferred to a polytetrafluoroethylene bottle, the mixture is subjected to hydrothermal reaction for 24 hours at 40 ℃ in an oven, and the mixture is naturally cooled, filtered by suction and washed to be neutral by deionized water. Drying overnight at 70 ℃ to obtain mesoporous silica containing surfactant; and (3) placing the mixture in a muffle furnace, calcining the mixture at 550 ℃ for 6 hours, and removing the surfactant P123 to obtain white powder, namely the mesoporous silica template.
2.3794g of cyanamide aqueous solution (50%) and 1.3085g of thiourea are taken and put in a polytetrafluoroethylene lining, 4g of mesoporous silica is added as a hard template, 40mL of absolute ethyl alcohol is added, stirring is carried out at 40 ℃ until the mixture is dried, the mixture is covered by a crucible cover and then calcined at 550 ℃ for 4 hours in air, and the calcining heating rate is 2 ℃/min; 200mL of NH at a concentration of 2M was added to the calcined product 4 HF 2 The solution was stirred at 400r/minAfter 2h, the mixture was centrifuged and washed to neutrality with deionized water to remove mesoporous silica template. The obtained S-doped ordered mesoporous carbon nitride material has a specific surface area of 292m 2 Per gram, pore volume 0.48cm 3 /g。
10mL of triethanolamine, 100mL of deionized water and 0.0006g of sodium sulfide nonahydrate are added into a photocatalytic degradation reactor, 50mg of the S-doped ordered mesoporous carbon nitride material is added into the reactor after the mixture is uniformly stirred, and 25.67uL of nickel chloride hexahydrate (0.1 mol/L) is quickly added into the reactor after the mixture is uniformly mixed. And vacuumizing the system, illuminating for 20min, taking down the reactor, centrifuging, washing with deionized water to remove the sacrificial agent on the surface of the material, and thus obtaining the high-load dispersed NiS ordered mesoporous carbon nitride photocatalytic degradation material. The specific surface area of the material is 224m 2 Per gram, pore volume 0.31cm 3 /g。
Example 2:
7.2g of surfactant P123, 260mL of water and 1.2mL of concentrated hydrochloric acid (37%) are taken and mixed at 35 ℃ and stirred for 12 hours until the surfactant is completely dissolved and uniformly dispersed, then 7.2g of n-butanol is added, after stirring for 2 hours, 15.48g of tetraethyl orthosilicate TEOS is added, after stirring for 24 hours, the mixture is filtered by suction and transferred to a polytetrafluoroethylene bottle, subjected to hydrothermal reaction at 40 ℃ in an oven for 24 hours, and after natural cooling, filtered by suction and washed to be neutral by deionized water. Drying overnight at 70 ℃ to obtain mesoporous silica containing surfactant; and (3) placing the mixture in a muffle furnace, calcining the mixture at 550 ℃ for 6 hours, and removing the surfactant P123 to obtain white powder, namely the mesoporous silica template.
2.3794g of cyanamide aqueous solution (50%) and 1.3085g of thiourea are taken and put in a polytetrafluoroethylene lining, 4g of mesoporous silica is added as a hard template, 40mL of absolute ethyl alcohol is added, stirring is carried out at 40 ℃ until the mixture is dried, the mixture is covered by a crucible cover and then calcined at 550 ℃ for 4 hours in air, and the calcining heating rate is 2 ℃/min; d) 200mL of 2M NH was added to the calcined product 4 HF 2 The solution was stirred at 400r/min for 2h and centrifuged and washed with deionized water to neutrality to remove mesoporous silica template. The specific surface area 292m of the obtained S-doped ordered mesoporous carbon nitride material 2 Per gram, pore volume 0.48cm 3 /g。
Xiang Guang10mL of triethanolamine, 100mL of deionized water and 0.0021g of sodium sulfide nonahydrate are added into a catalytic degradation reactor, 50mg of the S-doped ordered mesoporous carbon nitride material is added into the reactor after the mixture is uniformly stirred, and 85.6uL of nickel chloride hexahydrate (0.1 mol/L) is quickly added into the reactor after the mixture is uniformly mixed. And vacuumizing the system, illuminating for 20min, taking down the reactor, centrifuging, washing with deionized water to remove the sacrificial agent on the surface of the material, and thus obtaining the high-load dispersed NiS ordered mesoporous carbon nitride photocatalytic degradation material. The specific surface area of the material is 237m 2 Per gram, pore volume 0.30cm 3 /g。
Example 3:
7.2g of surfactant P123, 260mL of water and 1.2mL of concentrated hydrochloric acid (37%) are taken and mixed at 35 ℃ and stirred for 12 hours until the surfactant is completely dissolved and uniformly dispersed, then 7.2g of n-butanol is added, after stirring for 2 hours, 15.48g of tetraethyl orthosilicate TEOS is added, after stirring for 24 hours, the mixture is filtered by suction and transferred to a polytetrafluoroethylene bottle, subjected to hydrothermal reaction at 40 ℃ in an oven for 24 hours, and after natural cooling, filtered by suction and washed to be neutral by deionized water. Drying overnight at 70 ℃ to obtain mesoporous silica containing surfactant; and (3) placing the mixture in a muffle furnace, calcining the mixture at 550 ℃ for 6 hours, and removing the surfactant P123 to obtain white powder, namely the mesoporous silica template.
2.3794g of cyanamide aqueous solution (50%) and 1.3085g of thiourea are taken and put in a polytetrafluoroethylene lining, 4g of mesoporous silica is added as a hard template, 40mL of absolute ethyl alcohol is added, stirring is carried out at 40 ℃ until the mixture is dried, the mixture is covered by a crucible cover and then calcined at 550 ℃ for 4 hours in air, and the calcining heating rate is 2 ℃/min; d) 200mL of 2M NH was added to the calcined product 4 HF 2 The solution was stirred at 400r/min for 2h and centrifuged and washed with deionized water to neutrality to remove mesoporous silica template. The specific surface area 292m of the obtained S-doped ordered mesoporous carbon nitride material 2 Per gram, pore volume 0.48cm 3 /g。
Adding 10mL of triethanolamine, 100mL of deionized water and 0.0062g of sodium sulfide nonahydrate into a photocatalytic degradation reactor, stirring uniformly, adding 50mg of the S-doped ordered mesoporous carbon nitride material into the mixture, and rapidly adding 256.7uL of chloridizing hexahydrate into the mixture after the mixture is uniformly mixedNickel (0.1 mol/L). And vacuumizing the system, illuminating for 20min, taking down the reactor, centrifuging, washing with deionized water to remove the sacrificial agent on the surface of the material, and thus obtaining the high-load dispersed NiS ordered mesoporous carbon nitride photocatalytic degradation material. The specific surface area of the material is 271m 2 Per gram, pore volume 0.36cm 3 /g。
FIG. 1 is a pore distribution diagram of a high-load dispersed NiS ordered mesoporous carbon nitride material according to the embodiment, showing that the pores are dominant; fig. 2 is a TEM image of the high-load dispersed NiS ordered mesoporous carbon nitride obtained in this example, which demonstrates the ordered mesoporous structure.
Example 4:
7.2g of surfactant P123, 260mL of water and 1.2mL of concentrated hydrochloric acid (37%) are taken and mixed at 35 ℃ and stirred for 12 hours until the surfactant is completely dissolved and uniformly dispersed, then 7.2g of n-butanol is added, after stirring for 2 hours, 15.48g of tetraethyl orthosilicate TEOS is added, after stirring for 24 hours, the mixture is filtered by suction and transferred to a polytetrafluoroethylene bottle, subjected to hydrothermal reaction at 40 ℃ in an oven for 24 hours, and after natural cooling, filtered by suction and washed to be neutral by deionized water. Drying overnight at 70 ℃ to obtain mesoporous silica containing surfactant; and (3) placing the mixture in a muffle furnace, calcining the mixture at 550 ℃ for 6 hours, and removing the surfactant P123 to obtain white powder, namely the mesoporous silica template.
2.3794g of 50% aqueous solution of cyanamide is taken and put in a polytetrafluoroethylene lining, 2g of mesoporous silica is added as a hard template, 30mL of absolute ethyl alcohol is added, the mixture is stirred at 40 ℃ until the mixture is dried, the mixture is covered by a crucible cover and then calcined at 550 ℃ for 4 hours in air, and the calcining heating rate is 2 ℃/min; to the calcined product was added 100mL of 2M NH 4 HF 2 The solution was stirred for 2h, centrifuged and washed with deionized water to neutrality to remove mesoporous silica template. Thus obtaining the ordered mesoporous carbon nitride material. The specific surface area 292m of the obtained S-doped ordered mesoporous carbon nitride material 2 Per gram, pore volume 0.48cm 3 /g。
10mL of triethanolamine, 100mL of deionized water and 0.0104g of sodium sulfide nonahydrate are added into a photocatalytic degradation reactor, and 50mg of the S-doped ordered mesoporous carbon nitride material is added into the reactor after the mixture is uniformly stirredAfter being mixed uniformly, 427.84uL of nickel chloride hexahydrate (0.1 mol/L) was added thereto rapidly. And vacuumizing the system, illuminating for 20min, taking down the reactor, centrifuging, washing with deionized water to remove the sacrificial agent on the surface of the material, and thus obtaining the high-load dispersed NiS ordered mesoporous carbon nitride photocatalytic degradation material. The specific surface area of the material is 122m 2 Per gram, pore volume 0.13cm 3 /g。
Example 5:
7.2g of surfactant P123, 260mL of water and 1.2mL of concentrated hydrochloric acid (37%) are taken and mixed at 35 ℃ and stirred for 12 hours until the surfactant is completely dissolved and uniformly dispersed, then 7.2g of n-butanol is added, after stirring for 2 hours, 15.48g of tetraethyl orthosilicate TEOS is added, after stirring for 24 hours, the mixture is filtered by suction and transferred to a polytetrafluoroethylene bottle, subjected to hydrothermal reaction at 40 ℃ in an oven for 24 hours, and after natural cooling, filtered by suction and washed to be neutral by deionized water. Drying overnight at 70 ℃ to obtain mesoporous silica containing surfactant; and (3) placing the mixture in a muffle furnace, calcining the mixture at 550 ℃ for 6 hours, and removing the surfactant P123 to obtain white powder, namely the mesoporous silica template.
2.3794g of 50% aqueous solution of cyanamide is taken and put in a polytetrafluoroethylene lining, 2g of mesoporous silica is added as a hard template, 30mL of absolute ethyl alcohol is added, the mixture is stirred at 40 ℃ until the mixture is dried, the mixture is covered by a crucible cover and then calcined at 550 ℃ for 4 hours in air, and the calcining heating rate is 2 ℃/min; to the calcined product was added 100mL of 2M NH 4 HF 2 The solution was stirred for 2h, centrifuged and washed with deionized water to neutrality to remove mesoporous silica template. Thus obtaining the ordered mesoporous carbon nitride material. The specific surface area 292m of the obtained S-doped ordered mesoporous carbon nitride material 2 Per gram, pore volume 0.48cm 3 /g。
10mL of triethanolamine, 100mL of deionized water and 0.0207g of sodium sulfide nonahydrate are added into a photocatalytic degradation reactor, 50mg of the S-doped ordered mesoporous carbon nitride material is added into the reactor after the mixture is uniformly stirred, and 855.67uL of nickel chloride hexahydrate (0.1 mol/L) is quickly added into the reactor after the mixture is uniformly mixed. Vacuumizing the system, illuminating for 20min, taking down the reactor, centrifuging, washing with deionized water to remove the sacrificial agent on the surface of the material, and obtainingThe high-load dispersed NiS ordered mesoporous carbon nitride photocatalytic degradation material in the invention. The specific surface area of the material is 104m 2 Per gram, pore volume 0.08cm 3 /g。
Claims (1)
1. A carbon nitride high-load dispersed NiS photocatalytic degradation material is used for photocatalytic degradation and is characterized in that: is obtained by taking S-doped ordered mesoporous carbon nitride as a base and loading nickel sulfide; the preparation method comprises the following steps:
(a) Mixing 7.2g surfactant P123, 260mL water and 1.2mL 37% concentrated hydrochloric acid at 35 ℃, stirring 12h until the surfactant is completely dissolved and uniformly dispersed, then adding 7.2g n-butanol, stirring 2h, adding 15.48g tetraethoxysilane TEOS, stirring 24h, transferring to a polytetrafluoroethylene bottle after suction filtration, carrying out hydrothermal reaction 24h in an oven at 40 ℃, carrying out suction filtration after natural cooling, and washing to neutrality with deionized water; drying overnight at 70 ℃ to obtain mesoporous silica containing surfactant; placing the mixture in a muffle furnace to calcine at 550 ℃ for 6h to remove the surfactant P123, and obtaining white powder, namely the mesoporous silica template;
(b) 2.3794g of 50% aqueous solution of cyanamide and 1.3085g thiourea are taken and put in a polytetrafluoroethylene lining, 4g of the mesoporous silica template is added as a hard template, 40mL of absolute ethyl alcohol is added, stirring is carried out at 40 ℃ until the mixture is dried, the crucible cover is covered, and then the mixture is calcined at 550 ℃ in air for 4h, and the calcining heating rate is 2 ℃/min; to the calcined product was added 200. 200mL of 2M NH 4 HF 2 Stirring the solution at 400r/min for 2h, centrifuging, and washing with deionized water to neutrality to remove the mesoporous silica template; the specific surface area 292m of the obtained S-doped ordered mesoporous carbon nitride material 2 Per gram, pore volume 0.48cm 3 /g；
(c) Adding 10mL triethanolamine, 100mL deionized water and 0.0062g sodium sulfide nonahydrate into a photocatalytic degradation reactor, uniformly stirring, adding the S-doped ordered mesoporous carbon nitride material 50mg into the mixture, and rapidly adding 256.7uL of 0.1mol/L nickel chloride hexahydrate into the mixture after the mixture is uniformly mixed; vacuumizing the system, illuminating for 20min, taking down the reactor,centrifuging, washing with deionized water to remove the sacrificial agent on the surface of the material, and obtaining the high-load dispersed NiS ordered mesoporous carbon nitride photocatalytic degradation material; the specific surface area 271 and m of the material 2 Per gram, pore volume 0.36cm 3 /g。
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104877677A (en) * | 2015-05-29 | 2015-09-02 | 周口师范学院 | Mesoporous silica/carbon dot nanometer composite and preparation method thereof |
| CN105457618A (en) * | 2014-09-09 | 2016-04-06 | 华东理工大学 | Carbon quantum dot and titanium codoped mesoporous silica composite photocatalyst |
| CN106563470A (en) * | 2016-11-14 | 2017-04-19 | 江苏大学 | NiS2 nano-particle/g-C3N4 mesoporous nanosheet composite and preparation method thereof |
| CN107892284A (en) * | 2017-11-28 | 2018-04-10 | 铜仁学院 | A kind of NiS/C3N4Binary complex and its methods for making and using same |
| CN108067280A (en) * | 2017-11-23 | 2018-05-25 | 江南大学 | A kind of preparation method of nickel sulfide/class graphene carbon nitrogen compound composite catalyst |
| CN110280287A (en) * | 2019-06-28 | 2019-09-27 | 西安工程大学 | It is a kind of effectively to construct Z-type ternary heterojunction CdS/NiS/g-C3N4The preparation method of photochemical catalyst |
| CN111359652A (en) * | 2020-04-29 | 2020-07-03 | 中国计量大学 | Carbon nitride-based nickel-gold bimetallic supported catalyst and preparation method thereof |
| CN111686777A (en) * | 2019-12-31 | 2020-09-22 | 西安九天孵化器科技有限公司 | NiS-g-C3N4Method for preparing photocatalyst |
| WO2020230530A1 (en) * | 2019-05-13 | 2020-11-19 | 国立大学法人新潟大学 | Catalyst, electrode, water electrolysis method, and method for producing catalyst |
-
2021
- 2021-06-23 CN CN202110699753.6A patent/CN113600220B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105457618A (en) * | 2014-09-09 | 2016-04-06 | 华东理工大学 | Carbon quantum dot and titanium codoped mesoporous silica composite photocatalyst |
| CN104877677A (en) * | 2015-05-29 | 2015-09-02 | 周口师范学院 | Mesoporous silica/carbon dot nanometer composite and preparation method thereof |
| CN106563470A (en) * | 2016-11-14 | 2017-04-19 | 江苏大学 | NiS2 nano-particle/g-C3N4 mesoporous nanosheet composite and preparation method thereof |
| CN108067280A (en) * | 2017-11-23 | 2018-05-25 | 江南大学 | A kind of preparation method of nickel sulfide/class graphene carbon nitrogen compound composite catalyst |
| CN107892284A (en) * | 2017-11-28 | 2018-04-10 | 铜仁学院 | A kind of NiS/C3N4Binary complex and its methods for making and using same |
| WO2020230530A1 (en) * | 2019-05-13 | 2020-11-19 | 国立大学法人新潟大学 | Catalyst, electrode, water electrolysis method, and method for producing catalyst |
| CN110280287A (en) * | 2019-06-28 | 2019-09-27 | 西安工程大学 | It is a kind of effectively to construct Z-type ternary heterojunction CdS/NiS/g-C3N4The preparation method of photochemical catalyst |
| CN111686777A (en) * | 2019-12-31 | 2020-09-22 | 西安九天孵化器科技有限公司 | NiS-g-C3N4Method for preparing photocatalyst |
| CN111359652A (en) * | 2020-04-29 | 2020-07-03 | 中国计量大学 | Carbon nitride-based nickel-gold bimetallic supported catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 刘凯等.介孔NiS2/S-g-C3N4的制备及其光催化产氢性能研究.《功能材料》.2020,第51卷(第7期),第07007-07014页. * |
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