CN114950436A - Limited-domain high-dispersion metal-carbon shell persulfate catalyst and preparation method and application thereof - Google Patents
Limited-domain high-dispersion metal-carbon shell persulfate catalyst and preparation method and application thereof Download PDFInfo
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- CN114950436A CN114950436A CN202210713329.7A CN202210713329A CN114950436A CN 114950436 A CN114950436 A CN 114950436A CN 202210713329 A CN202210713329 A CN 202210713329A CN 114950436 A CN114950436 A CN 114950436A
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- persulfate
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 31
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 239000006185 dispersion Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 17
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- 238000005406 washing Methods 0.000 claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
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- 239000002243 precursor Substances 0.000 claims abstract description 5
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- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 claims description 11
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
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- 239000007787 solid Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 2
- 229940072172 tetracycline antibiotic Drugs 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims 2
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- 230000009471 action Effects 0.000 abstract description 2
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- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
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- 230000000694 effects Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 229940088710 antibiotic agent Drugs 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
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- 238000005470 impregnation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DNLGSMHAJWIINT-UHFFFAOYSA-N [dimethyl(propyl)silyl]methanamine Chemical compound CCC[Si](C)(C)CN DNLGSMHAJWIINT-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
- 229960005091 chloramphenicol Drugs 0.000 description 1
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
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- 239000002082 metal nanoparticle Substances 0.000 description 1
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- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 description 1
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- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical compound OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 1
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- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 1
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/394—
-
- B01J35/398—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a domain-limited high-dispersion metal carbon shell persulfate catalyst and a preparation method and application thereof. The invention also discloses a preparation method of the catalyst, which comprises the steps of taking the silicon dioxide nano microspheres S with different particle sizes and grafted with functional groups on the surfaces as sacrificial templates, taking inorganic metal salt M as a precursor, uniformly dispersing the inorganic metal salt M on the surfaces of the silicon dioxide nano spheres through electrostatic action or complexing action, removing the templates through hydrothermal carbon shell coating, high-temperature carbonization polymerization and alkali washing, and activating persulfate to generate active oxygen with strong oxidizing property by the prepared catalyst, so that the catalyst has high oxidation removal rate on various organic pollutants. The invention also discloses the catalysisThe application of the agent in catalyzing persulfate to oxidize and degrade organic pollutants can oxidize and degrade the organic pollutants into small molecular compounds or mineralize into CO 2 And H 2 O。
Description
Technical Field
The invention relates to a limited-area high-dispersion metal-carbon shell (HDM @ C) catalyst, a preparation method and application thereof, and particularly relates to a persulfate activating catalyst, a preparation method thereof and application of the catalyst in liquid-phase oxidative degradation of organic pollutants.
Background
With the rapid development of society, a large amount of organic pollutants such as drugs, dyes and the like are discharged into the environment, and the traditional sewage treatment technology has limited capability of removing the organic pollutants with low concentration and high stability in water. In recent years, sulfate radicals (SO) have been used 4 ·- ) The emerging advanced oxidation process based on the advantages of being superior to the traditional Fenton reaction in the aspect of organic pollutant removal is receiving more and more attention. For example, persulfate is a solid oxidant, is stable at normal temperature and normal pressure and is convenient to transport and store; SO produced thereby 4 ·- Has stronger oxidizing property (SO) than OH 4 ·- The redox potential of (A) is 2.5-3.1V, the redox potential of (OH) is 1.8-2.7V, higher selectivity and longer half-life (SO) 4 ·- Half-life of 30-40 μ s,. OH half-life of 10-3 μ s); has higher degradation activity under wider pH (2-11) condition.
The transition metal catalyst has potential application value in persulfate activation, such as iron-based, cobalt-based, manganese-based and copper-based catalysts. Currently, most of research focuses on the preparation and design of metal-based heterogeneous catalysts and supported transition metal catalysts, and exposed metal nanoparticles are easily exfoliated during the reaction process, so that there is a risk of metal ion leakage. To overcome this problem, a constrained-domain catalyst containing metal particles in a carrier has received great attention, such as Fe-S @ SNC, Fe @ SBA-15, CoP @ MOF-2-C, and generally, a carbon material having a high specific surface area and high chemical stability has been widely used as a constrained-domain catalyst shell layer.
Generally, the metal sites are coated in a particle state inside the carbon layer, so that the metal active sites are not fully utilized, contact between reactants and the catalytic active sites is hindered, and the efficiency of catalytic reaction is further influenced. Therefore, the development of a metal catalyst with highly dispersed and confined active sites is the key to inhibit the loss of metal elements and improve the utilization rate of the active sites of metals.
Disclosure of Invention
To overcome the disadvantages of the prior art, it is an object of the present invention to provide a constrained-domain, highly dispersed metal-carbon shell (HDM @ C) catalyst and a process for preparing the same.
The invention also aims to provide application of a domain-limited high-dispersion metal-carbon shell (HDM @ C) catalyst in degrading organic pollutants by efficiently activating persulfate.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a carbon shell (HDM @ C) catalyst is prepared as grafting silicon dioxide with specific functional group on surface as sacrificial template, uniformly dispersing inorganic metal salt M as precursor on surface of silicon dioxide nanosphere through electrostatic action or complexation, coating carbon shell by hydrothermal method, high-temperature carbonization polymerization and alkali washing to remove template to obtain the catalyst, and confining metal component in carbon shell in monoatomic or high-dispersion state. The specific surface area of the catalyst is 80-800 m 2 The particle size of the silicon dioxide nanospheres is 50-500 nm, and the content of metal elements is 0.1-0.5 at.%.
The limited domain amount and the dispersity of the metal components are closely related to the types and the contents of the grafting functional groups on the surface of the silicon dioxide and the concentration of the inorganic metal salt solution, and the content of the metal elements is adjusted by adjusting the concentrations of the grafting functional groups on the surface of the silicon dioxide and the metal salt solution.
Wherein, the type of the functional group grafted on the surface of the silicon dioxide can be amino (-NH) 2 ) Or a mercapto group (-SH).
In the process of mixing and adsorbing the silicon dioxide and the inorganic metal salt solution, the metal cations and the functional groups on the surface of the silicon dioxide are distributed on the surface of the silicon dioxide in a single-layer atomic state through electrostatic interaction or complexation, so that the dispersion degree and the utilization rate of the metal atoms are effectively improved.
A preparation method of a limited-area high-dispersion metal-carbon shell (HDM @ C) catalyst comprises the following specific steps:
1) adding the silica nano-microspheres into a flask containing toluene and a silane coupling agent at 120 DEG o C, refluxing and stirring in an oil bath for 2 hours, washing the mixture for multiple times by using methylbenzene after the mixture is cooled to room temperature, and placing the washed filter residue into a tank 80 o And C, drying in a constant-temperature drying oven for 12 hours to obtain the functionalized silicon dioxide nanosphere S.
2) A certain amount of functionalized silicon dioxide nanospheres S is weighed and added into an inorganic metal salt M solution with a certain concentration, and the solution is magnetically stirred for 6 hours to fully disperse and adsorb metal cations. Filtering, washing with distilled water to remove unadsorbed metal cations, and standing at 60 deg.C o And C, drying in an oven for 12 hours. Grinding the dried compound by using an agate mortar to obtain the SiO loaded with the transition metal 2 -M。
3) A certain amount of SiO obtained in step 2) 2 mixing-M with a small molecular organic matter C solution, transferring into a hydrothermal reaction kettle and reacting at 200 DEG C o And reacting for 12 hours under the condition of C. Cooling to room temperature, washing with deionized water, and standing at 60 deg.C o And (5) drying for 24 hours under C.
4) And 3) placing the black powder obtained in the step 3) in a tube furnace, heating to a preset temperature under an inert condition, keeping for 4 hours, and carbonizing.
5) Placing the carbonized polymer obtained in the step 4) in a polytetrafluoroethylene bottle containing NaOH solution 45 o C stirring for 6 h, filtering, washing to neutrality with deionized water, 80 o And C, drying and grinding to obtain the limited domain type HDM @ C catalyst with highly dispersed active sites.
The solid-liquid mass ratio of the added silicon dioxide nano microspheres to the silane coupling agent is 1: 1-1: 5; the concentration of the inorganic metal salt solution is 0.1-1 mol/L, SiO 2 The mass ratio of the-M to the small molecular organic matters is 1: 1-1: 5.
The silane coupling agent may be an aminosilane coupling agent or a mercaptosilane coupling agent.
The inorganic metal salt can be any one or more of iron salt, cobalt salt, manganese salt or copper salt.
The inert gas is nitrogen, helium or argon.
The HDM @ C catalyst prepared by the sacrificial template can be used for degrading organic pollutants by liquid-phase activated persulfate, and shows high-efficiency catalytic activity.
The application of a domain-limited high-dispersion metal HDM @ C catalyst can activate persulfate to degrade organic pollutants.
Wherein the HDM @ C is used as a catalyst, persulfate is used as an oxidant, organic pollutants are subjected to oxidative degradation in a water environment, and a final degradation product is CO 2 And H 2 O。
The persulfate salts include Peroxymonosulfate (PMS) and Peroxydisulfate (PDS).
The organic contaminants include various dyes, antibiotics or drugs. For example, selected from methylene blue, orange II, rhodamine, tetracycline antibiotics, sulfonamides or naproxen.
Specifically, under the condition of room temperature, adding the prepared catalyst into an organic pollutant aqueous solution with a certain concentration, stirring for 1 hour, adding a certain amount of persulfate to react, and generating active oxygen species by the activated persulfate so as to degrade the organic pollutants.
In the reaction, the addition amount of the HDM @ C catalyst is 5-40 mg, the volume of the organic pollutant solution is 50-500 mL, the concentration is 5-20 mg/L, and the addition amount of persulfate is 0.2-0.5 g.
Compared with the prior art, the invention has the advantages that:
(1) the invention relates to a limited-area high-dispersion HDM @ C catalyst, which is characterized in that (a) functionalized silicon dioxide is used as a template in the preparation process of the catalyst to adsorb and anchor metal cations, so that the dispersion degree and the utilization rate of the metal ions are improved. (b) For persulfate catalytic reaction, only persulfate contacts with active sites on the surface of the catalyst, and can be activated, so that the carbon shell is used as a reaction interface, has high adsorption capacity on various organic matters, and is favorable for promoting the degradation of the various organic matters. (c) The reaction liquid is acidic in the process of degrading organic matters by persulfate oxidation, the high-dispersion metal sites are confined in the carbon layer, the catalytic effect of the metal sites can be exerted by electron transfer of the carbon layer under the condition of not contacting the acidic reaction liquid, and the loss of metal elements is effectively inhibited.
(2) The domain-limited high-dispersion HDM @ C catalyst can efficiently degrade organic pollutants, orange II is selected as a representative pollutant in a reaction system, the concentration is 10 mg/L, the dosage of the CoCNx @ C catalyst is 20 mg and the dosage of PMS is 0.16 g when the reaction volume is 200 mL, complete degradation of the orange II can be realized when the reaction is carried out for 60 minutes, and the final degradation product is CO 2 And H 2 O, no secondary pollution and good environmental benefit.
Drawings
FIG. 1 is a graph of the HAADF-STEM and EDS face scan results for the HDM @ C catalyst prepared in the example;
FIG. 2 XRD patterns of HDM @ C catalysts prepared at different temperatures;
FIG. 3 is a schematic diagram showing the effect of different catalyst preparation methods on the degradation effect of orange II;
FIG. 4 the degradation effect of HDCo @ C-700 catalyst on different dyes and drugs;
FIG. 5 the degradation effect of HDCo @ C-700 catalyst on different antibiotics.
Detailed Description
The technical solutions of the present invention are further described in detail by the following specific examples, but it should be noted that the following examples are only used for describing the content of the present invention and should not be construed as limiting the scope of the present invention.
EXAMPLE 1 catalyst and preparation thereof (HDCo @ C)
1.0 g of silica nanospheres (SiO) 2 ) Added to a solution containing 60 mL of toluene (C) 7 H 8 ) And 2.5 mL Aminopropyltrimethylsilane (APTMS) in a flask, refluxing and stirring for 2 h in an oil bath at 120 ℃, washing for multiple times by using toluene after the mixture is cooled to room temperature, and drying the washed filter cake in a constant-temperature drying oven at 80 ℃ for 12 h to obtain aminated SiO 2 -NH 2 . 1.0 g of powdered SiO are weighed 2 -NH 2 Added to 30 mL of 0.1 mol/L Co (NO) 3 ) 2 ·6H 2 In O solution, the mixture is magnetically stirred for 6 hours to fully disperse and adsorb Co 2+ . Filtered and rinsed with 50 mL of distilled water to remove unadsorbed Co 2+ . Grinding the dried compound by using an agate mortar to obtain the SiO loaded with the transition metal 2 -Co. Finally, 1.0 g of powdery SiO is weighed 2 Co and 2.0 g glucose were dispersed in 30 mL deionized water by sonication, and the mixture was transferred to a 40 mL hydrothermal reaction kettle and reacted at 200 ℃ for 12 h. And naturally cooling to room temperature, centrifugally washing with deionized water until the supernatant is clear and colorless, and drying at 60 ℃ for 24 hours. The dried black powder was placed in a tube furnace and heated to a preset temperature (600, 700 and 800 ℃) at 5 ℃/min for 4 h under nitrogen for carbonization. And (3) placing the carbonized polymer in a polytetrafluoroethylene bottle containing 200 mL of 2 mol/L NaOH solution (prepared in a solution with the volume ratio of ethanol to water being 1: 1), stirring for 6 h at 45 ℃, carrying out suction filtration, washing to be neutral by using deionized water, drying at 80 ℃, and grinding to obtain the domain-limited HDCo @ C-X catalyst with highly dispersed active sites (X represents the carbonization temperature).
The HAADF and EDS element Mapping profiles of the synthesized HDCo @ C-700 catalyst are shown in FIG. 1. EDS spectrum images clearly show that the C and O elements are uniformly dispersed on the outer shell of the Co @ C catalyst. The Co element, which is a weak signal, is distributed along the carbon layer, confirming that the Co element is confined in the carbon shell. In addition, the content of cobalt element was 0.15 wt.% by EDS detection.
FIG. 2 is a wide angle XRD diffractogram of catalysts Co @ C-600, Co @ C-700 and Co @ C-800 obtained at different carbonization temperatures. All samples showed broad strong diffraction peaks at 2 θ = 23.7-25.2 ° and weak diffraction peaks at 2 θ = 42.3-43.4 °, corresponding to diffraction of (002) and (100) planes of the hexagonal graphite structure, respectively. The intensity of the diffraction peak slightly increases as the carbonization temperature increases from 600 ℃ to 800 ℃, since the graphite structure of the catalyst increases as the carbonization temperature increases.
Example 2 catalytic Activity of the catalyst
An HDCo @ C-X catalyst was prepared according to the method of example 1, with a sacrificial template, wherein the content of Co element was about 0.15 wt.%.
The catalyst is applied to the reaction of degrading orange II by activating persulfate, and the specific process comprises the following steps: an amount of orange II stock solution was added to a three-neck round-bottom flask containing deionized water, wherein the initial concentration of orange II was 10 mg/L and the volume was 200 mL. 10 mg of the constrained-domain catalyst prepared in example 1 were added, stirred vigorously for 1 hour, and 0.16 g of peroxymonosulfate was added to start the catalytic reaction. Samples were taken at regular intervals during the reaction and tested.
FIG. 3 shows the catalytic activity of the high dispersion state metal catalyst HDCo @ C-X prepared at different calcination temperatures, and it can be seen from the results that the degradation rate of AO7 is significantly improved when the catalyst Co @ C-X is added to the peroxymonosulfate system. The degradation rates of the HDCo @ C-600, HDCo @ C-700 and HDCo @ C-800 activated peroxymonosulfate to AO7 within 45 min are 69.2%, 96.1% and 90.7%, respectively, and the HDCo @ C-700 catalytic activity of the limited-area catalyst is the best.
Example 3 catalytic Activity of HDCo @ C-700 on various contaminants
The HDCo @ C is applied to the reaction of degrading different dyes, drugs, antibiotics and the like by activating persulfate, and the specific process is the same as that in example 2, namely 200 mL of organic pollutant solution with a certain concentration (the concentration of the dye and the drug pollutants is 10 mg/L, and the concentration of the pollutants of different antibiotics is 20 mg/L) is added into a three-neck round-bottom flask, 10 mg of catalyst is added, the mixture is stirred vigorously for 1 hour, 0.16 g of peroxymonosulfate is added, and the catalytic reaction is started. Samples were taken at regular intervals during the reaction and tested.
FIGS. 4 and 5 show that HDCo @ C-700 has high removal efficiency on various pollutants, and the removal rates on methylene blue, rhodamine B, naproxen, tetracycline, oxytetracycline, chloramphenicol, sulfamethoxazole are 86.3%, 69.4%, 100%, 73.5%, 72.8%, 76.1% and 65.5% respectively within the reaction time of 60 min.
Comparative example 1 catalyst and preparation thereof
For comparison, the Co/C-700 catalyst is synthesized by a common impregnation method, and the specific catalyst preparation process comprises the following steps:
2.5 g of powdered SiO are weighed 2 And 5.0 g of glucose were ultrasonically dispersed in 75 mL of deionized water, and the mixture was transferred to a 100 mL hydrothermal reaction vessel and reacted at 200 ℃ for 12 hours. Naturally cooling to room temperature, centrifugally washing with deionized water until the supernatant is clear and colorless, and drying at 60 deg.C for 24 hr. And (3) putting the dried black powder into a tube furnace, heating to the preset temperature of 700 ℃ at the speed of 5 ℃/min under the condition of nitrogen, keeping the temperature for 4 h, and carbonizing. And (3) placing the carbonized polymer in a polytetrafluoroethylene bottle containing 200 mL of 2 mol/L NaOH solution (prepared in a solution with the volume ratio of ethanol to water being 1: 1), stirring for 6 h at 45 ℃, carrying out suction filtration, washing to be neutral by using deionized water, drying at 80 ℃, and grinding to obtain the carbon material.
1 mL of 0.0761 mg/L Co (NO) was added to 1 g of the carbon material prepared by the above method 3 ) 2 ·6H 2 And (3) O solution, namely placing the uniformly mixed solution in a water bath at 60 ℃ and stirring until the water is basically evaporated, and placing the solution in a 60 ℃ oven to dry for 12 hours. The resulting black powder was labeled CoC-700.
Comparative example 2 catalyst Activity
CoC-700 catalyst prepared by impregnation method according to the method of comparative example 1, in which the Co element contents are 0.20 wt.%, respectively, and the loading is close to that of Co in example 1. The catalyst is applied to the reaction of degrading the orange II medicament by activating persulfate, the specific process is the same as that in example 2, namely 200 mL of orange II solution with the concentration of 10 mg/L is added into a three-neck round-bottom flask, 10 mg of the catalyst is added, the mixture is stirred vigorously for 1 hour, 0.16 g of peroxymonosulfate is added, and the catalytic reaction is started. Samples were taken at regular intervals during the reaction and tested.
FIG. 3 compares the catalytic activity results of limited-area high-dispersity metal HDM @ C-X catalyst and a catalyst synthesized by a common impregnation method (CoC-700) for activating peroxymonosulfate to degrade orange II. As can be seen from the results, compared with the domain-limited catalyst HDCo @ C-X, the degradation rate of AO7 by the peroxymonosulfate activated by the surface-supported catalyst CoC-700 is only 44.01%, which is significantly lower than that of the Co @ C-X catalyst.
Comparative example 3 stability of the catalyst
The catalyst stability test was the same as in example 2 and comparative example 2, i.e., 200 mL of a 10 mg/L orange II solution was added to a three-necked round-bottomed flask, 10 mg of the catalyst was added, vigorous stirring was carried out for 1 hour, and 0.16 g of hydrogen peroxymonosulfate was added to start the catalytic reaction. The Co ion content in the solution is sampled and detected at fixed intervals in the reaction.
Compared with the Co ion leaching amount of HDCo @ C-700 and CoC-700 in the reaction process, the Co ion leaching amount is 0.0054 mg/L and 0.0139 mg/L respectively when the reaction is carried out for 60 minutes, and the lower leaching amount of the Co ion leaching amount in the HDCo @ C-700 shows that the carbon layer confinement effect can effectively inhibit the loss of Co element, so that the catalyst has higher stability.
Claims (9)
1. A limited-area high-dispersion metal carbon shell catalyst is characterized in that a silicon dioxide nanosphere S with a grafted functional group on the surface is used as a sacrificial template, a metal-free salt M is used as a precursor, a small molecular organic matter C is used as a carbon shell precursor, the template is removed through pyrolysis and alkali washing to form the limited-area high-dispersion metal carbon shell catalyst in the carbon shell, metal active components are mainly limited in the carbon shell in a high-dispersion state, and the specific surface area of the catalyst is 80-800M 2 The particle diameter of the HDM @ C catalyst is 50-500 nm, and the content of metal elements is 0.1-0.5 at.%.
2. The domain-limited type highly dispersed metal-carbon shell catalyst according to claim 1, wherein said silica nanospheres S surface-grafted with a functional group of amino (-NH) group 2 ) Or sulfydryl (-SH), the particle size of the silicon dioxide nanosphere is 50-500 nm; the inorganic metal salt M is ferric salt, cobalt salt, manganese salt and copper salt; the micromolecular organic matter C is glucose and sucrose.
3. A method for preparing a confined-domain, highly dispersed metal carbon shell catalyst according to claim 1, comprising the steps of:
the silica nanospheres are hydrolyzed by a silane coupling agent and grafted with functional groups on the surfaces of the silica nanospheres;
mixing the silicon dioxide nanospheres grafted with the functional groups with 0.1-1 mol/L of inorganic metal salt precursor solution, and stirring for 2-6 hours at room temperature;
after the adsorption of metal ions by the silicon dioxide nanospheres reaches balance, filtering, washing with distilled water, placing at 60-80 ℃, drying in an oven for 5-12 h, grinding the dried compound with an agate mortar to obtain a transition metal-loaded intermediate SiO 2 -M；
Mixing SiO 2 mixing-M and micromolecular organic matter C according to a certain proportion, dispersing in ultrapure water, placing in a hydrothermal reaction kettle for reaction at the temperature of 200 ℃ and 250 ℃ for 12-24 h to obtain SiO 2 -M@C；
SiO 2 Drying the-M @ C at 60-100 ℃, and carbonizing at high temperature of 500-800 ℃ for 2-6 hours in an inert gas atmosphere to obtain a carbonized polymer SiO 2 -HDM@C；
SiO 2 Putting the HDM @ C into 200 mL of 2-4 mol/L NaOH solution, stirring for 6-8 h at 45-60 ℃, carrying out suction filtration, washing to be neutral by using deionized water, drying at 80-100 ℃, and grinding to obtain the limited-area high-dispersion metal carbon shell catalyst HDM @ C.
4. The method according to claim 3, wherein the silane coupling agent is an aminosilane coupling agent, a mercaptosilane coupling agent; the inorganic metal salt is any one or mixture of more of iron salt, cobalt salt, manganese salt or copper salt; the micromolecular organic matter C is glucose and sucrose.
5. The preparation method according to claim 4, wherein the mass ratio of the added solid to liquid of the silica nanospheres to the silane coupling agent is 1: 1-1: 5; the concentration of the inorganic metal salt solution is 0.1 mol/L-1 mol/L; SiO 2 2 The mass ratio of the-M to the small molecular organic matters is 1: 1-1: 5.
6. The use of a confined space high dispersion metal carbon shell catalyst as claimed in claim 1 wherein said catalyst is used in the liquid phase to activate persulfate salts for oxidative degradation of organic contaminants.
7. The use of claim 6 wherein the solution of organic contaminants is added to the catalyst under ambient conditions and pressure, and after agitation, persulfate is added as an oxidant, and the activated persulfate produces highly reactive oxygen species that degrade the dye contaminants into small molecules or mineralization.
8. Use according to claim 6, wherein the persulfate salt is PMS peroxymonosulfate or PDS peroxydisulfate; the organic pollutants are selected from methylene blue, orange II, rhodamine, tetracycline antibiotics, sulfonamide antibiotics or naproxen drugs.
9. Use according to claim 6 or 7, wherein the catalyst is added in an amount of 5-40 mg; the volume of the drug pollutant is 50-500 mL, and the concentration is 5-20 mg/L; the addition amount of the persulfate is 0.2-0.5 g.
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