CN114558597A - Preparation method and application of P-Co/CoO heterojunction nano material - Google Patents
Preparation method and application of P-Co/CoO heterojunction nano material Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 229960005404 sulfamethoxazole Drugs 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 10
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 238000006731 degradation reaction Methods 0.000 claims description 15
- 230000015556 catabolic process Effects 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims 2
- 230000000593 degrading effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001089 mineralizing effect Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000011068 loading method Methods 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- 230000000694 effects Effects 0.000 description 10
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- 239000002135 nanosheet Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 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
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 239000003642 reactive oxygen metabolite Substances 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- 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
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C02F2101/34—Organic compounds containing oxygen
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- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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Abstract
The invention discloses a preparation method and application of a P-Co/CoO heterojunction nano material, wherein Co (OH) is firstly prepared2The precursor is added with red phosphorus to be fired, and the obtained P-Co/CoO heterojunction material has good catalytic activity and stability. The P-Co/CoO heterojunction nano material can catalyze and activate PMS to generate high-oxidability SO4 ·—Active oxygen species such as (sulfate radical) and OH (hydroxyl radical) degrade pollutants harmful to the human body in the environment, such as sulfamethoxazole. In addition, the loading of the material is only 0.01g/L, and the amount of PMS is usedWhen the concentration is 0.1g/L, 99% removal rate of SMX (10mg/L) can be realized within 8min, and the stability and the cyclicity are good.
Description
Technical Field
The invention relates to a preparation method and application of a P-Co/CoO heterojunction nano material.
Background
Antibiotics are now widely used to treat diseases and to protect human and animal health. Sulfamethoxazole (SMX) is one of the most widely used antibiotics and is often detected in the environment. Furthermore, due to its resistance to natural biodegradation, there is a challenge to its removal, which can lead to the accumulation of SMX and pose a serious threat to the environment and human health. The removal of SMX has become a scientific problem to be solved urgently in the field of water treatment.
OH is a non-selective strong oxidizing group with an oxidation-reduction potential of 2.8V, which can effectively destroy the structure of the contaminants and to some extent mineralize them. In recent years, sulfate radicals (SO) have been used4 —·) The basic advanced oxidation process has attracted a great deal of attention. Among various water treatment technologies, the sulfate radical-based advanced oxidation technology (SR-AOPs) has proven to be an effective technology for removing refractory organic pollutants in water, since SO is compared to OH, SO4 —·With the same or even higher redox potential (2.5-3.2V). Furthermore, under certain conditions, SO4 —·Higher selectivity, broader pH conditions and longer half-life than OH. Sulfate radicals are therefore considered to degrade organic contaminants more efficiently and rapidly. SO (SO)4 —·Usually generated from Peroxymonosulfate (PMS) and Persulfate (PS) by activation with uv light, heat, alkali, transition metal or metal oxides and carbon materials. Cobalt-based catalysts have proven to be the most effective catalysts for activating PMS, and unfortunately, the inevitable aggregation of Co Nanoparticles (NPs) and leaching of cobalt ions have limited their further practical application. Therefore, there is a need to develop more efficient and environmentally friendly cobalt-based heterogeneous catalysts for advanced oxidation.
In recent years, researches show that the transition metal two-dimensional nanomaterial with high specific surface area and abundant reactive sites has excellent performance of activating PMS. E.g. CoO, Co3O4、MoS2FeOOH, LDH and the like are all synthesized into nanosheet deactivated PMS. In the field of aqueous environmental treatment, however, transition metal ion leaching has been a problem. The metal ions with higher concentration are not only difficult to remove, but also cause great harm to the environment and human bodies. Therefore, the preparation of the transition metal material with good catalytic performance and stability has profound significance to the environment.
Disclosure of Invention
In view of this, the invention aims to provide a preparation method and application of a P-Co/CoO heterojunction nano material. The material provided by the invention is a P-Co/CoO heterojunction material with good catalytic activity, and has the morphological characteristics of both sheet shape and particle shape. After the red phosphorus is added for firing, the P-Co/CoO heterojunction material has good catalytic activity and stability. The material can catalyze and activate PMS to generate high-oxidability SO4 ·—And OH (reactive oxygen species) degrades pollutants harmful to the human body in the environment. In addition, when the loading amount of the material is only 0.01g/L, 99% removal rate of SMX can be realized within 8min, and the material has good stability and cyclicity.
The preparation method of the P-Co/CoO heterojunction nano material comprises the following steps:
step 1: co (OH)2Preparation of sheet-like nanomaterial
150ml of deionized water was weighed into a round bottom flask, and 0.945g of HMT and 0.36g of CoCl were weighed2·6H2O is added into the reaction system, N2Heating to 95 ℃ under the atmosphere, refluxing, stirring for reaction for 4 hours, and naturally cooling to room temperature to obtain Co (OH)2Collecting the precursor by vacuum filtration, washing with water and ethanol for several times, and drying in a vacuum drying oven for 12 hr to obtain pink Co (OH)2A precursor.
Step 2: preparation of P-Co/CoO heterojunction nano
Weighing 40mgCo (OH)2Putting the precursor and 2mg of red phosphorus into a quartz tube with the outer diameter of 8mm, the inner diameter of 6mm and the length of 15cm, sealing the tube in vacuum, putting the tube into a muffle furnace, heating to 300 ℃, keeping the temperature for 12h, and naturally cooling to room temperature after the heating to obtain black P-Co/CoO heterojunction nano-deviceRice material.
The P-Co/CoO heterojunction nano material is a morphology characteristic of combination of particles and sheets, the length of the sheet material is 2-3 mu m, and the particle size of the particle material is 200-400 nm.
The P-Co/CoO heterojunction nano material is applied as a catalyst to catalyze and degrade pollutants which are difficult to degrade in the environment.
The P-Co/CoO heterojunction nano material has the capability of catalyzing and activating PMS, and can convert PMS into a highly-oxidative active species SO at room temperature4 ·—And OH, thereby the pollutants which are difficult to degrade in the environment are oxidized into harmless small molecular substances or directly mineralized into CO2And H2O。
The refractory contaminant comprises Sulfamethoxazole (SMX).
SMX (sulfamethoxazole) is one of the major drug contaminants detectable in aquatic environments due to its abuse in treating human diseases and incomplete metabolism in humans, and prolonged exposure to SMX may alter microbial community structure, induce the evolution and spread of drug-resistant bacteria and genes, and cause other adverse effects on ecosystem and human health. The material obtained by the invention can catalyze and activate PMS to generate high-oxidability SO4 ·—And OH (reactive oxygen species) degrades pollutants harmful to the human body in the environment. Meanwhile, under the condition of room temperature, when the adding amount of the material in the degradation reaction is only 0.01g/L (in the embodiment 4, the PMS dosage and the initial pH of the solution in the degradation reaction process are respectively regulated and controlled, and the influence of different PMS concentrations and different pH values on the degradation efficiency is analyzed), the 99% removal rate of the SMX can be realized within 8min, and the stability and the cyclicity are good.
On one hand, the P-Co/CoO heterojunction nano material obtained by the invention can activate PMS to generate SO4 ·—And. OH degradation of emerging pollutants in the environment; on the other hand, the prepared P-Co/CoO heterojunction nano material can remove pollutants with extremely small dosage.
Compared with the prior art, the invention has the beneficial effects that:
1. the preparation method is simple, low in cost and easy to operate, and the heterojunction material can be obtained by adopting simple reflux distribution and heat treatment.
2. The P-Co/CoO heterojunction nano material prepared by the invention can rapidly degrade organic pollutants in the environment with less catalyst and PMS.
3. The P-Co/CoO heterojunction nano material prepared by the invention can realize the removal of pollutants within a short time only by using the concentration of 0.01 g/L.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) of P-Co/CoO heterojunction nanomaterial, as can be seen from FIG. 1, Co (OH)2The surface of the CoO nanosheet is smooth and flaky, fine micropores are formed on the surface of the CoO nanosheet, and the P-Co/CoO calcined by adding red P is a heterojunction structure with both flaky and granular structures.
Fig. 2 is an XRD pattern of P-Co/CoO heterojunction nano material, and characteristic peaks of Co are found at 2 θ of 41.683 °, 44.762 °, 47.568 °, 62.726 ° and 75.939 °, respectively corresponding to (100), (002), (101), (102) and (110) crystal planes of Co (jcpdsno. 05-0727). Characteristic peaks of cubic CoO are found at 2 θ of 36.492 °, 42.387 °, 61.497 °, 73.673 ° and 77.532 °, and correspond to crystal planes (111), (200), (220), (311) and (222) (JCPDS nos. 48 to 1719), which proves that two crystal forms exist in the material.
FIG. 3 is a Fourier infrared spectrum of CoO and P-Co/CoO.
FIG. 4 is a diagram of a solution of P-Co/CoO heterojunction nanomaterial activated PMS degraded SMX (10 mg/L).
FIG. 5 is the effect of PMS on degradation in a P-Co/CoO/PMS system.
FIG. 6 is the effect of quencher on degradation in the P-Co/CoO/PMS system.
FIG. 7 is a cyclicity test of P-Co/CoO heterojunction nanomaterials.
Detailed Description
Example 1: preparation of the target product
1、Co(OH)2Preparation of nanosheets
Weighing 150ml of deionized water and putting into a round-bottom flask0.945gHMT and 0.36gCoCl were weighed2·6H2O is added into the reaction system, N2Heating to 95 ℃ under the atmosphere, refluxing, stirring for 12h, and naturally cooling to room temperature. Will produce Co (OH)2The precursor is collected by adopting a vacuum filtration method, washed by water and ethanol for a plurality of times and dried in a vacuum drying oven for 12 hours. Thus obtaining light green Co (OH)2A precursor.
2. Preparation of P-Co/CoO heterojunction
Weighing 40mgCo (OH)2And putting the precursor and 2mg of red phosphorus into a quartz tube with the outer diameter of 8mm, the inner diameter of 6mm and the length of 15cm, sealing the tube in vacuum, putting the tube into a muffle furnace, heating to 300 ℃, keeping the temperature for 12h, and naturally cooling to room temperature after the heating to obtain the black P-Co/CoO heterojunction nano material.
Example 2: activating PMS to generate SO4 ·—And OH degradation of SMX
1mg of P-Co/CoO material was uniformly dispersed in 100ml of 10mg/L SMX solution, and the change in concentration of SMX was measured by high performance liquid chromatography. FIG. 3 is a diagram of SMX solution of 10mg/L degradation of P-Co/CoO heterojunction nanomaterial activated PMS, and it can be seen from the diagram that pure PMS hardly degrades SMX in the absence of catalyst, and after the catalyst is added, the catalyst can degrade more than 99% within 8min, and Co (OH)2Compared with a CoO nanosheet activated PMS, the material is degraded by 33.1% and 42.9% within 8min respectively, and the material is proved to have the effect of activating PMS to degrade SMX.
Example 3: FT-IR of P-Co/CoO and Co/CoO
Wavenumber is 1186cm-1And 985cm-1Symmetric stretching vibration and asymmetric stretching vibration respectively belonging to P-O, and 1028cm-1 belongs to PO2 -、PO3 -The bending vibration of (2) proves that red phosphorus generates phosphate species on the surface of the catalyst.
Example 4:
FIG. 4 is the effect of PMS and pH on degradation in a P-Co/CoO/PMS system. It can be seen from the figure that four different concentrations of PMS were used to degrade SMX while keeping the other variables (temperature, pH, catalyst loading, contaminant concentration) constant. 90.5 percent, 99 percent, 97.1 percent and 83.9 percent of the PMS can be degraded within 8min under the four concentrations of 0.05g/L, 0.1g/L, 0.2g/L and 0.3g/L, wherein the effect of 0.1g/L is the best, and the effect of inhibiting the degradation effect can be generated by continuously increasing the concentration of the PMS. In addition, pH exhibits varying degrees of inhibitory effect on degradation reactions under both acidic and basic conditions.
Example 5:
FIG. 5 is a graph of the effect of a quencher on degradation in a P-Co/CoO/PMS system. Previous studies have shown that MeOH (methanol) is SO4 —·And effective quenching agent (k) of OHMeOH,SO4—.＝3.2×106M-1·s-1，kMeOH,·OH＝9.7×108M-1·s-1) TBA (t-Butanol) is a highly efficient quencher (k) for OHTBA,·OH＝3.8-7.6×108M-1·s-1). As can be seen from the figure, both MeOH and TBA have inhibition effect on the degradation of SMX by the P-Co/CoO/PMS system, and the higher the concentration of the alcohol, the more obvious the quenching effect is. Furthermore, MeOH inhibition was significantly greater than TBA. SO that the active species participating in the reaction contains SO4 —·And OH.
Example 6:
FIG. 6 is a cyclicity test of P-Co/CoO heterojunction nanomaterials. As shown in the figure, 5 cycles are performed, the degradation rates of SMX in 5 cycles respectively reach 99%, 98.6%, 96.5%, 92.2 and 87.2%, the former four cycles all reach more than 90%, and the fifth cycle can still reach more than 85%. The catalyst has better stability and circulation performance.
Claims (9)
1. A preparation method of a P-Co/CoO heterojunction nano material is characterized by comprising the following steps:
step 1: co (OH)2Preparation of sheet-like nanomaterial
Putting deionized water into a round-bottom flask, and weighing HMT and CoCl2·6H2O is added into the reaction system, N2Heating to 95 ℃ under the atmosphere for reflux, stirring for reaction for 4 hours, and naturally cooling to room temperatureWill produce Co (OH)2Collecting the precursor by vacuum filtration, washing with water and ethanol, and vacuum drying to obtain pink Co (OH)2A precursor;
step 2: preparation of P-Co/CoO heterojunction sheet material
Mixing Co (OH)2And putting the precursor and red phosphorus into a quartz tube, sealing the quartz tube in vacuum, putting the quartz tube into a muffle furnace, heating and sintering, and naturally cooling to room temperature after the sintering is finished to obtain the black P-Co/CoO heterojunction nano material.
2. The method of claim 1, wherein:
in step 1, the amount of HMT added was 0.945g and CoCl2·6H2The amount of O added was 0.36 g.
3. The production method according to claim 1, characterized in that:
in step 2, Co (OH)2The addition amount of the precursor was 40mg, and the addition amount of red phosphorus was 2 mg.
4. The method of claim 1, wherein:
in the step 2, the sintering temperature is 300 ℃, and the sintering time is 12 h.
5. The method of claim 1, wherein:
the P-Co/CoO heterojunction nano material is a morphology characteristic of combination of particles and sheets, the length of the sheet material is 2-3 mu m, and the particle size of the particle material is 200-400 nm.
6. The application of the P-Co/CoO heterojunction nano material prepared by the preparation method according to any one of claims 1 to 5 is characterized in that: the catalyst is used for catalyzing and degrading pollutants which are difficult to degrade in the environment.
7. Use according to claim 6, characterized in that:
the refractory contaminant comprises sulfamethoxazole.
8. Use according to claim 7, characterized in that:
the P-Co/CoO heterojunction sheet material has the capability of catalytically activating PMS, and can convert PMS into a highly-oxidative active species SO at room temperature4 ·—And OH, thereby oxidizing the refractory pollutants in the environment into harmless small molecular substances or directly mineralizing into CO2And H2O。
9. Use according to claim 7, characterized in that:
during catalytic degradation, the addition amount of the P-Co/CoO heterojunction sheet material is 0.01g/L, and the dosage of PMS is 0.1 g/L.
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