CN114130402B - Iron-molybdenum-loaded algae-based carbon material and preparation method and application method thereof - Google Patents
Iron-molybdenum-loaded algae-based carbon material and preparation method and application method thereof Download PDFInfo
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- 241000195493 Cryptophyta Species 0.000 title claims abstract description 68
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 28
- DSMZRNNAYQIMOM-UHFFFAOYSA-N iron molybdenum Chemical compound [Fe].[Fe].[Mo] DSMZRNNAYQIMOM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 27
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 20
- 238000004140 cleaning Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 10
- 231100000719 pollutant Toxicity 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 241000195649 Chlorella <Chlorellales> Species 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 6
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 235000016425 Arthrospira platensis Nutrition 0.000 claims description 4
- 240000002900 Arthrospira platensis Species 0.000 claims description 4
- 241000192656 Nostoc Species 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229940082787 spirulina Drugs 0.000 claims description 4
- 239000006228 supernatant Substances 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 230000003213 activating effect Effects 0.000 abstract description 6
- 150000002751 molybdenum Chemical class 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 238000011068 loading method Methods 0.000 abstract description 2
- POUMFISTNHIPTI-BOMBIWCESA-N hydron;(2s,4r)-n-[(1r,2r)-2-hydroxy-1-[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-methylsulfanyloxan-2-yl]propyl]-1-methyl-4-propylpyrrolidine-2-carboxamide;chloride Chemical compound Cl.CN1C[C@H](CCC)C[C@H]1C(=O)N[C@H]([C@@H](C)O)[C@@H]1[C@H](O)[C@H](O)[C@@H](O)[C@@H](SC)O1 POUMFISTNHIPTI-BOMBIWCESA-N 0.000 description 21
- 229960001595 lincomycin hydrochloride Drugs 0.000 description 21
- 230000003197 catalytic effect Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- 229910017116 Fe—Mo Inorganic materials 0.000 description 11
- 230000004913 activation Effects 0.000 description 6
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 5
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012851 eutrophication Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000701 chemical imaging Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/881—Molybdenum and iron
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an iron-molybdenum supported algae-based carbon material, a preparation method and an application method thereof, wherein the preparation method comprises the following steps: s1: dissolving algae powder in ferric salt, stirring and centrifuging to obtain algae cells; s2: performing alkali treatment on the algae cells obtained in the step S1 and cleaning; s3: calcining the algae cells obtained in the step S2 to obtain an iron-loaded algae-based carbon material, and drying and grinding the material; s4: dispersing molybdenum salt and the algae-based carbon material obtained in the step S3 in a solvent, and drying and grinding the materials into powder; s5: and (3) calcining the powder obtained in the step (S4), and cleaning and grinding the product obtained by calcining to obtain the iron-molybdenum supported algae-based carbon material. According to the iron-molybdenum-loaded algae-based carbon material, the preparation method and the application method thereof, active species can be generated by activating persulfate through nitrogen doping and iron-molybdenum loading, the degradation capability of target pollutants is improved, the preparation method is simple, the cost is low, the recycling treatment of algae is realized, and the method has a very good application prospect.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to an iron-molybdenum-loaded algae-based carbon material, and a preparation method and an application method thereof.
Background
Eutrophication of lakes has been the focus of attention in the field of water environments for nearly twenty years, and is one of the biggest environmental problems facing humans, and when microalgae are propagated in large quantities due to eutrophication in rivers and lakes, timely removal of microalgae biomass is still the most direct and effective method. The microalgae collected by the mechanical method can be further subjected to recycling treatment. Microalgae are rich in abundant nutrients, and are widely applied to the fields of foods, energy sources, medical science and the like at present, and the application in the field of water environment is still to be further explored.
Advanced oxidation techniques are novel pollution remediation techniques based on in situ generation of highly oxidizing active species, utilizing the generated active species to further interact with and remove target pollutants. It is now widely used in drinking water and wastewater treatment, it can complement and complement traditional water treatment technology, it is a high-efficiency and environment-friendly water treatment technology, and advanced oxidation technology based on persulfate treatment is increasingly attracting attention of researchers. In addition, the traditional advanced oxidation technology has the defects of high cost, too severe reaction, low effective utilization rate of active species and the like, and the method for activating the functional material aiming at persulfate also becomes a research hotspot. However, the following problems exist in the existing method for activating the functional material aiming at persulfate: first, the high cost limits large-scale applications, and second, the activation is less effective.
The foregoing background is only for the purpose of facilitating an understanding of the principles and concepts of the invention and is not necessarily in the prior art to the present application and is not intended to be used as an admission that such background is not entitled to antedate such novelty and creativity by the present application without undue evidence prior to the present application.
Disclosure of Invention
In order to solve the technical problems, the invention provides the iron-molybdenum supported algae-based carbon material, and the preparation method and the application method thereof, which greatly reduce the cost and simultaneously remarkably improve the catalytic activity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the invention discloses a preparation method of an iron-molybdenum supported algae-based carbon material, which comprises the following steps:
s1: dissolving algae powder in ferric salt, stirring and centrifuging to obtain algae cells;
s2: performing alkali treatment on the algae cells obtained in the step S1 and cleaning;
s3: calcining the algae cells obtained in the step S2 to obtain an iron-loaded algae-based carbon material, and drying and grinding the material;
s4: dispersing molybdenum salt and the algae-based carbon material obtained in the step S3 in a solvent, and drying and grinding the materials into powder;
s5: and (3) calcining the powder obtained in the step (S4), and cleaning and grinding the product obtained by calcining to obtain the iron-molybdenum supported algae-based carbon material.
Preferably, the algae powder in step S1 is at least one of chlorella powder, spirulina powder and nostoc powder.
Preferably, ferric sulfate is adopted as the ferric salt in the step S1, and the mass fraction of the ferric salt is 4% -7%.
Further, the rotational speed of the centrifugation step in step S1 is 5000 to 6000 rpm.
Preferably, naOH solution or NaHCO solution is used in step S2 3 And (3) carrying out alkali treatment and cleaning on the algae cells obtained in the step (S1) at a preset temperature by the solution.
Further, the preset temperature is 75-80 ℃ and the time is 2-4 hours.
Preferably, in the step S2, the washing step is performed using ultrapure water specifically until the ph of the supernatant is neutral.
Further, the washing step is repeated 8 to 10 times.
Preferably, the protective gas in the calcining step in the step S3 and the step S5 is nitrogen, the calcining temperature is 450-500 ℃, the calcining time is 2-3 h, and the heating rate is 2-2.5 ℃/min.
Preferably, the molybdenum salt in step S4 is ammonium molybdate tetrahydrate.
Further, step S4 specifically includes: dispersing 0.2-0.4 g of ammonium molybdate tetrahydrate and 0.8-1 g of the algae-based carbon material obtained in the step S3 in 100-200 mL of ethanol by ultrasonic treatment, vigorously stirring, drying and grinding into powder, wherein the temperature in the step of vigorously stirring is 70-80 ℃.
Preferably, in step S5, the calcined product is washed with ethanol and ultrapure water; the drying temperature is 60-70 ℃ after the cleaning is finished.
The invention also discloses an iron-molybdenum supported algae-based carbon material prepared by the preparation method.
The invention further discloses an application method of the iron-molybdenum supported algae-based carbon material, which comprises the following steps: adding persulfate and the iron-molybdenum supported algae-based carbon material prepared by the preparation method into water containing target pollutants, and fully stirring for reaction.
Further, potassium hydrogen persulfate is used as the persulfate, and the concentration of the persulfate is 0.1 mM-4 mM.
Compared with the prior art, the invention has the beneficial effects that: according to the preparation method of the iron-molybdenum-loaded algae-based carbon material, algae are used as a synthesis raw material, the algae are recycled, nitrogen-doped biochar materials are synthesized by utilizing nitrogen elements rich in the algae, persulfate can be efficiently activated to degrade organic pollutants, and the catalytic activity of the traditional carbon material is remarkably improved. The iron salt and the molybdenum salt are introduced, so that on one hand, the active site for catalyzing persulfate is increased, the catalytic activation efficiency of the algae-based carbon material is improved, and meanwhile, the synthesized magnetic material can be effectively separated, so that the method has a good application prospect.
Drawings
FIG. 1 is a flow chart of a method for preparing an iron-molybdenum supported algae-based carbon material in accordance with a preferred embodiment of the present invention;
FIG. 2a is a surface topography map image of an unmodified algae-based carbon material;
FIGS. 2b and 2c are surface topography images of an iron-molybdenum loaded algae-based carbon material of example 1;
FIGS. 2d to 2h are spectral imaging diagrams of the iron-molybdenum supported algae-based carbon material of example 1;
FIG. 3a is an XRD contrast analysis of 6 materials prepared;
FIG. 3b is a graph showing the diffraction peaks of NaOH-Fe-Mo@N-MBC material compared to those of a standard substance;
FIG. 4 is a graph of the effect of different catalytic materials to activate persulfate to degrade lincomycin hydrochloride versus time;
FIG. 5a is a graph showing the effect of removing lincomycin hydrochloride with time when PMS with different concentrations is added under the catalysis of NaOH-Fe-Mo@N-MBC;
FIG. 5b is a graph of the effect of different initial pH on lincomycin hydrochloride degradation over time;
FIG. 5c is a graph of the effect of different reaction temperatures on lincomycin hydrochloride degradation over time;
FIG. 6a is a graph showing the effect and recovery performance of NaOH-Fe-Mo@N-MBC for degrading lincomycin hydrochloride by activating persulfate in four continuous catalytic processes;
FIG. 6b shows the color of the solution after various times of reaction in the catalytic cycle.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved by the embodiments of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and the embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The nano metal material, the carbon nano tube, the graphene and the like can effectively activate persulfate to generate active species to degrade organic pollutants in the water body, but the large-scale application of the nano metal material is severely limited due to the high cost. The biochar-based material has the characteristics of large specific surface area, rich oxygen-containing functional groups, strong electron transfer capability and the like, and is initially researched to be used in persulfate activation research, but the common biochar has very limited activation effect on persulfate. Based on the analysis, the development of the recovered algae through modification treatment into the functional material capable of being used for persulfate activation has very important significance.
As shown in fig. 1, the preferred embodiment of the invention discloses a preparation method of an iron-molybdenum supported algae-based carbon material, which comprises the following steps:
s1: dissolving a certain amount of algae powder in ferric salt, stirring and centrifuging, and washing off redundant saline solution;
wherein the algae powder can be at least one of chlorella powder, spirulina powder and nostoc powder; the ferric salt is ferric sulfate, and the mass fraction of the ferric salt is 4% -7%; the rotation speed of centrifugal separation is 5000-6000 rpm;
s2: using NaOH solution or NaHCO solution respectively 3 Alkali treatment is carried out on the algae cells by the solution at high temperature and the algae cells are washed;
wherein the alkali treatment step is specifically hot alkali liquid treatment, the temperature of the hot alkali liquid treatment is 75-80 ℃ and the time can be 2-4 hours. The washing step is carried out by using ultrapure water, and the washing is carried out until the pH value of the supernatant is neutral, which is about 8-10 times.
S3: after the treatment is finished, transferring the algae cells into a tube furnace, firing under certain conditions, preparing the iron-loaded algae-based carbon material, and then drying and grinding;
wherein the calcination protecting gas is nitrogen in the firing step, the high-temperature calcination temperature is 450-500 ℃, the calcination time is 2-3 h, and the heating rate is 2-2.5 ℃/min.
S4: dispersing molybdenum salt and the prepared algae-based carbon material in ethanol by ultrasonic, and drying and grinding the obtained black mixture into powder under intense stirring;
specifically, the molybdenum salt is ammonium molybdate tetrahydrate, and 0.2-0.4 g of ammonium molybdate tetrahydrate and 0.8-1 g of prepared powder are dispersed in 100-200 mL of ethanol by ultrasonic treatment. The temperature in the vigorous stirring step is 70-80 ℃.
S5: and (3) putting the substances back into the tube furnace again, calcining under certain conditions, cleaning the calcined product, and grinding to obtain the metal-loaded algae-based carbon material.
Wherein the protective gas for gathering calcination in the tube furnace is nitrogen; the high-temperature calcination temperature is 450-500 ℃; the calcination time is 2-3 h, and the heating rate is 2-2.5 ℃/min; cleaning the calcined reactant by adopting ethanol and ultrapure water; the drying temperature after the cleaning is finished is 60-70 ℃.
Wherein the target pollutant in the water treatment in the above step can be lincomycin hydrochloride.
In the preferred embodiment of the invention, different kinds of microalgae are added into ferric salt solution, and after pretreatment, the microalgae are pyrolyzed at high temperature, and then metal Mo is further loaded, so that the microalgae are prepared by high-temperature carbonization. The method introduces the ferroferric oxide and the molybdenum dioxide with high-efficiency catalytic activity, improves the catalytic capability of the material, and simultaneously, the load of the ferroferric oxide can increase the magnetism of the material, so that the ferroferric oxide is easy to separate after reaction. The prepared material can efficiently activate persulfate to generate active species through nitrogen doping and metal loading, so that the degradation capability of target pollutants is improved.
Another preferred embodiment of the invention discloses an iron-molybdenum supported algae-based carbon material prepared by the preparation method.
The invention discloses an application method of an iron-molybdenum loaded algae-based carbon material, which comprises the following steps: adding potassium hydrogen persulfate and an iron-molybdenum supported algae-based carbon material into water containing target pollutants, and fully stirring for reaction. Wherein the persulfate is used at a concentration of 0.1 mM-4 mM.
The following describes the preparation method and application method of the iron-molybdenum supported algae-based carbon material according to the preferred embodiment of the present invention with specific examples.
Example 1:
firstly, 30g of chlorella powder, spirulina or nostoc are dissolved in 300ml of 4wt% ferric sulfate solution, after stirring continuously for 12 hours at room temperature, the chlorella cells are separated by centrifugation at 4000rpm for a plurality of times, the redundant salt solution is washed away, then the chlorella cells are subjected to alkali treatment at 80 ℃ for 4 hours by using 5% NaOH solution, after the treatment is finished, the chlorella cells are subjected to centrifugal cleaning by using pure water for a plurality of times until the pH value of supernatant is neutral. Transferring the algae cells into a tube furnace for pyrolysis, heating for 2 hours at 500 ℃ in a nitrogen environment at a heating rate of 2.5 ℃/min to prepare the iron-loaded microalgae-based carbon material (Fe-MBC), and then carrying out ultrasonic treatment on 0.4g of ammonium molybdate tetrahydrate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) and 1g of the prepared Fe-MBC were dispersed in 100mL of ethanol, and the resulting black mixture was dried under vigorous stirring at 80 ℃. The solid black precursor is ground to a fine powder and then at N 2 Calcining at 500 ℃ for 2h in the stream. The reaction product was harvested and expressed as Mo-Fe-MBC. Then cooling the temperature to room temperature to take out the sample for useAnd (3) cleaning organic impurities on the surface of the product by ethanol, cleaning part of inorganic impurities on the surface by ultrapure water, drying at 60 ℃, grinding for later use, and marking as NaOH-Fe-Mo@N-MBC.
Fig. 2a to 2h show scanning electron microscope images and energy spectrum analysis diagrams of the material prepared in example 1, fig. 2a shows images of an unmodified algae-based carbon material, fig. 2b and 2c show images after iron and molybdenum are loaded, and it can be seen that the prepared algae-based carbon material is in nano-particles, and can be found that Fe and Mo are successfully loaded in the material by combining with an energy spectrum, and an obvious thin rod-shaped structure is shown after molybdenum doping, and the material is doped in the nano-particles, so that a certain bridge effect is achieved. Fig. 2d to 2h are EDS element imaging cases, fig. 2d shows a case where C element is in the material, fig. 2e shows a case where O element is in the material, fig. 2f shows a case where Na element is in the material, fig. 2g shows a case where Fe element is in the material, and fig. 2h shows a case where Mo element is in the material.
Referring to the method of example 1, 6 kinds of microalgae carbon materials were synthesized in total, and the methods were as follows: (1) N-MBC; (2) NaOH@N-MBC; (3) NaOH-Fe@N-MBC; (4) NaOH-Mo@N-MBC; (5) NaOH-Fe-Mo@N-MBC; (6) NaHCO (NaHCO) 3 @ N-MBC, wherein Fe, mo represent the doping metal type.
Characterization is carried out on the activation performance of the prepared material, lincomycin hydrochloride (LCH) is selected as a target pollutant, and the catalytic activity of different catalytic materials is evaluated according to the degradation efficiency of the LCH. Adding 0.02g of sample into 100mL of LCH solution with initial concentration of 10mg/L, stirring for 30min to reach adsorption-desorption balance, then adding 1mmol/L of Peroxymonosulfate (PMS) to start catalytic degradation reaction, extracting 1mL of sample at specified time of 0min, 2min, 5min, 10min, 20min, 30min, 60min and 90 min), rapidly filtering the sample with a 0.22 mu m organic nylon filter head, adding 1mL of methanol to terminate the reaction, diluting for 10 times, and determining the LCH concentration by using liquid phase mass spectrometry (LC-MC/MC).
FIG. 3a is a XRD contrast analysis chart of 6 materials prepared, FIG. 3b shows a comparison chart of diffraction peaks of NaOH-Fe-Mo@N-MBC material and a standard substance, and as can be seen in combination with FIG. 3a and FIG. 3b, iron in the loaded material is mainly represented by fourIn the form of ferric oxide, molybdenum is mainly in the form of molybdenum dioxide, and in addition, fe 3 N is present.
FIG. 4 shows the effect of different catalytic materials for activating persulfate to degrade lincomycin hydrochloride, the catalytic effect of NaOH-Fe-Mo@N-MBC is optimal, target pollutants in a system can be completely degraded after 30min of reaction, N-MBC can play a certain role in activating persulfate through a special carbon hybridization form, and Mo with high-efficiency catalytic activity is successfully introduced. In FIG. 4, the initial concentration of PMS was 1mM, the initial concentration of lincomycin hydrochloride (LCH) was 10mg/L, and the concentration of catalyst was 0.2g/L.
FIG. 5a compares the degradation effect of different dosing amounts of the agents on lincomycin hydrochloride, with the reaction efficiency increasing as the dosing amount of the agent increases, and after reaching the concentration limit, the activity limit of the reacted catalyst. Figure 5b shows the effect on lincomycin hydrochloride degradation at different initial pH conditions, with less effect on the reaction at acidic and acidic conditions. Fig. 5c compares the effect of different reaction temperatures on the degradation effect of lincomycin hydrochloride, and it can be seen that the effect of temperature on the degradation effect is not great. In FIGS. 5a to 5c, the initial concentration of lincomycin hydrochloride (LCH) was 10mg/L and the concentration of NaOH-Fe-Mo@N-MBC was 0.2g/L.
FIG. 6a shows the recycling property and the recycling property of the prepared NaOH-Fe-Mo@N-MBC material, and it can be seen that the catalytic material still has high catalytic activity after 4 times of recycling and can be well separated from an aqueous solution. FIG. 6b shows the color of the solution after various times of the reaction in the catalytic cycle, from which it can be seen that the color of the solution has changed considerably after 10s of reaction and is almost transparent after 10min of reaction. In FIGS. 6a and 6b, the initial concentration of PMS was 1mM, the initial concentration of lincomycin hydrochloride (LCH) was 10mg/L, and the concentration of NaOH-Fe-Mo@N-MBC was 0.2g/L.
The result shows that the prepared NaOH-Fe-Mo@N-MBC material can well degrade target pollutants in water.
The background section of the present invention may contain background information about the problem or environment of the present invention rather than the prior art described by others. Accordingly, inclusion in the background section is not an admission of prior art by the applicant.
The foregoing is a further detailed description of the invention in connection with specific/preferred embodiments, and it is not intended that the invention be limited to such description. It will be apparent to those skilled in the art that several alternatives or modifications can be made to the described embodiments without departing from the spirit of the invention, and these alternatives or modifications should be considered to be within the scope of the invention. In the description of the present specification, reference to the terms "one embodiment," "some embodiments," "preferred embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction. Although embodiments of the present invention and their advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope as defined by the appended claims.
Claims (13)
1. The preparation method of the iron-molybdenum supported algae-based carbon material is characterized by comprising the following steps of:
s1: dissolving algae powder in ferric salt, stirring and centrifuging to obtain algae cells;
s2: performing alkali treatment on the algae cells obtained in the step S1 and cleaning;
s3: calcining the algae cells obtained in the step S2 to obtain an iron-loaded algae-based carbon material, and drying and grinding the material;
s4: dispersing 0.2-0.4 g of ammonium molybdate tetrahydrate and 0.8-1 g of the algae-based carbon material obtained in the step S3 in 100-200 mL of ethanol solvent by ultrasonic treatment, and carrying out vigorous stirring, drying and grinding into powder, wherein the temperature in the step of vigorous stirring is 70-80 ℃;
s5: calcining the powder obtained in the step S4, and cleaning and grinding the calcined product to obtain an iron-molybdenum supported algae-based carbon material, wherein the material supported by the algae-based carbon material comprises Fe 3 O 4 、MoO 2 、Fe 3 N。
2. The method according to claim 1, wherein the algae powder in step S1 is at least one of chlorella powder, spirulina powder and nostoc powder.
3. The preparation method according to claim 1, wherein the ferric salt in the step S1 is ferric sulfate, and the mass fraction of the ferric salt is 4% -7%.
4. The method according to claim 3, wherein the rotational speed of the centrifugation step in step S1 is 5000 to 6000 rpm.
5. The method according to claim 1, wherein in step S2, naOH solution or NaHCO solution is used 3 And (3) carrying out alkali treatment and cleaning on the algae cells obtained in the step (S1) at a preset temperature by the solution.
6. The preparation method according to claim 5, wherein the preset temperature is 75-80 ℃ and the time is 2-4 hours.
7. The method according to claim 1, wherein the washing step in step S2 is performed by using ultrapure water until the ph of the supernatant is neutral.
8. The method of claim 7, wherein the washing step is repeated 8-10 times.
9. The preparation method according to claim 1, wherein the protective gas in the calcining step in the step S3 and the step S5 is nitrogen, the calcining temperature is 450-500 ℃, the calcining time is 2-3 h, and the heating rate is 2-2.5 ℃/min.
10. The preparation method according to claim 1, wherein the calcined product is washed with ethanol and ultrapure water in step S5; and the drying temperature is 60-70 ℃ after the cleaning is finished.
11. An iron molybdenum supported algae based carbon material prepared by the preparation method of any one of claims 1 to 10.
12. An application method of an iron-molybdenum supported algae-based carbon material is characterized by comprising the following steps: adding persulfate and the iron-molybdenum-supported algae-based carbon material prepared by the preparation method of any one of claims 1 to 10 into water containing target pollutants, and fully stirring for reaction.
13. The method of claim 12, wherein the persulfate salt is potassium persulfate, and the concentration of the persulfate salt is 0.1mM to 4mM.
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