CN115430448A - Catalyst for activating peroxymonosulfate to selectively oxidize sulfamethoxazole as well as preparation and application of catalyst - Google Patents
Catalyst for activating peroxymonosulfate to selectively oxidize sulfamethoxazole as well as preparation and application of catalyst Download PDFInfo
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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 title claims abstract description 54
- 229960005404 sulfamethoxazole Drugs 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 230000003213 activating effect Effects 0.000 title claims abstract description 11
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 title claims abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229920001690 polydopamine Polymers 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002351 wastewater Substances 0.000 claims abstract description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000003115 biocidal effect Effects 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000001291 vacuum drying Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000004108 freeze drying Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 12
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 10
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 8
- 238000003837 high-temperature calcination Methods 0.000 claims description 8
- 238000000197 pyrolysis Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000006228 supernatant Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000004913 activation Effects 0.000 abstract description 8
- 150000003254 radicals Chemical class 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 5
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 230000008685 targeting Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000001994 activation Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- -1 sulfate radical Chemical class 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 206010061695 Biliary tract infection Diseases 0.000 description 1
- 206010013654 Drug abuse Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 206010062255 Soft tissue infection Diseases 0.000 description 1
- 229940123317 Sulfonamide antibiotic Drugs 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 206010048038 Wound infection Diseases 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 208000003167 cholangitis Diseases 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002289 effect on microbe Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 210000001035 gastrointestinal tract Anatomy 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical class S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000010801 sewage sludge Substances 0.000 description 1
- 210000004872 soft tissue Anatomy 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 208000011117 substance-related disease Diseases 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 208000019206 urinary tract infection Diseases 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
- C02F2101/40—Organic compounds containing sulfur
Abstract
The invention relates to a catalyst for selectively oxidizing sulfamethoxazole by efficiently activating peroxymonosulfate, and a preparation method and application thereof. The catalyst is polydopamine PDACB codoped with nitrogen and boron, wherein the atomic proportion of N element is 2.00-5.00%, and the atomic proportion of B element is 25.00-35.00%. By utilizing the self-polymerization characteristic of PDA, a PDA-derived nitrogen-doped carbon material (PDAC) is used as a carbon source and a nitrogen source, boric acid is used as a B source, the polydopamine-derived N, B co-doped targeting carbon-based catalyst PDACB activated PMS is prepared, and the purpose is to selectively oxidize and degrade the SMX which is a typical pollutant through a non-free radical way of interface electron transfer. The carbon-based material disclosed by the invention is green, environment-friendly and economical, can be synthesized on a large scale, has a simple synthesis process and low cost, can enhance the activation effect on PMS under a wide pH condition, can realize recycling, and can be applied to selective oxidation treatment of activated PMS on SMX in antibiotic wastewater.
Description
Technical Field
The invention relates to a catalyst for efficiently activating Permonosulfate (PMS) to selectively oxidize Sulfamethoxazole (SMX), and preparation and application thereof, belonging to the field of antibiotic wastewater treatment processes and novel catalytic materials and preparation, and being specifically applied to activating PMS to selectively oxidize SMX in antibiotic wastewater.
Background
Sulfamethoxazole (SMX) is a commonly used sulfonamide antibiotic and is mainly used for urinary tract infection, respiratory system infection, intestinal tract infection, biliary tract infection and local soft tissue or wound infection caused by sensitive bacteria. Although SMX is at a sustained low level in water (μ g.L) -1 Or ng.L -1 ) But it presents significant ecotoxicity. Human and animal drug abuse causes excessive residues in SMX surface and ground water, resulting in the development of drug resistance genes in humans. The residual SMX has strong inhibition effect on microorganisms, and the expected treatment effect cannot be achieved by the traditional biochemical treatment. Therefore, it is important to develop efficient and cost effective treatment techniques to remove residual SMX from aqueous environments.
To date, a number of water treatment technologies have been developed and applied to remove SMX from water bodies, mainly including adsorption, membrane bioreactor, biochemical and Advanced Oxidation Processes (AOPs). Most methods achieve ideal performance in the residual SMX treatment research in water, but have certain limitations. Therefore, to completely remove SMX from water, the activated persulfate advanced oxidation process is currently the first candidate for most researchers, with the following advantages: high oxidation potential of sulfate radical, (2) long half-life period, and (3) wide pH application range. The sulfate radical can be obtained by catalyzing Peroxymonosulfate (PMS) through thermal activation, alkali activation, ultrasonic activation, transition metal ion activation and the like. Although the activation method of transition metal ions (such as Co, mn, ni, zn and the like) is simple to operate and does not consume external energy, a large amount of metal ions are inevitably dissolved out all the time, secondary pollution is brought to the environment, and the wide practical application of PMS-AOPs in water treatment is obviously limited. Therefore, aiming at the typical target antibiotic SMX in water, it is imperative to design an efficient, environment-friendly and economical activated PMS catalyst.
Thus, based onAccording to the current research situation, the basic idea of the invention is to use a Polydopamine (PDA) derived nitrogen-doped carbon material (PDAC) as a carbon source and a nitrogen source, and dope a heteroatom B by a simple roasting method to prepare a polydopamine derived N, B co-doped targeting carbon-based catalyst PDACB. The catalyst is applied to a catalytic PMS system, and typical pollutants SMX are selectively oxidized and degraded by using non-radical active species generated in the system. In one aspect, the activation mechanism of the PMS driven by the N, B-co-doped carbon-based material comprises the following aspects: (1) The graphite N with higher electronegativity leads the adjacent carbon to be positively charged through electron transfer, and conversion of PMS is facilitated 1 O 2 (ii) a (2) Pyrrole N with lone pair electrons and pyridine N form an electron-rich region which can be used as an active center for PMS electrophilic attack; (3) B possesses 3 valence electrons in the 2s and 2p orbitals, which can form sp like carbon materials 2 A hybrid structure, so that the electrons can effectively break the O-O bond of PMS to generate active free radicals; (4) The pyridine N and the B in the graphitized carbon skeleton have a good synergistic effect, so that the generation of non-radical active species is facilitated; (5) The carbonyl group (C = O) on the surface of PDACB may act to induce electron transfer from the organic contaminant (electron donor) to PMS (electron acceptor). On the other hand, the active species selectivity of the general activated PMS oxidation method is low, the wastewater composition is complex, the coexisting substrates are various in types and high in concentration, the interference on the removal of target pollutants is large, and the effective removal of trace target pollutants can be realized by using excessive PMS addition or energy input. The method not only obviously improves the treatment cost, but also is easy to accompany and poison byproducts and increases the environmental risk. Therefore, the development of the selective activated PMS oxidation technology has important significance for advanced water treatment technical innovation. The key to the development of the selective activated PMS oxidation technology is to design a targeted catalyst, search for an active site and deeply understand the mechanism of activated PMS. According to the invention, through synergistically regulating the reactivity of an oxidant PMS and the accessibility of a target pollutant SMX, namely an interface electron transfer path, a polydopamine-derived N, B co-doped targeted carbon-based catalyst PDACB is designed so as to realize the selective oxidation of the SMX in a water body.
Removal of sulfanilamide by oxidation of high-efficiency activated PMSIn the research field of oxazole, yinghao Li et al synthesized cobalt ferrite materials with different molar ratios by a coprecipitation method to activate PMS to degrade SMX, and the removal rate of SMX under the optimal condition was 91.00%. Yanshan Wang et al found, through studies, that the cow dung biogas residue-derived biochar (DMDB-800) was optimum under the conditions (catalyst addition amount 1.0 g. L- 1 The amount of PMS added was 2.5mM, pH 5.56, SMX concentration 15 mg. L- 1 ) Then, the removal rate of SMX within 60min was 90.20%. The red mud sewage sludge-derived biochar (RSDBC) synthesized by Jia Wang et al can remove 82.50% of SMX within 50min under the optimal conditions. Yan Xu et al successfully synthesized N, S co-doped biochar (N, S-BC) with a hierarchical pore structure from nanocellulose and thiourea through a one-step pyrolysis method, and activated PMS can be oxidized and degraded to 91.32% of SMX within 60 min.
Disclosure of Invention
The invention aims to provide a novel polydopamine-derived N, B co-doped targeting carbon-based catalyst PDACB, and the invention also aims to provide a preparation method of the catalyst; the invention also aims to provide the application of the catalyst in activating PMS in antibiotic wastewater to degrade SMX.
The technical scheme of the invention is as follows: a catalyst for activating Permonosulfate (PMS) to selectively oxidize Sulfamethoxazole (SMX) is characterized in that the catalyst is nitrogen (N) and boron (B) codoped polydopamine PDACB, wherein the atom proportion of N element is 2.00-5.00%, and the atom proportion of B element is 25.00-35.00%.
The invention provides a method for preparing the catalyst, which comprises the following steps:
(1) N doping: firstly, dropwise adding ammonia water into an ethanol solution at normal temperature and stirring, then adding dopamine hydrochloride into the mixed solution, and stirring at normal temperature; dripping acetone into the mixed solution, and standing and settling after the dripping is finished; centrifuging to remove supernatant, vacuum drying excess acetone, and freeze drying to obtain polydopamine PDA; finally, carrying out high-temperature calcination carbonization treatment on the polydopamine PDA material in a tube furnace under the protective atmosphere, after the reaction is finished and the temperature of the tube furnace is reduced to room temperature, washing the material with deionized water until the pH value of the filtrate is 6.50-7.00, and carrying out vacuum drying to obtain the nitrogen-doped carbon material PDAC derived from the polydopamine PDA material;
(2) B doping: and (2) carrying out high-temperature pyrolysis on the mixture of the nitrogen-doped carbon material PDAC and boric acid in a tube furnace under the protective atmosphere, after the reaction is finished, cooling the tube furnace to room temperature, washing the material with deionized water until the pH value of the filtrate is 6.50-7.00, and carrying out vacuum drying to obtain the material PDACB.
Preferably, the ethanol solution in the step (1) is a mixture of absolute ethanol and deionized water, and the volume ratio of the absolute ethanol to the deionized water is 1.00: (4.00-5.00); the ammonia water is an aqueous solution containing 25.00-28.00% of ammonia by mass fraction; the volume ratio of the ammonia water to the ethanol solution is 1.00: (20.00-25.00); the ratio of the mass of the dopamine hydrochloride to the volume of the ethanol solution is 20-40 g.L- 1 (ii) a The volume ratio of the ethanol solution to the acetone is 1.00: (2.00-3.00).
Preferably, the stirring speed when the ammonia water is dripped in the step (1) is 200-300rpm, and the stirring time is 20-30min; adding dopamine hydrochloride, and stirring at 250-350rpm for 20-30h; standing for 24-48h.
Preferably, the temperature of the freeze drying in the step (1) is-60 ℃ to-45 ℃; the freeze drying time is 24-48h.
Preferably, the temperature for vacuum drying the excessive acetone in the step (1) is 50-60 ℃, and the vacuum drying time is 20-40min; the temperature of the vacuum drying is 80-100 ℃, and the time of the vacuum drying is 12-18h; the temperature of the vacuum drying in the step (2) is 80-100 ℃, and the time of the vacuum drying is 12-18h.
Preferably, the protective atmosphere in steps (1) and (2) is nitrogen or argon, the temperature of the high-temperature calcination carbonization treatment is 780-820 ℃, and the heating rate is 4-6 ℃ min ℃. - 1 The treatment time is 2-4h; the high-temperature pyrolysis temperature in the step (2) is 680-720 ℃, and the heating rate is 4-6 ℃ min- 1 The high-temperature pyrolysis time is 1-2h.
Preferably, the mass ratio of the PDAC to the boric acid mixture in the step (2) is 1.00: (3.00-4.00).
The invention also provides application of the catalyst in activating PMS and degrading SMX in antibiotic wastewater. The method comprises the following specific steps: adding PDACB catalyst and PMS into simulated SMX wastewater with pH adjusted to 2.00-12.00 and concentration of 0.05-0.50mM, wherein the catalyst addition amount is 0.50-1.00 g-L- 1 The dosage of PMS is 1.00-2.00mM, the PMS is placed in a constant temperature shaking bed, the rotating speed is set to be 150-250rpm, and the shaking reaction is carried out for 20-30min at the temperature of 20-60 ℃.
Has the advantages that:
(1) The carbon-based material of the catalyst is green and environment-friendly, has economic attraction, can be synthesized on a large scale, and has simple synthesis process and low cost;
(2) The catalyst provided by the invention takes a PDA-derived nitrogen-doped carbon material (PDAC) as a carbon source and a nitrogen source, and dopes heteroatom B by a simple roasting method to prepare a polydopamine-derived N, B co-doped targeting carbon-based catalyst PDACB, which has a good PMS activation effect under a wide pH condition and a good SMX degradation effect;
(3) In the process of activating PMS selective oxidation SMX by the catalyst, the activation effect of PMS is enhanced through single oxygen and interface electron transfer mediated non-free radical oxidation, the reaction process can be accelerated, the balance time is shortened, the catalyst has selectivity to SMX, and the problem of secondary pollution is avoided;
(4) The catalyst can be recycled and has good economical efficiency.
Detailed Description
In order to better understand the present invention, the following examples are further described, which are only used for explaining the present invention and do not limit the present invention.
Example 1:
(1) A simulated antibiotic wastewater containing SMX at a concentration of 0.05mM and a pH of 8.73 was prepared.
(2) A novel catalyst PDACB is prepared by the following steps:
(1) n doping step: firstly, at normal temperature, adding absolute ethyl alcohol and deionized water in a volume ratio of 1.00: 4mL of ammonia water with the mass fraction of 25.00 percent is dripped into 100mL of ethanol solution of 4.00 and stirred for 20min at 300rpm, then 2.00g of dopamine hydrochloride is added into the mixed solution and stirred for 24h at normal temperature and 300 rpm; and slowly dripping 200mL of acetone into the mixed solution under the condition of continuous stirring, and standing and settling for 24 hours after the dripping is finished. And centrifuging to remove supernatant, drying excess acetone in vacuum at 50 ℃ for 40min, freeze-drying the sample in a cold trap at-60 ℃ for 8h, and freeze-drying for 48h to obtain the material PDA. Finally, performing high-temperature calcination carbonization treatment on the PDA in a tubular furnace at 780 ℃ for 2 hours under the nitrogen atmosphere, after the reaction is finished, cooling the tubular furnace to room temperature, washing the material with deionized water until the pH value of the filtrate is 6.94, and performing vacuum drying at 80 ℃ for 18 hours to obtain a material PDAC;
(2) b, doping: and (2) pyrolyzing a mixture of 1.00g of PDAC and 3.00g of boric acid in a tube furnace at 680 ℃ for 1h under a nitrogen atmosphere, washing the material by using deionized water after the reaction is finished and the temperature of the tube furnace is reduced to room temperature until the pH value of the filtrate is 6.84, and drying the material in vacuum at 80 ℃ for 18h to obtain the material PDACB, wherein the atomic proportion of the N element is 2.20%, and the atomic proportion of the B element is 26.20%.
0.05g of the catalyst PDACB prepared in the embodiment is weighed and put into 100mL of SMX-containing simulated antibiotic wastewater prepared in the embodiment, 0.14mmol of PMS is added and placed in a constant-temperature shaking bed, the balance is achieved in 25min at the rotating speed of 200rpm at 20 ℃, and the removal rate of the SMX is 98.40%. The catalyst is repeatedly recycled for 5 times, and the treatment effect can still reach 88.42%.
Example 2:
(1) A simulated antibiotic wastewater containing SMX was prepared, the concentration of SMX was 0.50mM and the pH was 2.00.
(2) A novel catalyst PDACB is prepared by the following steps:
(1) n doping step: firstly, at normal temperature, adding absolute ethyl alcohol and deionized water in a volume ratio of 1.00:5.00 mL of 100mL of ethanol solution is dropwise added with 5mL of ammonia water with the mass fraction of 28.00 percent and stirred for 30min at 200rpm, then 4.00g of dopamine hydrochloride is added into the mixed solution, and stirred for 30h at the normal temperature of 250 rpm; and slowly dripping 300mL of acetone into the mixed solution under the condition of continuous stirring, and standing and settling for 48 hours after finishing dripping. And centrifuging to remove supernatant, drying in vacuum at 60 ℃ for 20min to dry excessive acetone, freeze-drying the sample in a cold trap at-45 ℃ for 4h, and freeze-drying for 24h to obtain the material PDA. Finally, carrying out high-temperature calcination carbonization treatment on PDA at 800 ℃ in a tubular furnace under the argon atmosphere for 4h, after the reaction is finished, cooling the tubular furnace to room temperature, washing the material with deionized water until the pH value of the filtrate is 6.91, and carrying out vacuum drying at 100 ℃ for 12h to obtain a material PDAC;
(2) b doping step: and (2) pyrolyzing a mixture of 1.00g of PDAC and 4.00g of boric acid in a tube furnace at 700 ℃ for 2h under an argon atmosphere, washing the material by using deionized water after the reaction is finished and the temperature of the tube furnace is reduced to room temperature until the pH value of the filtrate is 6.84, and performing vacuum drying at 100 ℃ for 12h to obtain the material PDACB, wherein the atomic proportion of the N element is 4.92%, and the atomic proportion of the B element is 33.89%.
0.10g of the catalyst PDACB prepared in the embodiment is weighed and put into 100mL of SMX-containing simulated antibiotic wastewater prepared in the embodiment, 0.10mmol of PMS is added and placed in a constant-temperature shaking bed, the balance is achieved in 30min at the rotating speed of 150rpm at 60 ℃, and the removal rate of the SMX is 94.38%. The catalyst is repeatedly recycled for 6 times, and the treatment effect can still reach 86.11%.
Example 3:
(1) SMX-containing simulated antibiotic wastewater was prepared, with SMX at a concentration of 0.10mM and a pH of 12.00.
(2) A novel catalyst PDACB is prepared by the following steps:
(1) n doping step: firstly, at normal temperature, adding absolute ethyl alcohol and deionized water in a volume ratio of 1.00: 4mL of ammonia water with the mass fraction of 26.00% is dripped into 100mL of ethanol solution with the mass fraction of 4.00, the mixture is stirred for 25min at 250rpm, then 3.00g of dopamine hydrochloride is added into the mixed solution, and the mixture is stirred for 20h at the normal temperature of 350 rpm; and slowly dripping 250mL of acetone into the mixed solution under the condition of continuous stirring, and standing and settling for 36 hours after the dripping is finished. And centrifuging to remove supernatant, drying excess acetone in vacuum at 55 ℃ for 30min, freeze-drying the sample in a cold trap at-50 ℃ for 6h, and freeze-drying for 36h to obtain the material PDA. Finally, carrying out high-temperature calcination carbonization treatment on the PDA in a tube furnace at 820 ℃ for 3h under the argon atmosphere, washing the material with deionized water after the reaction is finished and the tube furnace is cooled to room temperature until the pH value of the filtrate is 6.97, and carrying out vacuum drying at 90 ℃ for 15h to obtain a material PDAC;
(2) b, doping: and (2) pyrolyzing a mixture of 1.00g of PDAC and 3.50g of boric acid in a tube furnace at 720 ℃ for 1h under an argon atmosphere, washing the material by using deionized water after the reaction is finished and the temperature of the tube furnace is reduced to room temperature until the pH value of the filtrate is 6.92, and drying the material in vacuum at 90 ℃ for 15h to obtain the material PDACB, wherein the atomic proportion of the N element is 3.13 percent and the atomic proportion of the B element is 31.05 percent.
0.10g of the catalyst PDACB prepared in the embodiment is weighed and put into 100mL of SMX-containing simulated antibiotic wastewater prepared in the embodiment, 0.20mmol of PMS is added and placed in a constant-temperature shaking bed, the balance is achieved at 30 ℃ and 250rpm for 20min, and the removal rate of the SMX is 92.11%. The catalyst can be recycled for 5 times, and the treatment effect can still reach 86.09%.
Example 4:
(1) Preparing SMX-containing simulated antibiotic wastewater (1), adding 40mM Cl-and NO-into a part of the prepared simulated wastewater (1) 3 ˉ、HCO 3 ˉ、SO 4 2 - & PO 4 3 And 50 mg. L- 1 Labeled as simulated wastewater (2). The concentration of SMX labeled simulated wastewater was 0.05mM and the pH was 8.73.
(2) A novel catalyst PDACB is prepared by the following steps:
(1) n doping step: firstly, at normal temperature, adding absolute ethyl alcohol and deionized water in a volume ratio of 1.00:4.00 mL of ammonia water with the mass fraction of 25.00 percent is dripped into 100mL of ethanol solution and stirred for 20min at 300rpm, then 2.00g of dopamine hydrochloride is added into the mixed solution and stirred for 24h at normal temperature and 300 rpm; and slowly dripping 200mL of acetone into the mixed solution under the condition of continuous stirring, and standing and settling for 24 hours after the dripping is finished. And centrifuging to remove supernatant, drying excess acetone in vacuum at 50 ℃ for 40min, freeze-drying the sample in a cold trap at-60 ℃ for 8h, and freeze-drying for 48h to obtain the material PDA. Finally, carrying out high-temperature calcination carbonization treatment on the PDA in a tubular furnace at 800 ℃ for 2h under the nitrogen atmosphere, after the reaction is finished, cooling the tubular furnace to room temperature, washing the material with deionized water until the pH value of the filtrate is 6.94, and carrying out vacuum drying at 80 ℃ for 18h to obtain a material PDAC;
(2) b doping step: and (2) pyrolyzing a mixture of 1.00g of PDAC and 3.00g of boric acid in a tube furnace at 700 ℃ for 1h under the nitrogen atmosphere, washing the material with deionized water after the reaction is finished and the temperature of the tube furnace is reduced to room temperature until the pH value of the filtrate is 6.84, and carrying out vacuum drying at 80 ℃ for 18h to obtain the material PDACB, wherein the atomic proportion of N element is 3.22%, and the atomic proportion of B element is 28.37%.
This example is a comparative example of the effect of PDACB, a catalyst prepared according to the present invention, on SMX removal in the presence of other co-existing species. 0.05g of the catalyst PDACB prepared in the embodiment is weighed and put into 100mL of SMX-containing simulated antibiotic wastewater (1) and (2) prepared in the embodiment, 0.14mmol of PMS is added and placed in a constant-temperature shaking bed, the rotation speed of 200rpm at 20 ℃ reaches the balance in 25min, and the removal rate of the SMX is 98.40% and 89.77%. The catalyst is repeatedly recycled by 5, and the treatment effect can still reach 88.42% and 84.64%.
Claims (10)
1. The catalyst for selectively oxidizing sulfamethoxazole by activating peroxymonosulfate is characterized by being nitrogen and boron codoped polydopamine PDACB, wherein the atomic proportion of N element is 2.00-5.00%, and the atomic proportion of B element is 25.00-35.00%.
2. A method for preparing the catalyst of claim 1, comprising the following steps:
(1) N doping: firstly, dropwise adding ammonia water into an ethanol solution and stirring, then adding dopamine hydrochloride into the mixed solution and stirring; dripping acetone into the mixed solution, and standing and settling after the dripping is finished; centrifuging to remove supernatant, vacuum drying excess acetone, and freeze drying to obtain polydopamine PDA; finally, carrying out high-temperature calcination carbonization treatment on the polydopamine PDA under a protective atmosphere, after the reaction is finished and the temperature is reduced, washing the material until the pH value of the filtrate is 6.50-7.00, and carrying out vacuum drying to obtain the nitrogen-doped carbon material PDAC derived from the polydopamine PDA;
(2) B doping: and (3) carrying out high-temperature pyrolysis on the mixture of the nitrogen-doped carbon material PDAC and boric acid in a protective atmosphere, after the reaction is finished and the temperature is reduced, washing the material until the pH value of the filtrate is 6.50-7.00, and carrying out vacuum drying to obtain the material PDACB.
3. The method according to claim 2, wherein the ethanol solution in the step (1) is a mixture of absolute ethanol and deionized water, and the volume ratio of the absolute ethanol to the deionized water is 1.00: (4.00-5.00); the ammonia water is an aqueous solution containing 25.00-28.00% of ammonia by mass fraction; the volume ratio of the ammonia water to the ethanol solution is 1.00: (20.00-25.00); the volume ratio of the mass of the dopamine hydrochloride to the ethanol solution is 20-40 g.L ˉ1 (ii) a The volume ratio of the ethanol solution to the acetone is 1.00: (2.00-3.00).
4. The method according to claim 2, wherein the stirring speed in the dropwise addition of the ammonia water in the step (1) is 200 to 300rpm, and the stirring time is 20 to 30min; adding dopamine hydrochloride, and stirring at the speed of 250-350rpm for 20-30h; standing for 24-48h.
5. The method according to claim 2, wherein the temperature of the freeze-drying in the step (1) is-60 ℃ to-45 ℃; the freeze-drying time is 24-48h.
6. The method according to claim 2, wherein the temperature for vacuum drying the excess acetone in the step (1) is 50-60 ℃, and the vacuum drying time is 20-40min; the temperature of the vacuum drying is 80-100 ℃, and the time of the vacuum drying is 12-18h; the temperature of the vacuum drying in the step (2) is 80-100 ℃, and the time of the vacuum drying is 12-18h.
7. The method according to claim 2, wherein the protective atmosphere in steps (1) and (2) is nitrogen or argon, the temperature of the high-temperature calcination carbonization treatment is 780-820 ℃, and the temperature rise rate is 4-6 ℃ min ˉ1 The treatment time is 2-4h; the temperature of the high-temperature pyrolysis in the step (2) is 680-720 ℃, and the heating rate is 4-6 ℃ min ˉ1 The high-temperature pyrolysis time is 1-2h.
8. The method according to claim 2, wherein the mass ratio of the PDAC to the boric acid mixture in step (2) is 1.00: (3.00-4.00).
9. Use of a catalyst according to claim 1 in activating PMS in degrading SMX in antibiotic wastewater.
10. The application of claim 9, comprising the following specific steps: adding PDACB catalyst and PMS into simulated SMX wastewater with pH adjusted to 2.00-12.00 and concentration of 0.05-0.50mM, wherein the catalyst addition amount is 0.50-1.00 g.L ˉ1 The dosage of PMS is 1.00-2.00mM, the PMS is placed in a constant temperature shaking bed, the rotating speed is set to be 150-250rpm, and the shaking reaction is carried out for 20-30min at the temperature of 20-60 ℃.
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