CN116174009B - Nitrogen-sulfur doped porous carbon catalyst and application thereof - Google Patents
Nitrogen-sulfur doped porous carbon catalyst and application thereof Download PDFInfo
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- CN116174009B CN116174009B CN202310256852.6A CN202310256852A CN116174009B CN 116174009 B CN116174009 B CN 116174009B CN 202310256852 A CN202310256852 A CN 202310256852A CN 116174009 B CN116174009 B CN 116174009B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 22
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001690 polydopamine Polymers 0.000 claims abstract description 19
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 18
- 229960003151 mercaptamine Drugs 0.000 claims abstract description 18
- 239000002028 Biomass Substances 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 238000000197 pyrolysis Methods 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 32
- 229960003638 dopamine Drugs 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007853 buffer solution Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002699 waste material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 18
- 238000006731 degradation reaction Methods 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003344 environmental pollutant Substances 0.000 abstract description 6
- 231100000719 pollutant Toxicity 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 abstract description 3
- 231100000049 endocrine disruptor Toxicity 0.000 abstract description 2
- 239000000598 endocrine disruptor Substances 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 26
- 239000003575 carbonaceous material Substances 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009303 advanced oxidation process reaction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 235000001759 Citrus maxima Nutrition 0.000 description 3
- 244000276331 Citrus maxima Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000002149 hierarchical pore Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- -1 sulfate radical Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005202 decontamination Methods 0.000 description 2
- 230000003588 decontaminative effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021392 nanocarbon Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000005385 peroxodisulfate group Chemical group 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007847 structural defect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PUKLDDOGISCFCP-JSQCKWNTSA-N 21-Deoxycortisone Chemical compound C1CC2=CC(=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@@](C(=O)C)(O)[C@@]1(C)CC2=O PUKLDDOGISCFCP-JSQCKWNTSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- FCYKAQOGGFGCMD-UHFFFAOYSA-N Fulvic acid Natural products O1C2=CC(O)=C(O)C(C(O)=O)=C2C(=O)C2=C1CC(C)(O)OC2 FCYKAQOGGFGCMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000012425 OXONE® Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 229940095100 fulvic acid Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 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
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- OKBMCNHOEMXPTM-UHFFFAOYSA-M potassium peroxymonosulfate Chemical group [K+].OOS([O-])(=O)=O OKBMCNHOEMXPTM-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
The invention discloses a nitrogen-sulfur doped porous carbon catalyst and application thereof. The catalyst disclosed by the invention is prepared by the following steps: coating melamine sponge or biomass with polydopamine membranes, modifying the polydopamine membranes with mercaptoethylamine, and performing high-temperature pyrolysis to obtain the modified polydopamine membranes. The catalyst obtained by the invention has a three-dimensional interconnected super macroporous structure and a large specific surface area, and the specific surface area can reach 1050cm 2 /g; the porous carbon catalyst is used for activating the peroxymonosulfate to remove the endocrine disruptors which are difficult to degrade in the water body, and shows high degradation efficiency. The preparation method of the nitrogen-sulfur atom double-doped porous carbon catalyst has the advantages of simple operation flow, high pollutant degradation rate and high degradation efficiency, and has good application prospect in the field of treatment of novel pollutants in environmental water body.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a nitrogen-sulfur doped porous carbon catalyst and application thereof.
Background
The increasing demand for clean water has led to tremendous research effort to develop advanced techniques for effectively removing the refractory novel micro-pollutants in complex background waters. The Advanced Oxidation Process (AOPs) has the advantages of mild reaction conditions, high reaction rate, excellent effect of treating organic pollutants in the environment and wide application prospect in the aspect of water purification.
Advanced oxidation technology (SR-AOPs) based on persulfates, due to theirHas high catalytic degradation activity and selectivity to complex water environment pollutants, and has high applicability and effectiveness in disinfection and sewage treatment. The Peroxomonosulphate (PMS) of asymmetric structure is compared with hydrogen peroxide (H) of symmetric structure 2 O 2 ) And Peroxodisulfate (PDS) are activated more easily, sulfate radical [ ]E 0 =2.5-3.1V vs NHE (standard hydrogen electrode)) has a specific hydroxyl radical (·oh, E 0 =1.8-2.7V vs NHE), is relatively stable and has a long lifetime, especially under neutral and slightly alkaline conditions, certain contaminants, which are not oxidizable by hydroxyl radicals, are oxidizable by sulfate radicals.
In recent years, heteroatom doped carbon based activated persulfate advanced oxidation technology has attracted widespread attention in wastewater treatment. PMS is difficult to oxidize directly from organic contaminants and often requires the addition of an activator to increase the yield of PMS to free radicals having high oxidizing power. In the aspect of catalytic material selection of the advanced oxidation process, compared with a metal-based catalyst in heterogeneous catalysis, the heteroatom (nitrogen, phosphorus and sulfur) doped carbon material not only can effectively avoid the secondary pollution problem caused by metal dissolution, but also can improve the surface defects (edge defects: edge sites (zigzag edges and armchair edges) of the carbon material have certain metallic and local limited electrons, strong covalent bond affinity and can promote free radical chain reaction, structural defects can damage the structural integrity of graphene lattices and generate electron local areas to damage conjugated pi systems), and conductivity and hydrophilicity can promote the carbon material to activate PMS to generate more active species (free radicals). In addition, the highly graphitized 3D porous structure nano carbon with large specific surface area is beneficial to the adsorption of reactants and the exposure of active sites. The confinement effect in the porous structure can enhance the mass transfer process and the reactive oxygen species (ros) utilization. However, the stability and recycling of the catalyst have been a problem in catalyst research; practical application of the carbon material activated persulfate for repairing the actual polluted water environment is still limited; the synthesis of nanocarbon materials with controlled properties generally requires cumbersome synthesis methods, using rather expensive precursors, complex equipment for high temperature processing, limiting their mass production and commercialization. Therefore, there is a need to prepare heteroatom doped carbon catalysts that are simple in process, low in cost, environmentally friendly, and efficient and stable.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nitrogen-sulfur atom double-doped porous carbon catalyst and application thereof. The preparation method of the porous carbon catalyst is simple, the pollutant degradation rate is high, the degradation efficiency is high, and the porous carbon catalyst has good application prospect in the field of treating the novel trace pollutants in the environmental water body.
The technical purpose of the invention is realized by the following technical scheme:
the invention provides a nitrogen-sulfur doped porous carbon catalyst, which is prepared by the following steps: coating melamine sponge or biomass with polydopamine membranes, modifying the polydopamine membranes with mercaptoethylamine, and performing high-temperature pyrolysis to obtain the modified polydopamine membranes.
Further, the specific steps of the poly-dopamine membrane coated melamine sponge or biomass are as follows: dispersing melamine sponge or biomass in methanol solution containing dopamine (if waste sponge is adopted, the waste sponge needs to be used after impurity removal), stirring uniformly, and adding Tris-HCl buffer solution.
Preferably, the melamine sponge or biomass, dopamine, methanol and Tris-HCl buffer solution is used in an amount of 0.01g (0.5-1.5 g) to 90mL (80-150 mL).
Further, the specific steps of the mercaptoethylamine modified polydopamine membrane are as follows: adding dopamine, mercaptoethylamine and Tris-HCl buffer solution into the poly-dopamine membrane coated melamine sponge or biomass, and filtering and cleaning after the reaction is completed.
Preferably, the dosage ratio of the dopamine to the mercaptoethylamine to the Tris-HCl buffer solution is (0.5-1.5) g (0.1-1.5) g (40-80) mL.
Further, the concentration of the Tris-HCl buffer solution of the present invention was 10.+ -. 0.5mM, pH=8.5.+ -. 0.1.
Further, the melamine sponge according to the invention is selected from waste sponges.
Preferably, the melamine sponge according to the invention has a volume of 1cm by 1cm.
Further, the conditions of the pyrolysis are as follows: at N 2 Under the protection, the temperature is raised to 800-1000 ℃ at a heating rate of 5-10 ℃/min, and the baking is carried out for 1-2h.
Another technical object of the present invention is to provide an application of the nitrogen-sulfur doped porous carbon catalyst in wastewater treatment. Bisphenol A can be completely degraded in a system with coexisting various anions or organic matters, the concentration of the anions ranges from about 0mM to about 20mM, and the concentration of the organic matters (humic acid and fulvic acid) ranges from about 0mg/L to about 5mg/L.
Compared with the prior art, the invention has the following beneficial effects:
1) The raw materials of the preparation method can be derived from waste household water-absorbing decontamination sponge, and the waste household water-absorbing decontamination sponge is converted into a carbon material with a multistage pore structure, so that the high added value conversion of environmental wastes is realized;
2) The prepared carbon material has a large specific surface area and a 3D hierarchical pore structure, and is beneficial to the adsorption of reactants and the exposure of active sites;
3) The heterogeneous atoms (nitrogen and sulfur atoms) introduced by the prepared carbon material can change the structural defects of the carbon material, so that the catalytic performance of the carbon material is improved by changing the local electronic structure;
4) The nitrogen-sulfur co-doped porous carbon material has a strong catalytic effect on PMS, and the generated active free radicals can efficiently degrade endocrine disruptors in water body so as to achieve the purpose of solving the water pollution problem;
5) The synthesis method of the carbon material is simple and easy to operate, is easy to separate and recycle, does not produce secondary pollution, and has good development prospect in the field of sewage purification.
Drawings
FIG. 1 is a scanning electron microscope photograph of a catalyst of co-doping carbon with nitrogen and sulfur prepared in example 1 of the present invention.
FIG. 2a shows an embodiment of the present inventionN of the carbon co-doped Nitrogen and sulfur catalyst prepared in example 1 2 An adsorption and desorption curve; FIG. 2b is a graph showing the pore size distribution of the carbon co-doped nitrogen-sulfur catalyst prepared in example 1 of the present invention.
FIG. 3 is an X-ray diffraction pattern of the carbon co-doped nitrogen-sulfur catalyst prepared in example 1 of the present invention.
Fig. 4 is a high resolution transmission electron microscope picture of the nitrogen-sulfur co-doped carbon catalyst prepared in example 1 of the present invention.
FIG. 5 is a graph showing the kinetics of degradation of bisphenol A by the carbon co-doped nitrogen and sulfur catalyst prepared in example 1 of the present invention under neutral conditions.
FIG. 6 is a graph showing the kinetics of bisphenol A degradation under neutral conditions for a carbon co-doped nitrogen-sulfur catalyst prepared by varying the ratio of dopamine to mercaptoethylamine in example 1 of the present invention.
Fig. 7 is a kinetic curve of degradation of bisphenol a by the co-carbon catalyst of nitrogen and sulfur prepared by substituting the shaddock peel powder for the melamine carrier in example 1 of the present invention.
FIG. 8 is a graph showing the kinetics of degradation of bisphenol A by the carbon co-doped nitrogen and sulfur catalyst prepared in example 1 of the present invention under different water quality conditions.
Detailed Description
For a better description of technical objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the accompanying drawings and specific embodiments.
1. Preparation of the catalyst
Example 1
Cutting melamine sponge into square blocks (1 cm multiplied by 1 cm), washing with NaOH solution, distilled water and ethanol to remove impurities, dispersing in 90mL of methanol solution, adding 1g of dopamine, stirring for 2h, adding 100mL of Tris-HCl buffer solution (10 mM, pH=8.5, and mixed solution of Tris and hydrochloric acid) to promote dopamine polymerization; continuously stirring for 4 hours, continuously adding 1g of dopamine, 0.4g of mercaptoethylamine and 40mL of Tris-HCl buffer solution, stirring for 4 hours, filtering after the reaction is completed, and cleaning to obtain melamine sponge of the mercaptoethylamine modified polydopamine membrane; wherein, during the polymerization process of dopamine, the pH value of the solution needs to be kept at about 8.5.
Washing and drying the melamine sponge of the mercaptoethylamine modified polydopamine membrane, and carrying out N-phase reaction on the melamine sponge 2 Heating to 800-1000 ℃ in a tube furnace at a heating rate of 5-10 ℃/min under protection, and roasting for 1-2 h; and roasting at high temperature to obtain the blocky carbon material.
The three-dimensional connected hierarchical pore structure of the carbon material is shown in the scanning electron microscope photograph of fig. 1, and it can be seen that the carbon material has a connected pore structure and has a rough surface. FIGS. 2a and 2b present N thereof 2 The adsorption and desorption curve/pore diameter distribution diagram proves that the carbon material has a large specific surface area and a micropore, mesopore and macropore hierarchical pore structure. The defect structure of the above carbon material was confirmed by the (002) crystal plane in the X-ray diffraction chart of fig. 3 and the high curvature graphite lattice fringes and the large interplanar spacing (0.37 nm) in the high resolution transmission electron microscope picture shown in fig. 4.
Examples 2 to 9
The preparation methods of examples 2 to 9 are the same as in example 1, except that a series of carbon materials with different nitrogen and sulfur doping amounts can be controllably synthesized by adjusting the addition amounts of dopamine and mercaptoethylamine in example 1.
Table 1 examples 2 to 9 amounts of dopamine and mercaptoethylamine added
Example 10
The melamine sponge carrier used in example 1 was replaced with shaddock peel powder in the same amount, reaction conditions and preparation method as in example 1.
Comparative example 1
Nitrogen-doped carbon catalyst (NC): the preparation was the same as in example 1, except that mercaptoethylamine was not added during the catalyst preparation.
Comparative example 2
Undoped carbon material (C): the carbon material obtained by directly carbonizing the shaddock peel powder was prepared under the same carbonization conditions as in example 1.
2. Effect testing
1.8 mg of the porous carbon catalyst prepared in example 1 and 1mM of peroxymonosulfate are simultaneously added into a bisphenol A aqueous solution (volume is 200 mL) with the concentration of 10mg/L and vibrated at a constant speed, and the degradation of bisphenol A is completed within 1.5h, wherein the degradation rate can reach 100%, and the peroxymonosulfate is potassium peroxymonosulfate. Tests show that the catalysis performance of the nitrogen-sulfur co-doped catalyst (NSC) prepared in the example 1 is better than that of the nitrogen-doped carbon catalyst (NC) prepared in the comparative example 1, and the degradation kinetics curves are shown in figure 5.
2. As shown in FIG. 6, NSCs prepared in examples 2 to 9 all showed excellent catalytic performance, and bisphenol A degradation rates were higher than 50%, wherein the degradation rates of bisphenol A corresponding to NSCs prepared in examples 2 to 5 were 100%.
3. Through tests, the degradation performance of the nitrogen-sulfur co-doped carbon material (NSC) prepared in the example 10 on bisphenol A is superior to that of the nitrogen-doped carbon material (NC) described in the comparative example 1 and the undoped carbon material (C) in the comparative example 2, and the degradation kinetic curve is shown in FIG. 7, wherein dopamine is 1g; mercaptoethylamine was 0.4g. Catalytic reaction conditions: the catalyst was 10mg, potassium persulfate was 1mM, the volume of the solution was 100mL, and the bisphenol A concentration was 10mg/L.
4. The NSC catalyst prepared in example 1 was used to degrade bisphenol A in an actual water body, and the water quality index of different water bodies is shown in Table 2, wherein ultrapure water is used as a control group. Through the test: BPA in seawater, groundwater and tap water was almost completely degraded within 1.5 h; more than 2 times of catalyst is needed to be added in the system of the Yangtze river water with more complex water quality and the wastewater of the sewage treatment plant so as to completely degrade the BPA. Catalytic reaction conditions: the catalyst was 8mg, potassium persulfate was 1mM, the volume of the solution was 200mL, and the bisphenol A concentration was 10mg/L. The degradation kinetics curves are shown in figure 8.
TABLE 2 Water quality index (concentration units of each component (mg/L))
The above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, but the present invention may be implemented in other ways, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention, but these modifications or substitutions are all within the scope of the present invention.
Claims (7)
1. The nitrogen-sulfur doped porous carbon catalyst is characterized by being prepared by the following steps: coating melamine sponge or biomass with a polydopamine membrane, modifying the polydopamine membrane with mercaptoethylamine, and performing high-temperature pyrolysis to obtain the modified polydopamine membrane; the specific preparation steps of the poly-dopamine membrane coated melamine sponge or biomass are as follows: dispersing melamine sponge or biomass in a methanol solution containing dopamine, stirring uniformly, and adding a Tris-HCl buffer solution; the specific preparation steps of the mercaptoethylamine modified polydopamine membrane are as follows: adding dopamine, mercaptoethylamine and Tris-HCl buffer solution into the melamine sponge or biomass coated with the polydopamine film, and filtering and cleaning after the reaction is completed; the conditions of the pyrolysis are as follows: at N 2 Under the protection, the temperature is raised to 800-1000 ℃ at a heating rate of 5-10 ℃/min, and the mixture is baked to 1-2h.
2. The nitrogen-sulfur doped porous carbon catalyst according to claim 1, wherein in the preparation step of the polydopamine membrane coated melamine sponge or biomass, the usage ratio of the melamine sponge or biomass, dopamine, methanol and Tris-HCl buffer solution is 0.01g (0.5-1.5) g to 90mL (80-150) mL.
3. The nitrogen-sulfur doped porous carbon catalyst according to claim 1, wherein in the preparation step of the mercaptoethylamine modified polydopamine membrane, the usage ratio of the dopamine, mercaptoethylamine and Tris-HCl buffer solution is (0.5-1.5) g (0.1-1.5) g (40-80) mL.
4. The nitrogen-sulfur doped porous carbon catalyst according to claim 1, wherein the Tris-HCl buffer solution has a concentration of 10±0.5mM, ph=8.5±0.1.
5. The nitrogen-sulfur doped porous carbon catalyst according to claim 1, wherein the melamine sponge is selected from waste sponges.
6. The nitrogen-sulfur doped porous carbon catalyst according to claim 5, wherein the melamine sponge has a volume of 1cm x 1cm x 1cm.
7. The use of the nitrogen-sulfur doped porous carbon catalyst according to any one of claims 1 to 6 in wastewater treatment.
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