CN115337948A - Preparation and application of low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst - Google Patents
Preparation and application of low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst Download PDFInfo
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- CN115337948A CN115337948A CN202210878148.XA CN202210878148A CN115337948A CN 115337948 A CN115337948 A CN 115337948A CN 202210878148 A CN202210878148 A CN 202210878148A CN 115337948 A CN115337948 A CN 115337948A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 157
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 70
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 82
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229960003638 dopamine Drugs 0.000 claims abstract description 41
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 18
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 6
- 229920000642 polymer Polymers 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 49
- 230000015556 catabolic process Effects 0.000 claims description 38
- 238000006731 degradation reaction Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 16
- 239000005543 nano-size silicon particle Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 150000002505 iron Chemical class 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 7
- SEQUALWBCFCDGP-UHFFFAOYSA-N [C].[N].[Fe] Chemical compound [C].[N].[Fe] SEQUALWBCFCDGP-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 239000010891 toxic waste Substances 0.000 claims 1
- 239000003344 environmental pollutant Substances 0.000 abstract description 16
- 231100000719 pollutant Toxicity 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 230000003213 activating effect Effects 0.000 abstract description 10
- 150000003254 radicals Chemical class 0.000 abstract description 7
- 239000002351 wastewater Substances 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 4
- 230000002588 toxic effect Effects 0.000 abstract description 4
- 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 98
- 230000000694 effects Effects 0.000 description 31
- 239000000463 material Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002638 heterogeneous catalyst Substances 0.000 description 6
- 238000001994 activation Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 5
- 239000004098 Tetracycline Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 4
- 229940043267 rhodamine b Drugs 0.000 description 4
- 229960005404 sulfamethoxazole Drugs 0.000 description 4
- JLKIGFTWXXRPMT-UHFFFAOYSA-N sulphamethoxazole Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 JLKIGFTWXXRPMT-UHFFFAOYSA-N 0.000 description 4
- 229960002180 tetracycline Drugs 0.000 description 4
- 229930101283 tetracycline Natural products 0.000 description 4
- 235000019364 tetracycline Nutrition 0.000 description 4
- 150000003522 tetracyclines Chemical class 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 229910017053 inorganic salt Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012425 OXONE® Substances 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 231100001239 persistent pollutant Toxicity 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/23—
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- B01J35/51—
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
-
- 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
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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 discloses a preparation method and application of a low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst, wherein the catalyst takes a nano-scale silicon dioxide sphere as a core, and an iron source and dopamine are combined to form a polymerized dopamine shell layer with the iron source; calcining and washing to obtain the low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst, wherein iron loaded in the catalyst does not contain iron polymers and is monatomic iron. The catalyst has a hollow structure, large reaction contact area and high catalytic site exposure rate, can efficiently activate persulfate to degrade toxic and harmful organic pollutants in water, can resist a low-temperature environment and effectively avoid various ionic interferences under an actual wastewater complex pollution system by activating persulfate to degrade the pollutants through a non-free radical way, maintains high efficiency to remove target pollutants, and maintains high efficiency pollutant removal performance after repeated calcination for five times.
Description
Technical Field
The invention relates to the field of environmental catalytic functional materials and the technical field of water treatment, in particular to a preparation method and application of a low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst.
Background
Organic chemical/pharmaceutical wastewater contains a large amount of Persistent Organic Pollutants (POPs), has high toxicity and poor biodegradability, and often needs to be pretreated by an advanced oxidation method. The traditional Fenton pretreatment method has low reaction efficiency, high input cost and heavy secondary pollution, and is difficult to adapt to the increasingly strict pollution control requirement under the current 'double-carbon' background, so that the development of a novel efficient wastewater pretreatment technology is urgently needed. Compared with the method for degrading pollutants by generating active free radicals such as hydroxyl free radicals, sulfate free radicals and the like, the method has more stable oxidation reduction capability in non-free radical ways including singlet oxygen, electron transfer and other ways, wider selectivity and higher reaction rate, can avoid the interference of background impurities such as inorganic salt and the like in a complex pollution system, has wide pH adaptation range, can hardly influence the reaction system by temperature, and can be used as a novel wastewater pretreatment process to realize the high-efficiency degradation of persistent organic pollutants.
Persulfate can generate active oxygen species to degrade persistent organic pollutants in various modes such as physical activation, homogeneous catalysis, heterogeneous catalysis and the like, however, physical activation such as thermal activation and photoactivation require a large amount of additional energy input, and the method belongs to a high-energy-consumption treatment technology. Homogeneous catalysis usually requires a large amount of homogeneous catalysts, and the homogeneous catalysts are difficult to recycle and easily cause secondary pollution. Most of heterogeneous catalysts have high reaction activation energy and low active site density, so that the high-efficiency degradation of target pollutants in a complex pollution system is difficult to realize, and the practical application of the heterogeneous catalysts is limited. The metal atom active site of the monatomic-based heterogeneous catalyst has a utilization rate of 100%, so that persistent pollutants can be efficiently removed from the heterogeneous catalyst under the condition of trace monatomic doping, and due to the high stability and low loading capacity of the monatomic, the iron element doping mass fraction of the material is only 0.3%, and secondary pollution caused by metal ion leakage hardly exists in the catalysis process. The heterogeneous catalyst with the composite structure of the monatomic iron and the hollow carbon spheres is constructed, so that the reaction contact area can be greatly increased, the exposure rate of active sites is increased, and the confined hollow structure can form a short charge electron transmission path, so that the target pollutant is subjected to collapse type fracture in situ at the interface of the heterogeneous catalyst, and the degradation rate and the mineralization rate of the target pollutant are greatly improved.
Disclosure of Invention
Aiming at the problems that the heterogeneous metal catalyst in the prior persulfate catalysis technology has defects, such as low catalysis efficiency, potential secondary pollution, easy interference of temperature, background inorganic salt, natural organic matters and the like on performance, poor cycle performance and the like; the invention aims to provide a preparation method and application of a low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst takes a nano-scale silicon dioxide sphere as a core, and an iron source and dopamine are combined to form a polymerized dopamine shell layer with the iron source; after calcining and washing, the low-temperature nitrogen-resistant self-doped hollow carbon sphere supported iron catalyst is prepared, and iron loaded in the catalyst does not contain iron polymers and is monatomic iron.
The catalyst disclosed by the invention has the advantages that the active site of the monatomic iron is greatly exposed through a hollow structure, the pollutants are degraded through a non-free radical path including a singlet oxygen and electron transfer path, the interference of background factors such as temperature and inorganic salt is effectively resisted, and the target pollutants are removed at high selectivity and high efficiency under a complex pollution system.
A preparation method of a low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst comprises the following steps:
1) Adding tetraethyl silicate into a mixed solution of ammonia water, absolute ethyl alcohol and deionized water, and stirring to form a nano silicon dioxide sphere dispersion solution;
2) Respectively preparing a pure dopamine solution and a dopamine solution containing soluble iron salt, alternately injecting the pure dopamine solution and the dopamine solution into the nano-silica dispersion liquid, continuously stirring, and centrifugally collecting to obtain a nano-silica ball with an iron source and a polymerized dopamine shell layer;
3) Calcining the nano-silica spheres obtained in the step 2) under the protection of inert gas to obtain nano-silica spheres containing iron-nitrogen carbon layers, wherein the sum of the mass of graphite nitrogen and pyridine nitrogen in the nano-silica spheres is 50-90% of the total mass of nitrogen elements;
4) Dispersing the nano silicon dioxide spheres obtained in the step 3) in an ammonium bifluoride solution, stirring, carrying out suction filtration and collection, dispersing the nano silicon dioxide spheres in a sulfuric acid solution again, and washing a product to be neutral after stirring to obtain the low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst.
The nitrogen element is doped into the carbon material as a heteroatom, and the intrinsic inertia of the carbon material can be broken by the nitrogen element or the auxiliary monatomic iron, so that the material has better conductivity and catalytic performance; the incorporation of nitrogen into carbon materials upon high temperature calcination generally results in the formation of four types of nitrogen: nitrogen oxides, graphite nitrogen, pyridine nitrogen, and pyrrole nitrogen; the graphite nitrogen is beneficial to adsorbing persulfate and organic pollutants, the pyridine nitrogen is beneficial to generation of monoatomic iron sites, and the higher the content ratio of the graphite nitrogen to the pyridine nitrogen is, the higher the efficiency of the catalyst for activating persulfate to remove pollutants is.
The volume ratio of ammonia water, absolute ethyl alcohol, deionized water and tetraethyl silicate in the step 1) is 3.
Fe in dopamine solution in step 2) of the invention 3+ The concentration of (A) is 25-100 ug/ml; the soluble ferric salt is one or a mixture of ferric chloride, ferric nitrate, ferric sulfate and ferric acetate; fe 3+ Is not too high, and Fe is not too high 3+ It is easy to agglomerate to form iron polymer, so that pure single-atom iron environment cannot be created, and the low-temperature resistance of the catalyst is affected.
In the step 2), the concentration of dopamine in the pure dopamine solution and the dopamine solution containing soluble iron salt is 5mg/L, and the volume ratio of the pure dopamine solution to the dopamine solution containing soluble iron salt is 1; the pure dopamine solution and the dopamine solution containing soluble iron salt are alternately injected every 5min, and the injection is finished within 35 min.
In the step 3), the calcination temperature is 600-800 ℃, the calcination time is 5h, and the heating rate is 2 ℃/min.
In the step 4), the concentration of the ammonium bifluoride solution is 3.5mol/L, the concentration of sulfuric acid is 0.5mol/L, the mass-to-volume ratio of the nano-silica spheres containing the iron-nitrogen-carbon layer to the ammonium bifluoride solution is 1; the temperature at which the material collected by centrifugation was stirred with the sulfuric acid solution was 80 ℃.
The application of the low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst in degrading organic pollutants in toxic wastewater comprises the following treatment steps: mixing a nitrogen self-doped hollow carbon sphere supported iron catalyst with a solution containing organic pollutants, and adding persulfate to react to degrade the organic pollutants in the solution; the temperature of the reaction system is not more than 35 ℃, and the reaction time is not more than 8min; when the reaction time is not more than 2min, the catalyst of the invention can also obtain higher degradation effect; the catalyst has the advantages that the catalyst can achieve higher catalytic degradation effect at lower temperature; organic contaminants useful in the present invention include, but are not limited to, bisphenol A, sulfamethoxazole, tetracycline, rhodamine B.
The mass concentration ratio of the catalyst, the persulfate and the organic pollutant is 2-4; the persulfate is any one or mixture of sodium persulfate, potassium persulfate and potassium hydrogen persulfate composite salt.
The invention has the advantages that:
(1) According to the preparation method of the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst, the green and environment-friendly biomass dopamine with wide sources is used as a carbon sphere substrate raw material, cheap and non-toxic iron atoms are used as a catalytic center, the iron loading capacity is only 0.3%, and secondary pollution caused by metal ion leakage hardly exists in the catalytic process.
(2) The nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst provided by the invention can remove 99.7% of bisphenol A target pollutants in a very short time under the conditions of low material addition and low persulfate addition, and the fitting calculation of a first-order reaction kinetic constant is 11.39min -1 Compared with the conventional metal catalyst (transition metal catalyst such as iron, cobalt and the like), the rate is one to two orders of magnitude higher.
(3) The nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst provided by the invention mainly degrades pollutants through a non-free radical approach (singlet oxygen and electron transfer) in the persulfate activation process, can effectively resist the interference of multiple factors such as the temperature of a reaction system, inorganic salts and natural organic matters, and can remove target pollutants with high selectivity and high efficiency under a complex pollution system.
(4) The nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst provided by the invention still keeps the removal rate of more than 80% after being recycled for three times, and after being calcined and regenerated, the catalytic performance is recovered to be the original high performance, so that the catalyst can be recycled for multiple times, and the use cost is reduced again.
Drawings
A in FIG. 1 is a transmission electron microscope image of the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst of the present invention;
b in FIG. 1 is a scanning transmission electron microscope (AC-STEM) chart of spherical aberration correction of the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst according to the present invention;
in FIG. 1, c is a Mapping diagram of the distribution of nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst elements;
FIG. 2 is a graph showing the effect of nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst activated persulfate on degradation of bisphenol A, prepared with different amounts of soluble iron salt;
FIG. 3 is a diagram showing the effect of the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst of the present invention in activating persulfate to degrade bisphenol A at different persulfate addition amounts;
FIG. 4 is a diagram showing the effect of the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst of the present invention in activating persulfate to degrade bisphenol A at different reaction temperatures;
FIG. 5 is a diagram showing the effect of the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst of the present invention in activating persulfate to degrade bisphenol A at different initial pH values;
FIG. 6 is a diagram showing the effect of activated persulfate on degradation of bisphenol A in the presence of 10mM of different inorganic salts in the presence of a nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst according to the present invention;
FIG. 7 is a graph showing the effect of activated persulfate on a nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst of the present invention on the degradation of various pollutants;
FIG. 8 is a graph showing the effect of recycling the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst according to the present invention;
FIG. 9 is a graph showing the effect of degrading contaminants by the catalyst in comparative example 4 according to the present invention;
the left graph in fig. 10 is a proportion graph of a plurality of nitrogen elements in the catalyst in comparative example 2 of the present invention;
the right graph in FIG. 10 is a graph showing the effect of various types of catalysts in comparative example 2 of the present invention on the degradation of bisphenol A.
Detailed Description
The invention is described in further detail below with reference to the following description of the drawings and the detailed description.
Example 1: a preparation method of a nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst comprises the following specific steps:
1) Mixing 6.0ml of ammonia water, 140ml of absolute ethyl alcohol and 20ml of deionized water, adding 5.6ml of Tetraethyl Silicate (TEOs), and stirring for 25min to form nano silicon dioxide sphere dispersion liquid;
2) Dissolving 0.8g of dopamine in 160ml of deionized water to prepare a pure dopamine solution; 0.8g dopamine and 0.046g ferric chloride hexahydrate were dissolved in 160ml deionized water to prepare a dopamine solution (Fe) containing soluble iron salts 3+ The concentration of the solution is 100 ug/ml), alternately injecting the two solutions into the nano silicon dioxide ball dispersion liquid at intervals of 5min in sequence, 40ml each time, stirring for 12h after 35min injection, centrifuging and collecting a sample to obtain the nano silicon dioxide ball with the iron source polymerization dopamine shell layer;
3) Placing the nano-silica spheres with the polymerized dopamine shell layer of the iron source obtained in the step 2) into a crucible, covering the crucible with a cover, placing the crucible into a tubular furnace, and heating to 800 ℃ at a speed of 2 ℃/min under the protection of nitrogen atmosphere to calcine for 5 hours. After the reaction is finished, naturally cooling the reaction product to room temperature by using a tube furnace, and taking out a sample to obtain a nano silicon dioxide ball containing the iron-nitrogen carbon layer; the sum of the mass of graphite nitrogen and pyridine nitrogen in the nano silicon dioxide spheres is 80.42 percent of the total mass of nitrogen elements;
4) Dispersing 0.5g of the nano silicon dioxide spheres containing the iron-nitrogen carbon layer obtained in the step 3) into 250ml of ammonium bifluoride solution with the molar concentration of 3.5mol/L, stirring for 12h at room temperature, performing suction filtration, collecting a sample, re-dispersing the sample into 500ml of sulfuric acid solution with the molar concentration of 0.5mol/L, stirring and reacting for 4h at 80 ℃, naturally cooling to room temperature, washing the product with deionized water to be neutral, and performing vacuum drying to obtain the nitrogen self-doped hollow carbon sphere supported iron monoatomic catalyst.
In this embodiment, a Transmission Electron Microscope (TEM) of the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst for efficiently activating persulfate obtained in step 4) (fig. 1 (a), a spherical aberration correction scanning transmission electron microscope (AC-STEM) of the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst (fig. 1 (b)) and an element distribution mapping of the nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst (fig. 1) show that the catalyst is in a hollow sphere shape and a plurality of monatomic irons are distributed on the surface of the catalyst.
Bisphenol A is one of widely applied chemical raw materials, and is widely used as a typical endocrine disrupter in various environmental water bodies. In the example, the prepared nitrogen self-doped hollow carbon sphere supported iron monatomic catalyst is used for activating oxone to detect the degradation performance of the oxone on bisphenol A.
The specific implementation conditions are as follows: dispersing 8mg of catalyst into 100mL of bisphenol A solution, wherein the concentration of bisphenol A is 20mg/L, the initial pH is 6.70, the pH is not adjusted in the experiment process, the experiment temperature is 25 ℃, the catalyst is subjected to ultrasonic treatment for 10min to achieve the complete dispersion effect, magnetic stirring is carried out on the mixed system, the stirring speed is controlled to be 300rpm, adsorption-desorption balance is achieved after continuous stirring is carried out for 30min, then 0.5mL of 20g/L potassium hydrogen persulfate composite salt solution is added to initiate reaction, 0.5mL of sample is taken at set time intervals, 1.0mL of methanol is immediately added into the sample after sampling to terminate the reaction, a filter head with the aperture of 0.22 mu m is adopted to filter to obtain a sample to be tested, and the concentration of bisphenol A in the sample is measured through high performance liquid chromatography. The degradation effect of the bisphenol A is shown in figure 2, the degradation rate of the bisphenol A in 8min reaches 99.5%, and the high efficiency of the catalyst is verified.
Example 2: the other process conditions were the same as in example 1, except that:
in the step b, the adding amount of ferric chloride hexahydrate is changed to 0.0115g (Fe) 3+ Concentration of (2) is 25 ug/ml)
The degradation effect of bisphenol A of the obtained catalyst under the same experimental conditions as in example 1 is shown in FIG. 2, and the degradation rate of bisphenol A in 8min is 68.5%.
Example 3: other process conditions are the same as example 1, except that:
in the step b, the adding amount of ferric chloride hexahydrate is changed to 0.023g (Fe) 3+ The concentration of (2) is 50 ug/ml)
The degradation effect of bisphenol A of the obtained catalyst under the same experimental conditions as in example 1 is shown in FIG. 2, and the degradation rate of bisphenol A in 8min is 83.7%.
Example 4: the other process conditions were the same as in example 1, except that:
in the step b, the adding amount of ferric chloride hexahydrate is changed to 0.0345g (Fe) 3+ Concentration of (2)75 ug/ml)
The degradation effect of bisphenol A of the obtained catalyst under the same experimental conditions as in example 1 is shown in FIG. 2, and the degradation rate of bisphenol A within 8min is 91.2%.
Example 5: in this example, the effect of the amount of potassium monopersulfate added on the bisphenol A removal effect was examined, and the same procedure as in example 1 was repeated except that the amount of the catalyst added was changed.
In this example, the effect of potassium monopersulfate addition amounts of 0.025g/L, 0.05g/L, 0.075g/L and 0.10g/L on the bisphenol A removal effect was examined.
FIG. 3 shows that when the addition amount of potassium hydrogen persulfate is increased, the removal effect of bisphenol A is obviously improved, and when the addition amount of the catalyst is increased from 0.025g/L to 0.10g/L, the removal rate of bisphenol A can be increased from 58.4% to 99.7% within 8min.
Example 6: in this example, the influence of the reaction temperature of the system on the bisphenol A removal effect was examined, and the reaction temperature was the same as in example 1 except that the reaction temperature was different.
This example specifically examined the effect of bisphenol A removal at 5 ℃, 15 ℃, 25 ℃ and 35 ℃.
FIG. 4 shows that the removal rates of bisphenol A in 8min were 98.5%, 98.3%, 99.7% and 98.0% at 5 ℃, 15 ℃, 25 ℃ and 35 ℃. Indicating that the catalyst can maintain high performance at different reaction temperatures.
Example 7: this example discusses the effect of initial pH on SDZ removal, and is the same as example 1 except that the initial pH of the reaction system is different.
This example specifically discusses the effect of initial pH values of 3.14, 5.36, 6.70, 8.72, and 10.84 on bisphenol A removal. Wherein the condition of the initial pH can be adjusted by using hydrochloric acid with a concentration of 1mol/L or sodium hydroxide solution with a concentration of 1 mol/L.
FIG. 5 shows that when the initial pH of the reaction system was 3.14, 5.36, 6.70, 8.72, and 10.84, the removal rate of bisphenol A in 8min was 99.8%, 99.5%, 99.7%, 98.6%, 98.2%, and 97.6%, respectively.
The catalyst is shown to be capable of activating persulfate to efficiently degrade bisphenol A over a very broad pH range, indicating that the catalyst does not require pH preconditioning for contaminant treatment.
Example 8: in order to detect the anti-interference capability of the catalyst in a complex environment system, cl is respectively added into bisphenol A solution - 、SO 4 2- 、NO 3 - 、H 2 PO 4 - 、HCO 3 - The concentrations were 10mmol/L, and the rest was the same as in example 1.
FIG. 6 shows Cl under the same experimental conditions as in example 1 - 、SO 4 2- 、NO 3 - 、H 2 PO 4 - And HCO 3 - In the presence of each of the above-mentioned compounds, the removal rates of bisphenol A in 8min were 99.8%, 99.7%, 99.8%, 98.2% and 77.5%, respectively. Except for HCO 3 - The presence of ions partially inhibits the effect of the catalyst, while the presence of other anions has no effect.
Example 9: in order to detect the degradation effect of the catalyst on different toxic organic pollutants, the bisphenol A pollutant is replaced by sulfamethoxazole, tetracycline and rhodamine B, the concentration of the sulfamethoxazole, the tetracycline and the rhodamine B are all 20mg/L, and the rest is the same as that in the example 1.
FIG. 7 shows that under the same experimental conditions as in example 1, within 8min
The degradation rate of sulfamethoxazole is 96.7 percent; (ii) a
The degradation rate of the tetracycline is 92.3 percent;
the degradation rate of rhodamine B is 99.7 percent.
The catalyst has wide application range and excellent removal effect on various toxic and harmful organic pollutants in water.
Example 10: in order to detect the recycling performance of the catalyst, after the catalyst is used each time, the material is soaked in 50% methanol solution for 3 hours to desorb pollutants, and the material is washed for three times by pure water and then dried for reuse.
FIG. 8 shows that the removal rates of bisphenol A in 8min after two, three, and four uses were 99.1%, 99.0%, and 82.5%, respectively. After three times of use, the material is calcined and regenerated at 800 ℃ by a tube furnace, and the removal rate of bisphenol A in 8min after the regenerated material is used for the fifth time is 98.3%.
Comparative example 1: in order to highlight the important role of the iron monoatomic atoms dispersed on the surface of the nitrogen self-doping hollow carbon sphere loaded iron monoatomic catalyst for efficiently activating persulfate in the catalysis process, a catalyst (DA) without adding soluble iron salt is prepared, and the catalytic effects of the catalysts obtained in comparative example 1 are different. The preparation method was the same as example 1, except that no soluble iron salt was added to the dopamine solution containing iron salt in step b.
As shown in FIG. 2, the degradation rate of bisphenol A in 8min was 32.7% in the catalyst obtained under the same conditions as in example 1.
Comparative example 2: in order to highlight the influence of the calcination temperature on the catalytic performance of the material in the preparation process of the material, the calcination temperature of the material is changed, and the catalytic effect of the catalyst obtained in comparative example 1 is different. The preparation method was the same as example 1, except that the calcination temperature was changed to 600 deg.C, 650 deg.C, 700 deg.C in step c. As shown in fig. 10:
at the temperature of 600 ℃, the sum of the mass of graphite nitrogen and pyridine nitrogen in the nano silicon dioxide spheres is 55.27 percent of the total mass of nitrogen elements;
at 650 ℃, the sum of the mass of the graphite nitrogen and the pyridine nitrogen in the nano silicon dioxide spheres is 61.38 percent of the total mass of the nitrogen element;
at 700 ℃, the sum of the mass of graphite nitrogen and pyridine nitrogen in the nano silicon dioxide spheres is 72.38 percent of the total mass of nitrogen elements.
As shown in fig. 2, the obtained catalysts prepared at different calcination temperatures were subjected to the same conditions as in example 1,
the degradation rate of the catalyst calcined at 600 ℃ to bisphenol A within 8min is 58.7 percent;
the degradation rate of the catalyst calcined at 650 ℃ within 8min to bisphenol A is 65.4 percent;
the degradation rate of bisphenol A in 8min of the catalyst calcined at 700 ℃ is 79.6%.
Comparative example 3: in order to highlight the excellent effect of the nitrogen self-doping hollow carbon sphere supported iron monatomic catalyst iron element for efficiently activating persulfate, catalysts of different soluble metal salts are prepared, and the catalytic effect of the catalysts obtained in comparative example 1 is different. The preparation method is the same as example 1, except that ferric chloride hexahydrate is changed into nickel chloride, copper chloride, manganese chloride and cobalt chloride (hexahydrate) in the ferric salt-containing dopamine solution in the step b, and the adding amount is respectively 0.022g, 0.023g, 0.021g and 0.040g, so as to ensure that the added Fe 3+ And Ni + 、Cu 2+ 、Mn 2+ 、Co 2+ The molar concentration of (c) was kept consistent.
As shown in fig. 2, the obtained catalysts of different soluble metal salts were subjected to the same conditions as in example 1,
doping with Ni + The degradation rate of the catalyst to the bisphenol A within 8min is 88.5 percent;
doping with Cu 2+ The degradation rate of the catalyst to the bisphenol A within 8min is 66.3 percent;
incorporation of Mn 2+ The degradation rate of the catalyst to the bisphenol A within 8min is 66.9 percent;
incorporation of Co 2+ The degradation rate of bisphenol A in 8min of the catalyst (2) is 90.3%.
The cheap and nontoxic monatomic iron material has unique efficiency excellence, and although the catalytic effect is not much different when the metal salt is changed into cobalt salt, the toxicity of the metal cobalt is far greater than that of the metal iron.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and any combination or equivalent changes made on the basis of the above-mentioned embodiments are also within the scope of the present invention.
Comparative example 4: in order to highlight the low temperature resistance effect brought by the activation environment of pure monatomic iron, fe 3+ The prepared material of concentration of (1) of (2) was subjected to a low temperature test at 5 ℃.
As shown in fig. 9, when the reaction system temperature was 25 ℃;
Fe 3+ the catalyst with the concentration of 200ug/ml is used for the reaction within 8minThe degradation rate of bisphenol A is 98.5 percent;
Fe 3+ the degradation rate of the catalyst with the concentration of 400ug/ml to the bisphenol A within 8min is 85.0 percent;
Fe 3+ the degradation rate of bisphenol A in 8min of the catalyst with the concentration of 800ug/ml is 58.5 percent.
When the temperature of the reaction system is 5 ℃;
Fe 3+ the degradation rate of the catalyst with the concentration of 200ug/ml to the bisphenol A within 8min is 83.7 percent;
Fe 3+ the degradation rate of the catalyst with the concentration of 400ug/ml to the bisphenol A within 8min is 65.2 percent;
Fe 3+ the degradation rate of bisphenol A in 8min of the catalyst with the concentration of 800ug/ml is 49.4%.
It should be noted that the above-mentioned embodiments are merely preferred embodiments of the present invention, and are not intended to limit the scope of the present invention, and any combination or equivalent changes made on the basis of the above-mentioned embodiments are also within the scope of the present invention.
Claims (10)
1. The low-temperature-resistant nitrogen self-doped hollow carbon sphere supported iron catalyst is characterized in that a nano-scale silicon dioxide sphere is taken as a core of the catalyst, and an iron source and dopamine are combined to form a polymerized dopamine shell layer with the iron source; calcining and washing to obtain the low-temperature nitrogen-resistant self-doped hollow carbon sphere supported iron catalyst; the iron supported in the catalyst does not contain iron polymers and is all monoatomic iron.
2. The preparation method of the low-temperature nitrogen-resistant self-doped hollow carbon sphere supported iron catalyst according to claim 1, wherein the preparation method comprises the following steps:
1) Adding tetraethyl silicate into a mixed solution of ammonia water, absolute ethyl alcohol and deionized water, and stirring to form a nano silicon dioxide sphere dispersion solution;
2) Respectively preparing a pure dopamine solution and a dopamine solution containing soluble iron salt, alternately injecting the pure dopamine solution and the dopamine solution into the nano-silica dispersion liquid, continuously stirring, and centrifugally collecting to obtain a nano-silica ball with an iron source and a polymerized dopamine shell layer;
3) Calcining the nano-silica spheres obtained in the step 2) under the protection of inert gas to obtain nano-silica spheres containing iron-nitrogen carbon layers, wherein the sum of the mass of graphite nitrogen and pyridine nitrogen in the nano-silica spheres is 50-90% of the total mass of nitrogen elements;
4) Dispersing the nano silicon dioxide spheres obtained in the step 3) in an ammonium bifluoride solution, stirring, carrying out suction filtration and collection, dispersing the nano silicon dioxide spheres in a sulfuric acid solution again, and washing a product to be neutral after stirring to obtain the low-temperature nitrogen-resistant self-doped hollow carbon sphere supported iron catalyst.
3. The preparation method according to claim 2, wherein the volume ratio of the ammonia water, the absolute ethyl alcohol, the deionized water and the tetraethyl silicate in the step 1) is 3.
4. The method according to claim 2, wherein the dopamine solution containing the soluble iron salt in step 2) contains Fe 3+ The concentration of (A) is 25-100 ug/ml; the soluble ferric salt is one or a mixture of ferric chloride, ferric nitrate, ferric sulfate and ferric acetate.
5. The preparation method according to claim 2, wherein the concentration of dopamine in the pure dopamine solution and the dopamine solution containing soluble iron salt in step 2) is 5mg/L, and the volume ratio of the pure dopamine solution to the dopamine solution containing soluble iron salt is 1.
6. The method according to claim 2, wherein the pure dopamine solution and the dopamine solution containing the soluble iron salt in step 2) are injected alternately every 5min, and the injection is completed within 35 min.
7. The preparation method of claim 2, wherein the calcination temperature in step 3) is 600-800 ℃, the calcination time is 5h, and the temperature rise rate is 2 ℃/min.
8. The preparation method according to claim 2, wherein in the step 4), the concentration of the ammonium bifluoride solution is 3.5mol/L, the concentration of the sulfuric acid is 0.5mol/L, the mass-to-volume ratio of the nano-silica spheres containing the iron-nitrogen-carbon layer to the ammonium bifluoride solution is 1.
9. Use of a catalyst according to claim 1 for the degradation of organic pollutants in toxic waste water, wherein the degradation application comprises the following process steps: mixing a nitrogen self-doped hollow carbon sphere supported iron catalyst with a solution containing organic pollutants, and adding persulfate to react to degrade the organic pollutants in the solution; the temperature of the reaction system is not more than 35 ℃, and the reaction time is not more than 8min.
10. The use according to claim 9, wherein the mass ratio of the catalyst, persulfate and organic pollutant is 2-4; the persulfate is any one or mixture of several of sodium persulfate, potassium persulfate and potassium hydrogen persulfate composite salt.
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